JP2012153878A - Resin, resist composition, and method of manufacturing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition that can manufacture a resist pattern of excellent CD uniformity.SOLUTION: A resin has a structural unit (aa) shown by formula (aa) and a structural unit (ab) shown by formula (ab). The resist composition includes the resin. In the formulas, Rand Rdenote a hydrogen atom or a methyl group, Rdenotes a hydrogen atom or a fluorinated alkyl group, Rdenotes a fluorinated alkyl group, Rdenotes an atom or a group in which a bond [O-R] with an oxygen atom is not cut by the action of an acid, and ndenotes 1 or 2.

Description

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

In recent years, as a semiconductor microfabrication technique, an optical lithography technique using short-wavelength light such as an ArF excimer laser (wavelength: 193 nm) as an exposure source has been actively studied. A resist composition is used in the optical lithography technology, and examples of the resin used in such a resist composition include a structural unit represented by the formula (u-A) and a formula (u-B). Resins composed of structural units are known. Further, the resin, a structural unit represented by the formula (u-C), a structural unit represented by the formula (u-D), a structural unit represented by the formula (u-E), and the formula (u-F) A resist composition containing a resin composed of a structural unit represented by (II) and an acid generator is also known (Patent Document 1).

JP 2009-191151 A

  A resist pattern produced from a conventionally known resist composition containing the above resin may not always satisfy CD uniformity (CDU).

［式（ａａ）中、
Ｒ^aa１は、水素原子又はメチル基を表す。
Ｒ^aa2は、水素原子又は炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa３は、炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa４は、酸の作用により、酸素原子との間の結合〔Ｏ−Ｒ^aa４〕が切断されない原子又は基を表す。
ｎ^aa１は１又は２を表す。ｎ^aa１が２の場合、２つのＲ^aa２は同一又は相異なり、２つのＲ^aa３は同一又は相異なり、２つのＲ^aa４は同一又は相異なる。
Ａ^aa１は、置換基を有していてもよい炭素数１〜１０の炭化水素基を表し、該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（ａｂ）中、
Ｒ^ab1は、水素原子又はメチル基を表す。
Ａ^ab1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を表し、該アルカンジイル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^ab2は、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族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。］
〔２〕前記式（ａｂ）のＡ^ab1が、炭素数１〜６のアルカンジイル基である〔１〕記載の樹脂。
〔３〕前記式（ａｂ）のＡ^ab1が、エチレン基である〔１〕記載の樹脂。
〔４〕〔１〕〜〔３〕のいずれか記載の樹脂と、酸発生剤とを含有するレジスト組成物。
〔５〕前記酸発生剤が、式（Ｂ１）で表される酸発生剤である〔４〕記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜１７の脂肪族炭化水素基を表し、該脂肪族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の脂肪族炭化水素基を表し、該脂肪族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。
Ｚ⁺は、有機カチオンを表す。］
〔６〕前記式（Ｂ１）のＹが、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である〔５〕記載のレジスト組成物。
〔７〕アルカリ水溶液に不溶又は難溶であり、酸の作用によりアルカリ水溶液に可溶となる樹脂を、さらに含有する〔４〕〜〔６１〕のいずれか記載のレジスト組成物。
〔８〕さらに溶剤を含む〔４〕〜〔７〕のいずれか記載のレジスト組成物。
〔９〕（１）前記〔４〕〜〔８〕のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層を露光する工程、
（４）露光後の組成物層を加熱する工程、
（５）加熱後の組成物層を現像する工程及び
を含むレジストパターンの製造方法。 As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
That is, the present invention includes the following inventions.
[1] A resin having a structural unit (aa) represented by the formula (aa) and a structural unit (ab) represented by the formula (ab).

[In the formula (aa)
R ^aa1 represents a hydrogen atom or a methyl group.
R ^aa2 represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa3 represents a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa4 represents an atom or group in which the bond [O—R ^aa4 ] to the oxygen atom is not ^broken by the action of an acid.
n ^aa1 represents 1 or 2; When n ^aa1 is 2, two R ^aa2 are the same or different, two R ^aa3 are the same or different, and two R ^aa4 are the same or different.
A ^aa1 represents an ^optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

[In the formula (ab),
R ^ab1 represents a hydrogen atom or a methyl group.
A ^ab1 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
R ^ab2 represents an ^optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. Good. ]
[2] The resin according to [1], wherein A ^{ab1 in the} formula (ab) is an alkanediyl group having 1 to 6 carbon atoms.
[3] The resin according to [1], wherein A ^{ab1 in the} formula (ab) is an ethylene group.
[4] A resist composition containing the resin according to any one of [1] to [3] and an acid generator.
[5] The resist composition according to [4], wherein the acid generator is an acid generator represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group. May be.
Z ⁺ represents an organic cation. ]
[6] The resist composition according to [5], wherein Y in the formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
[7] The resist composition according to any one of [4] to [61], further containing a resin that is insoluble or hardly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid.
[8] The resist composition according to any one of [4] to [7], further containing a solvent.
[9] (1) A step of applying the resist composition according to any one of [4] to [8] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A step of heating the composition layer after exposure,
(5) A step of developing the composition layer after heating, and a method for producing a resist pattern.

［式（Ｒ^４−１）中、
Ｒ⁴⁴〜Ｒ⁴⁶は、それぞれ独立に、炭素数１〜６の脂肪族飽和炭化水素基を表すか、又は、Ｒ⁴⁴〜Ｒ⁴⁶のうちの２つが互いに結合して環を形成し、残りの１つは水素原子又は炭素数１〜６の脂肪族飽和炭化水素基である。］
〔１３〕前記式（ａａ）のＲ^aa4が、以下の式（Ｂ２−１）又は式（Ｂ２−２）で表される基である〔１〕記載の樹脂。

［式（Ｂ２−１）及び式（Ｂ２−２）中、
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ｌは、０〜５の整数を表す。
Ｒ^３は、炭素数１〜２０の炭化水素基を表し、該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。ｌが２以上のとき、複数のＲ^３は同一でも異なっていてもよく、複数のＲ^３のうち、２つのＲ^３が互いに結合して、それらが結合する炭素原子とともに、炭素数３〜２０の環を形成していてもよい。
ｌ’は、０〜３の整数を表す。
Ｒ^４は、カルボキシ基、シアノ基又は炭素数１〜２０の炭化水素基を表し、該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。ｌ’が２以上のとき、複数のＲ^４は同一でも異なっていてもよく、複数のＲ^４のうち、２つのＲ^４が互いに結合して、それらが結合する炭素原子とともに、炭素数３〜２０の環を形成していてもよい。］
〔１４〕前記式（ａａ）のＡ^aa1が、炭素数２〜１０の分岐した鎖式炭化水素基又は炭素数３〜１０の脂環式炭化水素基である〔１〕記載の樹脂。 The present invention also includes the following inventions.
[10] The resin according to [1], wherein R ^{aa4 in the} formula (aa) is a hydrogen atom.
[11] The resin according to [1], wherein R ^{aa4 in the} formula (aa) is an acyl group having 2 to 12 carbon atoms.
[12] The resin according to [1], wherein R ^{aa4 in the} formula (aa) is a group represented by the following formula (R ⁴ -1).

[In the formula (R ⁴ -1),
R ^{44 to} R ⁴⁶ each independently represents an aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, or two of R ^{44 to} R ⁴⁶ are bonded to each other to form a ring, and the rest One is a hydrogen atom or an aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. ]
[13] The resin according to [1], wherein R ^{aa4 in the} formula (aa) is a group represented by the following formula (B2-1) or formula (B2-2).

[In Formula (B2-1) and Formula (B2-2),
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
l represents an integer of 0 to 5.
R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. When l is 2 or more, the plurality of R ³ may be the same or different, and among the plurality of R ³ , two R ³ are bonded to each other, and together with the carbon atom to which they are bonded, the number of carbon atoms is 3 to 20 The ring may be formed.
l ′ represents an integer of 0 to 3.
R ⁴ represents a carboxy group, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. When l ′ is 2 or more, the plurality of R ⁴ may be the same or different, and among the plurality of R ⁴ , two R ⁴ are bonded to each other, and together with the carbon atom to which they are bonded, 20 rings may be formed. ]
[14] The resin according to [1], wherein A ^{aa1 in the} formula (aa) is a branched chain hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.

  By using the resin of the present invention in a resist composition, a resist pattern having excellent CD uniformity (CDU) can be produced.

The resin of the present invention has a structural unit represented by the formula (aa) (hereinafter sometimes referred to as “structural unit (aa)”) and a structural unit represented by the formula (ab) (hereinafter “structural unit (ab)”). And a resin (hereinafter sometimes referred to as “resin (X)”).
The resist composition of the present invention (hereinafter sometimes referred to as “the present resist composition”) contains a resin (X) and an acid generator.
When this resist composition contains the resin (X), a resist pattern having excellent CD uniformity can be produced.

  In the present specification, unless otherwise specified, the following examples of substituents are applied to any chemical structural formula having the same substituents while appropriately selecting the number of carbon atoms. Those which can be linear, branched or cyclic include any of them, and they may be mixed. When stereoisomers exist, all stereoisomers are included. * Represents a bond. In the following examples of substituents, the numerical value attached to “C” indicates the number of carbon atoms of each group.

  In the present specification, the “hydrocarbon group” refers to an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group is further classified into a chain type and an alicyclic type. Unless otherwise defined, the term “aliphatic hydrocarbon group” in the present specification includes an aliphatic hydrocarbon group in which a chain and alicyclic aliphatic hydrocarbon group are combined.

Of the chain aliphatic hydrocarbon groups (chain hydrocarbon groups), the monovalent one is typically an alkyl group. Examples of the alkyl group include a methyl group (C ₁ ), an ethyl group (C ₂ ), Propyl group (C ₃ ), butyl group (C ₄ ), pentyl group (C ₅ ), hexyl group (C ₆ ), heptyl group (C ₇ ), octyl group (C ₈ ), decyl group (C ₁₀ ) , Dodecyl group (C ₁₂ ), hexadecyl group (C ₁₄ ), pentadecyl group (C ₁₅ ), hexyldecyl group (C ₁₆ ), heptadecyl group (C ₁₇ ), octadecyl group (C ₁₈ ), etc. It may be linear or branched.
Unless particularly limited, this chain hydrocarbon group may contain a carbon-carbon double bond in a part of the alkyl groups exemplified herein, but does not have such a carbon-carbon double bond, etc. Of these, a chain hydrocarbon group, particularly a saturated alkyl group, is preferred. The divalent chain hydrocarbon group corresponds to an alkanediyl group obtained by removing one hydrogen atom from the alkyl group shown here.

などが挙げられる。
多環式の脂環式炭化水素は例えば、
式（ＫＡ−８）で示されるビシクロ〔２．２．１〕ヘプタン（以下「ノルボルナン」ということがある。）（Ｃ_７）、
式（ＫＡ−９）で示されるアダマンタン（Ｃ₁₀）及び
式（ＫＡ−１０）〜式（ＫＡ−２２）で示される脂環式炭化水素

などが挙げられる。なお、ここに示した脂環式炭化水素を「式（ＫＡ−１）〜式（ＫＡ−２２）の脂環式炭化水素」ということがある。
２価の脂環式炭化水素基とは、式（ＫＡ−１）〜式（ＫＡ−２２）の脂環式炭化水素から水素原子を２個取り去った基が該当する。 Monovalent alicyclic aliphatic hydrocarbon groups (hereinafter sometimes referred to as “alicyclic hydrocarbon groups”) typically remove one hydrogen atom from an alicyclic hydrocarbon. It is a group. The alicyclic hydrocarbon group may be an unsaturated alicyclic hydrocarbon group containing about one carbon-carbon unsaturated bond, or may be a saturated alicyclic hydrocarbon group containing no such carbon-carbon unsaturated bond. The alicyclic hydrocarbon group referred to in the present specification is preferably saturated. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Here, an alicyclic hydrocarbon group will be illustrated by illustrating an alicyclic hydrocarbon before removing a hydrogen atom. Monocyclic alicyclic hydrocarbons are typically cycloalkanes, specific examples of which are:
Cyclopropane (C ₃ ) represented by the formula (KA-1),
Cyclobutane (C ₄ ) represented by the formula (KA-2),
Cyclopentane (C ₅ ) represented by the formula (KA-3),
Cyclohexane (C ₆ ) represented by the formula (KA-4),
Formula cycloheptane represented by _{(KA-5) (C 7} ),
Cyclooctane (C ₈ ) represented by the formula (KA-6), and
Cyclododecane (C ₁₂ ) represented by the formula (KA-7)

Etc.
Examples of polycyclic alicyclic hydrocarbons include:
Bicyclo [2.2.1] heptane represented by the formula (KA-8) (hereinafter sometimes referred to as “norbornane”) (C ₇ ),
Adamantane (C ₁₀ ) represented by formula (KA-9) and alicyclic hydrocarbon represented by formula (KA-10) to formula (KA-22)

Etc. In addition, the alicyclic hydrocarbon shown here may be called "the alicyclic hydrocarbon of a formula (KA-1)-a formula (KA-22)."
The divalent alicyclic hydrocarbon group corresponds to a group in which two hydrogen atoms are removed from the alicyclic hydrocarbon of the formula (KA-1) to the formula (KA-22).

The aromatic hydrocarbon group is a monovalent aromatic hydrocarbon group and is typically an aryl group. Specific examples include a phenyl group (C ₆ ), a naphthyl group (C ₁₀ ), an anthryl group (C ₁₄ ), a biphenyl group (C ₁₂ ), a phenanthryl group (C ₁₄ ), and a fluorenyl group (C ₁₃ ). .

  The aliphatic hydrocarbon group may have a substituent. Such substituents are defined each time, and here, representative examples of the substituents are given. Examples of the substituent include a halogen atom, an alkoxy group, an acyl group, an aryl group, an aralkyl group, and an aryloxy group.

The halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom unless otherwise specified.
Examples of alkoxy groups include methoxy group (C ₁ ), ethoxy group (C ₂ ), propoxy group (C ₃ ), butoxy group (C ₄ ), pentyloxy group (C ₅ ), hexyloxy group (C ₆ ), heptyl Examples thereof include an oxy group (C ₇ ), an octyloxy group (C ₈ ), a decyloxy group (C ₁₀ ), and a dodecyloxy group (C ₁₂ ), and these alkoxy groups may be linear or branched.
Specific examples of the acyl group are acetyl group (C ₂ ), propionyl group (C ₃ ), butyryl group (C ₄ ), valeryl group (C ₅ ), hexanoyl group (C ₆ ), heptanoyl group (C ₇ ), octanoyl In addition to those in which an alkyl group such as a group (C ₈ ), decanoyl group (C ₁₀ ) and dodecanoyl group (C ₁₂ ) and a carbonyl group are bonded, an aryl group and a carbonyl group such as a benzoyl group (C ₇ ) Including the combination of Among these acyl groups, an alkyl group and a carbonyl group bonded to each other may be linear or branched.
Specific examples of the aryl group are the same as those exemplified as the aryl group of the above-mentioned aromatic hydrocarbon group, and specific examples of the aryloxy group are those in which the aryl group and an oxygen atom are bonded.
Specific examples of the aralkyl group include a benzyl group (C ₇ ), a phenethyl group (C ₈ ), a phenylpropyl group (C ₉ ), a naphthylmethyl group (C ₁₁ ), and a naphthylethyl group (C ₁₂ ).

  The aromatic hydrocarbon group may also have a substituent. Although such a substituent is defined each time, a halogen atom, an alkoxy group, an acyl group, an alkyl group, and an aryloxy group can be mentioned. Among these, the alkyl group is the same as those exemplified as the chain aliphatic hydrocarbon group, and among the substituents optionally present in the aromatic hydrocarbon group, those other than the alkyl group are aliphatic hydrocarbon groups. The same thing as what was illustrated as a substituent of is included.

<Resin (X)>
The resin (X) has a structural unit (aa) represented by the formula (aa) and a structural unit (ab) represented by the formula (ab).

［式（ａａ）中、
Ｒ^aa１は、水素原子又はメチル基を表す。
Ｒ^aa2は、水素原子又は炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa３は、炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa４は、酸の作用により、酸素原子との間の結合〔Ｏ−Ｒ^aa４〕が切断されない原子又は基を表す。
ｎ^aa１は１又は２を表す。ｎ^aa１が２の場合、２つのＲ^aa２は同一又は相異なり、２つのＲ^aa３は同一又は相異なり、２つのＲ^aa４は同一又は相異なる。
Ａ^aa１は、置換基を有していてもよい炭素数１〜１０の炭化水素基を表し、該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。］ <Structural unit (aa)>
The structural unit (aa) is a structural unit represented by the formula (aa).

[In the formula (aa)
R ^aa1 represents a hydrogen atom or a methyl group.
R ^aa2 represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa3 represents a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa4 represents an atom or group in which the bond [O—R ^aa4 ] to the oxygen atom is not ^broken by the action of an acid.
n ^aa1 represents 1 or 2; When n ^aa1 is 2, two R ^aa2 are the same or different, two R ^aa3 are the same or different, and two R ^aa4 are the same or different.
A ^aa1 represents an ^optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

A ^aa1 represents a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a hydrocarbon group obtained by combining them. May be. Furthermore, the aliphatic hydrocarbon group may be a chain hydrocarbon group, an alicyclic hydrocarbon group, or a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group. In addition, the aliphatic hydrocarbon group is a saturated aliphatic hydrocarbon group (saturated hydrocarbon group) that does not have such a carbon-carbon double bond even though it has a carbon-carbon multiple bond in a part thereof. There may be.

In the case where n ^aa1 is 1, A ^aa1 is typically an alkanediyl group or a divalent alicyclic hydrocarbon group, and specific examples thereof include those already exemplified in the range of 10 or less carbon atoms. 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- Linear alkanediyl group such as 1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group And branched alkanediyl groups such as 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.
The divalent alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include those in which two hydrogen atoms are bonded from a cycloalkane such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, and cyclooctane. Is mentioned. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, adamantane, norbornane and methylnorbornane, and those having two hydrogen atoms as a bond from the groups shown below.

In the case where n ^aa1 is 2, A ^aa1 is typically a group obtained by removing one hydrogen atom from the alkanediyl group or divalent alicyclic hydrocarbon group mentioned in the case where n ^aa1 is 1. Is applicable.
Specific examples of A ^aa1 when n ^aa1 is 2 include methine group, ethane-1,1,1-triyl group, ethane-1,1,2-triyl group, propane-1,1,3- Examples include triyl group, propane-1,2,3-triyl group, cyclohexane-1,3,5-triyl group and adamantane-1,3,5-triyl group.

The hydrocarbon group for A ^aa1 may have a substituent. As a substituent, a hydroxy group or a C1-C6 alkoxy group is preferable. However, the number of carbon atoms in this substituent is not included in the number of carbon atoms of A ^aa1 . In view of the ease of production of the compound that derives the structural unit (aa) described later, a hydrocarbon group having no substituent is particularly preferable as A ^aa1 .

Examples of the group in which the methylene group contained in the hydrocarbon group of A ^aa1 is replaced with an oxygen atom or a carbonyl group, when ^naa1 is 1, include the following groups. In this specific example, * indicates a bond with a carbonyloxy group.

などが挙げられる。 As A ^aa1 when one or two of the methylene groups are replaced by oxygen atoms,

Etc.

などが挙げられる。 A ^aa1 when one or two of the methylene groups are replaced with a carbonyl group,

Etc.

などが挙げられる。さらに、後述する、Ａ^ab1のアルカンジイル基に含まれるメチレン基が酸素原子又はカルボニル基に置き換わったものとして例示したものが挙げられる。 2 in turn, each of the methylene group, the preferably A ^aa1 when replaced by an oxygen atom and a carbonyl group, those containing a carbonyl group, its specific examples,

Etc. Furthermore, what was illustrated as what replaced the methylene group contained in the alkanediyl group of ^{Aab1 mentioned} later by the oxygen atom or the carbonyl group is mentioned.

などが挙げられる。 As A ^aa1 when three methylene groups are replaced by oxygen atoms and / or carbonyl groups,

Etc.

When n ^aa1 is 2, one in which one of the hydrogen atoms contained in these specific examples is replaced with a bond to C (R ^aa2 ) (R ^aa3 ), the methylene group is replaced with an oxygen atom or a carbonyl group. This corresponds to a specific example of the substituted aliphatic hydrocarbon group.
However, even if the group bonded to the carbonyloxy group side in A ^aa1 is a methylene group, that is, the methylene group at the bonding position with the oxygen atom is not replaced with an oxygen atom or a carbonyl group.

Among these, A ^aa1 is preferably an aliphatic hydrocarbon group, more preferably a branched chain hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 1-amyl-1 , 2-ethylene group, cyclohexane-1,3,5-triyl group and adamantane-1,3,5-triyl group are more preferred. A ^aa1 is preferably an aliphatic saturated hydrocarbon group, and more preferably an aliphatic saturated hydrocarbon group not containing a carbon-carbon multiple bond in a chain hydrocarbon group.

The fluorinated alkyl group having 1 to 6 carbon atoms of R ^aa2 and R ^aa3 is the alkyl group having 1 to 6 carbon atoms exemplified above, and part or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. It means what was done. Specific examples of the fluorinated alkyl group include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and a 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, 3- (trifluoromethyl) -2,2,3,4,4,4-hexafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) (Romethyl) -2,2,2-trifluoroethyl group, 2- (perfluoropropyl) 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, perfluoro Pentyl 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, perfluoropentylmethyl group and perfluorohexyl group, among which trifluoromethyl group, perfluoroethyl group, 3- (trifluoromethyl group) 2,2,3,4,4,4-hexafluoro-butyl group.
In the structural unit (aa), R ^aa2 and R ^aa3 may be hydrogen atoms, but R ^aa2 and R ^aa3 are not both hydrogen atoms.

R ^aa4 represents a monovalent atom or group in which the bond [O—R ^aa4 ] to the oxygen atom is not ^broken by the action of an acid. Here, the "O-R ^aa4 bond is not cleaved by the action of an acid" properties, in later-described resist composition, an acid which acid generator is generated by receiving exposure energy, O-R ^aa4 bond cleavage It means that it is not done.
Such R ^aa4 is a hydrogen atom. In this case, the group represented by —O—R ^aa4 is a hydroxy group.

Specific examples of the structural unit (aa) when R ^aa4 is a hydrogen atom are as follows.

Ｒ^aa4が水素原子である、前記の構造単位（ａａ）の具体例の中でも、式（ａａ−１１）、式（ａａ−１２）、式（ａａ−１３）、式（ａａ−１４）、式（ａａ−１５）及び式（ａａ−１９）のいずれかで表されるものが好ましい。 In the structural unit (aa) represented by any one of the formulas (aa-1) to (aa-20), a structural unit (aa) in which the partial structure M shown below is replaced with a partial structure A shown below ).

Among the specific examples of the structural unit (aa) in which R ^aa4 is a hydrogen atom, the formula (aa-11), the formula (aa-12), the formula (aa-13), the formula (aa-14), the formula What is represented by either (aa-15) or formula (aa-19) is preferable.

（式（ａａ１）中の符号はいずれも、前記と同義である。）
かかる化合物（ａａ１）は、例えば、特開２００８−１２２９３２号公報に記載の方法などの公知の方法により製造することができる。また、例えば、前記特許文献１記載の化合物を用いてもよい。 The structural unit (aa) in which R ^aa4 is a hydrogen atom is derived from a compound represented by the following formula (aa1) (hereinafter sometimes referred to as “compound (aa1)”).

(All symbols in formula (aa1) have the same meanings as described above.)
Such a compound (aa1) can be produced by a known method such as the method described in JP-A-2008-122932. Further, for example, the compound described in Patent Document 1 may be used.

A second preferred example of R ^aa4 is a hydrocarbon group having 1 to 20 carbon atoms. When the hydrocarbon group includes a methylene group, the methylene group is replaced by an oxygen atom, a sulfur atom or a carbonyl group. Also good. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

式（ａａ−２１）〜式（ａａ−２５）のいずれかで表される構造単位（ａａ）〔Ｒ^aa4が脂肪族炭化水素基である場合の構造単位（ａａ）〕の具体例において、式（ａａ−１）で表される構造単位（ａａ）などと同様に、部分構造Ｍを部分構造Ａに置き換えたものも構造単位（ａａ）の具体例として挙げることができる。 Specific examples in the case where R ^aa4 is a hydrocarbon group, particularly an aliphatic hydrocarbon group, are as follows.

In a specific example of the structural unit (aa) represented by any one of the formulas (aa-21) to (aa-25) [the structural unit (aa) when R ^aa4 is an aliphatic hydrocarbon group], Similarly to the structural unit (aa) represented by (aa-1), a structural unit (aa) obtained by substituting the partial structure M with the partial structure A can be given as a specific example.

［式（Ｒ^４−０）中、
Ｒ⁴¹は、置換基を有していてもよい炭素数１〜１８の炭化水素基を表す。］ A third preferred example of R ^aa4 is an acyl group having 2 to 20 carbon atoms, and the carbon number is more preferably in the range of 2 to 12. Such an acyl group is typically represented by the following formula (R4-0), and specific examples thereof include an acetyl group, a propanoyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and cyclohexanecarbonyl. And a group in which an aliphatic hydrocarbon group such as an adamantanecarbonyl group and a carbonyl group are linked, and a group in which an aromatic group such as a benzoyl group and a carbonyl group are linked.

Wherein ^(R 4 -0),
R ⁴¹ represents a C 1-18 hydrocarbon group which may have a substituent. ]

［式（Ｒ^４−１）中、
Ｒ⁴⁴〜Ｒ⁴⁶は、それぞれ独立に、置換基を有していてもよい炭素数１〜６の脂肪族飽和炭化水素基を表すか、または、Ｒ⁴⁴〜Ｒ⁴⁶のうちの２つが互いに結合して環を形成し、残りの１つは置換基を有していてもよい炭素数１〜６の脂肪族飽和炭化水素基又は水素原子である。］ One of the more preferable acyl groups for R ^aa4 is represented by the following formula (R ⁴ -1).

[In the formula (R ⁴ -1),
R ^{44 to} R ⁴⁶ each independently represents an optionally substituted aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, or two of R ^{44 to} R ⁴⁶ are bonded to each other. Thus, a ring is formed, and the remaining one is an optionally saturated aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom. ]

Among the acyl groups represented by the formula (R ⁴ -1), preferred examples of the acyl group in which R ^{44 to} R ⁴⁶ are all aliphatic saturated hydrocarbon groups having 1 to 6 carbon atoms include a pivaloyl group. It is done.

Two of R ^{44 to} R ⁴⁶ are bonded to each other to form a ring, and the remaining one is a hydrogen atom or an aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the acyl group include a cyclohexylcarbonyl group and In addition to an adamantylcarbonyl group and the like, a group in which a methylene group contained in a ring in the acyl group is replaced with an oxygen atom or a carbonyl group, and the like can be given.

Further, as the acyl group R ^aa4, R ⁴¹ in the formula (R 4 ^-0) are those also preferably a group containing a lactone ring. Such a lactone ring is preferably in the range of 4 to 18 carbon atoms, more preferably in the range of 4 to 12 carbon atoms. As used herein, “the number of carbon atoms in the lactone ring” refers to the number of carbon atoms constituting the lactone ring. This lactone ring includes monocyclic lactone rings such as γ-lactone ring and δ-lactone ring, and polycyclic lactone rings in which γ-lactone ring or δ-lactone ring is condensed with other alicyclic rings. Further, the hydrogen atom contained in the lactone ring may be substituted with a substituent other than a hydrogen atom. The substituent here is preferably a carboxy group, a cyano group or a methyl group. However, when the lactone ring has the substituent shown here, the total number of carbon atoms (carbon number) included in the substituent is included in the number of carbon atoms of the above lactone ring (carbon number of the ring atom). I can't.

［式（Ｂ２−１）、式（Ｂ２−２）、式（Ｂ２−３）中、
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。＊は結合手を表す。
ｌは、０〜５の整数を表し、
Ｒ^３は、炭素数１〜２０の炭化水素基を表し、該炭化水素基にメチレン基が含まれる場合、そのメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。ｌが２以上のとき、複数のＲ^３は同一でも異なっていてもよく、複数のＲ^３のうち、２つのＲ^３が互いに結合して、それらが結合する炭素原子とともに、炭素数３〜２０の環を形成していてもよい。
ｌ’は、０〜３の整数を表し、
Ｒ^４は、カルボキシ基、シアノ基又は炭素数１〜２０の炭化水素基を表し、該炭化水素基にメチレン基が含まれる場合、そのメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。ｌ’が２以上のとき、複数のＲ^４は同一でも異なっていてもよく、複数のＲ^４のうち、２つのＲ^４が互いに結合して、それらが結合する炭素原子とともに、炭素数３〜２０の環を形成していてもよい。
ｌ”は、０〜３の整数を表し、
Ｒ⁶は、カルボキシ基、シアノ基又は炭素数１〜２０の炭化水素基を表し、該炭化水素基にメチレン基が含まれる場合、そのメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。ｌ’’が２以上のとき、複数のＲ^６は同一でも異なっていてもよく、複数のＲ^６のうち、２つのＲ^４が互いに結合して、それらが結合する炭素原子とともに、炭素数３〜２０の環を形成していてもよい。］ Such R ^aa4 is, for example, a group represented by any of the following formulas (B2-1), (B2-2), and (B2-3) [formula (B2-1) to formula (B2- Group represented by 3)] and the like.

[In Formula (B2-1), Formula (B2-2), and Formula (B2-3),
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group. * Represents a bond.
l represents an integer of 0 to 5;
R ³ represents a hydrocarbon group having 1 to 20 carbon atoms. When the hydrocarbon group includes a methylene group, the methylene group may be replaced with an oxygen atom or a carbonyl group. When l is 2 or more, the plurality of R ³ may be the same or different, and among the plurality of R ³ , two R ³ are bonded to each other, and together with the carbon atom to which they are bonded, the number of carbon atoms is 3 to 20 The ring may be formed.
l ′ represents an integer of 0 to 3,
R ⁴ represents a carboxy group, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, and when the hydrocarbon group includes a methylene group, the methylene group may be replaced with an oxygen atom or a carbonyl group. . When l ′ is 2 or more, the plurality of R ⁴ may be the same or different, and among the plurality of R ⁴ , two R ⁴ are bonded to each other, and together with the carbon atom to which they are bonded, 20 rings may be formed.
l ″ represents an integer of 0 to 3;
R ⁶ represents a carboxy group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. When the hydrocarbon group includes a methylene group, the methylene group may be replaced with an oxygen atom or a carbonyl group. . When l ″ is 2 or more, the plurality of R ⁶ may be the same or different, and among the plurality of R ⁶ , two R ⁴ are bonded to each other, and together with the carbon atom to which they are bonded, the number of carbon atoms is 3 -20 rings may be formed. ]

Of the substituents (R ³ , R ⁴ and R ⁶ ) in the groups represented by the formulas (B2-1) to (B2-3), the hydrocarbon groups have already been exemplified in the above-mentioned range. Including things. The alkanediyl group of B ¹ includes those already exemplified in the range of 1 to 6 carbon atoms. The methylene group contained in the alkanediyl group is an oxygen atom (—O—, the oxygen atom may be represented by “—O—” in this specification) or a carbonyl group (—CO—, A carbonyl group may be represented by “—CO—” in this specification.) Examples of the group replaced by * —O—CO—CH ₂ —O—, * —O—CO—CH ₂ —O—, and the like. _{CO -, * - CH 2 -O} -CO- or _* is -CH 2 -CO-O-a.
In Formula (B2-1) to Formula (B2-3), B ¹ is preferably a single bond.

Among groups represented by formula (B2-1) to formula (B2-3), a group represented by any of formula (B2-1) and formula (B2-2) is more preferable as R ^aa4 .

Specific examples of the structural unit (aa) when R ^aa4 is an acyl group are as follows.

式（ａａ−２６）〜式（ａａ−６６）のいずれかで表される構造単位（ａａ）〔Ｒ^aa4がアシル基である場合の構造単位（ａａ）〕において、式（ａａ−１）で表される構造単位（ａａ）などと同様に、部分構造Ｍを部分構造Ａに置き換えたものも構造単位（ａａ）の具体例として挙げることができる。

In the structural unit (aa) represented by any of the formulas (aa-26) to (aa-66) [the structural unit (aa) when R ^aa4 is an acyl group], in the formula (aa-1) Similar to the structural unit (aa) and the like, those in which the partial structure M is replaced with the partial structure A can be given as specific examples of the structural unit (aa).

［式（ａａａ）中、
Ｒ^aa11は、水素原子又はメチル基を表す。
Ｒ^aa12は、水素原子又は炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa13は、炭素数１〜６のフッ化アルキル基を表す。
Ｒ^aa14は、水素原子又は−ＣＯ−Ｒ^aa15を表す。
Ｒ^aa15は、炭素数１〜１０のアルキル基又は炭素数３〜１０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メチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
ｎ^aa11は、１又は２を表す。
Ａ^aa１は、炭素数１〜１０の炭化水素基を表す。］ The structural unit (aa) is preferably a structural unit (aaa).

[In the formula (aaa),
R ^aa11 represents a hydrogen atom or a methyl group.
R ^aa12 represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa13 represents a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa14 represents a hydrogen atom or —CO—R ^aa15 .
R ^aa15 represents an alkyl group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group is replaced with an oxygen atom or a carbonyl group. May be.
^naa11 represents 1 or 2.
A ^aa1 represents a hydrocarbon group having 1 to 10 carbon atoms. ]

R ^aa12 is preferably a hydrogen atom or a trifluoromethyl group.
R ^aa13 is preferably a trifluoromethyl group or a branched fluorinated alkyl group having 3 to 6 carbon atoms.
R ^aa14 is preferably —CO—R ^aa15 . When R ^aa14 is —CO—R ^aa15 , the resist pattern obtained from the resist composition tends to have fewer defects.
R ^aa15 preferably represents a branched alkyl group or an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group is replaced with an oxygen atom or a carbonyl group. It may be.
A ^aa1 is preferably an alkanediyl group having 1 to 10 carbon atoms or a cycloalkanediyl group having 3 to 10 carbon atoms.

（式（ａａ２）中、
Ｒ^aa5は、炭素数１〜２０の炭化水素基又は炭素数２〜２０のアシル基を表す。その他の符号はいずれも、前記と同義である。） The structural unit (aa) in which R ^aa4 is a hydrocarbon group or an acyl group is derived from a compound represented by the following formula (aa2) (hereinafter sometimes referred to as “compound (aa2)”).

(In the formula (aa2),
R ^aa5 represents a hydrocarbon group having 1 to 20 carbon atoms or an acyl group having 2 to 20 carbon atoms. All other symbols are as defined above. )

反応剤であるカルボン酸（Ｒ^aa5−ＣＯＯＨ）は、所望のＲ^aa5の種類に応じて、例えば市場から容易に入手できるものを選択したり、公知の方法により製造したりすることにより入手すればよい。この反応は通常、溶媒の存在下で行われる。この溶媒は例えば、アセトニトリルなどである。なお、カルボニルジイミダゾールなどを触媒として用いることもできる。 Compound (aa2) can be easily produced from compound (aa1). If the example is given, it will be represented by the following reaction formula.

The carboxylic acid (R ^aa5 —COOH) as the reactant can be obtained, for example, by selecting one that can be easily obtained from the market according to the desired type of R ^aa5 or by producing it by a known method. Good. This reaction is usually performed in the presence of a solvent. This solvent is, for example, acetonitrile. In addition, carbonyldiimidazole etc. can also be used as a catalyst.

［式（ａｂ）中、
Ｒ^ab1は、水素原子又はメチル基を表す。
Ａ^ab1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を表し、該アルカンジイル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^ab2は、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族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。］ <Structural unit (ab)>
The structural unit (ab) is a structural unit represented by the formula (ab).

[In the formula (ab),
R ^ab1 represents a hydrogen atom or a methyl group.
A ^ab1 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
R ^ab2 represents an ^optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. Good. ]

A ^ab1 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms. Specific examples of the alkanediyl group include those already exemplified in the range of 1 to 6 carbon atoms. Including. The substituent that the alkanediyl group may have is preferably a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the like, similarly to A ^aa1 of the structural unit (aa). In addition, the methylene group contained in the alkanediyl group of A ^ab1 may be replaced with an oxygen atom or a carbonyl group. Specific examples thereof include the followings in addition to those described for A ^aa1 in which n ^aa1 is 1.

Among these, A ^ab1 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.

R ^ab2 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. The aliphatic hydrocarbon group may partially have a carbon-carbon unsaturated bond, but a saturated aliphatic hydrocarbon group having no carbon-carbon unsaturated bond (aliphatic saturated hydrocarbon group) preferable. Preferable aliphatic hydrocarbon groups include alkyl groups (the alkyl group may be linear or branched) and alicyclic hydrocarbon groups. These specific examples include those having 18 or less carbon atoms among those already exemplified. R ^ab2 may be an aliphatic hydrocarbon group in which two or more of these alkyl groups and alicyclic hydrocarbon groups are combined.

The methylene group contained in the aliphatic hydrocarbon group for R ^ab2 may be replaced with an oxygen atom or a carbonyl group. In this case, the maximum number of methylene groups that can be replaced by oxygen atoms or carbonyl groups is about two.

Furthermore, the aliphatic hydrocarbon group for R ^ab2 may have a substituent, and ^examples thereof include a halogen atom, an alkoxy group, an acyl group, and an alkoxycarbonyl group. Among these, a fluorine atom is preferable.
Examples of the aliphatic hydrocarbon group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 1,1,1-trifluoroethyl group, 2, 2,2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,1,2,2-pentafluoropropyl 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 1,1,1,2,2,3,3-peptafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3, 4,4-oct Fluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3 , 4,4-octafluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl 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, perfluoropentylmethyl, pe Fluorohexyl group, perfluoroheptyl group and a perfluorooctyl group.
Among them, the aliphatic hydrocarbon group having a fluorine atom is preferably a triperfluoromethyl group, 1,1,1-trifluoroethyl group, perfluoroethyl group, 1,1,1,2,2-pentafluoropropyl. Group, perfluoropropyl group, 1,1,1,2,2,3,3-heptafluorobutyl group, perfluorobutyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl Group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group and perfluorooctyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. It is a group.

式（ａｂ−１）〜式（ａｂ−１４）のいずれかで表される構造単位（ａｂ）の具体例において、以下に示す部分構造Ｍを、以下に示す部分構造Ａに置き換えたものも構造単位（ａｂ）の具体例として挙げることができる。

Here, specific examples of a suitable structural unit (ab) in which A ^ab1 is an ethylene group are shown.

In the specific example of the structural unit (ab) represented by any one of the formulas (ab-1) to (ab-14), the partial structure M shown below is replaced with the partial structure A shown below. Specific examples of the unit (ab) can be given.

（式（ａｂ’）中の符号はいずれも、前記と同義である。） The structural unit (ab) is derived from a compound represented by the formula (ab ′).

(All symbols in the formula (ab ′) have the same meanings as described above.)

式（ａｂｓ−１）で表される化合物と式（ａｂｓ−２）で表される化合物とを、溶媒中、触媒の存在下で反応させることが好ましい。
かかる溶媒としては、ジメチルホルムアミドなどが挙げられる。触媒としては、炭酸カリウム及びヨウ化カリウムなどを用いればよい。
式（ａｂｓ−１）で表される化合物としては、典型的には、市場から容易に入手できるもの（市販品）が好ましい。かかる市販品は、メタクリル酸などである。 Compound (ab ′) can be produced, for example, by a method represented by the following reaction formula.

It is preferable to react the compound represented by the formula (abs-1) and the compound represented by the formula (abs-2) in a solvent in the presence of a catalyst.
Examples of such a solvent include dimethylformamide. As the catalyst, potassium carbonate, potassium iodide, or the like may be used.
As the compound represented by the formula (abs-1), typically, a compound that can be easily obtained from the market (commercial product) is preferable. Such commercial products are methacrylic acid and the like.

式（ａｂｓ−３）で表される化合物としては例えば、クロロアセチルクロリドなどが挙げられる。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（ａｂｓ−４）で表される化合物は、所望のＲ^ab2の種類に応じたアルコール化合物を選択し、該アルコール化合物を公知の方法により製造したり、市場から容易に入手できるアルコール化合物を入手したりすればよい。市場から容易に入手できるアルコール化合物としては、２，２，３，３，４，４，４−ヘプタフルオロ−１−ブタノールなどがある。 The compound represented by the formula (abs-2) can be produced, for example, by reacting a compound represented by the formula (abs-3) with a compound represented by the formula (abs-4). This reaction is carried out in a solvent in the presence of a base catalyst. Examples of the solvent used in this reaction include tetrahydrofuran. As the base catalyst, pyridine or the like is used.

Examples of the compound represented by the formula (abs-3) include chloroacetyl chloride. This chloroacetyl chloride is readily available from the market.
As the compound represented by the formula (abs-4), an alcohol compound corresponding to the desired type of R ^ab2 is selected, and the alcohol compound is produced by a known method, or an alcohol compound that can be easily obtained from the market is obtained. You can do it. Alcohol compounds that are readily available from the market include 2,2,3,3,4,4,4-heptafluoro-1-butanol.

  In the resin (X), the structural unit (aa) and the structural unit (ab) may each be one kind, or only one or both may be plural kinds. Examples of combinations of the structural unit (aa) and the structural unit (ab) are shown in Table 1 below. In Table 1, the structural unit (aa) represented by the formula (aa-1) is represented as “(aa-1)” according to the formula number, and the formula (ab-1) ) Is expressed as “(ab-1)” or the like according to the formula number. For example, the notation “(aa-19) / (aa-41)” is represented by the structural unit (aa), the structural unit represented by the formula (aa-19), and the formula (aa-41). Together with a structural unit.

As long as the structural unit (aa) is within the range in which the O—R ^aa4 bond is not cleaved by the action of an acid as described above, the O—A ^aa1 bond may be cleaved by the same action.
Similarly, the ^{OA Ab1} bond contained in the structural unit (ab) may be cleaved by the action of an acid. Resin (X) having a structural unit (aa) capable of cleaving the O-A ^aa1 bond by the action of an acid or a structural unit (ab) capable of cleaving the O-A ^ab1 bond is one having acid-acting properties. Become.
The resin (X) may have a structural unit other than the structural unit (aa) and the structural unit (ab). Even when the structural unit other than the structural unit (aa) and the structural unit (ab) has an acid labile group, the resin (X) may have acid action characteristics (here, “acid labile”). The definition of “group” will be described later). Thus, the resin composition (X) containing the resin (X) has an excellent CD uniformity (CDU) resist pattern, whether or not the resin (X) has acid action characteristics. However, it is preferable that the resin (X) does not have acid action characteristics in producing a resist pattern having a better CD uniformity (CDU).

  The resin (X) may have a structural unit other than the structural unit (aa) and the structural unit (ab). As the structural unit other than the structural unit (aa) and the structural unit (ab) (or the structural unit (I)), a structural unit that may be contained in the resin (A) described later, an acid stable monomer (a4) described later And structural units derived from.

The total content of the structural unit (aa) and the structural unit (ab) with respect to the total structural unit (100 mol%) of the resin (X) may be 10 mol% or more, but is substantially 100 mol%, that is, the resin (X) is more preferably composed of the structural unit (aa) and the structural unit (ab).
The content of each of the structural unit (aa) and the structural unit (ab) with respect to all the structural units of the resin (X) is more preferably in the range of 5 to 95 mol%, and still more preferably in the range of 10 to 90 mol%.
In the resin (X), the molar ratio of the structural unit (aa) and the structural unit (ab) (or the structural unit (I)) is preferably 1:99 to 99: 1, and 3:97 to 97. : 3 is preferable, and 50:50 to 95: 5 is more preferable.
Incidentally, the resin (X) having the structural unit (aa) and the structural unit (ab) at such a content ratio is the compound (aa ′) and the compound (ab) with respect to the total molar amount of all monomers used in the production of the resin (X). It can be produced by adjusting the molar amount of ').

<Resist composition>
As described above, the resist composition of the present invention (hereinafter sometimes referred to as “the present resist composition”) contains the resin (X) and an acid generator.
Furthermore, this resist composition is insoluble or hardly soluble in the solvent (D), the basic compound (C) and the alkaline aqueous solution, and is soluble in the alkaline aqueous solution by the action of acid (hereinafter referred to as “acidic action” in some cases At least selected from the group consisting of a resin having a characteristic (hereinafter referred to as “resin (A)”) (but not having both a structural unit (aa) and a structural unit (ab)). It is preferable to contain 1 type.

<Resin (A)>
In order to produce a resist pattern by interacting with an acid generator with this resist composition, a resin having acid action characteristics is required. As described above, the resin (X) itself may have acid action characteristics, but when the resin (X) having no acid action characteristics is used in the present resist composition, in addition to the resin (X), A resin having acid action characteristics (hereinafter sometimes referred to as “resin (A)”) is required. Such a resin (A) has an acid labile group in the molecule. Specifically, a structural unit containing an acid labile group (hereinafter referred to as a structural unit containing an acid labile group, In some cases, it is referred to as “structural unit (a1)”.
The term “acid labile group” as used herein means a hydrophilic group protected by a protecting group that can be removed by contact with an acid. Examples of such a hydrophilic group include a hydroxy group or a carboxy group. And a carboxy group is more preferred.
Again, this resist composition contains resin (X) with acid action characteristics

式（１）中、Ｒ^a1、Ｒ^a2及びＲ^a3は、それぞれ独立に、炭素数１〜８の脂肪族炭化水素基を表すか、Ｒ^a1及びＲ^a2が結合して、それらが結合する炭素原子とともに炭素数３〜２０の環を形成する。Ｒ^a1及びＲ^a2が結合して形成される環、及び該脂肪族炭化水素基に含まれるメチレン基は、酸素原子、硫黄原子又はカルボニル基に置き換わっていてもよい。＊は結合手を表す。 <Acid labile group>
In the case where the hydrophilic group is a carboxy group, the acid labile group is such that the hydrogen atom of the carboxy group is replaced with an organic residue, and the atom of the organic residue bonded to —O— of the carboxy group is a tertiary carbon. Examples include groups that are atoms (ie, esters of tertiary alcohols). Among such acid labile groups, preferred acid labile groups are, for example, those represented by the following formula (1) (hereinafter sometimes referred to as “acid labile groups (1)”).

In formula (1), R ^a1 , R ^a2 and R ^a3 each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or R ^a1 and R ^a2 are bonded to each other, and the carbon to which they are bonded. A ring having 3 to 20 carbon atoms is formed together with the atoms. The ring formed by combining R ^a1 and R ^a2 and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom, a sulfur atom or a carbonyl group. * Represents a bond.

The aliphatic hydrocarbon group for R ^{a1 to} R ^a3 is an alkyl group or an alicyclic hydrocarbon group. Specific examples of this alkyl group include those already exemplified in the range of 1 to 8 carbon atoms among the already exemplified alkyl groups. The alicyclic hydrocarbon group also includes those already exemplified in the range of 8 or less carbon atoms.

The combination of R ^a1 and R ^a2 to form a ring means that the group represented by —C (R ^a1 ) (R ^a2 ) (R ^a3 ) is any of the followings. The number of carbon atoms in such a ring is preferably in the range of 3-12.

As the acid labile group (1), a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are all alkyl groups, one of these alkyl groups is tert-butyl A 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are bonded to each other to form an adamantane ring together with the carbon atom to which they are bonded), and R ^a3 Is a group in which R ¹ is an alkyl group) and 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group) ) And the like.

式（２）中、Ｒ^b1及びＲ^b2は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を表し、Ｒ^b3は、炭素数１〜２０の炭化水素基を表すか、或いは、Ｒ^b2及びＲ^b3が結合して、それらが各々結合する炭素原子及び酸素原子とともに炭素数３〜２０の環を形成する。該環又は該炭化水素基がメチレン基を含む場合、そのメチレン基は、酸素原子、硫黄原子又はカルボニル基に置き換わっていてもよく、Ｒ^b2及びＲ^b3が結合して形成される環に含まれるメチレン基も、酸素原子、硫黄原子又はカルボニル基に置き換わっていてもよい。＊は結合手を表す。 On the other hand, examples of the acid labile group in the case where the hydrophilic group is a hydroxy group include those in which a hydrogen atom of the hydroxy group is replaced with an organic residue to become a group containing an acetal structure or a ketal structure. Among such acid labile groups, preferred acid labile groups are, for example, those represented by the following formula (2) (hereinafter sometimes referred to as “acid labile groups (2)”).

In formula (2), R ^b1 and R ^b2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^b3 represents a hydrocarbon group having 1 to 20 carbon atoms, or , R ^b2 and R ^b3 are combined to form a ring having 3 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. When the ring or the hydrocarbon group includes a methylene group, the methylene group may be replaced with an oxygen atom, a sulfur atom or a carbonyl group, and is included in the ring formed by combining R ^b2 and R ^b3. The methylene group may also be replaced with an oxygen atom, a sulfur atom or a carbonyl group. * Represents a bond.

The hydrocarbon group of R ^{b1 to} R ^b3 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and specific examples thereof include those already exemplified as long as the upper limit of the carbon number is 20 or less. ^Examples of the ring formed by combining R ^b2 and R ^b3 include those in which one carbon atom of the ring formed by combining R ^a1 and R ^a2 described above is replaced with one oxygen atom.
Of R ^b1 and R ^b2 , at least one is preferably a hydrogen atom.

Specific examples of the acid labile group (2) include the following groups.

The structural unit (a1) is preferably derived from a monomer having an acid labile group and a carbon-carbon double bond, more preferably derived from a (meth) acrylic monomer having an acid labile group. .
The structural unit (a1) preferably has an acid labile group (1) or an acid labile group (2), and may have both of these acid labile groups. More preferred is the structural unit (a1) having an acid labile group (1).

  Among the structural units (a1) having an acid labile group (1), those in which the acid labile group (1) has an aliphatic ring having 5 to 20 carbon atoms as a partial structure are preferable. The resin (A) having such a sterically bulky group structural unit (a1) has a better resolution when a resist pattern is produced using the present resist composition containing the resin (A). A resist pattern can be manufactured.

式（ａ１−１）中、
Ｌ^a1は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−（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。）で表される基を表す。
Ｒ^a4は、水素原子又はメチル基を表す。
Ｒ^a6は、炭素数１〜１０の脂肪族炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
式（ａ１−２）中、
Ｌ^a2は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−（ｋ１は前記と同義である。
）で表される基を表す。
Ｒ^a5は、水素原子又はメチル基を表す。
Ｒ^a7は、炭素数１〜１０の脂肪族炭化水素基を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。 Among the structural units (a1) having an acid labile group (1) having an aliphatic ring as a partial structure, a structural unit represented by the formula (a1-1) (hereinafter, “structural unit (a1-1) And a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as “structural unit (a1-2)”).

In formula (a1-1),
L ^a1 represents an oxygen atom or a group represented by ^* —O— (CH ₂ ) _k1 —CO—O— (k1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group). To express.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
m1 represents the integer of 0-14.
In formula (a1-2),
L ^a2 is an oxygen atom or ^* —O— (CH ₂ ) _k1 —CO—O— (k1 is as defined above).
) Represents a group represented by
R ^a5 represents a hydrogen atom or a methyl group.
R ^a7 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3.

L ^a1 and L ^a2 are preferably an oxygen atom or a group represented by * —O— (CH ₂ ) _k1 —CO—O—, wherein k1 is an integer of 1 to 4, more preferably an oxygen atom. or * -O-CH ₂ -CO-O- and, still more preferably an oxygen atom.
R ^a4 and R ^a5 are preferably methyl groups.
Of the aliphatic hydrocarbon groups of R ^a6 and R ^a7 , preferably an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and within the range of the upper limit of the carbon number, Includes the same as those already exemplified. The aliphatic hydrocarbon groups for R ^a6 and R ^a7 are each independently preferably an alkyl group having 8 or less carbon atoms or an alicyclic hydrocarbon group having 8 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms. Or it is an alicyclic hydrocarbon group having 6 or less carbon atoms.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

Here, specific examples of the structural unit (a1-1) are given.

式（ａ１−１−１）〜式（ａ１−１−３８）のいずれかで表される構造単位（ａ１−１）の具体例において、構造単位（ａａ）の具体例と同様に、部分構造Ｍを部分構造Ａに置き換えたものも構造単位（ａ１−１）の具体例として挙げることができる。

In the specific example of the structural unit (a1-1) represented by any one of the formulas (a1-1-1) to (a1-1-38), the partial structure is similar to the specific example of the structural unit (aa). What replaced M with the partial structure A can also be mentioned as a specific example of a structural unit (a1-1).

  Among the examples of the structural unit (a1-1), the structural unit represented by any one of the formula (a1-1-1), the formula (a1-1-2), and the formula (a1-1-3) (A1-1) and those obtained by substituting the partial structure M of these structural units (a1-1) with the partial structure A are preferred, and are represented by formulas (a1-1-1), (a1-1-2) and The structural unit (a1-1) represented by any one of the formula (a1-1-3) is more preferable, and is represented by any one of the formula (a1-1-1) and the formula (a1-1-2). The structural unit (a1-1) is more preferable. In addition, the resin (A) having these preferred structural units (a1-1) is obtained by producing 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl when producing the resin (A). Ir (meth) acrylate or 2-isopropyladamantan-2-yl (meth) acrylate or the like may be used as a raw material (monomer) for production.

式（ａ１−２−１）〜式（ａ１−２−１２）のいずれかで表される構造単位（ａ１−２）の具体例において、構造単位（ａａ）の具体例と同様に、部分構造Ｍを部分構造Ａに置き換えたものも構造単位（ａ１−２）の具体例として挙げることができる。 Specific examples of the structural unit (a1-2) are shown below.

In the specific example of the structural unit (a1-2) represented by any one of the formulas (a1-2-1) to (a1-2-12), the partial structure is similar to the specific example of the structural unit (aa). What replaced M with the partial structure A can also be mentioned as a specific example of a structural unit (a1-2).

  In the above specific examples, it is represented by any one of formula (a1-2-1), formula (a1-2-2), formula (a1-2-4), and formula (a1-2-5). It is more preferable that the structural unit (a1-2) or the partial structure M of these structural units (a1-2) is replaced by the partial structure A, and the formula (a1-2-4) and the formula (a1-2) The structural unit represented by any one of (-5), or those in which the partial structure M of these structural units (a1-2) is replaced by the partial structure A is more preferable. In order to produce the resin (A) having such a structural unit (a1-2), 1-ethylcyclohexane-1-yl (meth) acrylate or the like may be used as a monomer.

  When the resin (A) having the structural unit (a1-1) and / or the structural unit (a1-2) is produced, when the total structural unit of the resin (A) is 100 mol%, the structural unit (a1-1) ) And / or the total content of the structural unit (a1-2) is preferably in the range of 10 to 95 mol%, more preferably in the range of 15 to 90 mol%, and still more preferably in the range of 20 to 85 mol%. In order to make the total content of the structural unit (a1-1) and / or the structural unit (a1-2) within such a range, when the resin (A) is produced, What is necessary is just to adjust the usage-amount of the monomer which induces | guides | derives a structural unit (a1-1) and / or a structural unit (a1-2). Moreover, when manufacturing resin (X) which has a structural unit (a1-1) and / or a structural unit (a1-2), a structural unit (a1-1) and / or a structural unit (a1-2) are changed. What is necessary is just to adjust the ratio of the usage-amount of the monomer to guide | induced and the total usage-amount of a compound (aa ') and a compound (ab').

式（ａ１−３）中、
Ｒ^a9は、水素原子、ヒドロキシ基を有していてもよい炭素数１〜３のアルキル基、カルボキシ基、シアノ基又は−ＣＯＯＲ^a13（Ｒ^a13は、炭素数１〜２０の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基に置換されていてもよく、該脂肪族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。）を表す。
Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１〜２０の脂肪族炭化水素基を表すか、或いは、Ｒ^a10及びＲ^a11が結合して、これらが結合している炭素原子とともに、炭素数３〜２０の環を形成する。なお、この脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基などに置換されていてもよく、該脂肪族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。 Examples of the structural unit (a1) include those derived from a monomer having a norbornene ring represented by the following formula (a1-3) (hereinafter sometimes referred to as “monomer (a1-3)”).

In formula (a1-3),
R ^a9 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms that may have a hydroxy group, a carboxy group, a cyano group, or —COOR ^a13 (R ^a13 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Wherein a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group, and a methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. .)
R ^a10 , R ^a11 and R ^a12 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or R ^a10 and R ^a11 are bonded together with the carbon atom to which they are bonded. To form a ring having 3 to 20 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group or the like, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. .

Examples of the alkyl group having a hydroxyl group for R ^a9 include a hydroxymethyl group and a 2-hydroxyethyl group.
The aliphatic hydrocarbon group for R ^{a10 to} R ^a12 may be either a chain hydrocarbon group (for example, an alkyl group) or an alicyclic hydrocarbon group, and specific examples thereof are already in the range of 20 or less carbon atoms. Includes examples.
The ring formed by combining R ^a10 and R ^a11 is preferably an aliphatic ring, and specifically, a cyclohexane ring and an adamantane ring are more preferable.

^Examples of —COOR ^{a13 for} R ^a9 include groups in which a carbonyl group is further bonded to the alkoxy group already exemplified, such as a methoxycarbonyl group and an ethoxycarbonyl group.

  As the monomer (a1-3), 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl Cyclohexyl, 2-methyl-2-adamantyl 5-norbornene-2-carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 1- (4-methylcyclohexyl) 5-norbornene-2-carboxylic acid -1-methylethyl, 1- (4-hydroxycyclohexyl) -1-methylethyl 5-norbornene-2-carboxylate, 1-methyl-1- (4-oxocyclohexyl) ethyl 5-norbornene-2-carboxylate and 1- (1-adamantyl) -1-methylethyl 5-norbornene-2-carboxylate Etc., and the like.

  When the resin (A) is produced using the monomer (a1-3), the resin (A) includes a sterically bulky structural unit derived from the monomer (a1-3). Thus, if a resist pattern is manufactured with this resist composition containing resin (A) which has a three-dimensionally bulky structural unit, a resist pattern can be obtained with a better resolution. Furthermore, since a rigid norbornane ring can be introduced into the main chain of the resin (A) by using the monomer (a1-3), this resist composition containing the resin (A) is a resist excellent in dry etching resistance. There is a tendency that a pattern is easily obtained.

  As described above, in terms of the ability to produce a resist pattern with good resolution and the ease of obtaining a resist pattern with excellent dry etching resistance, the monomers (100 mol%) with respect to all structural units (100 mol%) of the resin (A) The content of the structural unit derived from a1-3) is preferably in the range of 10 to 95 mol%, more preferably in the range of 15 to 90 mol%, and still more preferably in the range of 20 to 85 mol%.

式（ａ１−４）中、
Ｒ^a32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（ハロアルキル基）、水素原子又はハロゲン原子を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上である場合、複数のＲ^a33は同一でも異なっていてもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｘ^a2は、単結合又は炭素数１〜１７の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基及び炭素数２〜４のアシルオキシ基からなる群より選ばれる基に置換されていてもよい。ここに示す置換基の具体例は、炭素数が各々の上限である範囲において、すでに例示したものを含む。Ｘ^a2の脂肪族炭化水素基は、鎖式炭化水素基であると好ましく、アルキル基であるとさらに好ましい。なお、該脂肪族炭化水素基に含まれるメチレン基は、酸素原子、硫黄原子、カルボニル基、スルホニル基又は−Ｎ（Ｒ^ｃ）−で示される基に置き換わっていてもよい。ここで、Ｒ^ｃは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｙ^a3は、炭素数１〜１８の炭化水素基であり、さらに好ましくは、炭素数３〜１８の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基であり、これらの炭化水素基は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基又は炭素数２〜４のアシルオキシ基を有していてもよい。 Examples of the monomer having an acid labile group (2) include a monomer represented by the following formula (a1-4) (hereinafter sometimes referred to as “monomer (a1-4)”).

In formula (a1-4),
R ^a32 represents a C 1-6 alkyl group (haloalkyl group), a hydrogen atom or a halogen atom which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyl group, or methacryloyl. Represents a group.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same or different.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^a2 represents a single bond or an aliphatic hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, carbon It may be substituted with a group selected from the group consisting of an acyl group having 2 to 4 carbon atoms and an acyloxy group having 2 to 4 carbon atoms. Specific examples of the substituents shown here include those already exemplified in the range where the carbon number is the upper limit of each. The aliphatic hydrocarbon group for X ^a2 is preferably a chain hydrocarbon group, and more preferably an alkyl group. The methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a group represented by —N (R ^c ) —. Here, R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ^a3 is a hydrocarbon group having 1 to 18 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen group has a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms. Also good.

R ^a32, R ^a33, specific examples of R ^a34, R ^a35 and X ^a2 of the formula (a1-4).
Of the “alkyl group ^optionally having a halogen atom” for R ^a32 , specific examples of the alkyl group include those already exemplified in the range of 1 to 6 carbon atoms. As the haloalkyl group, a part or all of the hydrogen atoms contained in the alkyl group are substituted with halogen atoms. Specific examples of the haloalkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl. Group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
Specific examples of the halogen atom, alkoxy group and acyl group for R ^a32 and R ^a33 include those already exemplified.
Hydrocarbon group R ^a34 and R ^a35 are chain hydrocarbon groups may be either an alicyclic hydrocarbon group and aromatic hydrocarbon group. Specific examples thereof include those already exemplified in each carbon number range. Among these, as the chain hydrocarbon group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group are preferable. As the formula hydrocarbon group, a cyclohexyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group and an isobornyl group are preferable. The aromatic hydrocarbon group is phenyl group, naphthyl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, anthryl. Group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl are preferred.

When R ^a32 and R ^a33 are alkyl groups, an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
As the alkoxy group for R ^a33 , a methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable.

As described above, X ^a2 and Y ^a3 may have a hydrogen atom contained therein substituted by a substituent such as a halogen atom or a hydroxy group, but when a hydrogen atom is substituted in this way, The substituent is preferably a hydroxy group.

Here, specific examples of the monomer (a1-4) will be given.

上記モノマーにおいて、Ｒ^a32に相当する水素原子がメチル基に置き換わったモノマーも、モノマー（ａ１−４）の具体例として挙げることができる。

In the above monomer, a monomer in which a hydrogen atom corresponding to R ^a32 is replaced with a methyl group can also be mentioned as a specific example of the monomer (a1-4).

  When the resin (A) has a structural unit derived from the monomer (a1-4), the content ratio is in the range of 10 to 95 mol% with respect to the total structural unit (100 mol%) of the resin (A). Is preferable, the range of 15-90 mol% is more preferable, and the range of 20-85 mol% is further more preferable.

［式（ａ１−５）中、
Ｒ^３１は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｌ^１〜Ｌ^３は、酸素原子又は硫黄原子又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−で表される基を表す。ここで、ｋ１は１〜７の整数を表し、＊はカルボニル基（−ＣＯ−）との結合手である。
Ｚ^１は、単結合又は炭素数１〜６のアルカンジイル基であり、該アルカンジイル基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。
ｓ１及びｓ２１’は、それぞれ独立して、０〜４の整数を表す。］ As the monomer having an acid labile group (2), for example, a monomer represented by the formula (a1-5) (hereinafter sometimes referred to as “monomer (a1-5)”) may also be used.

[In the formula (a1-5),
R ³¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
L ^{1 to} L ³ represent an oxygen atom, a sulfur atom, or a group represented by ^* —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * is a bond with a carbonyl group (—CO—).
Z ¹ is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
s1 and s21 ′ each independently represents an integer of 0 to 4. ]

R ³¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably an oxygen atom.
One of L ² and L ³ is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ¹ is preferably a single bond or —CH ₂ —CO—O—.

Specific examples of the monomer (a1-5) are as follows.

上記モノマーにおいて、Ｒ³¹に相当するメチル基が水素原子に置き換わったモノマーも、モノマー（ａ１−５）の具体例として挙げることができる。

In the above monomer, a monomer in which the methyl group corresponding to R ³¹ is replaced with a hydrogen atom can also be mentioned as a specific example of the monomer (a1-5).

  When the resin (A) has a structural unit derived from the monomer (a1-5), the content is in the range of 10 to 95 mol% with respect to the total structural unit (100 mol%) of the resin (A). Is preferable, the range of 15-90 mol% is more preferable, and the range of 20-85 mol% is further more preferable.

<Acid stable structural unit>
The resin (A) preferably has a structural unit having no acid labile group (hereinafter, sometimes referred to as “acid-stable structural unit”) in addition to the structural unit (a1).
In addition, the resin (X) may have an acid stable structural unit in addition to the structural unit (aa) and the structural unit (ab). The acid stable structural unit can be introduced into the resin (A) by copolymerization using a monomer having no acid stable group.

When the resin (A) has an acid stable structural unit, the content ratio of the acid stable structural unit may be determined based on the content ratio of the structural unit (a1). The ratio of the content ratio of the structural unit (a1) and the content ratio of the acid-stable structural unit is represented by [structural unit (a1)] / [acid-stable structural unit], and preferably 10 to 80 mol% / 90 to It is 20 mol%, More preferably, it is 20-60 mol% / 80-40 mol%. When the structural unit (a1) includes a structural unit having an adamantane ring, particularly the structural unit (a1-1), the structural unit (a1-1) is based on the total amount (100 mol%) of the structural unit (a1). The ratio is preferably 15 mol% or more. If it does in this way, there exists a tendency for the dry etching tolerance of the resist pattern obtained from this resist composition containing resin (A) to become more favorable.
When the resin (X) has an acid stable structural unit, the structural unit (aa) and the structural unit (ab) of the resin (X) are converted into an O-A ^aa1 bond and an O— by the action of an acid. Considering whether the A ^ab1 bond is cleaved, a part or all of the structural unit (aa) corresponds to the structural unit (a1), or a part or all of the structural unit (ab) is the structural unit (a1 Then, the content ratio of the acid stable structural unit other than the structural unit (aa) and the structural unit (ab) is calculated.

  The acid stable structural unit is preferably a structural unit having a hydroxy group or a lactone ring. An acid stable structural unit having a hydroxy group (hereinafter sometimes referred to as “acid stable structural unit (a2)”) and / or an acid stable structural unit having a lactone ring (hereinafter referred to as “acid stable structural unit (a3)”). When the present resist composition containing the resin (A) having the above is applied to the substrate, the coating film formed on the substrate or the composition layer obtained from the coating film is excellent between the substrate and the substrate. This resist composition can produce a resist pattern with high resolution.

<Acid stable structural unit (a2)>
When this resist composition is used for exposure using a KrF excimer laser (wavelength: 248 nm) as an exposure source, or exposure using a high energy beam such as an electron beam or EUV light as an exposure source, the acid stable structural unit (a2) It is preferable to introduce an acid stable structural unit (a2-0) having a phenolic hydroxy group into the resin (A).
On the other hand, when using exposure using a short wavelength ArF excimer laser (wavelength: 193 nm) as an exposure source, an acid stable structural unit represented by the formula (a2-1) described later is used as the acid stable structural unit (a2). It is preferable to introduce into the resin (A). Thus, each of the acid stable structural units (a2) possessed by the resin (A) can be selected according to the exposure source used for producing the resist pattern, but the acid stable structural units possessed by the resin (A) ( a2) may have only one type of acid stable structural unit (a2) suitable for the type of exposure source, and two or more types of acid stable structural unit (a2) suitable for the type of exposure source. Or an acid stable structural unit (a2) suitable for the type of exposure source and a combination of other acid stable structural units (a2).

式（ａ２−１）中、
Ｌ^a3は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−（ｋ２は１〜７の整数を表す。）を表し、＊はカルボニル基（−ＣＯ−）との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。 <Acid stable structural unit (a2-1)>
Examples of the acid stable structural unit (a2-1) include a structural unit represented by the following formula (a2-1) (hereinafter sometimes referred to as “acid stable structural unit (a2-1)”).

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), and * represents a bond with a carbonyl group (—CO—). Represent.
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.

L ^a3 is preferably an oxygen atom or a group represented by —O— (CH ₂ ) _k2 —CO—O—, wherein k2 is an integer of 1 to 4, more preferably an oxygen atom or — O—CH ₂ —CO—O—, more preferably 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.

As an acid stable structural unit (a2-1), the following are mentioned, for example.

式（ａ２−１−１）〜式（ａ２−１−１７）のいずれかで表される酸安定構造単位（ａ２−１）の具体例において、構造単位（ａａ）の具体例と同様に、部分構造Ｍを部分構造Ａに置き換えたものも酸安定構造単位（ａ２−１）の具体例として挙げることができる。

In the specific example of the acid stable structural unit (a2-1) represented by any one of the formula (a2-1-1) to the formula (a2-1-17), as in the specific example of the structural unit (aa), What substituted the partial structure M to the partial structure A can also be mentioned as a specific example of an acid stable structural unit (a2-1).

  Among the exemplified acid stable structural units (a2-1), those represented by formula (a2-1-1), formula (a2-1-2), formula (a2-1-13) and formula (a2-1-15) The acid-stable structural unit (a2-1) represented by any of these, and those in which the partial structure M of these acid-stable structural units (a2-1) is replaced by the partial structure A are preferred, and the formula (a2-1-1) ), An acid stable structural unit (a2-1) represented by any one of formula (a2-1-2), formula (a2-1-13) and formula (a2-1-15) is more preferable. Resin (A) which has these acid stable structural units (a2-1) is 3-hydroxyadamantan-1-yl (meth) acrylate, 3,5-dihydroxyadamantan-1-yl (meth) acrylate or (meth) 1- (3,5-dihydroxyadamantan-1-yloxycarbonyl) methyl acrylate or the like may be used as a monomer for producing the resin (A).

When the resin (A) has an acid stable structural unit (a2-1), the content ratio is preferably in the range of 3 to 45 mol% with respect to all the structural units (100 mol%) of the resin (A). The range of 5-40 mol% is more preferable, and the range of 5-35 mol% is more preferable.
When the resin (X) has an acid stable structural unit (a2-1), the content thereof is preferably in the range of 3 to 45 mol% with respect to all the structural units (100 mol%) of the resin (X). The range of 5-40 mol% is more preferable, and the range of 5-35 mol% is more preferable.

式（ａ２−０）中、
Ｒ^a30は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は同一でも異なっていてもよい。 <Acid stable structural unit (a2-0)>
Examples of the acid stable structural unit (a2) include a structural unit represented by the following formula (a2-0) (hereinafter sometimes referred to as “acid stable structural unit (a2-0)”).

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

Specific examples of the alkyl group and a halogen atom having 1 to 6 halogen atoms carbon atoms which may have a R ^a30 are the same as those exemplified in R ^a32 of formula (a1-4). Among these, R ^a30 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
As the alkyl group for R ^a31 , an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
Specific examples of the alkoxy group for R ^a31 include those already exemplified. Among these, R ^a31 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.

ここに例示する具体例において、ベンゼン環に結合しているメチル基やエチル基を、Ｒ^a31として例示したその他の置換基に置き換えたものも、酸安定モノマー（ａ２−０）の具体例である。 Examples of the monomer for deriving the acid stable structural unit (a2-0) (hereinafter sometimes referred to as “acid stable monomer (a2-0)”) include the following.

In the specific examples illustrated here, those in which the methyl group or ethyl group bonded to the benzene ring is replaced with other substituents exemplified as R ^a31 are also specific examples of the acid stable monomer (a2-0). .

  When the resin (A) is produced using such an acid stable monomer (a2-0), a monomer in which the phenolic hydroxy group in the acid stable monomer (a2-0) is protected with a protecting group ( Monomers having a protected phenolic hydroxy group) can also be used. As the protecting group, for example, a protecting group capable of leaving with an acid or a base is preferable. The phenolic hydroxy group protected with a protecting group capable of leaving with an acid or a base is deprotected by contact with an acid or a base, whereby an acid stable structural unit (a2-0) is obtained. However, since the resin (A) has a structural unit (a1) having an acid labile group, when the phenolic hydroxy group protected with a protective group is deprotected, the structural unit (a1) Deprotection by contact with a base is preferred so that the acid labile group is not significantly impaired. As the protective group, for example, an acetyl group, a benzoyl group and the like are preferable. Examples of the base include 4-dimethylaminoviridine, triethylamine and the like.

  Among the examples of the acid stable monomer (a2-0) described above, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferable. Of course, when the resin (A) is produced using 4-hydroxystyrene or 4-hydroxy-α-methylstyrene, it is also possible to use those obtained by protecting the phenolic hydroxy group in these with a suitable protecting group. it can.

When the resin (A) has an acid stable structural unit (a2-0), the content is preferably in the range of 5 to 95 mol% with respect to all the structural units (100 mol%) of the resin (A). The range of 10-80 mol% is more preferable, and the range of 15-80 mol% is more preferable.
When the resin (X) has an acid stable structural unit (a2-0), the content is preferably 5 to 95 mol% with respect to the total structural unit (100 mol%) of the resin (X). The range of -80 mol% is more preferable, and the range of 15-80 mol% is more preferable.

<Acid stable structural unit (a3)>
The lactone ring possessed by the acid stable structural unit (a3) may be monocyclic such as β-propiolactone ring, γ-butyrolactone ring and δ-valerolactone ring, monocyclic lactone ring and other rings. Or a condensed ring. Among these lactone rings, a γ-butyrolactone ring and a condensed ring of a γ-butyrolactone ring and another ring are preferable.

［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。）を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表し、ｐ１が２以上の場合、複数のＲ^a21は同一でも異なっていてもよい。
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。）を表す。＊はカルボニル基との結合手を表す。
ｑ１は、０〜３の整数を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｑ１が２以上の場合、複数のＲ^a22は同一でも異なっていてもよい。
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。）を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
ｒ１は、０〜３の整数を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｒ１が２以上の場合、複数のＲ^a23は同一でも異なっていてもよい。］ The acid stable structural unit (a3) is preferably one represented by the following formula (a3-1), formula (a3-2) or formula (a3-3). Resin (A) may have only 1 type among these, and may have 2 or more types. In the following description, the formula (a3-1) may be referred to as “acid-stable structural unit (a3-1)”, and the formula (a3-2) may be referred to as “acid-stable structure”. “Unit (a3-2)” may be referred to, and the compound represented by formula (a3-3) may be referred to as “acid-stable structural unit (a3-3)”.

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

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 each independently represent an oxygen atom or * —O— (CH ₂ ) _k3 —CO in which k3 is an integer of 1 to 4. A group represented by —O— is preferable, an oxygen atom and * —O—CH ₂ —CO—O— are more preferable, and an oxygen atom is more preferable.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are preferably integers of 0 to 2, more preferably 0 or 1.

Examples of the acid stable structural unit (a3-1) having a γ-butyrolactone ring include the following.

Examples of the acid stable structural unit (a3-2) having a condensed ring of γ-butyrolactone ring and norbornane ring include the following.

式（ａ３−１−１）〜式（ａ３−１−１１）のいずれかで表される酸安定構造単位（ａ３−１）、式（ａ３−２−１）〜式（ａ３−２−１１）のいずれかで表される酸安定構造単位（ａ３−２）及び式（ａ３−３−１）〜式（ａ３−３−６）のいずれかで表される酸安定構造単位（ａ３−３）において、構造単位（ａａ）の具体例と同様に、部分構造Ｍを部分構造Ａに置き換えたものも、各々酸安定構造単位（ａ３−１）、酸安定構造単位（ａ３−２）及び酸安定構造単位（ａ３−３）の具体例として挙げることができる。また、この例示において、ラクトン環が有する置換基（Ｒ^a21〜Ｒ^a23）としてメチル基を有するものも例示したが、このメチル基を上述のような基に置き換えたものも、酸安定構造単位（ａ３）の具体例として挙げられる。 Examples of the acid stable structural unit (a3-3) having a condensed ring of γ-butyrolactone ring and cyclohexane ring include the following.

The acid stable structural unit (a3-1) represented by any one of formula (a3-1-1) to formula (a3-1-11), formula (a3-2-1) to formula (a3-2-11) The acid stable structural unit (a3-2) represented by any one of the formula (a3-3-1) and the acid stable structural unit (a3-3) represented by any one of the formulas (a3-3-1) to (a3-3-6) In the same manner as in the specific examples of the structural unit (aa), those in which the partial structure M is replaced with the partial structure A are the acid stable structural unit (a3-1), the acid stable structural unit (a3-2) and the acid. Specific examples of the stable structural unit (a3-3) can be given. Moreover, in this illustration, those having a methyl group as an example of the substituent (R ^{a21 to} R ^a23 ) of the lactone ring are also exemplified, but those in which this methyl group is replaced with the above-described groups are also acid stable structural units ( Specific examples of a3) are mentioned.

Among the acid stable structural units (a3), α- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α -(Meth) acryloyloxy-α-methyl-γ-butyrolactone, β- (meth) acryloyloxy-α-methyl-γ-butyrolactone, (meth) acrylic acid (5-oxo-4-oxatricyclo [4.2.1 .0 ^3,7] nonane-2-yl, (meth) acrylic acid 2- tetrahydro-2-oxo-3-furyl, and (meth) acrylic acid (5-oxo-4-oxa-tricyclo [4.2.1 .0 ^3,7] nonane-2-yloxy) -2-oxoethyl acid derived from such stable structural unit (a3) is preferable.

The resin (A) has an acid stable structural unit (a3) selected from the group consisting of an acid stable structural unit (a3-1), an acid stable structural unit (a3-2), and an acid stable structural unit (a3-3). In this case, the total content is preferably in the range of 5 to 70 mol%, more preferably in the range of 10 to 65 mol%, and more preferably 10 to 60 mol, based on the total structural unit (100 mol%) of the resin (A). % Range is more preferred. The content of each of the acid stable structural unit (a3-1), the acid stable structural unit (a3-2) and the acid stable structural unit (a3-3) is the total structural unit (100 mol%) of the resin (A2). On the other hand, the range of 5-60 mol% is preferable, the range of 10-55 mol% is more preferable, the range of 20-50 mol% is more preferable, and the range of 20-45 mol% is still more preferable.
The resin (X) has an acid stable structural unit (a3) selected from the group consisting of an acid stable structural unit (a3-1), an acid stable structural unit (a3-2), and an acid stable structural unit (a3-3). In this case, the total content is selected from the range of 5 to 70 mol%, preferably 10 to 65 mol%, preferably 10 to 60 mol, based on the total structural unit (100 mol%) of the resin (X). % Range is more preferred.

［式（ａ４−３）中、
Ｒ^a25及びＲ^a26は、それぞれ独立に、水素原子、ヒドロキシ基を有していてもよい炭素数１〜３のアルキル基、シアノ基、カルボキシ基又は−ＣＯＯＲ^a27〔Ｒ^a27は、炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族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。但し−ＣＯＯＲ^a27が酸不安定基となるものは除く（すなわち、Ｒ^a27は、３級炭素原子が−Ｏ−と結合するものを含まない）〕を表すか、或いはＲ^a25及びＲ^a26が結合して−ＣＯ−Ｏ−ＣＯ−を形成する。］ <Acid-stable monomer (a4)>
The resin (A) may have a structural unit derived from an acid-stable monomer other than the above-described structural unit (hereinafter sometimes referred to as “acid-stable monomer (a4)”).
The structural unit derived from the acid stable monomer (a4) is preferable among the structural units that the resin (X) may have in addition to the structural unit (aa) and the structural unit (ab).
The acid stable monomer (a4) is represented by maleic anhydride represented by the following formula (a4-1), itaconic anhydride represented by the formula (a4-2), and formula (a4-3). And an acid-stable monomer having a norbornene ring (hereinafter sometimes referred to as “acid-stable monomer (a4-3)”).

[In the formula (a4-3),
R ^a25 and R ^a26 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms that may have a hydroxy group, a cyano group, a carboxy group, or —COOR ^a27 [R ^a27 represents 1 to 1 carbon atoms; 18 represents an aliphatic hydrocarbon group, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. Provided that —COOR ^a27 is an acid labile group (that is, R ^a27 does not include those in which a tertiary carbon atom is bonded to —O—)), or R ^a25 and R ^a26 are bonded. To form -CO-O-CO-. ]

In R ^a25 and R ^a26 in formula (a4-3), the alkyl group which may have a hydroxy group is preferably a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a 2-hydroxyethyl group, or the like.
The aliphatic hydrocarbon group for R ^a27 is preferably an alkyl group having 1 to 8 carbon atoms and an alicyclic hydrocarbon group having 4 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms and a carbon number. 4 to 12 alicyclic hydrocarbon groups, more preferably a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

  Examples of the acid stable monomer (a4-3) include 2-norbornene, 2-hydroxy-5-norbornene, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2- Examples thereof include 2-hydroxy-1-ethyl carboxylate, 5-norbornene-2-methanol and 5-norbornene-2,3-dicarboxylic acid anhydride.

The resin (A) is a structural unit derived from maleic anhydride represented by the formula (a4-1), a structural unit derived from itaconic anhydride represented by the formula (a4-2), and a monomer (a4-3). In the case of having a structural unit selected from the group consisting of structural units derived from, the total content is preferably in the range of 2 to 40 mol% with respect to all structural units (100 mol%) of the resin (A), The range of 3-30 mol% is preferable, and the range of 5-20 mol% is more preferable.
Resin (X) is a structural unit derived from maleic anhydride represented by formula (a4-1), a structural unit derived from itaconic anhydride represented by formula (a4-2), and a monomer (a4-3) In the case of having a structural unit selected from the group consisting of structural units derived from the total content thereof is preferably in the range of 2 to 40 mol% with respect to all structural units (100 mol%) of the resin (X), The range of 3-30 mol% is more preferable, and the range of 5-20 mol% is more preferable.

［式（ａ４−４）中、
Ｌ^a7は、酸素原子又は^＊−Ｔ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を（ｋ２は１〜７の整数を表す。Ｔは酸素原子又はＮＨである。）表し、＊はカルボニル基との結合手を表す。
Ｒ^a28は、水素原子又はメチル基を表す。
Ｗ¹⁰は、置換基を有していてもよいスルトン環基を表す。］ Furthermore, examples of the acid stable monomer (a4) include those having a sultone ring represented by the formula (a4-4) (hereinafter, sometimes referred to as “acid stable monomer (a4-4)”).

[In the formula (a4-4),
L ^a7 represents an oxygen atom or ^* -T— (CH ₂ ) _k2 —CO—O— (k2 represents an integer of 1 to 7. T is an oxygen atom or NH), and * represents a carbonyl group Represents the bond hand.
R ^a28 represents a hydrogen atom or a methyl group.
W ¹⁰ represents a sultone ring group which may have a substituent. ]

置換基を有していてもよいスルトン環基とは、上述の結合手に置き換わった水素原子以外の水素原子がさらに置換基（水素原子以外の１価の基）に置換されたものであり、該置換基は、ヒドロキシ基、シアノ基、炭素数１〜６のアルキル基、炭素数１〜６のフッ化アルキル基、炭素数１〜６のヒドロキシアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜７のアルコキシカルボニル基、炭素数１〜７のアシル基及び炭素数１〜８のアシルオキシ基からなる群より選ばれる。 As the sultone ring contained in the sultone ring group, among the methylene groups constituting the alicyclic hydrocarbon, two adjacent methylene groups are replaced with one oxygen atom and the other with a sulfonyl group, that is, in the ring skeleton. Examples of the ring having —O—SO ₂ — include those shown below. A typical example of the sultone ring group is one in which one of the hydrogen atoms in the sultone ring shown below is replaced with a bond, and in the formula (a4-4), the bond with L ^a7 corresponds.

The sultone ring group which may have a substituent is a group in which a hydrogen atom other than a hydrogen atom replaced with the above bond is further substituted with a substituent (a monovalent group other than a hydrogen atom), The substituent is a hydroxy group, a cyano group, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, It is selected from the group consisting of an alkoxycarbonyl group having 1 to 7 carbon atoms, an acyl group having 1 to 7 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms.

Specific examples of the acid stable monomer (a4-4) are shown below.

上記のモノマーにおいて、Ｒ^a28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（ａ４−４）の具体例として挙げることができる。

In the above monomer, a structural unit in which a methyl group corresponding to R ^a28 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a4-4).

When the resin (A) has a structural unit derived from the acid-stable monomer (a4-4), the content is 2 to 40 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range is preferably 3 to 35 mol%, more preferably 5 to 30 mol%.
When the resin (X) has a structural unit derived from the acid-stable monomer (a4-4), the content thereof is 2 to 40 mol% with respect to the total structural unit (100 mol%) of the resin (X). The range is preferably 3 to 35 mol%, more preferably 5 to 30 mol%.

Examples of the acid stable monomer (a4) include a monomer having a fluorine atom as shown below [hereinafter referred to as “acid stable monomer (a4-5)” in some cases. ] Can also be used.

Among such acid stable monomers (a4-5), 5- (3,3,3-trifluoro-2-hydroxy-2- (meth) acrylic acid having a monocyclic or polycyclic aliphatic ring [Trifluoromethyl] propyl) bicyclo [2.2.1] hept-2-yl, 6- (3,3,3-trifluoro-2-hydroxy-2- [trifluoromethyl] propyl (meth) acrylate ) Bicyclo [2.2.1] hept-2-yl, 4,4-bis (trifluoromethyl) -3-oxatricyclo [4.2.1.0 ^2,5 ] nonyl (meth) acrylate preferable.

When the resin (A) has a structural unit derived from the acid-stable monomer (a4-5), the total content is 1 to 20 mol relative to the total structural unit (100 mol%) of the resin (A). % Range is preferable, the range of 2-15 mol% is more preferable, and the range of 3-10 mol% is more preferable.
When the resin (X) has a structural unit derived from the acid-stable monomer (a4-5), the total content is 1 to 50 mol with respect to the total structural unit (100 mol%) of the resin (X). % Range is preferable, the range of 2-45 mol% is more preferable, and the range of 3-40 mol% is more preferable.

［式（３）中、Ｒ¹⁰は、炭素数１〜６のフッ化アルキル基を表す。＊は結合手を表す。］ For the production of the resin (A), an acid stable monomer (a4) having a group represented by the following formula (3) can also be used.

[In Formula (3), R ¹⁰ represents a fluorinated alkyl group having 1 to 6 carbon atoms. * Represents a bond. ]

As the fluorinated alkyl group for R ¹⁰ , a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 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- (perfluoropropyl) 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, perfluoropentylmethyl group and A perfluorohexyl group may be mentioned.

The fluorinated alkyl group for R ¹⁰ preferably has 1 to 4 carbon atoms, more preferably a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group, and particularly preferably a trifluoromethyl group.

上記のモノマーにおいて、部分構造Ｍ’を部分構造Ａ’に置き換えたものも、酸安定モノマー（ａ４−６）の具体例として挙げることができる。

As the acid stable monomer (a4) having a group represented by the formula (3), the following acid stable monomer [hereinafter referred to as “acid stable monomer (a4-6)” in some cases. ].

In the above monomer, those in which the partial structure M ′ is replaced with the partial structure A ′ can also be mentioned as specific examples of the acid stable monomer (a4-6).

Moreover, the following can also be mentioned as an acid stable monomer (a4-6).

When the resin (A) has a structural unit derived from the acid stable monomer (a4-6), the content is 5 to 90 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range is preferably 10 to 80 mol%, more preferably 20 to 70 mol%.
When the resin (X) has a structural unit derived from the acid-stable monomer (a4-6), the content thereof is 1 to 70 mol% with respect to the total structural unit (100 mol%) of the resin (X). Is preferable, the range of 3 to 60 mol% is more preferable, and the range of 5 to 50 mol% is more preferable.

［式（４）中、
Ｒ¹¹は置換基を有してもよい炭素数６〜１２の芳香族炭化水素基を表す。
Ｒ¹²は、置換基を有してもよい炭素数１〜１２の炭化水素基を表し、該炭化水素基は、ヘテロ原子を含んでいてもよい。
Ａ^３は、単結合、−（ＣＨ_２）_ｍ10−ＳＯ_２−Ｏ−＊又は−（ＣＨ_２）_ｍ10−ＣＯ−Ｏ−＊を表し、ここに示すアルキレン鎖〔−（ＣＨ_２）_ｍ10−〕に含まれるメチレン基は、酸素原子、カルボニル基又はスルホニル基に置き換わっていてもよく、当該アルキレン鎖に含まれる水素原子は、フッ素原子に置き換わっていてもよい。
ｍ１０は、１〜１２の整数を表す。］ The resin (A) can contain a structural unit derived from the acid stable monomer (a4) having a group represented by the following formula (4).

[In Formula (4),
R ¹¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.
R ¹² represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group may contain a hetero atom.
A ³ represents a single bond, — (CH ₂ ) _{m 10} —SO ₂ —O— * or — (CH ₂ ) _{m 10} —CO—O— *, and an alkylene chain [— (CH ₂ ) _{m 10} —] shown here. The methylene group contained in may be replaced with an oxygen atom, a carbonyl group or a sulfonyl group, and the hydrogen atom contained in the alkylene chain may be replaced with a fluorine atom.
m10 represents an integer of 1 to 12. ]

Specific examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms in R ¹¹ include those already exemplified in this range. When these aromatic hydrocarbon groups have a substituent, the substituent is an alkyl group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a nitro group, a cyano group, a hydroxy group, a phenyloxy group, and tert-butylphenyl. Group.

Examples of R ¹¹ include the following groups. Note that * is a bond with a carbon atom.

The hydrocarbon group having 1 to ¹² carbon atoms in R ¹² may be any of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group is typically an alkyl group, and specific examples thereof include those already exemplified in the range of 1 to 12 carbon atoms. Examples of the alicyclic hydrocarbon group include those already exemplified in the range of 12 or less carbon atoms.
In addition, when R < ¹² > is an aliphatic hydrocarbon group, this aliphatic hydrocarbon group may contain the hetero atom. The hetero atom is a halogen atom, a sulfur atom, an oxygen atom, a nitrogen atom or the like [a sulfonyl group or a carbonyl group may be included as a linking group].
Examples of R ¹² containing such a heteroatom include the following groups.

When R ¹² is an aromatic hydrocarbon group, specific examples thereof are the same as those for R ¹¹ .

Examples of A ³ include the following groups.

［式（ａ４−７）中、
Ｒ¹³は、水素原子又はメチル基を表す。
Ｒ¹¹、Ｒ¹²及びＡ^３は、上記と同じ意味を表す。］ Examples of the acid stable monomer (a4) containing a group represented by the formula (4) include those represented by the formula (a4-7) [hereinafter referred to as “acid stable monomer (a4-7)” in some cases. ].

[In the formula (a4-7),
R ¹³ represents a hydrogen atom or a methyl group.
R ¹¹ , R ¹² and A ³ represent the same meaning as described above. ]

ここに示した酸安定モノマー（ａ４−７）の具体例において、酸安定モノマー（ａ４−４）の具体例と同様に、部分構造Ｍ’を部分構造Ａ’に置き換えたものも、酸安定モノマー（ａ４−７）の具体例として挙げることができる。 Examples of the acid stable monomer (a4-7) include the following.

In the specific example of the acid-stable monomer (a4-7) shown here, as in the specific example of the acid-stable monomer (a4-4), the partial structure M ′ is replaced with the partial structure A ′. It can mention as a specific example of (a4-7).

When the resin (A) has a structural unit derived from the acid-stable monomer (a4-7), the content is 5 to 90 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range is preferably 10 to 80 mol%, more preferably 20 to 70 mol%.
When the resin (X) has a structural unit derived from the acid-stable monomer (a4-7), the content thereof is 1 to 30 mol% with respect to the total structural unit (100 mol%) of the resin (X). Is preferable, the range of 3 to 25 mol% is more preferable, and the range of 5 to 20 mol% is more preferable.

［式（ａ４−８）中、
環Ｗ^２は、炭素数３〜３６の脂肪族環を表す。
Ａ^４は、単結合又は炭素数１〜１７の脂肪族炭化水素基を表す。該脂肪族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が、Ａ^４のうち、酸素原子に結合している原子は炭素原子である。
Ｒ¹⁴は、水素原子、ハロゲン原子、炭素数１〜６のアルキル基又は炭素数１〜６のハロアルキル基を表す。
Ｒ¹⁵及びＲ¹⁶は、それぞれ独立に、炭素数１〜６のアルキル基又は炭素数１〜６のハロアルキル基を表す。］ As the acid stable monomer (a4), a monomer represented by the following formula (a4-8) [hereinafter referred to as “acid stable monomer (a4-8)” in some cases). ] Can also be mentioned.

[In the formula (a4-8),
Ring ^{W 2} represents an aliphatic ring of 3 to 36 carbon atoms.
A ⁴ represents a single bond or an aliphatic hydrocarbon group having 1 to 17 carbon atoms. The methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group, but among A ⁴ , the atom bonded to the oxygen atom is a carbon atom.
R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms.
R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 6 carbon atoms or a haloalkyl group having 1 to 6 carbon atoms. ]

で示される部分構造は、式（ＫＡ−１）〜式（ＫＡ−２２）の脂環式炭化水素を構成する水素原子の１個がＡ^４との結合手に、脂環式炭化水素環原子に含まれる炭素原子の１つに結合している２つの水素原子が、−Ｏ−ＣＯ−Ｒ¹⁵及び−Ｏ−ＣＯ−Ｒ¹⁶との結合手に置き換わったものを挙げることができる。
Ｗ^２の脂肪族環は、シクロヘキサン環、アダマンタン環、ノルボルナン環及びノルボルネン環が特に好ましい。 Ring W ² is a monocyclic or polycyclic aliphatic ring carbon atoms 3 to 36, the number of carbon atoms is preferably from 5 to 18, 6 to 12 more preferably in the range of. More specifically, in the description of the alicyclic hydrocarbon group, the aliphatic ring shown in the form of the alicyclic hydrocarbon represented by the formula (KA-1) to the formula (KA-22) may be mentioned. it can. That is, in formula (a4-8)

Partial structure represented in the formula (KA-1) ~ expression bond one hydrogen atom constituting the alicyclic hydrocarbon (KA-22) is the A ^4, an alicyclic hydrocarbon ring atoms Can be mentioned in which two hydrogen atoms bonded to one of the carbon atoms contained in is replaced with a bond to —O—CO—R ¹⁵ and —O—CO—R ¹⁶ .
The aliphatic ring for W ² is particularly preferably a cyclohexane ring, an adamantane ring, a norbornane ring or a norbornene ring.

式中、
Ｘ^Ｘ１及びＸ^Ｘ２は、それぞれ独立に、単結合又は置換基を有していてもよい炭素数１〜６のアルキレン基を表し、Ｘ^Ｘ１及びＸ^Ｘ２がともに単結合であることはなく、式（Ｘ^ｘ−Ａ）、式（Ｘ^ｘ−Ｂ）又は式（Ｘ^ｘ−Ｃ）で表される基の総炭素数はそれぞれ１７以下である。 Examples of the aliphatic hydrocarbon group for A ⁴ include the alkanediyl groups and divalent alicyclic hydrocarbon groups exemplified above in the range of 17 or less carbon atoms, and those having a carbon number of 17 or less. For example, it may be an aliphatic hydrocarbon group in which an alkanediyl group and an alicyclic hydrocarbon group are combined. Further, the aliphatic hydrocarbon group of A ⁴ may have a substituent.
Here, a representative example of an aliphatic hydrocarbon group in which an alkanediyl group and an alicyclic hydrocarbon group are combined is shown. Examples of the aliphatic hydrocarbon group include groups represented by formula (X ^x -A), formula (X ^x -B), or formula (X ^x -C).

Where
X ^X1 and X ^X2 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may have a substituent, and X ^X1 and X ^X2 are not both single bonds, The total number of carbon atoms of the group represented by (X ^x -A), formula (X ^x -B) or formula (X ^x -C) is 17 or less.

Examples of the group in which the methylene group contained in the aliphatic hydrocarbon group of A ⁴ is replaced with an oxygen atom or a carbonyl group include a methylene group contained in the hydrocarbon group of A ^{aa1 in} the formula (aa) as an oxygen atom or a carbonyl group And those exemplified by the group replaced by.
Among them, ^{A 4} represents a single _{bond, * - (CH 2) s1} -CO-O - (* represents a binding position to -O-, s1 is an integer of 1-6.) Represented by A group is preferable, and a group represented by a single bond or * —CH ₂ —CO—O— (* represents a bond to —O—) is more preferable.

Specific examples of the alkyl group represented by R ^{14 to} R ¹⁶ include those already exemplified in the range of 1 to 6 carbon atoms. As the halogenated alkyl group, an alkyl group having a fluorine atom is particularly preferable. Among the halogenated alkyl groups of R ¹⁵ and R ¹⁶ , preferred are trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group and the like, among which trifluoromethyl group, perfluoroethyl group and A perfluoropropyl group is preferred.
R ¹⁴ is preferably a hydrogen atom or a methyl group.

これらの中でも、

で示される酸安定モノマー（ａ４−８）がより好ましい。 Examples of the acid stable monomer (a4-8) include those shown below. R ^{14 to} R ¹⁶ and A ⁴ represent the same meaning as described above.

Among these,

The acid-stable monomer (a4-8) shown by these is more preferable.

ここに示した酸安定モノマー（ａ４−８）の具体例において、酸安定モノマー（ａ４−４）の具体例と同様に、部分構造Ｍ’を部分構造Ａ’に置き換えたものも、酸安定モノマー（ａ４−８）の具体例として挙げられる。 Specific examples of the acid-stable monomer (a4-8) include those represented below.

In the specific example of the acid stable monomer (a4-8) shown here, as in the specific example of the acid stable monomer (a4-4), the partial structure M ′ is replaced with the partial structure A ′. Specific examples of (a4-8) are mentioned.

［式（ａ４−８−ａ）及び式（ａ４−８−ｂ）中の符号はいずれも、前記と同義である。
］ A preferable acid stable monomer (a4-8) can be produced, for example, as follows. That is, the acid stable monomer (a4-8) can be produced by reacting the compound represented by the formula (a4-8-a) with the compound represented by the formula (a4-8-b). it can. Examples of the compound represented by the formula (a4-8-a) include 1-methacryloyloxy-4-oxoadamantane described in JP-A-2002-226436. Examples of the compound represented by the formula (a4-8-b) include pentafluoropropionic anhydride, heptafluorobutyric anhydride, and trifluoroacetic anhydride. This reaction is preferably carried out by heating near the boiling point of the compound represented by the formula (a4-8-b) to be used.

[The symbols in formula (a4-8-a) and formula (a4-8-b) are as defined above.
]

When the resin (A) has a structural unit derived from the acid-stable monomer (a4-8), the content is 5 to 90 mol% with respect to the total structural unit (100 mol%) of the resin (AA). The range is preferably 10 to 80 mol%, more preferably 20 to 70 mol%.
When the resin (X) has a structural unit derived from the acid-stable monomer (a4-8), the content thereof is 1 to 30 mol% with respect to the total structural unit (100 mol%) of the resin (X). Is preferable, the range of 3 to 25 mol% is more preferable, and the range of 5 to 20 mol% is more preferable.

  When the resin (X) has a structural unit derived from the acid-stable monomer (a4), the acid-stable monomer (a4-6) having a group represented by the formula (3) and / or the formula (4) The structural unit derived from the acid stable monomer (a4-7) having the group represented is preferable, and the structural unit derived from the acid stable monomer (a4-6) is more preferable.

<Production method of resin>
Resin (X) is polymerized with compound (aa ′) and compound (ab ′) by being subjected to a known polymerization method (for example, radical polymerization method), or compound (aa ′) and compound (ab ') And a monomer (preferably acid-stable monomer (a4)) from which other structural units are derived can be obtained by polymerization.
Resin (X) is a copolymer of compound (aa ′) and compound (ab ′), and a copolymer of compound (aa ′), compound (ab ′), and acid stable monomer (a4). A copolymer of compound (aa ′) and compound (ab ′), and compound (aa ′), compound (ab ′), acid-stable monomer (a4-6) and / or acid-stable monomer A copolymer with (a4-7) is more preferred.

  The weight average molecular weight of the resin (X) is preferably from 8,000 to 80,000, more preferably from 10,000 to 60,000. In addition, the weight average molecular weight here is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis. Detailed analysis conditions for this analysis are described in the Examples of the present application.

On the other hand, the resin (A) is obtained by copolymerizing a monomer that derives the structural unit (a1) [preferably, a monomer that induces the structural unit (a1-1) or the structural unit (a1-2)]. Preferably, a monomer derived from the structural unit (a1) and a monomer derived from the acid stable structural unit are copolymerized, and more preferably, the structural unit (a1-1) and / or the structural unit (a1). -2), a monomer that induces acid stable structural unit (a2) and / or a monomer that induces acid stable structural unit (a3).
The resin (A) preferably has at least one of the structural unit (a1-1) having an adamantyl group and the structural unit (a1-2) having a cyclohexyl group as the structural unit (a1). It is more preferable to have a structural unit (a1-1) having an adamantyl group. As the acid stable structural unit (a2), it is preferable to use a structural unit (a2-1) having a hydroxyadamantyl group. The acid stable structural unit (a3) includes at least an acid stable structural unit (a3-1) having a γ-butyrolactone ring and an acid stable structural unit (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornane ring. It is preferable to have one. The resin (A) can be produced by polymerizing (copolymerizing) the above-described monomer by subjecting it to a known polymerization method (for example, radical polymerization method).

  The weight average molecular weight of the resin (A) is preferably 2,500 or more and 50,000 or less, and more preferably 3,000 or more and 30,000 or less. The definition of the weight average molecular weight and the measuring means here are the same as in the case of the resin (X).

<This resist composition>
By including the resin (X), the present resist composition exhibits an effect that an excellent CD uniformity resist pattern can be produced. When resin (X) itself does not have an acid action characteristic, resin (A) is contained in this resist composition as already demonstrated. In addition to these resins, the present resist composition contains components such as an acid generator and a solvent (D), and, if necessary, an additive such as a basic compound called a quencher in the art. May contain. Hereinafter, components other than the resin, that is, an acid generator, an additive, and a solvent will be described in this order. In the following description, what removed the solvent (D) from this resist composition may be called "solid content" of this resist composition. The content ratio of the solid content to the total mass of the resist composition can be measured by a known analysis means such as liquid chromatography and gas chromatography.

<Acid generator (hereinafter sometimes referred to as “acid generator (B)”)>
The acid generator (B) is classified into a nonionic type and an ionic type. The acid generator contained in the resist composition may be a nonionic acid generator, an ionic acid generator, or a combination thereof. 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, a diazonium salt, a phosphonium salt, a sulfonium salt, or an 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 include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, and JP-A 63-163452. No. 62-153853, Japanese Patent Laid-Open No. 63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. Compounds that generate acids by the described radiation can be used.

式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、置換基を有していてもよい炭素数１〜１７の２価の脂肪族炭化水素基を表す。該脂肪族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の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれるメチレン基は、酸素原子、カルボニル基又はスルホニル基に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。 The acid generator contained in the resist composition is preferably an acid generator represented by the following formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”). In the following description, among the acid generators (B1), Z ⁺ having a positive charge is referred to as “organic cation”, and a negative charge obtained by removing the organic cation is referred to as “sulfonate anion”. There is.

In formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a C 1-17 divalent aliphatic hydrocarbon group which may have a substituent. The methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group is replaced with an oxygen atom, a carbonyl group or a sulfonyl group. May be.
Z ⁺ represents an organic cation.

Specific examples of the perfluoroalkyl group of Q ¹ and Q ² include those in which all of the hydrogen atoms constituting the alkyl group are replaced by fluorine atoms in the alkyl group having 1 to 6 carbon atoms among the already exemplified alkyl groups. Applicable.
As the acid generator (B1) contained in the resist composition, Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom acid generator (B1). Q ¹ and Q ² An acid generator (B1) in which both are fluorine atoms is more preferred.

Specific examples of the aliphatic hydrocarbon group represented by L ^b1 include the removal of two hydrogen atoms from the alkanediyl group already exemplified and the alicyclic hydrocarbons of the above formulas (KA-1) to (KA-22). Group.

式（ｂ１−１）〜式（ｂ１−６）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の脂肪族炭化水素基を表し、この脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の脂肪族炭化水素基を表し、この脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。
Ｌ^b4は、炭素数１〜１３の２価の脂肪族炭化水素基を表し、この脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。但しＬ^b3及びＬ^b4の合計炭素数の上限は１３である。
Ｌ^b5は、炭素数１〜１５の２価の脂肪族炭化水素基を表し、この脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。
Ｌ^b6及びＬ^b7は、それぞれ独立に、炭素数１〜１５の２価の脂肪族炭化水素基を表し、これらの脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。但しＬ^b6及びＬ^b7の合計炭素数の上限は１６である。
Ｌ^b8は、炭素数１〜１４の２価の脂肪族炭化水素基を表し、この脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。
Ｌ^b9及びＬ^b10は、それぞれ独立に、炭素数１〜１１の２価の脂肪族炭化水素基を表し、これらの脂肪族炭化水素基は脂肪族飽和炭化水素基が好ましい。但しＬ^b9及びＬ^b10の合計炭素数の上限は１２である。 Examples of the methylene group contained in the divalent aliphatic hydrocarbon group of L ^b1 replaced by an oxygen atom or a carbonyl group include the following formulas (b1-1), (b1-2), and ( a group represented by any one of b1-3), formula (b1-4), formula (b1-5) and formula (b1-6) [formula (b1-1) to formula (b1-6)]. . Incidentally, the formula (b1-1) ~ formula (b1-6) is coupled to the left and right have been described in accordance with the formula (B1), the left bond * is a ^{C (Q 1) (Q 2} ) The right hand * is bonded to Y. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

In formula (b1-1) to formula (b1-6),
L ^b2 represents a single bond or a C 1-15 divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group.
L ^b3 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, and the aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group.
L ^b4 represents a divalent aliphatic hydrocarbon group having 1 to 13 carbon atoms, and the aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, and the aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group.
L ^b6 and L ^b7 each independently represent a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, and these aliphatic hydrocarbon groups are preferably aliphatic saturated hydrocarbon groups. However, the upper limit of the total carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a divalent aliphatic hydrocarbon group having 1 to 14 carbon atoms, and the aliphatic hydrocarbon group is preferably an aliphatic saturated hydrocarbon group.
L ^b9 and L ^b10 each independently represent a divalent aliphatic hydrocarbon group having 1 to 11 carbon atoms, and these aliphatic hydrocarbon groups are preferably aliphatic saturated hydrocarbon groups. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 12.

L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), and more preferably any one of formulas (b1-1) to (b1-3). It is a group represented.
Among these, as the acid generator used in the present resist composition, an acid generator (B1) having a divalent group represented by the formula (b1-1) as L ^b1 is preferable, and L ^b2 is a single bond or The acid generator (B1) having a divalent group represented by the formula (b1-1) which is a methylene group as L ^b1 is more preferable.

  Here, the specific example of group represented by either the formula (b1-1)-a formula (b1-6) is given. The definition of * is as described above.

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

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

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

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

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

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

The aliphatic hydrocarbon group for L ^b1 may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, 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, and a glycidyloxy group. Can be mentioned.
Specific examples of the aromatic hydrocarbon group, the aralkyl group, and the acyl group are as described above.

  As above-mentioned, Y represents the C1-C18 aliphatic hydrocarbon group which may have a substituent. Among these aliphatic hydrocarbon groups, Y is preferably an alkyl group and an alicyclic hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, 3-12 alicyclic hydrocarbon groups are particularly preferred.

When the aliphatic hydrocarbon group of Y has a substituent, the substituent is, for example, a halogen atom (excluding a fluorine atom), a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an aromatic having 6 to 18 carbon atoms. Group represented by a group hydrocarbon group, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group or — (CH ₂ ) _j2 —O—CO—R ^b1 (wherein R ^b1 represents a hydrocarbon group having 1 to 16 carbon atoms, j2 represents an integer of 0 to 4, and the like. The aromatic hydrocarbon group and aralkyl group referred to here may further have, for example, an alkyl group, a halogen atom or a hydroxy group.

  The methylene group contained in the aliphatic hydrocarbon group for Y may be replaced with a group (divalent group) selected from the group consisting of an oxygen atom, a sulfonyl group and a carbonyl group. Examples of the group in which the methylene group constituting the alicyclic hydrocarbon group is replaced by an oxygen atom, a sulfonyl group or a carbonyl group include, for example, a cyclic ether group (one or two of the methylene groups contained in the alicyclic hydrocarbon group are A group in which an oxygen atom is substituted), a cyclic ketone group (a group in which one or two methylene groups contained in an alicyclic hydrocarbon group are substituted with a carbonyl group), a sultone ring group (included in an alicyclic hydrocarbon group) Two adjacent methylene groups in the methylene group are groups in which an oxygen atom and a sulfonyl group are substituted, respectively, and a lactone ring group (two methylene groups adjacent to each other among methylene groups contained in the alicyclic hydrocarbon group, A group in which an oxygen atom and a carbonyl group are substituted, respectively).

A preferred group of the alicyclic hydrocarbon group of Y is an alicyclic group represented by any of the following formula (Y1), formula (Y2), formula (Y3), formula (Y4), and formula (Y5). Of these, an alicyclic hydrocarbon group represented by any one of the formula (Y1), the formula (Y2), the formula (Y3), and the formula (Y5) is more preferable, and the formula (Y1 ) And the alicyclic hydrocarbon group represented by any one of the formulas (Y2) are particularly preferable. Of course, the hydrogen atoms contained in these alicyclic hydrocarbon groups are
It may be substituted with a substituent.

Specific examples of the alicyclic hydrocarbon group having a substituent are as follows.

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

  The alicyclic hydrocarbon group of Y is preferably a group having an adamantane ring as shown in the formulas (Y1) and (Y2), and when these have a substituent, the substituent is preferably a hydroxy group . That is, as the alicyclic hydrocarbon group having a substituent, a hydroxyadamantyl group is particularly preferable as Y.

Specifically, preferred examples of the sulfonate anion include formula (b1-1-1), formula (b1-1-2), formula (b1-1-3), formula (b1-1-4), formula (B1-1-5), formula (b1-1-6), formula (b1-1-7), formula (b1-1-8) and formula (b1-1-9) [hereinafter referred to as "formula (b1 -1-1) to formula (b1-1-9) ". The sulfonate anion represented by this can be mentioned. In the sulfonate anion represented by any one of formulas (b1-1-1) to (b1-1-9), L ^b1 is preferably a group represented by formula (b1-1). R ^b2 and R ^b3 are each independently defined as a substituent that may optionally be present in the aliphatic hydrocarbon group of Y, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms, A methyl group is particularly preferred.

  Specific examples of the sulfonate anion represented by any one of the formulas (b1-1-1) to (b1-1-9) include sulfonate anions described in JP 2010-204646 A, for example. be able to.

Hereinafter, as a preferable sulfonate anion, L ^b1 is a group represented by the formula (b1-1), and Y is an alicyclic hydrocarbon group represented by the formula (Y1) or the formula (Y2). A specific example is given.
Examples of the sulfonate anion in which Y is an unsubstituted alicyclic hydrocarbon group include those represented by any of the following formulas (b1-s-1) to (b1-s-9).

Examples of the sulfonate anion in which Y is an alicyclic hydrocarbon group having a hydroxy group include those represented by any of the following formulas (b1-s-10) to (b1-s-18). .

Examples of the sulfonate anion in which Y is a cyclic ketone group include those represented by any of the following formulas (b1-s-19) to (b1-s-29).

Examples of the sulfonate anion in which Y is an alicyclic hydrocarbon group having an aromatic group include those represented by any of the following formulas (b1-s-30) to (b1-s-35). It is done.

Examples of the sulfonate anion in which Y is the lactone ring group or the sulfonic acid ring group include those represented by any of the following formulas (b1-s-36) to (b1-s-41). It is done.

Y may be an alkyl group. Examples of such a sulfonate anion include those represented by the following formula (b1-s-42).

Examples of the organic cation (Z ⁺ ) in the acid generator (B1) include an organic onium cation such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, an organic benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and more preferably, the following formula (b2-1), formula (b2-2), formula (b2-3) and formula (b2-4) [hereinafter, It describes like "Formula (b2-1)-Formula (b2-4)." ] Is an organic cation represented by any of the above.

In formula (b2-1) to formula (b2-4),
R ^b4 , R ^b5 and R ^b6 each independently represent a hydrocarbon group having 1 to 30 carbon atoms, and among these hydrocarbon groups, an alkyl group having 1 to 30 carbon atoms and an oil having 3 to 18 carbon atoms A cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 18 carbon atoms are preferred. The alkyl group may have a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon group includes a halogen atom and a carbon number. It may have 2 to 4 acyl groups or glycidyloxy groups, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alicyclic group having 3 to 18 carbon atoms. You may have a hydrocarbon group or a C1-C12 alkoxy group.
R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b9 , R ^b10 and R ^b11 (hereinafter referred to as “R ^{b9 to} R ^b11 ”) are each independently an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is an alkyl group. In this case, the carbon number is preferably 1 to 12, and when the aliphatic hydrocarbon group is an alicyclic hydrocarbon group, the carbon number is preferably 3 to 18, and more preferably 4 to 12. preferable.
R ^b12 represents a hydrocarbon group having 1 to 18 carbon atoms. Among these hydrocarbon groups, the aromatic hydrocarbon group is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or 1 to 12 carbon atoms. It may have an alkylcarbonyloxy group.
The combination of R ^b9 and R ^b10 and / or the combination of R ^b11 and R ^b12 are independently bonded to each other to form a 3-membered ring to 12-membered ring (preferably a 3-membered ring to 7-membered ring). These 3-membered ring to 12-membered ring (preferably 3-membered ring to 7-membered ring) may be an aliphatic ring or a methylene group contained in the aliphatic ring is an oxygen atom, a sulfur atom or A ring that replaces a carbonyl group.

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

The alkylcarbonyloxy group for R ^b12 is a group in which the acyl group already exemplified and an oxygen atom are bonded.

^Examples of the alkyl group ^{represented by} R ^{b9 to} R ^b12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 -Ethylhexyl group and the like.
Preferable examples of the alicyclic hydrocarbon group represented by R ^{b9 to} R ^b11 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 2-alkyladamantan-2-yl group, 1- ( Adamantan-1-yl) alkane-1-yl group and isobornyl group.
^As the aromatic hydrocarbon group for R ^b12 , phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, biphenylyl group And a naphthyl group.
A group in which an aromatic hydrocarbon group of R ^b12 and an alkyl group are bonded is typically an aralkyl group.
Examples of the ring formed by combining the combination of R ^b9 and R ^b10 include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. Etc.
Examples of the ring formed by combining the combination of R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Specific examples of the organic cation represented by the formulas (b2-1) to (b2-4) include those described in JP2010-204646A.

式（ｂ２−１−１）中、
Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１８の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
この脂肪族炭化水素基としては、炭素数１〜１２のアルキル基及び炭素数４〜１８の脂環式炭化水素基が好ましく、脂肪族炭化水素基は、置換基として、ハロゲン原子、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数６〜１８の芳香族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基を有していてもよい。
ｖ２、ｗ２及びｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。
ｖ２が２以上のとき、複数のＲ^b19は同一でも異なっていてもよく、ｗ２が２以上のとき、複数のＲ^b20は同一でも異なっていてもよく、ｘ２が２以上のとき、複数のＲ^b21は同一でも異なっていてもよい。
なかでも、Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、好ましくは、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１２のアルキル基、又は炭素数１〜１２のアルコキシ基である。 Among the exemplified organic cations, the cation (b2-1) is preferable, and an organic cation represented by the following formula (b2-1-1) [hereinafter referred to as “cation (b2-1-1)”. ] Is more preferable, and triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cation (in formula (b2-1-1), v2 = w2 = 0, x2 = 1 and R ^b21 is a methyl group) or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and More preferably, R ^b21 is a methyl group.

In formula (b2-1-1),
R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
As the aliphatic hydrocarbon group, an alkyl group having 1 to 12 carbon atoms and an alicyclic hydrocarbon group having 4 to 18 carbon atoms are preferable, and the aliphatic hydrocarbon group includes a halogen atom, a hydroxy group, You may have a C1-C12 alkoxy group, a C6-C18 aromatic hydrocarbon group, a C2-C4 acyl group, or a glycidyloxy group.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, a plurality of R ^b19 may be the same or different. When w2 is 2 or more, a plurality of R ^b20 may be the same or different. When x2 is 2 or more, a plurality of R ^{b19 b21} may be the same or different.
Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. It is a group.

Here, the specific example of the cation (b2-1-1) which is a suitable organic cation is shown.

Moreover, as an organic cation, the following organic cations can also be mentioned as a suitable thing among the organic cations represented by Formula (b2-3).

  The acid generator (B1) has been described for each of the sulfonate anion and the organic cation constituting the acid generator (B1). The acid generator (B1) is a combination of the sulfonate anion and the organic cation. The sulfonate anion and the organic cation can be arbitrarily combined. Table 2 shows combinations of the sulfonate anion and the organic cation. In Table 2, the sulfonate anion represented by the formula (b1-s-1) is represented as “(b1-s-1)” according to the formula number, and the formula (b2-c- The organic cation represented by 1) is represented as “(b2-c-1)” or the like according to the formula number.

  More preferred acid generator (B1) is specifically shown. Such an acid generator (B1) has the following formula (B1-1), formula (B1-2), formula (B1-3), formula (B1-4), formula (B1-5), formula (B) B1-6), formula (B1-7), formula (B1-8), formula (B1-9), formula (B1-10), formula (B1-11), formula (B1-12), formula (B1) −13), Formula (B1-14), Formula (B1-15), Formula (B1-16), and Formula (B1-17). Among them, formula (B1-2), formula (B1-3), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1-13) And (B1-14) are more preferred. In addition, as already described, Y is preferably an alicyclic hydrocarbon group which may have a substituent. Therefore, in this respect, the formula (B1-2), formula (B1-3), (B1- 6), what is represented by any one of formula (B1-7) and formula (B1-11) is more preferable.

  As described above, the acid generator (B) may contain an acid generator different from the acid generator (B1). In this case, the acid generator (B1) in the total amount of the acid generator (B). ) Is preferably 70% by mass or more, and more preferably 90% by mass or more. However, it is more preferable that the acid generator (B) in the resist composition of the present invention is substantially only the acid generator (B1).

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition may contain a basic compound (C). The “basic compound” as used herein means a compound having a property of capturing an acid, particularly a compound having a property of capturing an acid generated from the acid generator described above.

［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。］ The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and basic ammonium salts. As the amine, either an aliphatic amine or an aromatic amine may be used. Aliphatic amines include primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably a compound represented by the formula (C1) to a compound represented by the formula (C8), more preferably a compound represented by the formula (C1-1). It is done.

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

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

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

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

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

［式（Ｃ５）及び式（Ｃ６）中、
Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に０〜３の整数を表し、ｏ３が２以上であるとき、複数のＲ^c14は同一でも異なっていてもよく、ｐ３が２以上であるとき、複数のＲ^c15は同一でも異なっていてもよい。
Ｌ^c1は、炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

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

［式（Ｃ７）及び式（Ｃ８）中、
Ｒ^c18、Ｒ^c19及びＲ^c20は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｑ３、ｒ３及びｓ３は、それぞれ独立に０〜３の整数を表し、ｑ３が２以上であるとき、複数のＲ^c18は同一でも異なっていてもよく、ｒ３が２以上であるとき、複数のＲ^c19は同一でも異なっていてもよく、ｓ３が２以上であるとき、複数のＲ^c20は同一でも異なっていてもよい。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C7) and Formula (C8),
R ^c18, R ^c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represents an integer of 0 to 3, and when q3 is 2 or more, a plurality of R ^c18 may be the same or different. When r3 is 2 or more, a plurality of Rc18 ^c19 may be the same or different, and when s3 is 2 or more, a plurality of ^Rc20 may be the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

  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- And diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and the like. Diisopropylaniline are preferred, 2,6-diisopropylaniline particularly preferred.

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 Examples include ammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

<Solvent>
The resist composition preferably contains a solvent (D). The solvent (D) is applied to the resist composition on the substrate in the production of a resist pattern, which will be described later, according to the type and amount of the resin (X) to be used and the type and amount of the acid generator. From the viewpoint that the applicability at the time becomes good, an optimum one can be selected as appropriate.

  Examples of suitable solvents 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 ethyl pyruvate And esters such as acetone; methyl isobutyl ketone; ketones such as 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. Only 1 type may be used for a solvent and it may use 2 or more types together.

<Other ingredients>
The resist composition may contain components other than the resin (X), the acid generator, the solvent, and the basic compound (C) used as necessary, as necessary. This component is referred to as “component (F)”. Such component (F) is an additive widely used in the present technical field, such as a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, and a dye.

<This resist composition and its preparation method>
This resist composition mixes resin [especially combination of resin (A) and resin (X)], an acid generator, and the basic compound (C) used as needed, a solvent, and a component (F). Can be prepared. Furthermore, a component (F) may be mixed as needed. In such mixing, the mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature range from the range of 10-40 degreeC according to the solubility with respect to types, such as resin (X), and resin (X). 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 0.01 to 0.2 μm.

As described above, the content of the solvent can be appropriately adjusted according to the type of the resin (X), but is preferably 90% by mass or more, more preferably 92% by mass or more, based on the total mass of the resist composition. Yes, more preferably 94% by mass or more, preferably 99% by mass or less, more preferably 99.9% by mass or less. The present resist composition containing the solvent in such a content ratio can form a composition layer having a thickness of about 30 to 300 nm in, for example, a resist pattern manufacturing method described later.
The content ratio of the solvent can be controlled by the amount of the solvent used in preparing the resist composition. After preparing the resist composition, the resist composition is subjected to, for example, liquid chromatography or gas chromatography. It can also be obtained by using a known analysis means such as a graph.

  A preferable range of the content ratio of the resin to the resist composition is selected from the total amount of the resin [resin (A) and resin (X)] with respect to the total mass of the solid content of the resist composition. Specifically, the resin content relative to the total mass of the solid content is preferably 80% by mass or more and 99% by mass or less.

  The content of the acid generator in the resist composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 30 parts by mass or less, relative to 100 parts by mass of the resin. Preferably it is 25 mass parts or less.

  When using a basic compound (C) for this resist composition, it is preferable that the content rate is about 0.01-1 mass% with respect to the total mass of solid content of this resist composition.

  The suitable content of each of these resins [resin (A) and resin (X) or resin (X)], acid generator and solvent, and basic compound (C) used as necessary is It can be controlled by the amount of each used in preparing the resist composition. After the present resist composition is prepared, the present resist composition can be obtained by subjecting it to a known analysis means such as gas chromatography or liquid chromatography.

  In addition, when using a component (F) for this resist composition, an appropriate content rate can also be adjusted according to the kind of the said component (F).

<Method for producing resist pattern>
Then, the manufacturing method of the resist pattern using this resist composition is demonstrated.
The method for producing a resist pattern of the present invention comprises:
(1) a step of applying the resist composition on a substrate;
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating are included. Hereinafter, each of the steps shown here is referred to as “step (1)” to “step (5)”.

  Application of the resist composition on the substrate in the step (1) can be performed by a coating apparatus widely used for applying a resist material for semiconductor microfabrication, such as a spin coater. Thus, a coating film made of the present resist composition is formed on the substrate. The film thickness of the coating film can be adjusted by variously adjusting the conditions (coating conditions) of the coating apparatus, and the coating film can be coated to have a desired film thickness by performing appropriate preliminary experiments. You can choose the conditions. Various substrates to be subjected to microfabrication can be selected as the substrate before applying the resist composition. The substrate may be washed or an antireflection film may be formed before applying the resist composition. As the antireflection film, for example, a commercially available composition for organic antireflection film can be used.

In the step (2), for example, drying is performed using a heating device such as a hot plate (so-called pre-baking), using a decompression device, or using a combination of these means. The drying conditions are adjusted according to the type of the solvent contained in the resist composition. For example, when a hot plate is used, the surface temperature of the hot plate is preferably about 50 to 200 ° C. Further, in the decompression means, it is preferable that the internal pressure of the decompressor is about 1 to 1.0 × 10 ⁵ Pa after the substrate on which the coating film is formed is sealed in an appropriate decompressor.

Step (3) is a step of exposing the composition layer, and preferably the composition layer is exposed using an exposure machine. At this time, exposure is performed through a mask corresponding to a desired pattern to be finely processed. As an exposure light source of the exposure machine, an ultraviolet light source such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm), or a solid-state laser light source (YAG In addition, various lasers such as those that emit laser light from a far ultraviolet region or a vacuum ultraviolet region by converting the wavelength of laser light from a semiconductor laser or the like can be used. The exposure machine may be an immersion exposure machine.
As described above, by exposing through a mask, an exposed portion (exposed portion) and an unexposed portion (unexposed portion) are generated in the composition layer. In the composition layer of the exposed portion, the acid generator contained in the composition layer receives exposure energy to generate an acid, and the acid labile group in the resin (A) is deprotected by the action of the generated acid. As a result, the resin (A) in the composition layer of the exposed portion becomes soluble in the alkaline aqueous solution. On the other hand, since the exposure energy is not received in the unexposed area, the resin (A) remains insoluble or hardly soluble in the alkaline aqueous solution. Thus, the composition layer in the exposed portion and the composition layer in the unexposed portion are significantly different in solubility in the alkaline aqueous solution.

  In step (4), a heat treatment for further promoting the progress of the deprotecting group reaction that may occur in the exposed portion is performed. For the heat treatment, a heating means using a hot plate shown in the step (2) is employed. In the hot plate heating in step (4), the surface temperature of the hot plate is preferably about 50 to 200 ° C, more preferably about 70 to 150 ° C.

Step (5) is a step of developing the heated composition layer, and preferably the heated composition layer is developed with a developing device. The development referred to here is by bringing the composition layer after heating into contact with an alkaline aqueous solution, thereby dissolving the exposed composition layer in the alkaline aqueous solution and leaving the unexposed composition layer on the substrate. A resist pattern is manufactured on the substrate.
The alkaline aqueous solution used here is referred to as “alkaline developer”, and those used in this technical field can be used. Examples of the alkaline aqueous solution include an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).

  After the development, it is preferable to perform a rinsing treatment with ultrapure water or the like, and to further remove water remaining on the substrate and the resist pattern.

  According to the resist pattern manufacturing method including the steps (1) to (5) as described above, the present resist composition can manufacture a resist pattern having excellent CD uniformity (CDU).

<Application>
The resist composition includes a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, and further immersion exposure It is suitable as a resist composition.
Can be used for construction.

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 weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

以下、これらのモノマーを「モノマー（Ｍ−Ａ）」〜「モノマー（Ｍ−Ｑ）」という。 Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

Hereinafter, these monomers are referred to as “monomer (MA)” to “monomer (MQ)”.

Example 1 [Synthesis of Resin X1]
Monomer (MG) and monomer (MF) are used as monomers, and mixed so that the molar ratio (monomer (ME): monomer (MG)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. 0.9 mol% and 2.7 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of about 5% at 72 ° C., respectively. Heated for hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X1 (copolymer) having a weight average molecular weight of 1.6 × 10 ^{4 in} a yield of 88%. It was. This resin X1 has the following structural units.

Example 2 [Synthesis of Resin X2]
Monomer (MG) and monomer (MH) are used as monomers and mixed so that the molar ratio (monomer (MG): monomer (MH)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total monomer amount, and these were added at 72 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X2 (copolymer) having a weight average molecular weight of 1.5 × 10 ^{4 in} a yield of 85%. It was. This resin X2 has the following structural units.

Example 3 [Synthesis of Resin X3]
Monomer (MG) and monomer (MI) are used as monomers and mixed so that the molar ratio (monomer (MG): monomer (MI)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total monomer amount, and these were added at 72 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X3 (copolymer) having a weight average molecular weight of 1.5 × 10 ^{4 in} a yield of 82%. It was. This resin X3 has the following structural units.

Example 4 [Synthesis of Resin X4]
Monomer (MG) and monomer (MJ) are used as the monomers, and mixed so that the molar ratio (monomer (MG): monomer (MJ)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total monomer amount, and these were added at 72 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X4 (copolymer) having a weight average molecular weight of 1.4 × 10 ^{4 in} a yield of 83%. It was. This resin X4 has the following structural units.

Example 5 [Synthesis of Resin X5]
Monomer (MG) and monomer (M-K) are used as the monomers and mixed so that the molar ratio (monomer (MG): monomer (M-K)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total monomer amount, and these were added at 72 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X5 (copolymer) having a weight average molecular weight of 1.5 × 10 ^{4 in} a yield of 80%. It was. This resin X5 has the following structural units.

Example 6 [Synthesis of Resin X6]
Monomer (MG) and monomer (ML) are used as monomers and mixed so that the molar ratio (monomer (MG): monomer (ML)) is 90:10. A 1.2 mass times amount of dioxane was added to form a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total monomer amount, and these were added at 72 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin X6 (copolymer) having a weight average molecular weight of 1.6 × 10 ^{4 in} a yield of 80%. It was. This resin X6 has the following structural units.

Synthesis Example 1 [Synthesis of Resin A1]
As a monomer, a monomer (MM), a monomer (MN), a monomer (MD), a monomer (MO), and a monomer (MP) are used, and the molar ratio (monomer (MM) : Monomer (MN): monomer (MD): monomer (MO): monomer (MP)) were mixed so as to be 50: 5: 4: 33: 8. 1.2 mass times dioxane was added to make a solution. To the solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.8 mol% and 5.4 mol%, respectively, with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated, and the resin was filtered twice. 7 × 10 ³ resin A1 (copolymer) was obtained with a yield of 71%. This resin A1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A2]
As a monomer, a monomer (MC), a monomer (MD), a monomer (ME), and a monomer (MF) are used, and the molar ratio (monomer (MC): monomer (MD) : Monomer (ME): monomer (MF)) was mixed so as to be 25: 25: 40: 10, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, and heated at 77 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 6 × 10 ³ resin A2 (copolymer) was obtained with a yield of 71%. This resin A2 has the following structural units.

Synthesis Example 3 [Synthesis of Resin A3]
Monomer (M), monomer (N), monomer (D), monomer (P) and monomer (O) are mixed in a molar ratio [monomer (M): monomer (N): monomer (D): monomer (P): Monomer (O)] is mixed at a ratio of 30: 14: 6: 30: 20, and further, 1.5 mass times dioxane is mixed into this monomer mixture with respect to the total mass of all monomers. did. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators so as to be 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. Then, this was heated at 73 ° C. for about 5 hours to carry out polymerization. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. After purification, a resin A3 (copolymer) having a weight average molecular weight of about 7.9 × 10 ³ was obtained in a yield of 60%. This resin A3 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A4]
Monomer (M), monomer (Q), monomer (D), monomer (P) and monomer (O) are mixed in a molar ratio [monomer (M): monomer (Q): monomer (D): monomer (P): Monomer (O)] is mixed at a ratio of 30: 14: 6: 30: 20, and further, 1.5 mass times dioxane is mixed into this monomer mixture with respect to the total mass of all monomers. did. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators so as to be 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. Then, this was heated at 73 ° C. for about 5 hours to carry out polymerization. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. After purification, a resin A4 (copolymer) having a weight average molecular weight of about 7.8 × 10 ³ was obtained in a yield of 62%. This resin A4 has the following structural units.

Synthesis Example 5 [Synthesis of Resin Z1]
Monomer (MA) and monomer (MB) are used as the monomers and mixed so that the molar ratio (monomer (MA): monomer (MB)) is 50:50. An amount of 1.5 mass times dioxane was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 80 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 9. 3 × 10 ³ resin Z1 (copolymer) was obtained with a yield of 55%.
This resin Z1 has the following structural units.

Examples 7 to 13 and Comparative Example 1
<Preparation of resist composition>
Resins obtained in Examples 1 to 6 and Synthesis Examples 2 to 4;
Acid generator B1 shown below;
Basic compound C1 shown below;
Each was dissolved in the following solvent in the parts by mass shown in Table 3 and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

<Acid generator>
B1: Synthesis according to examples of JP 2010-152341 A

<Basic compound: Quencher>
C1: 2,6-Diisopropylaniline (manufactured by Tokyo Chemical Industry)
<Solvent>
Propylene glycol monomethyl ether acetate 265.0 parts Propylene glycol monomethyl ether 20.0 parts 2-heptanone 20.0 parts γ-butyrolactone 3.5 parts

<Defect evaluation>
The resist composition was applied (spin coated) to a 12-inch silicon wafer (substrate) so that the film thickness after drying was 0.15 μm. After coating, the composition layer was formed on the wafer by pre-baking (PB) for 60 seconds at a temperature shown in the PB column of Table 3 on a direct hot plate.
The wafer on which the composition layer was formed in this manner was subjected to water rinsing for 60 seconds using a developing machine [ACT-12; manufactured by Tokyo Electron Ltd.].
Thereafter, the number of defects on the wafer was measured using a defect inspection apparatus [KLA-2360; manufactured by KLA Tencor]. The results are shown in Table 4.

<Immersion exposure evaluation of resist composition>
An organic antireflection film having a thickness of 780 mm is formed by applying a composition for organic antireflection film (ARC-29; manufactured by Nissan Chemical Co., Ltd.) to a silicon wafer and baking it at 205 ° C. for 60 seconds. Formed. Subsequently, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm. The silicon wafer coated with the resist composition was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 3 for 60 seconds to form a resist film. ArF excimer stepper for immersion exposure (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which a resist film is formed, and a contact hole pattern (hole pitch 100 nm / Using a mask for forming a hole diameter of 70 nm, exposure was performed while changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, the silicon wafer was post-exposure baked on a hot plate for 60 seconds at the temperature described in the “PEB” column of Table 3. Next, this silicon wafer was subjected to paddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

  In the obtained resist pattern, an exposure amount at which the hole diameter of the pattern formed with a mask having a hole diameter of 70 nm was 55 nm was defined as effective sensitivity.

<Evaluation of CD uniformity (CDU)>
In terms of effective sensitivity, the resist pattern formed using the mask was evaluated as follows. 24 hole diameters were measured for each hole, and the average value was taken as the average hole diameter of one hole. For the same resist pattern, the same average hole diameter measurement was performed at 400 locations, and the standard deviation was obtained using them as a population. The results are shown in Table 4.

  The resist pattern obtained using this resist composition (Example 7 to Example 21) was able to produce a resist pattern with excellent CD uniformity. On the other hand, in the resist composition of Comparative Example 1, the CD uniformity of the resulting resist pattern was poor. Moreover, the resist pattern obtained using this resist composition (Examples 7 to 21) was good in that the number of defects generated was smaller than that of the resist composition of Comparative Example 1.

  According to the resist composition of the present invention, a resist pattern having excellent CD uniformity (CDU) can be produced. Further, the obtained resist pattern has a small number of defects. Therefore, the resist composition of the present invention is useful for fine processing of semiconductors.

Claims (9)

A resin having a structural unit (aa) represented by the formula (aa) and a structural unit (ab) represented by the formula (ab).

[In the formula (aa)
R ^aa1 represents a hydrogen atom or a methyl group.
R ^aa2 represents a hydrogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa3 represents a fluorinated alkyl group having 1 to 6 carbon atoms.
R ^aa4 represents an atom or group in which the bond [O—R ^aa4 ] to the oxygen atom is not ^broken by the action of an acid.
n ^aa1 represents 1 or 2; When n ^aa1 is 2, two R ^aa2 are the same or different, two R ^aa3 are the same or different, and two R ^aa4 are the same or different.
A ^aa1 represents an ^optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

[In the formula (ab),
R ^ab1 represents a hydrogen atom or a methyl group.
A ^ab1 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
R ^ab2 represents an ^optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. Good. ] The resin according to claim 1, wherein A ^{ab1 in the} formula (ab) is an alkanediyl group having 1 to 6 carbon atoms. The resin according to claim 1, wherein A ^{ab1 in the} formula (ab) is an ethylene group.   A resist composition comprising the resin according to claim 1 and an acid generator. The resist composition according to claim 4, wherein the acid generator is an acid generator represented by formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group. May be.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 5, wherein Y in the formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.   The resist composition according to any one of claims 4 to 6, further comprising a resin that is insoluble or hardly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid.   Furthermore, the resist composition in any one of Claims 4-7 containing a solvent. (1) The process of apply | coating the resist composition in any one of Claims 4-8 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: