JP2013127051A - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition in which a depth of focus (DOF) in a resist pattern is satisfied.SOLUTION: This compound is expressed by formula (I). In formula (I), Lrepresents a single bond, *-X-, *-X-A- or the like; Lrepresents *-A-X-A- or the like; X, Xor the like each independently represents an alkanediyl group; Aand the like each independently represents an oxygen atom or the like; ring Wrepresents an aromatic ring; ring Wrepresents a sultone ring; Rrepresents a hydroxy group or the like; Rrepresents an alkyl group or the like; Rrepresents an alkyl group which may have a halogen atom, or the like; and s and t each denotes an integer of 0 to 2.

Description

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

Patent Document 1 describes a resin having a structural unit represented by the formula (u-A) shown below.

JP 2010-210796 A

  Conventionally known resist compositions containing the above resins may not always satisfy the focus margin (DOF) of the resulting resist pattern.

［式（Ｉ）中、
Ｌ^１は、単結合、＊−Ｘ^１−、＊−Ｘ^２−Ａ^１−、＊−Ｘ^３−Ａ^２−Ｘ^４−又は＊−Ｘ^５−Ａ^３−Ｘ^６−Ａ^４−（＊は、Ｏとの結合手を表す。）を表す。
Ｌ^２は、＊−Ａ^５−Ｘ^７−Ａ^６−、＊−Ａ^７−Ｘ^８−Ａ^８−Ｘ^９−、＊−Ａ^９−Ｘ^１０−Ａ^１０−Ｘ^１１−Ａ^１１−、＊−Ａ^１２−又は＊−Ａ^１３−Ｘ^１２−（＊は、環Ｗ^１との結合手を表す。）を表す。
Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１及びＸ^１２は、それぞれ独立に炭素数１〜６のアルカンジイル基を表す。
Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５、Ａ^６、Ａ^７、Ａ^８、Ａ^９、Ａ^１０、Ａ^１１、Ａ^１２及びＡ^１３は、それぞれ独立に、酸素原子又は−ＣＯ−Ｏ−を表す。
環Ｗ^１は、炭素数６〜１８の芳香族環を表す。
環Ｗ^２は、炭素数４〜３４のスルトン環を表す。
Ｒ^１は、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^２は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又は炭素数１〜６のアルコキシカルボニル基を表す。
Ｒ^３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。
ｓは、０〜２の整数を表す。ｓが２のとき、複数存在するＲ^１は、互いに同一であっても異なっていてもよい。
ｔは、０〜２の整数を表す。ｔが２のとき、複数存在するＲ^２は、互いに同一であっても異なっていてもよい。］ The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In the formula (I),
L ¹ is a single bond, * -X ^1- , * -X ² -A ^1- , * -X ³ -A ² -X ⁴ -or * -X ⁵ -A ³ -X ⁶ -A ⁴ -(* Represents a bond with O).
L ^{2 is, * - A 5 -X 7 -A} 6 -, * - A 7 -X 8 -A 8 -X 9 -, * - A 9 -X 10 -A 10 -X 11 -A 11 -, * -A < ¹² >-or * -A < ¹³ > -X < ¹² >-(* represents a bond with the ring W < ¹ >).
X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently an alkanediyl group having 1 to 6 carbon atoms. Represent.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , A ¹¹ , A ¹² and A ¹³ are each independently an oxygen atom or —CO— Represents O-.
Ring ^{W 1} represents an aromatic ring having 6 to 18 carbon atoms.
Ring ^{W 2} represents a sultone ring 4 to 34 carbon atoms.
R ¹ represents a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms.
R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
s represents the integer of 0-2. When s is 2, a plurality of R ¹ may be the same as or different from each other.
t represents an integer of 0-2. When t is 2, a plurality of R ² may be the same as or different from each other. ]

[2] The above L ¹ is * —CHR ⁴ — or * —CH ₂ — (R ⁴ represents an alkyl group having 1 to 6 carbon atoms. * Represents a bond with O). [1] The compound described in [1].
[3] The above [1] or [2], wherein L ² is * —O—CH ₂ —CO—O— or * —CO—O— (* represents a bond to ring W ¹ ). The described compound.
[4] The compound according to any one of [1] to [3], wherein W ¹ is a benzene ring.
[5] A resin having a structural unit derived from the compound according to any one of [1] to [4].
[6] The resin according to [5], further comprising a structural unit derived from a monomer having an acid labile group (however, not a compound represented by the formula (I)).

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表す。ここで、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１０の脂環式炭化水素基又はこれらを組み合わせた基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］ [7] The resin according to [6], wherein the monomer having an acid labile group is a monomer represented by formula (a1-1) or a monomer represented by formula (a1-2).

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

［式（ａ２−１）中、
Ｌ^ａ３は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ２−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^ａ１４は、水素原子又はメチル基を表す。
Ｒ^ａ１５及びＲ^ａ１６は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］ [8] The resin according to any one of [5] to [7], further including a structural unit derived from an acid-stable monomer having a hydroxyadamantyl group.
[9] The resin according to [8], wherein the acid-stable monomer having a hydroxyadamantyl group is a monomer represented by the formula (a2-1).

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

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、単結合又は２価の炭素数１〜１７の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれるメチレン基は、酸素原子、スルホニル基又はカルボニル基で置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ [10] A resist composition comprising the resin according to any one of [5] to [9] and an acid generator.
[11] The resist composition according to [10], wherein the acid generator is 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 a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The methylene group contained in the alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group.
Z ⁺ represents an organic cation. ]

[12] The resist composition according to [11], wherein Y in formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
[13] The resist composition according to any one of [10] to [12], further containing a basic compound.
[14] (1) A step of applying the resist composition according to any one of [10] to [13] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  If a resist composition containing a resin having a structural unit derived from the compound of the present invention is used, a resist pattern having an excellent focus margin (DOF) 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. Among the aliphatic hydrocarbon groups, those that can be linear or branched, such as an alkyl group, include any of them. When stereoisomers exist, all stereoisomers are included. In the following examples of substituents, the numerical value attached to “C” indicates the number of carbon atoms of each group.
Further, in the present specification, "(meth) acrylic monomer", _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " at least one monomer having the structure Means. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
The hydrocarbon group may contain a carbon-carbon double bond in a part thereof, but a saturated group (saturated hydrocarbon group) is preferable.
Among the aliphatic hydrocarbon groups, a monovalent one typically includes an alkyl group.
Examples of the alkyl group include a methyl group (C ₁ ), an ethyl group (C ₂ ), a propyl group (C ₃ ), a butyl group (C ₄ ), a pentyl group (C ₅ ), a hexyl group (C ₆ ), a 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 ) and octadecyl group (C ₁₈ ) and the like.
Examples of the divalent aliphatic hydrocarbon group include alkanediyl groups in which one hydrogen atom has been removed from an alkyl group.
Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl Group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1 , 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3 - Group, 2-methylpropane-1,2-diyl, pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.

The alicyclic hydrocarbon group typically means a cycloalkyl group, and includes any of the monocyclic and polycyclic groups shown below.
As a monovalent alicyclic hydrocarbon group, a monocyclic aliphatic hydrocarbon group represents 1 hydrogen atom of a cycloalkane represented by the following formulas (KA-1) to (KA-7). It is a group that has been removed.

The polycyclic aliphatic hydrocarbon group is a group in which one hydrogen atom of a cycloalkane represented by the following formulas (KA-8) to (KA-22) is removed.

Examples of the divalent alicyclic hydrocarbon group include groups in which two hydrogen atoms have been removed from the alicyclic hydrocarbon of formula (KA-1) to formula (KA-22).
The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, an alkylthio group, an acyl group, an acyloxy group, an aryl group, an aralkyl group, and an aryloxy group, unless particularly limited.
Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
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 ).

Examples of the acyl group include acetyl group (C ₂ ), propionyl group (C ₃ ), butyryl group (C ₄ ), valeryl group (C ₅ ), hexanor group (C ₆ ), heptanol group (C ₇ ), octanoyl group ( Examples include those in which an alkyl group such as C ₈ ), decanoyl group (C ₁₀ ) and dodecanoyl group (C ₁₂ ) and a carbonyl group are bonded, and those in which an aryl group such as benzoyl group (C ₇ ) and a carbonyl group are bonded. It is done.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
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 ).
Aryloxy groups include phenyloxy group (C ₆ ), naphthyloxy group (C ₁₀ ), anthryloxy group (C ₁₄ ), biphenyloxy group (C ₁₂ ), phenanthryloxy group (C ₁₄ ) and full Examples include an aryl group such as an oleenyloxy group (C ₁₃ ) and an oxygen atom bonded to each other.

A typical example of the aromatic hydrocarbon group is an aryl group.
Examples of the aryl group 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 aromatic hydrocarbon group may also have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an acyl group, an alkyl group, and an aryloxy group. The alkyl group is the same as that exemplified as the aliphatic hydrocarbon group, and among the substituents optionally present in the aromatic hydrocarbon group, those other than the alkyl group are used as the substituents of the aliphatic hydrocarbon group. Includes the same as illustrated.

［式（Ｉ）中、
Ｌ^１は、単結合、＊−Ｘ^１−、＊−Ｘ^２−Ａ^１−、＊−Ｘ^３−Ａ^２−Ｘ^４−又は＊−Ｘ^５−Ａ^３−Ｘ^６−Ａ^４−（＊は、Ｏとの結合手を表す。）を表す。
Ｌ^２は、＊−Ａ^５−Ｘ^７−Ａ^６−、＊−Ａ^７−Ｘ^８−Ａ^８−Ｘ^９−、＊−Ａ^９−Ｘ^１０−Ａ^１０−Ｘ^１１−Ａ^１１−、＊−Ａ^１２−又は＊−Ａ^１３−Ｘ^１２−（＊は、環Ｗ^１との結合手を表す。）を表す。
Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１及びＸ^１２は、それぞれ独立に炭素数１〜６のアルカンジイル基を表す。
Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５、Ａ^６、Ａ^７、Ａ^８、Ａ^９、Ａ^１０、Ａ^１１、Ａ^１２及びＡ^１３は、それぞれ独立に、酸素原子又は−ＣＯ−Ｏ−を表す。
環Ｗ^１は、炭素数６〜１８の芳香族環を表す。
環Ｗ^２は、炭素数４〜３４のスルトン環を表す。
Ｒ^１は、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^２は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又は炭素数１〜６のアルコキシカルボニル基を表す。
Ｒ^３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。
ｓは、０〜２の整数を表す。ｓが２のとき、複数存在するＲ^１は、互いに同一であっても異なっていてもよい。
ｔは、０〜２の整数を表す。ｔが２のとき、複数存在するＲ^２は、互いに同一であっても異なっていてもよい。］ <Compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”)>
Compound (I) of the present invention is represented by formula (I).

[In the formula (I),
L ¹ is a single bond, * -X ^1- , * -X ² -A ^1- , * -X ³ -A ² -X ⁴ -or * -X ⁵ -A ³ -X ⁶ -A ⁴ -(* Represents a bond with O).
L ^{2 is, * - A 5 -X 7 -A} 6 -, * - A 7 -X 8 -A 8 -X 9 -, * - A 9 -X 10 -A 10 -X 11 -A 11 -, * -A < ¹² >-or * -A < ¹³ > -X < ¹² >-(* represents a bond with the ring W < ¹ >).
X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently an alkanediyl group having 1 to 6 carbon atoms. Represent.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , A ¹¹ , A ¹² and A ¹³ are each independently an oxygen atom or —CO— Represents O-.
Ring ^{W 1} represents an aromatic ring having 6 to 18 carbon atoms.
Ring ^{W 2} represents a sultone ring 4 to 34 carbon atoms.
R ¹ represents a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms.
R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
s represents the integer of 0-2. When s is 2, a plurality of R ¹ may be the same as or different from each other.
t represents an integer of 0-2. When t is 2, a plurality of R ² may be the same as or different from each other. ]

The divalent alkanediyl group having 1 to 6 carbon atoms contained in L ^1, include straight chain alkanediyl group, or a branched alkanediyl group.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 A linear alkanediyl group such as, 6-diyl group; and an alkyl group (preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, having an alkyl group having 1 to 4 carbon atoms such as tert-butyl group), for example, ethane-1,1-diyl group, propane-1,1-diyl group, butane-1,3-diyl Branched alkanes such as 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group A diyl group is mentioned.

Examples of * —X ² —A ¹ — (* represents a bond with O) included in L ¹ include, for example, * —CH ₂ —CO—O—, * —CH ₂ —O—CO—. Etc.
Examples of * —X ³ —A ² —X ⁴ — contained in L ¹ include * —CH ₂ —CO—O—CH ₂ —, * —CH ₂ —O—CO—CH ₂ — and the like. .
Examples of * —X ⁵ —A ³ —X ⁶ —A ⁴ — contained in L ¹ include * —CH ₂ —CO—O—CH ₂ —CO—O—, * —CH ₂ —O—CO—. CH ₂ —CO—O— and the like can be mentioned.
L ¹ is preferably * —CHR ⁴ — or * —CH ₂ — (R ⁴ represents an alkyl group having 1 to 6 carbon atoms. * Represents a bond with O).

Examples of * —A ⁵ —X ⁷ —A ⁶ — contained in L ² include, for example, * —O—CH ₂ —CO—O—, * —O—CO—CH ₂ —O—, * —CO—O. —CH ₂ —O—, * —CO—O—CH ₂ —O—CO—, * —CO—O—CH ₂ —CO—O— and the like can be mentioned.
Examples of * —A ⁷ —X ⁸ —A ⁸ —X ⁹ — contained in L ² include * —O—CH ₂ —CO—O—CH ₂ —, * —O—CH ₂ —O—CO—. _{CH 2 -, * - CO-} O-CH 2 -O-CH 2 -, * - CO-O-CH 2 -O-CO-CH 2 -, * - CO-O-CH 2 -CO-O-CH ₂ etc. are mentioned.
Examples of * —A ⁹ —X ¹⁰ —A ¹⁰ —X ¹¹ —A ¹¹ — contained in L ² include * —O—CH ₂ —CO—O—CH ₂ —CO—O— and * —O—. CH ₂ —O—CO—CH ₂ —CO—O—, * —CO—O—CH ₂ —O—CH ₂ —CO—O—, * —CO—O—CH ₂ —O—CO—CH ₂ —. _{CO-O -, * - CO} -O-CH 2 -CO-O-CH 2 -CO-O- , and the like.
Examples of * -A ^12- contained in L ² include * -CO-O-.
Examples of * —A ¹³ —X ¹² — contained in L ² include * —CO—O—CH ₂ — and the like.
L ² _{is, * - O-CH 2 -CO} -O -, * - O-CO-CH 2 -O -, * - CO-O-CH 2 -O -, * - CO-O-CH 2 -O -CO -, * - CO-O- or * -CO-O-CH ₂ - is _{preferably, * - O-CH 2 -CO} -O -, * - O-CO-CH 2 -O- or * —CO—O— is more preferable, * —O—CH ₂ —CO—O— or * —CO—O— is further preferable, and * —O—CH ₂ —CO—O— Even more preferably.

Examples of the aromatic ring having 6 to 18 carbon atoms represented by the ring W ¹ include an anthracene ring such as a benzene ring and a naphthalene ring, and a benzene ring is preferable.
The sultone ring having 4 to 34 carbon atoms represented by the ring W ² refers to a ring containing —SO ₂ —O— as an atomic group constituting the ring. The sultone ring following formula ^(T 1 -1), tables in any of the formulas ^(T 1 -2), formula ^(T 1 -3), formula ^(T 1 -4) and formula ^(T 1 -5) Ring. The sultone ring may be monocyclic or polycyclic, but is preferably polycyclic. The polycyclic sultone ring refers to a ring in which two or more monocycles are condensed, and at least one of the two or more monocycles is a monocyclic sultone ring. Further, sultone ring, the atomic group forming a ring, other than -SO 2 _-O-, an oxygen atom, may contain a hetero atom such as sulfur or nitrogen atom. When the sultone ring contains a hetero atom, it is preferably an oxygen atom.

環Ｗ^２としては、化合物（Ｉ）の製造が容易であるという観点から、ｔが０である置換基を有さないスルトン環であるものが好ましい。

Ring W ² is preferably a sultone ring having no substituent in which t is 0, from the viewpoint of easy production of compound (I).

［式（Ｔ１）中、
Ｚ^１２は、酸素原子、硫黄原子又はメチレン基を表す。］ The ring W ² is preferably represented by the following formula (T1).

[In the formula (T1),
Z ¹² represents an oxygen atom, a sulfur atom or a methylene group. ]

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² include those already exemplified, for example, methyl group, ethyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group. , A pentyl group, a hexyl group, and the like.
Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ² include those already exemplified, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the alkoxycarbonyl group having 1 to 6 carbon atoms represented by R ² include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and a pentyloxycarbonyl group.
The halogen atom of R ³ includes those already exemplified.
Of the “alkyl group having 1 to 6 carbon atoms which may have a halogen atom” of R ³ , the alkyl group is as described for R ^{1 and the} like. A group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with halogen atoms corresponds to a C 1-6 alkyl group having a halogen atom. Among the alkyl groups having a halogen atom, an alkyl group having a fluorine atom is preferable, and a perfluoroalkyl group in which all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms is more preferable. Examples of the perfluoroalkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, and perfluorohexyl group. Can be mentioned.

As for the compound represented by Formula (I), the compound represented by the following is mentioned, for example.

In the compounds (I) represented by the formulas (I-1) to (I-16) shown here, the partial structure M shown below is replaced with the partial structure A shown below to give the compound (I) It can mention as a specific example.

［式中、環Ｗ^１、環Ｗ^２、Ｒ^１、Ｒ^２、Ｒ^３、ｓ及びｔは、それぞれ上記と同じ意味を表す。Ｒ^４は、炭素数１〜６のアルキル基を表す。］ In the formula (I), for example, L ¹ is * —CHR ⁴ — (* represents a bond with O), L ² is * —O—CH ₂ —CO—O— (* represents ring W Compound (I) [compound represented by formula (IA)] which is a bond with ¹ can be produced by the following production method.

[Wherein, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , s and t each have the same meaning as described above. R ⁴ represents an alkyl group having 1 to 6 carbon atoms. ]

［Ｙ^１及びＹ^２は、ハロゲン原子を表す。］
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。Ｙ^１とＹ^２とはそれぞれ異なっていてもよいが、ともに塩素原子であることが好ましい。 A compound represented by formula (IA-c) can be obtained by reacting a compound represented by formula (IA-a) with a compound represented by formula (IA-b) under a basic catalyst. it can. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

[Y ¹ and Y ² represent a halogen atom. ]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Y ¹ and Y ² may be different from each other, but both are preferably chlorine atoms.

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

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

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

式（ＩＡ−ｄ）で表される化合物としては、以下で表される化合物などが挙げられる。

By reacting the compound represented by the formula (IA-c) and the compound represented by the formula (IA-d) in a solvent in the presence of a catalyst, the compound represented by the formula (IA-e) is obtained. Can be obtained. Examples of the solvent include tetrahydrofuran. Examples of the catalyst include pyridine.

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

The compound represented by the formula (IA-f) can be obtained by reducing the compound represented by the formula (IA-e) in a solvent. Examples of the solvent include acetonitrile. Examples of the reducing agent include sodium borohydride.

［Ｙ^３は、ハロゲン原子又は（メタ）アクリロイルオキシ基を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］
触媒としては、例えば、Ｎ−メチルピロリジンなどが挙げられる。
溶剤としては、例えば、メチルイソブチルケトン、ジメチルホルムアミドなどが挙げられる。
式（ＩＡ−ｇ）で表される化合物としては、（メタ）アクリル酸クロライド、（メタ）アクリル酸無水物等が挙げられる。 The compound represented by the formula (IA) is obtained by reacting the compound represented by the formula (IA-f) with the compound represented by the formula (IA-g) in a solvent in the presence of a catalyst. be able to.

[Y ³ represents a halogen atom or a (meth) acryloyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]
Examples of the catalyst include N-methylpyrrolidine.
Examples of the solvent include methyl isobutyl ketone and dimethylformamide.
Examples of the compound represented by the formula (IA-g) include (meth) acrylic acid chloride and (meth) acrylic anhydride.

［式中、環Ｗ^１、環Ｗ^２、Ｒ^１、Ｒ^２、Ｒ^３、ｓ及びｔは、それぞれ上記と同じ意味を表す。］ Further, for example, L ¹ is * —CH ₂ — (* represents a bond with O), and L ² is * —CO—O— (* represents a bond with ring W ¹ ). The manufacturing method of the compound represented by the formula (IB) which is is shown below.

[Wherein, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , s and t each have the same meaning as described above. ]

式（ＩＢ−ａ）で表される化合物としては、以下で表される化合物などが挙げられる。

The compound represented by the formula (IB-c) can be obtained by reacting the compound represented by the formula (IB-a) and the compound represented by the formula (IB-b) in a solvent. Examples of the solvent include acetonitrile, chloroform and the like.

Examples of the compound represented by the formula (IB-a) include compounds represented by the following.

式（ＩＢ−ｄ）で表される化合物としては、以下で表される化合物などが挙げられる。

A compound represented by the formula (IB-e) can be obtained by reacting a compound represented by the formula (IB-c) with a compound represented by the formula (IB-d) in a solvent. Examples of the solvent include acetonitrile, chloroform and the like.

Examples of the compound represented by the formula (IB-d) include compounds represented by the following.

The compound represented by the formula (IB-f) can be obtained by reducing the compound represented by the formula (IB-e) in a solvent. Examples of the solvent include acetonitrile. Examples of the reducing agent include lithium aluminum hydride.

［Ｙ^２は、ハロゲン原子又は（メタ）アクリロイルオキシ基を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］
触媒としては、例えば、Ｎ−メチルピロリジンなどが挙げられる。
溶剤としては、例えば、メチルイソブチルケトン、ジメチルホルムアミドなどが挙げられる。
式（ＩＢ−ｇ）で表される化合物としては、（メタ）アクリル酸クロライド、（メタ）アクリル酸無水物等が挙げられる。 The compound represented by the formula (IB) is obtained by reacting the compound represented by the formula (IB-f) with the compound represented by the formula (IB-g) in a solvent in the presence of a catalyst. be able to.

[Y ² represents a halogen atom or a (meth) acryloyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]
Examples of the catalyst include N-methylpyrrolidine.
Examples of the solvent include methyl isobutyl ketone and dimethylformamide.
Examples of the compound represented by the formula (IB-g) include (meth) acrylic acid chloride and (meth) acrylic anhydride.

  The resin having a structural unit derived from compound (I) and the compound (I) described later is a novel compound, and in particular, the resin having a structural unit derived from compound (I) is a resist composition containing the resin. By using the product, an effect that a resist pattern having an excellent shape can be produced is exhibited.

<Resin>
The resin of the present invention contains a structural unit derived from compound (I).
In addition to the structural unit derived from compound (I), the resin of the present invention used for the resist composition further has a structural unit derived from a monomer having an acid labile group, particularly a (meth) acrylic monomer. Is preferred. However, the monomer having an acid labile group is not a compound represented by the formula (I). Hereinafter, a resin having a structural unit derived from compound (I) and a structural unit derived from a monomer having an acid labile group may be referred to as “resin (A)”.
This resin (A) is preferably insoluble or hardly soluble in an alkaline aqueous solution, and more preferably a resin that can be dissolved in an alkaline aqueous solution by the action of an acid.
The phrase “can be dissolved in an alkali by the action of an acid” means “insoluble or hardly soluble in an alkaline aqueous solution before contact with an acid, but soluble in an alkaline aqueous solution after contact with an acid”. .
Resin (A) which becomes alkali-soluble by the action of such an acid includes compound (I) and a monomer having an acid-labile group (hereinafter sometimes referred to as “acid-labile monomer (a1)”). Can be produced by polymerization. In the production of the resin (A), the acid labile monomer (a1) may be used alone or in combination of two or more.
In the resin (A), the content ratio of the structural unit derived from the compound represented by the formula (I) with respect to all the structural units (100 mol%) of the resin (A) is preferably in the range of 1 to 50 mol%. The range of -45 mol% is more preferable, and the range of 5-40 mol% is more preferable.

［式（１）中、Ｒ^ａ１〜Ｒ^ａ３は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^ａ１及びＲ^ａ２は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］ <Acid labile monomer (a1)>
The “acid-labile group” means a group that forms a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving a leaving group when it comes into contact with an acid. Examples of the acid labile group include a group represented by the formula (1) (acid labile group (1)) or a group represented by the formula (2) (acid labile group (2)). Can be mentioned.

[In formula (1), R ^<a1 > -R < ^a3 > respectively independently represents a C1-C8 alkyl group, a C3-C20 alicyclic hydrocarbon group, or the group which combined these, or R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合して炭素数２〜２０の２価の複素環基を形成し、前記炭化水素基及び２価の炭化水素基に含まれるメチレン基は、酸素原子又は硫黄原子で置き換わっていてもよい。＊は結合手を表す。］
Ｒ^ａ１〜Ｒ^ａ３のアルキル基及び脂環式炭化水素基の具体例は、炭素数が各々の範囲で、すでに例示したものを含む。該脂環式炭化水素基の炭素数は、好ましくは炭素数３〜１６である。

[In formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent heterocyclic group having 2 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group and the divalent hydrocarbon group is oxygen It may be replaced by an atom or a sulfur atom. * Represents a bond. ]
Specific examples of the alkyl group and the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 include those already exemplified in the respective ranges of carbon number. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms.

When R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group, examples of the —C (R ^a1 ) (R ^a2 ) (R ^a3 ) group include the following groups.

The divalent hydrocarbon group preferably has 3 to 12 carbon atoms.
Examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2- An alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and a carbon atom form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).
Examples of the hydrocarbon group for R ^{a1 ′} and R ^{a2 ′} include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These specific examples include those already exemplified in each carbon number range.
In the divalent heterocyclic group formed by combining R ^{a2 ′} and R ^{a3 ′,} one carbon atom of the divalent hydrocarbon group formed by combining R ^a1 and R ^a2 is replaced with one oxygen atom. Can be mentioned.
Preferably, at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.

酸不安定モノマー（ａ１）は、好ましくは、炭素数５〜２０の脂環式炭化水素基を有するものが挙げられる。脂環式炭化水素基のような嵩高い構造を有する酸不安定モノマー（ａ１）を重合して得られる樹脂（Ａ）を用いることにより、より一層解像度に優れたレジスト組成物を得ることができる。
酸不安定基モノマー（ａ１）は、好ましくは、酸不安定基（１）と炭素−炭素二重結合とを有するモノマーであり、より好ましくは酸不安定基（１）を有する（メタ）アクリル系モノマーである。 Specific examples of the acid labile group (2) include the following groups.

The acid labile monomer (a1) is preferably one having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. By using a resin (A) obtained by polymerizing an acid labile monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group, a resist composition with even better resolution can be obtained. .
The acid labile group monomer (a1) is preferably a monomer having an acid labile group (1) and a carbon-carbon double bond, more preferably a (meth) acryl having an acid labile group (1). Monomer.

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１０の脂環式炭化水素基又はこれらを組み合わせた基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］ As the (meth) acrylic monomer having an acid labile group and an alicyclic hydrocarbon group, a monomer represented by the formula (a1-1) and a monomer represented by the formula (a1-2) are preferable. It is done. In manufacture of resin (A), these may be used independently and may use 2 or more types together.

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

In Formula (a1-1) and Formula (a1-2), L ^a1 and L ^a2 are preferably —O— or * —O— (CH ₂ ) _k1 —CO—O— (k1 is preferably An integer of 1 to 4, more preferably 1, and more preferably —O—.
R ^a4 and R ^a5 are preferably methyl groups.
Specific examples of the alkyl group of R ^a6 and ^{R a7} in the range of 1 to 8 carbon atoms, including those already ^exemplified, an alkyl group of ^{R a6} and ^{R a7} preferably not more than 6 carbon atoms.
Specific examples of the alicyclic hydrocarbon group represented by R ^a6 and R ^a7 include those already exemplified in the range of 3 to 10 carbon atoms, and the alicyclic hydrocarbon group is preferably 8 or less carbon atoms, more Preferably it is 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

Examples of the monomer represented by the formula (a1-1) include monomers described in JP 2010-204646 A. Monomers respectively represented by formula (a1-1-1) to formula (a1-1-8) are preferred, and monomers represented by formula (a1-1-1) to formula (a1-1-4) respectively. More preferred.

樹脂（Ａ）が式（ａ１−１）で表されるモノマー及び／又は式（ａ１−２）で表されるモノマーに由来する構造単位を含む場合、これらの合計含有率は、樹脂（Ａ）の全構造単位に対して、通常１０〜９５モル％であり、好ましくは１５〜９０モル％であり、より好ましくは２０〜８５モル％であり、さらに好ましくは３０〜６０モル％である。 Examples of the monomer represented by the formula (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptane-1 -Yl (meth) acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-isopropylcyclohexane-1-yl (meth) acrylate, etc. . Monomers respectively represented by formula (a1-2-1) to formula (a1-2-12) are preferred, and formula (a1-2-3), formula (a1-2-4) and formula (a1-2-2) are preferred. 9) and monomers represented by formula (a1-2-10) are more preferred, and monomers represented by formula (a1-2-3) or formula (a1-2-9) are more preferred.

When the resin (A) includes a structural unit derived from the monomer represented by the formula (a1-1) and / or the monomer represented by the formula (a1-2), the total content thereof is the resin (A). It is 10-95 mol% normally with respect to all the structural units of, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%, More preferably, it is 30-60 mol%.

［式（ａ１−５）中、
Ｒ^３１は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^ａ１は、単結合又は＊−［ＣＨ_２］_ｋ４−ＣＯ−Ｌ^ａ４−を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^ａ１との結合手を表す。
Ｌ^ａ１、Ｌ^ａ２、Ｌ^ａ３及びＬ^ａ４は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。］ As the other monomer (a1), for example, a monomer represented by the formula (a1-5) (hereinafter sometimes referred to as “monomer (a1-5)”) may be used.

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

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

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

When the resin (A) has a structural unit derived from the monomer (a1-5), the content is preferably from 1 to 95 mol%, more preferably from 3 to 90 mol, based on all structural units of the resin (A). % Is more preferable, and 5-85 mol% is more preferable.
Resin (A) is a monomer having no acid-labile group in addition to the structural unit derived from compound (I) and the structural unit derived from acid-labile monomer (a1) (hereinafter referred to as “acid-stable monomer”). It is preferable to have a structural unit derived from In this case, the resin (A) may have one or more structural units derived from the acid stable monomer.

When the resin (A) is a copolymer of the compound (I), the acid labile monomer (a1), and the acid stable monomer, the structural unit derived from the acid labile monomer (a1) is a resin (A ) Is preferably 10 to 80 mol%, more preferably 20 to 60 mol%. Further, the content of the structural unit derived from the acid labile monomer (a1) having an adamantyl group (particularly the monomer represented by the formula (a1-1)) is preferably derived from the acid labile monomer (a1). It is 15 mol% or more with respect to the total of structural units. When the ratio of the monomer having an adamantyl group is increased, the dry etching resistance of a resist pattern produced from the resist composition containing the resin (A) is improved.
As an acid stable monomer, Preferably, the monomer which has a hydroxyl group or a lactone ring is mentioned. Acid-stable monomer having a hydroxy group (hereinafter sometimes referred to as “acid-stable monomer having a hydroxy group (a2)”) or acid-stable monomer having a lactone ring (hereinafter referred to as “acid-stable monomer having a lactone ring (a3)”) In some cases, the resist composition containing the resin (A) having a structural unit derived from the resist composition can produce a resist pattern with an excellent resolution. There exists a tendency for the adhesiveness with respect to to become favorable.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition of the present invention is used for KrF excimer laser exposure (248 nm) or high energy ray irradiation such as electron beam or EUV light, it is contained in the resist composition as an acid stable monomer (a2) having a hydroxy group. The resin (A) to be produced is preferably produced using an acid stable monomer (a2-0) having a phenolic hydroxy group, for example, hydroxystyrenes. When used for short wavelength ArF excimer laser exposure (193 nm) or the like, the resin (A) contained in the resist composition is preferably represented by the formula (a2-1) as an acid stable monomer having a hydroxy group. Prepared using an acid stable monomer having a hydroxyadamantyl group. In the production of the resin (A) in this case, the acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

［式（ａ２−０）中、
Ｒ^ａ３０は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^ａ３１は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^ａ３１は互いに同一であるか相異なる。］ Examples of the acid-stable monomer having a phenolic hydroxy group include styrene monomers such as p- or m-hydroxystyrene represented by the formula (a2-0).

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

Examples of the halogen atom in R ^a30 and R ^a31 include fluorine, chlorine, bromine and iodine atoms.
^Examples of the alkyl group which may have a halogen atom for R ^a30 include, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert-butyl group. Perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
^Examples of the alkyl group in R ^a30 and R ^a31 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Can be mentioned. R ^a30 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably a methyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and an n-hexoxy group. , Preferably, it is a C1-C4 alkoxy group, More preferably, it is a C1-C2 alkoxy group, Most preferably, it is a methoxy group.
Examples of the acyl group for R ^a31 include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group for R ^a31 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
ma is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

  The resin (A) having a structural unit derived from the acid-stable monomer (a2) having such a phenolic hydroxy group is obtained by radical polymerization of a monomer in which the phenolic hydroxy group is protected with a protective group and a monomer to be copolymerized. It can be produced by deprotection with acid or base. Since the resin (A) has a structural unit derived from the acid labile group monomer (a1), when deprotecting the phenolic hydroxy group protected by the protecting group, the acid labile group is removed. It is preferable to deprotect by contact with a base so as not to be significantly impaired. As the protecting group, for example, an acetyl group is preferable. Examples of the base include 4-dimethylaminoviridine, triethylamine and the like.

樹脂（Ａ）が式（ａ２−０）で表されるスチレン系モノマーに由来する構造単位を有する場合、その含有率は、樹脂（Ａ）の全構造単位に対して、通常５〜９０モル％であり、好ましくは１０〜８５モル％であり、より好ましくは１５〜８０モル％である。 As an acid stable monomer which has a phenolic hydroxy group, the monomer described in Unexamined-Japanese-Patent No. 2010-204634 is mentioned, for example. Monomers represented by formula (a2-0-1) and formula (a2-0-2) are preferred. When manufacturing resin (A), what protected the phenolic hydroxy group in these with the suitable protective group can also be used.

When the resin (A) has a structural unit derived from the styrenic monomer represented by the formula (a2-0), the content is usually 5 to 90 mol% with respect to all the structural units of the resin (A). Preferably, it is 10-85 mol%, More preferably, it is 15-80 mol%.

［式（ａ２−１）中、
Ｌ^ａ３は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ２−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^ａ１４は、水素原子又はメチル基を表す。
Ｒ^ａ１５及びＲ^ａ１６は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］ Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

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

In Formula (a2-1), L ^a3 is preferably —O—, —O— (CH ₂ ) _f1 —CO—O— (wherein f1 is an integer of 1 to 4), and more preferably. Is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

樹脂（Ａ）が式（ａ２−１）で表されるモノマーに由来する構造単位を有する場合、その含有率は、樹脂（Ａ）の全構造単位に対して、通常３〜４５モル％であり、好ましくは５〜４０モル％であり、より好ましくは５〜３５モル％であり、さらに好ましくは５〜１５モル％である。 As an acid stable monomer which has a hydroxyadamantyl group, the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A monomer represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, and represented by any one of formula (a2-1-1) to formula (a2-1-4). The monomer represented by Formula (a2-1-1) or Formula (a2-1-3) is more preferable.

When the resin (A) has a structural unit derived from the monomer represented by the formula (a2-1), the content is usually 3 to 45 mol% with respect to all the structural units of the resin (A). , Preferably it is 5-40 mol%, More preferably, it is 5-35 mol%, More preferably, it is 5-15 mol%.

<Acid-stable monomer (a3) having a lactone ring>
The lactone ring possessed by the acid stable monomer (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a monocyclic lactone ring and other rings The condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring or a condensed ring of γ-butyrolactone ring and another ring is preferable.
The acid-stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). In the production of the resin (A), one of these may be used alone, or two or more may be used in combination.

［式（ａ３−１）〜式（ａ３−３）中、
Ｌ^ａ４〜Ｌ^ａ６は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^ａ１８〜Ｒ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２１は、炭素数１〜４のアルキル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^ａ２２及びＲ^ａ２３は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４のアルキル基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上のとき、それぞれ、複数のＲ^ａ２１、Ｒ^ａ２２又はＲ^ａ２３は、互いに同一であるか相異なる。］

[In Formula (a3-1)-Formula (a3-3),
L ^{a4 to} L ^a6 each independently represent —O— or * —O— (CH ₂ ) _k3 —CO—O—.
k3 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^{a18 to} R ^a20 each independently represents a hydrogen atom or a methyl group.
R ^a21 represents an alkyl group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1, q1 or r1 is 2 or more, the plurality of R ^a21 , R ^a22 or R ^a23 are the same as or different from each other. ]

L ^{a4 to} La ^{6 in} formula (a3-1) to formula (a3-3) are each independently —O— or * —O— (CH ₂ ) _k3 —CO—O— (k3 is It is preferably an integer of 1 to 4, more preferably 1.), and more preferably —O—.
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 each independently preferably 0 to 2, more preferably 0 or 1.

樹脂（Ａ）がラクトン環を有する酸安定モノマー（ａ３）に由来する構造単位を有する場合、その含有率は、樹脂（Ａ）の全構造単位に対して、通常５〜７０モル％であり、好ましくは１０〜６５モル％であり、より好ましくは１０〜６０モル％である。 Examples of the acid-stable monomer (a3) having a lactone ring include monomers described in JP 2010-204646 A. Formula (a3-1-1) to Formula (a3-1-4), Formula (a3-2-1) to Formula (a3-2-4), Formula (a3-3-1) to Formula (a3-3) -4) is preferable, and the monomers represented by formula (a3-1-1) to formula (a3-1-2) and formula (a3-2-3) to formula (a3-2-4) are preferable. The monomer represented by either is more preferable, and the monomer represented by the formula (a3-1-1) or the formula (a3-2-3) is more preferable.

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

<Other monomer (a4)>
The resin may have a structural unit derived from other known monomers (hereinafter sometimes referred to as “monomer (a4)”) other than the above-mentioned monomers.
Examples of the monomer (a4) include a compound represented by the formula (a4-1) having a fluorine atom (hereinafter sometimes referred to as “monomer (a4-1)”).

［式（ａ４−１）中、
Ｒ^４１は、水素原子又はメチル基を表す。
Ａ^４１は、式（ａ４−ｇ１）で表される基を表す。

（式（ａ４−ｇ１）中、
ｓｓは０〜２の整数を表す。
Ａ^４０及びＡ^４３は、それぞれ独立に、炭素数１〜５の脂肪族炭化水素基を表す。
ｓｓが２のとき、複数存在するＡ^４０は、互いに同一であるか相異なる。
Ｘ^４０は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を表す。
ｓｓが２のとき、複数存在するＸ^４０は、互いに同一であるか相異なる。）
Ｒ^４２は、フッ素原子を有する炭素数１〜１８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。］

[In the formula (a4-1),
R ⁴¹ represents a hydrogen atom or a methyl group.
A ⁴¹ represents a group represented by the formula (a4-g1).

(In the formula (a4-g1),
ss represents an integer of 0-2.
A ⁴⁰ and A ⁴³ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When ss is 2, a plurality of A ⁴⁰ are the same or different from each other.
X ⁴⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
When ss is 2, a plurality of X ⁴⁰ are the same or different from each other. )
R ⁴² represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms having a fluorine atom. The methylene group contained in the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

Group (a4-g1), like the X ^40, an oxygen atom, a carbonyl group, a divalent group which may include an atom or an atomic group such as a carbonyl group or an oxycarbonyl group. However, in group (a4-g1), if ss is 0, the group (a4-g1) is the ^{A 43.}
Specific examples of the aliphatic hydrocarbon group of A ⁴⁰ and A ⁴³ include the alkanediyl group or divalent alicyclic hydrocarbon group already exemplified in the range of 1 to 5 carbon atoms. ⁴⁰ and A ⁴³ are preferably an alkanediyl group having 1 to 5 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and particularly preferably an ethylene group.

などが挙げられる（＊は結合手を表す）。 As the group having an oxygen atom (a4-g1),

(* Represents a bond).

などが挙げられる（＊は結合手を表す）。 As the group having a carbonyl group (a4-g1),

(* Represents a bond).

などが挙げられる（＊は結合手を表す）。 As the group having a carbonyloxy group (a4-g1),

(* Represents a bond).

などが挙げられる（＊は結合手を表す）。 As the group having an oxycarbonyl group (a4-g1),

(* Represents a bond).

The A ^41, a ss is 0 in the formula ^(a4-g1), is preferably one ^{A 43} is alkanediyl group having 1 to 5 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, ethylene The group is particularly preferred.
The aliphatic hydrocarbon group having a fluorine atom of R ⁴² may partially have a carbon-carbon unsaturated bond, but is preferably a saturated one having no carbon-carbon unsaturated bond. Examples of the aliphatic saturated hydrocarbon group include alkyl groups (straight and branched) and alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups obtained by combining alkyl groups and alicyclic hydrocarbon groups. A part or all of the hydrogen atoms contained in the group is substituted with a fluorine atom. In addition, the specific example of an alkyl group and an alicyclic hydrocarbon group includes what was already illustrated in the range of each carbon number.

An aliphatic hydrocarbon group R ⁴² is a fluorine ^atom, and ^{A 41} is an ethylene group (a4-1) is the following formula (a4-1-1) ~ formula (a4-1-22) The monomer (a4-1) represented, respectively is mentioned.

The aliphatic hydrocarbon group having a fluorine atom of R ⁴² is a perfluoroalkyl group in which all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms (for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group). Group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, etc.), and a perfluorocycloalkyl group in which all of the hydrogen atoms contained in the cycloalkyl group are substituted with fluorine atoms are more preferred.
The compound in which R ⁴² is a perfluoroalkyl group or a perfluorocycloalkyl group includes the above-described formula (a4-1-3), formula (a4-1-4), formula (a4-1-7), and formula (a4- 1-8), formula (a4-1-11), formula (a4-1-12), formula (a4-1-15), formula (a4-1-16), formula (a4-1-19), A compound represented by any one of formula (a4-1-20), formula (a4-1-21) and formula (a4-1-22) is applicable.
R ⁴² is preferably a perfluoroalkyl group. More preferably, it is a C1-C6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group.

［式（ａ−ｇ２）中、
Ａ^１３は、炭素数１〜１８の２価の脂肪族炭化水素基を表し、Ａ^１４は、炭素数１〜１７の脂肪族炭化水素基を表すが、Ａ^１３及びＡ^１４の炭素数の合計は１８以下である。Ａ^１３及びＡ^１４のうち少なくとも一方がフッ素原子を有する脂肪族炭化水素基である。
Ｘ^１２は、カルボニルオキシ基又はオキシカルボニル基を表す。］ R ⁴² may be interrupted with a group containing an oxygen atom. Preferred ^{R 42} in this case, for example, represented by the formula (a-g2).

[In the formula (a-g2),
A ¹³ represents a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, but the total number of carbon atoms of A ¹³ and A ¹⁴ Is 18 or less. At least one of A ¹³ and A ¹⁴ is an aliphatic hydrocarbon group having a fluorine atom.
X ¹² represents a carbonyloxy group or an oxycarbonyl group. ]

In the formula (a-g2), the divalent aliphatic hydrocarbon group of A ¹³ is typically an alkanediyl group or a divalent alicyclic hydrocarbon group, and the alkanediyl group and the divalent aliphatic group. The cyclic hydrocarbon group may have a fluorine atom as described above. In addition, the hydrogen atom contained in the alkanediyl group and the divalent alicyclic hydrocarbon group may be substituted with a substituent, and the substituent in that case is preferably a halogen atom other than a fluorine atom. On the other hand, the aliphatic hydrocarbon group of A ¹⁴ is typically an alkyl group or a monovalent alicyclic hydrocarbon group, the alkyl group and monovalent alicyclic hydrocarbon group, fluorine as described above May have atoms. In addition, the hydrogen atom contained in the said alkyl group and a bivalent alicyclic hydrocarbon group may be substituted by the substituent, and the substituent in that case, Preferably, they are halogen atoms other than a fluorine atom. At least one of A ¹³ and A ¹⁴ is an aliphatic hydrocarbon group having a fluorine atom, and among them, A ¹³ is preferably an aliphatic hydrocarbon group having a fluorine atom.

Preferred examples of * -A ¹³ -X ¹² -A ¹⁴ (* is a bond to a carbonyl group) include the following structures.

［式（ａ４−１’）中、
全ての符号はいずれも、上記と同じ意味である。］ As the monomer (a4-1) in which R ⁴² is a group represented by the formula (a-g2), those represented by the following formula (a4-1 ′) (hereinafter referred to as “monomer (a4-1 ′) ) ").

[In the formula (a4-1 ′),
All symbols have the same meaning as above. ]

In the monomer (a4-1 ′), as described above, it is preferable that A ¹⁴ is an aliphatic hydrocarbon group having a fluorine atom, and among these, those having an alkanediyl group having a fluorine atom are more preferable. More preferred is an alkanediyl group. The “perfluoroalkanediyl group” refers to an alkanediyl group in which all hydrogen atoms are substituted with fluorine atoms.

A ¹³ is perfluoro alkanediyl ^group, the monomer ^{A 41} is an ethylene group (a4-1 '), described in equation (a4-1'-1) ~ formula (a4-1'-22) The compound which is made is mentioned.

The number of carbon atoms of A ¹³ and ^{A 14} are, these sums are arbitrarily selected in the range of 17 or ^less, the number of carbon atoms of ^{A 13} are ^members preferably 1-6, 1-3 is more preferable.
The number of carbon atoms of A ¹⁴ is preferably 4 to 15, 5 to 12 is more preferable. Further preferred A ¹⁴ is an alicyclic hydrocarbon group having 6 to 12 carbon atoms, and a cyclohexyl group and an adamantyl group are particularly preferred.
When the resin (A) has a structural unit derived from the monomer (a4-1), the content thereof is usually 1 to 20 mol% with respect to all the structural units of the resin (A), and 2 to 15 Mol% is preferable, and 3 to 10 mol% is more preferable.
Resin (A) is preferably a structural unit derived from a compound represented by formula (I), a monomer (a1) having an acid-labile group different from the compound represented by formula (I), hydroxy It is a copolymer obtained by polymerizing an acid stable monomer (a2) having a group and / or an acid stable monomer (a3) having a lactone ring. In the copolymer, the monomer (a1) having an acid labile group is more preferably at least one of a monomer (a1-1) having an adamantyl group and a monomer (a1-2) having a cyclohexyl group. (More preferably, the monomer (a1-1) having an adamantyl group), and the acid-stable monomer (a2) having a hydroxy group preferably has an acid-stable monomer (a2-0) having a hydroxystyrene or a hydroxyadamantyl group The acid-stable monomer (a2-1) and the acid-stable monomer (a3) having a lactone ring are more preferably an acid-stable monomer (a3-1) having a γ-butyrolactone ring and a γ-butyrolactone ring and a norbornane ring. It is at least 1 type of the acid stable monomer (a3-2) which has a condensed ring.

A preferred structural ratio of the structural unit of the resin (A) is a structural unit derived from the compound represented by the formula (I): a monomer having an acid labile group different from the compound represented by the formula (I) (A1): Acid-stable monomer having a hydroxy group (a2) and / or acid-stable monomer having a lactone ring (a3): Other monomer (a4) = 1-50: 20-60: 30-30-70: 1-20 (Preferably, 3-45: 25-55: 35-65: 2-15, more preferably 5-40: 25-50: 35-65: 3-10).
As a more preferable structural ratio of the structural unit of the resin (A), the structural unit derived from the compound represented by the formula (I): having an acid-labile group different from the compound represented by the formula (I) Monomer (a1): acid-stable monomer (a2) having a hydroxy group and / or acid-stable monomer (a3) having a lactone ring = 1-50: 20-60: 30-70 (preferably 3-45: 25 55: 35-65, more preferably 5-40: 25-50: 35-65).
As a more preferable structural ratio of the structural unit of the resin (A), the structural unit derived from the compound represented by the formula (I): having an acid labile group different from the compound represented by the formula (I) Monomer (a1): Acid-stable monomer having a hydroxy group (a2): Acid-stable monomer having a lactone ring (a3) = 1-50: 20-60: 3-35: 25-65 (preferably 3-45: 25 to 55: 4 to 30:30 to 65, and more preferably 5 to 40:25 to 50: 5 to 25:35 to 60).

More preferable specific examples of the resin (A) include the following resins (A-1) to (A-12).

  The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably Is 10,000 or less). The weight average molecular weight is a value determined by gel permeation chromatography using a polystyrene standard, and the analysis conditions are described in the examples of the present application.

<Resist composition>
The resist composition of the present invention contains a resin having a structural unit derived from the compound (I), preferably the resin (A) described above, and an acid generator.
Moreover, it is preferable that the resist composition of this invention contains a basic compound further.
In the resist composition of this invention, it is preferable that content of resin (A) is 80 to 99 mass% in solid content of a composition. The “solid content in the composition” means the total of resist composition components excluding the solvent (D) described later. The solid content in the composition and the content of the resin (A) relative thereto can be measured, for example, by a known analysis means such as liquid chromatography or gas chromatography.
In addition to the resin (A), the resist composition of the present invention may further contain a resin (X) having a structural unit derived from a monomer having a fluorine atom. Here, the monomer (a4-1) mentioned above is mentioned as a monomer which has a fluorine atom. Resin (X) can be used as an additive resin in the resist composition.
The resin (X) may have a structural unit derived from the compound (I).

When the resin (X) has a structural unit derived from the compound (I), another resin having a structural unit derived from the acid labile monomer (a1) may be contained in the resist composition of the present invention.
When the resin (X) contains a structural unit derived from the monomer (a4-1), the content is preferably from 70 to 100 mol%, preferably from 80 to 100 mol, based on all structural units of the resin (X). % Is more preferable, and 90 to 100 mol% is more preferable.
When the resin (X) has a structural unit derived from the monomer (a4-1) and a structural unit derived from the compound (I), the preferred structural ratio of the structural unit of the resin (X) is based on the molar ratio. Structural unit derived from monomer (a4-1): Structural unit derived from compound (I) = 70 to 99: 1 to 30, preferably 80 to 97: 3 to 20, more preferably 85 ~ 99: 1-15.
In addition, as resin used together when resin (X) which has a structural unit derived from compound (I) is contained in a resist composition, acid labile monomer (a1), acid stable monomer (a2) which has a hydroxy group And / or a copolymer obtained by polymerizing an acid-stable monomer (a3) having a lactone ring.
In the resin contained in the resist composition of the present invention, when the resin (X) is contained in addition to the resin (A), the content of the resin (X) is 0 based on the solid content of the resist composition. 0.1 to 10% by mass is preferable, 0.3 to 5% by mass is more preferable, and 0.5 to 3% by mass is more preferable. When the resin having no structural unit derived from the compound (I) and the resin (X) having a structural unit derived from the compound (I) are used in combination, the resin (A) and the resin (X) shown here In this case, the resin (A) may be replaced with a resin having no structural unit derived from the compound (I).

<Acid generator (hereinafter sometimes referred to as “acid generator (B)”)>
Acid generators used in the resist field are classified into nonionic and ionic. The acid generator (B) contained in the resist composition of the present invention 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). -Sulfonate), sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

Examples of the acid generator (B) include not only acid generators (particularly photoacid generators) used in the resist field, but also photoinitiators for photocationic polymerization, photodecolorants for dyes, and photochromic agents. Known compounds that generate an acid by radiation (light) and mixtures thereof can also be used as appropriate. For example, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, Acid is generated by radiation described in Japanese Utility Model Publication 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. Can be used.
The acid generator (B) is preferably a fluorine-containing acid generator, more preferably one represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”). Among the acid generators (B1), Z ⁺ having a positive charge is referred to as an “organic cation”, and a negative charge obtained by removing the organic cation is sometimes referred to as a “sulfonate anion”.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれるメチレン基は、酸素原子、スルホニル基又はカルボニル基で置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The methylene group contained in the alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a triperfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group.
In formula (B1), Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.
Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and these groups Two or more of them may be combined. Specific examples of these alkanediyl groups and divalent alicyclic hydrocarbon groups include those already exemplified for each carbon number range.
Examples of the group in which the methylene group contained in the divalent saturated hydrocarbon group in L ^b1 is replaced by an oxygen atom or a carbonyl group include any of the following formulas (b1-1) to (b1-7): The group shown by these is mentioned. L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably a group represented by formula (b1-1) or formula (b1-3). is there. Incidentally, the formula (b1-1) ~ formula (b1-7) has its left and right are described in accordance with the formula (B1), ^-C on the left ^{(Q 1) (Q 2)} - and the carbon atoms in Bond on the right side with -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-7).

［式（ｂ１−１）〜式（ｂ１−７）中、
Ｌ^ｂ２は、単結合又は炭素数１〜１５の飽和炭化水素基を表す。
Ｌ^ｂ３は、単結合又は炭素数１〜１２の飽和炭化水素基を表す。
Ｌ^ｂ４は、炭素数１〜１３の飽和炭化水素基を表す。但しＬ^ｂ３及びＬ^ｂ４の合計炭素数の上限は１３である。
Ｌ^ｂ５は、単結合又は炭素数１〜１４の飽和炭化水素基を表す。
Ｌ^ｂ６は、炭素数１〜１５の飽和炭化水素基を表す。但しＬ^ｂ５及びＬ^ｂ６の合計炭素数の上限は１５である。
Ｌ^ｂ７は、単結合又は炭素数１〜１５の飽和炭化水素基を表す。
Ｌ^ｂ８は、炭素数１〜１５の飽和炭化水素基を表す。但しＬ^ｂ７及びＬ^ｂ８の合計炭素数の上限は１６である。
Ｌ^ｂ９は、単結合又は炭素数１〜１３の飽和炭化水素基を表す。
Ｌ^ｂ１０は、炭素数１〜１４の飽和炭化水素基を表す。但しＬ^ｂ９及びＬ^ｂ１０の合計炭素数の上限は１４である。
Ｌ^ｂ１１及びＬ^ｂ１２は、単結合又は炭素数１〜１１の飽和炭化水素基を表す。
Ｌ^ｂ１３は、炭素数１〜１２の飽和炭化水素基を表す。但しＬ^ｂ１１、Ｌ^ｂ１２及びＬ^ｂ１３の合計炭素数の上限は１２である。
Ｌ^ｂ１４及びＬ^ｂ１５は、それぞれ独立に、単結合又は炭素数１〜１３の飽和炭化水素基を表す。
Ｌ^ｂ１６は、炭素数１〜１４の飽和炭化水素基を表す。但しＬ^ｂ１４、Ｌ^ｂ１５及びＬ^ｂ１６の合計炭素数の上限は１４である。］

[In Formula (b1-1) to Formula (b1-7),
L ^b2 represents a single bond or a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a single bond or a saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b6 represents a saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b5 and L ^b6 is 15.
L ^b7 represents a single bond or a saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b8 represents a saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b7 and L ^b8 is 16.
L ^b9 represents a single bond or a saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b10 represents a saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 14.
L ^b11 and L ^b12 represent a single bond or a saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b13 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b11 , L ^b12 and L ^b13 is 12.
L ^b14 and L ^b15 each independently represent a single bond or a saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b16 represents a saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 14. ]

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

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

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

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

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

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

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

Among these, L ^b1 is preferably a group represented by the formula (b1-1), and L ^b2 is represented by the formula (b1-1), which is a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms. More preferably, it is a divalent group.
Examples of the alkyl group for Y include methyl, ethyl, isopropyl, tert-butyl, 2,2-dimethylethyl, propyl, 1-methylpropyl, 2,2-dimethylpropyl, Ethylpropyl group, butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-propylbutyl group, pentyl group, 1-methylpentyl group, hexyl group, 1,4-dimethylhexyl group, heptyl group 1-methylheptyl group, octyl group, methyloctyl group, methylnonyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.
As the alicyclic hydrocarbon group for Y, for example, groups represented by the following formulas (Y1) to (Y11) are preferable.

The methylene group contained in the alkyl group and the alicyclic hydrocarbon group is, for example, a group in which the methylene group contained in the alkyl group is replaced with an oxygen atom, a carbonyl group or an oxygen atom. Examples include a group replaced with a carbonyl group, and groups represented by the following formulas (Y12) to (Y26).

Of these, groups represented by formulas (Y1) to (Y19) are preferred, and more preferably, groups represented by formula (Y11), formula (Y14), formula (Y15) and formula (Y19), respectively. A group represented by formulas (Y11) and (Y14).
Examples of the substituent of the aliphatic hydrocarbon group in Y include a halogen atom (excluding a fluorine atom), a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and carbon. A group represented by an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _{j 2} —O—CO—R ^b1 (wherein R ^b1 is a carbon number of 1; Represents a hydrocarbon group of ˜16. J2 represents an integer of 0 to 4). The aromatic hydrocarbon group and aralkyl group which are substituents for Y may further have, for example, an alkyl group, a halogen atom or a hydroxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, n-hexoxy group and the like.
Aromatic hydrocarbon groups include phenyl, naphthyl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, anthryl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl group, naphthylethyl group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

Among them, Y is preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a substituent. A 3-12 alicyclic hydrocarbon group is more preferable, an adamantyl group which may have a substituent is further preferable, and an adamantyl group, an oxoadamantyl group or a hydroxyadamantyl group is particularly preferable.
The sulfonate anion in the salt represented by the formula (B1) is preferably an anion represented by any one of the formulas (b1-1-1) to (b1-1-9). In the following formulas, the definitions of the symbols have the same meaning as described above, and R ^b2 and R ^b3 each independently represent an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).

Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

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-0) 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).

The sulfonate anion in which Y is an alicyclic hydrocarbon group having an aromatic hydrocarbon group is represented by any of the following formulas (b1-s-30) to (b1-s-35) Is mentioned.

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

  Examples of the cation contained in the acid generator (B) include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, organic benzothiazolium cation, and organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an organic cation represented by any one of the following formulas (b2-1) to (b2-4) [hereinafter, the number of each formula is Accordingly, they may be referred to as “cation (b2-1)”, “cation (b2-2)”, “cation (b2-3)”, and “cation (b2-4)”. ].

[In Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The aliphatic hydrocarbon 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 may be a halogen atom. May have an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, or 3 carbon atoms. It may have an -18 alicyclic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. Two selected from R ^b4 , R ^b5 and R ^b6 may be combined to form a ring containing a sulfur atom together with the sulfur atom to which they are bonded.
Examples of the ring that may be formed together with the sulfur atom to which two members selected from R ^b4 , R ^b5 and R ^b6 are bonded together include monocyclic, polycyclic, aromatic and non-aromatic The ring may be any of nature, saturated and unsaturated, and may contain one or more sulfur atoms and / or one or more oxygen atoms as long as it contains one or more sulfur atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 13 carbon atoms is more preferable.

R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, the plurality of R ^b7 may be the same or different from each other. When n2 is 2 or more, the plurality of R ^b8 may be the same or different from each other.
R ^b9 and R ^b10 are independently of each other an aliphatic hydrocarbon group having 1 to 18 carbon atoms (preferably having 1 to 12 carbon atoms) or an alicyclic hydrocarbon group having 3 to 18 carbon atoms (preferably having a carbon number). 4-12).
R ^b9 and R ^b10 may be bonded to each other to form a 3-membered to 12-membered ring (preferably a 3-membered to 7-membered ring) alicyclic hydrocarbon ring containing a sulfur atom, The methylene group contained in the alicyclic hydrocarbon ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms (preferably 1 to 12 carbon atoms), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (preferably 4 to 12 carbon atoms). Alternatively, it represents an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^{b9 to} R ^b11 may be the same or different from each other.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group is And having an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 1 to 12 carbon atoms. Also good.
R ^b11 and R ^b12 may be bonded to each other to form a 3- to 12-membered (preferably 3- to 7-membered) ring, and the methylene group constituting the ring is an oxygen atom or a sulfur atom. Or it may be replaced by a carbonyl group.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents an oxygen atom or a sulfur atom.
o2, p2, s2, and t2 each independently represent 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 from each other. When p2 is 2 or more, the plurality of R ^b14 may be the same or different from each other, and q2 is When it is 2 or more, the plurality of R ^b15 may be the same as or different from each other. When r2 is 2 or more, the plurality of R ^b16 may be the same or different from each other, and s2 is 2 or more. In this case, the plurality of R ^b17 may be the same as or different from each other, and when t2 is 2 or more, the plurality of R ^b18 may be the same as or different from each other. ]

An alkyl group is mentioned as an aliphatic hydrocarbon group.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the acyl group include acetyl, propionyl, butyryl and the like.
Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group. Group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

^Among the aliphatic hydrocarbon groups ^{represented by} R ^{b9 to} R ^b12 , preferred groups are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl. Group, octyl group and 2-ethylhexyl group.
Among the alicyclic hydrocarbon groups represented by R ^{b9 to} R ^b11 , preferred groups are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and an isobornyl group.
^Among the aromatic hydrocarbon groups for R ^b12 , preferred groups are a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, and a 4-methoxyphenyl group. A biphenylyl group and a naphthyl group.
The aromatic hydrocarbon group having an aliphatic hydrocarbon group represented by R ^b12 is typically an aralkyl group, and specific examples include a benzyl group.

Examples of the ring formed by combining R ^b9 and R ^b10 together with the sulfur atom to which they are bonded include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and 1, 4-oxathian-4-ium ring etc. are mentioned.
Examples of the ring formed by combining R ^b11 and R ^b12 together with the carbon atom to which they are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

［式（ｂ２−１−１）中、
Ｒ^ｂ１９、Ｒ^ｂ２０及びＲ^ｂ２１は、互いに独立に、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、炭素数３〜１８の脂環式炭化水素基又は炭素数１〜１２のアルコキシ基を表し、Ｒ^ｂ１９、Ｒ^ｂ２０及びＲ^ｂ２１から選ばれる２つが一緒になって単結合、−Ｏ−又は炭素数１〜４の２価の脂肪族炭化水素基を表し、イオウ原子を含む環を形成してもよい。
脂肪族炭化水素基は、好ましくは炭素数は１〜１２であり、より好ましくは炭素数１〜１２のアルキル基であり、置換基として、ヒドロキシ基、炭素数１〜１２のアルコキシ基又は炭素数６〜１８の芳香族炭化水素基を有していてもよい。
脂環式炭化水素基は、好ましくは炭素数は４〜１８であり、置換基として、ハロゲン原子、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、互いに独立に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は互いに同一でも異なってもよく、ｗ２が２以上のとき、複数のＲ^ｂ２０は互いに同一でも異なってもよく、ｘ２が２以上のとき、複数のＲ^ｂ２１は互いに同一でも異なってもよい。
なかでも、Ｒ^ｂ１９、Ｒ^ｂ２０及びＲ^ｂ２１は、互いに独立に、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 above-mentioned 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)” may be used. ], More preferably a triphenylsulfonium cation (in formula (b2-1-1), v2, w2 and x2 are all 0) or a tolylsulfonium cation (in formula (b2-1-1), v2, w2 and x2 are both 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups.

[In the 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 alicyclic hydrocarbon having 3 to 18 carbon atoms. ^Represents a group or an alkoxy group having 1 to 12 carbon atoms, and two selected from R ^b19 , R ^b20 and R ^b21 are combined to form a single bond, —O— or a divalent aliphatic hydrocarbon having 1 to 4 carbon atoms. Represents a group and may form a ring containing a sulfur atom.
The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and as a substituent, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or a carbon number. It may have 6-18 aromatic hydrocarbon groups.
The alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms, and may have a halogen atom, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group as a substituent.
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 as or different from each other. When w2 is 2 or more, a plurality of R ^b20 may be the same or different from each other. When x2 is 2 or more, a plurality of R ^{b19 b21} may be the same as or different from each other.
Among these, R ^b19 , R ^b20 and R ^b21 are preferably independently of each other preferably 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. ]

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

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

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

The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, and preferably a combination of any one of anion (b1-1-1) to anion (b1-1-9) and cation (b2-1-1), and A combination of any one of anions (b1-1-1) to (b1-1-9) and a cation (b2-3) may be mentioned.
The acid generator (B1) is preferably a salt represented by any one of the formulas (B1-1) to (B1-24), more preferably a salt containing a triarylsulfonium cation. Formula (B1-1), Formula (B1-2), Formula (B1-3), Formula (B1-6), Formula (B1-7), Formula (B1-11), Formula (B1-12), Formula (B1-13), Formula (B1-14), Formula (B1-18), Formula (B1-19), Formula (B1-20), Formula (B1-21), Formula (B1-22), Formula ( B1-23) and formula (B1-24).

A preferable range of the content of the acid generator (B) in the resist composition of the present invention is determined on the basis of the total amount of resins contained in the resist composition. When the resin is the resin (A), the content of the acid generator (B) with respect to the total amount of the resin (A) is preferably 1% by mass or more (more preferably 3% by mass or more), preferably Is 40% by mass or less (more preferably 35% by mass or less). In addition, when resin contained in the resist composition of this invention is a mixture of resin (A) and resin (X), for example, in the preferable content rate of the acid generator (B) already demonstrated, "resin (A) The “total amount” may be replaced with “resin (A) and resin (X)”.
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 of the present invention preferably contains a basic compound (C). The basic compound (C) acts as a quencher.
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably a compound represented by the formula (C1) to a compound represented by the formula (C8), more preferably a compound represented by the formula (C1-1). It is done.

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

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

［式（Ｃ１−１）中、Ｒ^ｃ２及びＲ^ｃ３は、上記と同じ意味を表す。
Ｒ^ｃ４は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基を表す。
ｍ３は０〜３の整数を表し、ｍ３が２以上のとき、複数のＲ^ｃ４は、互いに同一であるか相異なる。］

[In formula (C1-1), R ^c2 and R ^c3 represent the same meaning as described above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, the plurality of R ^c4s are the same or different from each other. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^ｃ５、Ｒ^ｃ６、Ｒ^ｃ７及びＲ^ｃ８は、それぞれ独立に、Ｒ^ｃ１と同じ意味を表す。
Ｒ^ｃ９は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアシル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^ｃ９は、互いに同一であるか相異なる。］

[In Formula (C2), Formula (C3), and Formula (C4), R ^c5 , R ^c6 , R ^c7, and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of ^Rc9s are the same or different from each other. ]

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

[In Formula (C5) and Formula (C6), R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 each independently represent the same meaning as R ^c1 .
R ^c14 , R ^c15 and R ^c17 each independently represent the same meaning as R ^c4 .
o3 and p3 each independently represent an integer of 0 to 3, and when o3 or p3 is 2 or more, the plurality of R ^c14 and R ^c15 are the same as or different from each other.
L ^c1 represents a C1-C6 alkanediyl group, -CO-, -C (= NH)-, -S-, or a divalent group obtained by combining these. ]

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

Wherein (C7) and formula ^{(C8), R c18, R} c19 and ^{R c20} in each occurrence independently ^represent the same meaning as ^{R c4.}
q3, r3 and s3 each independently represent an integer of 0 to 3, when q3, r3 and s3 is 2 or more, respectively, or different multiple ^{R c18, R c19} and ^{R c 20} are identical to each other .
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In the formulas (C1) to (C8), examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group, and acyl group are the same as those described above.
Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and preferably diisopropylethane. Niline is mentioned, and 2,6-diisopropylaniline is 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 Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.
When the basic composition (C) is contained in the resist composition of the present invention, the content is preferably about 0.01 to 5% by mass, more preferably 0, based on the solid content of the resist composition. About 0.01 to 3% by mass, particularly preferably about 0.01 to 1% by mass.

<Solvent (sometimes referred to as “solvent (D)”)
When the resist composition of the present invention contains a solvent (D), it is preferable because the production of a resist pattern described later becomes easier. In this case, the content of the solvent (D) is, for example, 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more in the resist composition, for example, 99.9% by mass or less, preferably 99%. It is below mass%.
The content rate of a solvent (D) can be measured with well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.
Examples of the solvent (D) 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 Examples thereof include esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone. A solvent (D) may be used individually by 1 type, and may use 2 or more types together.

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

<This resist composition and its preparation method>
The resist composition comprises a resin (preferably, a resin (A) or a mixture of a resin (A) and a resin (X)), an acid generator (B), and a solvent (D) and a base used as necessary. It can prepare by mixing a sex compound (C) or other ingredients (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing may be selected from a range of 10 to 40 ° C., and an appropriate temperature range may be selected according to the type of resin, the solubility in the solvent (D) such as resin, and the mixing time depends on the mixing temperature. And 0.5 to 24 hours are preferable. The mixing means is not particularly limited, and stirring and mixing can be used.
As described above, after mixing the resin (A) and the acid generator (B) and the solvent (D), the basic compound (C), or the component (F), which are used as necessary, at a preferable content, The resist composition can be prepared by filtration using a filter having a pore size of about 0.003 to 0.2 μm.

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

Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater.
The composition after application is dried to remove the solvent. Drying is performed, for example, by evaporating volatile components such as a solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device to form a dried composition layer. The As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. As an exposure light source, a laser beam emitting in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm), a solid-state laser light source (YAG or semiconductor laser) Etc.) can be used such as those that convert the wavelength of the laser light from the above and radiate the harmonic laser light in the far ultraviolet region or the vacuum ultraviolet region. The exposure machine may irradiate an electron beam or extreme ultraviolet light (EUV) generated from plasma. In this specification, irradiating these radiations may be collectively referred to as “exposure”. When the exposure light source is an electron beam, a desired pattern may be directly drawn without using a photomask.

The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) for promoting the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example.
By selecting the type of developer, a positive resist pattern or a negative resist pattern can be produced.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.
In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.

Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.
It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) irradiation, or a resist composition for EUV exposure. Yes, it can be used for fine processing of semiconductors.

Hereinafter, the present invention will be described in detail by way of examples.
In Examples and Comparative Examples, “%” and “part” representing content and use amount are based on mass unless otherwise specified.
In the examples, the weight average molecular weight was determined by gel permeation chromatography (HLC-8120GPC type manufactured by Tosoh Corporation, three columns are “TSKgel Multipore HXL-M”, the solvent is tetrahydrofuran) under the following conditions using polystyrene as a standard product. This is the value obtained in.
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)
The structure of the compound was confirmed by measuring the molecular peak using mass spectrometry (LC is model 1100 manufactured by Agilent, and MASS is LC / MSD manufactured by Agilent). In the following examples, the value of this molecular peak is indicated by “MASS”.

式（Ｉ１−ａ）で表される化合物１００部及びテトラヒドロフラン１０００部を仕込み、室温で攪拌し、式（Ｉ１−ａ）で表される化合物の溶解確認後、ピリジン５０部を仕込み、４０℃に昇温した。さらに、クロロアセチルクロリド８９部及びテトラヒドロフラン８９部の混合溶液を１時間かけて滴下した。滴下後、４０℃で５時間攪拌し、５℃に温度を下げた。５℃に冷却したイオン交換水５０部を添加、攪拌し、分液により水層を回収した。回収された水層に酢酸エチル１０００部を添加し、分液して有機層を回収した。回収された有機層に、５℃の１０％炭酸カリウム水溶液５００部を添加して洗浄し、分液して有機層を回収した後、回収された有機層にさらに、イオン交換水５００部を添加して水洗し、分液を行って有機層を回収した。この水洗操作を３回繰り返して行った。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（Ｉ１−ｂ）で表される化合物８４．２部を得た。 Example 1: Synthesis of compound represented by formula (I-1)

100 parts of the compound represented by the formula (I1-a) and 1000 parts of tetrahydrofuran were charged, stirred at room temperature, and after confirming the dissolution of the compound represented by the formula (I1-a), 50 parts of pyridine was charged to 40 ° C. The temperature rose. Further, a mixed solution of 89 parts of chloroacetyl chloride and 89 parts of tetrahydrofuran was added dropwise over 1 hour. After dropping, the mixture was stirred at 40 ° C. for 5 hours, and the temperature was lowered to 5 ° C. 50 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. To the recovered aqueous layer, 1000 parts of ethyl acetate was added, and liquid separation was performed to recover the organic layer. 500 parts of 10% aqueous potassium carbonate solution at 5 ° C. is added to the collected organic layer for washing, liquid separation is performed to collect the organic layer, and then 500 parts of ion-exchanged water is added to the collected organic layer. The organic layer was recovered by washing with water and liquid separation. This washing operation was repeated 3 times. After the collected organic layer was concentrated, a compound (I1-b) represented by formula (I1-b) was obtained by fractionating a column (silica gel 60-200 mesh; developed solvent: ethyl acetate) under the following conditions. Two parts were obtained.

式（Ｉ１−ｃ）で表される化合物４７部、テトラヒドロフラン１５０部及びピリジン３０部を反応器に仕込み、２３℃で３０分間攪拌した後、０℃まで冷却した。得られた混合物に、同温度を保持したまま、式（Ｉ１−ｂ）で表される化合物８３部を、１時間かけて添加した。さらに、温度を１０℃まで上げ、１０℃に到達した時点から、同温度で１時間攪拌した。得られた反応混合物に、酢酸エチル１０００部、５％塩酸水溶液６０部及びイオン交換水５００部を加え、２３℃で３０分間攪拌し、静置後、分液した。回収された有機層に、イオン交換水５００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（Ｉ１−ｄ）で表される化合物５０．１部を得た。

47 parts of the compound represented by the formula (I1-c), 150 parts of tetrahydrofuran and 30 parts of pyridine were charged into a reactor, stirred at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, 83 parts of the compound represented by the formula (I1-b) was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to 10 ° C., and when the temperature reached 10 ° C., the mixture was stirred at the same temperature for 1 hour. To the obtained reaction mixture, 1000 parts of ethyl acetate, 60 parts of a 5% aqueous hydrochloric acid solution and 500 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and then separated. To the recovered organic layer, 500 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, and then allowed to stand and liquid-separated to wash the organic layer with water. Such water washing operation was repeated 4 times. After the collected organic layer was concentrated, the compound (I1-d) represented by the formula (I1-d) was separated by separating the column (silica gel 60-200 mesh; developed solvent: ethyl acetate) under the following conditions. 1 part was obtained.

式（Ｉ１−ｄ）で表される化合物３４部及びアセトニトリル１００部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、水素化ホウ素ナトリウム１．８部及びイオン交換水２６．６部を仕込み、５℃で３時間攪拌した。得られた混合物に、イオン交換水２００部及び酢酸エチル５００部を加えて攪拌し、分離した。回収された有機層にイオン交換水２００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（Ｉ１−ｅ）で表される化合物１９．３部を得た。

34 parts of the compound represented by the formula (I1-d) and 100 parts of acetonitrile were charged, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. To the obtained mixture, 1.8 parts of sodium borohydride and 26.6 parts of ion-exchanged water were added and stirred at 5 ° C. for 3 hours. To the obtained mixture, 200 parts of ion-exchanged water and 500 parts of ethyl acetate were added, stirred and separated. 200 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and separated to wash the organic layer with water. Such washing operation was repeated 5 times. After the collected organic layer was concentrated, a compound (I1-e) represented by the formula (I1-e) was collected by fractionating a column (silica gel 60-200 mesh; developed solvent: ethyl acetate) under the following conditions. 3 parts were obtained.

式（Ｉ１−ｅ）で表される化合物１８部、Ｎ−メチルピロリジン１４．６部、メチルイソブチルケトン２００部を仕込み、攪拌下、式（Ｉ１−ｆ）で表される化合物６．２部を添加し、６０℃で５時間攪拌した。その後、反応マスにイオン交換水１０部を添加、攪拌後、分液水洗を行った。この水洗の操作を５回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ１）で表される化合物１５．６部を得た。
ＭＳ：４３６．１

18 parts of a compound represented by the formula (I1-e), 14.6 parts of N-methylpyrrolidine and 200 parts of methyl isobutyl ketone were charged, and 6.2 parts of a compound represented by the formula (I1-f) were added with stirring. The mixture was added and stirred at 60 ° C for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mass, and after stirring, the solution was washed with liquid. This washing operation was performed 5 times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 15.6 parts of a compound represented by the formula (I1).
MS: 436.1

式（Ｉ１１−ａ）で表される塩１０．００部及びアセトニトリル６０部を仕込み、４０℃で３０分間攪拌し、式（Ｉ１１−ｂ）で表される化合物１０．７９部を仕込み、６０℃で１時間攪拌することにより、式（Ｉ１１−ｃ）で表される化合物を含む溶液を得た。 Example 2: Synthesis of compound represented by formula (I-11)

10.00 parts of the salt represented by the formula (I11-a) and 60 parts of acetonitrile are charged, and the mixture is stirred for 30 minutes at 40 ° C., and 10.79 parts of the compound represented by the formula (I11-b) is charged. Was stirred for 1 hour to obtain a solution containing the compound represented by the formula (I11-c).

得られた式（Ｉ１１−ｃ）で表される化合物を含む溶液に、式（Ｉ１１−ｄ）で表される化合物１０．６５部を仕込み、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応マスに、酢酸エチル２００部及びイオン交換水１００部を仕込み、攪拌、分液を行った。水洗を５回行った。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（Ｉ１１−ｅ）で表される化合物１３．５８部を得た。

10.65 parts of the compound represented by the formula (I11-d) was charged into the obtained solution containing the compound represented by the formula (I11-c), and stirred at 23 ° C. for 1 hour. For 18 hours. Into the obtained reaction mass, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 5 times. After the collected organic layer is concentrated, a compound (I11-e) represented by formula (I11-e) is obtained by fractionating a column (silica gel 60-200 mesh; developed solvent: ethyl acetate) under the following conditions. 58 parts were obtained.

テトラヒドロフラン６２．５部に、５℃で、リチウムアルミニウムハイドライド１．５９部を仕込み、その後、式（Ｉ１１−ｅ）１３．４１部及びテトラヒドロフラン４０．２４部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸２４．５４部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液１００部を加えて攪拌し、分離した。回収された有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（Ｉ１１−ｆ）で表される化合物１１．２１部を得た。

62.5 parts of tetrahydrofuran was charged with 1.59 parts of lithium aluminum hydride at 5 ° C., and then a mixed solution of 13.41 parts of the formula (I11-e) and 40.24 parts of tetrahydrofuran was added at 5 ° C. over 1 hour. Then, the mixture was stirred at 23 ° C. for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. After dropping 24.54 parts of 10% sulfuric acid into the obtained mixture, 200 parts of chloroform and 100 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and separated to wash the organic layer with water. Such washing operation was repeated 5 times. After the collected organic layer was concentrated, a column (silica gel 60-200 mesh; developing solvent manufactured by Merck & Co., Ltd .: developing solvent: ethyl acetate) was fractionated under the following conditions to obtain a compound represented by the formula (I11-f) 11. 21 parts were obtained.

式（Ｉ１１−ｆ）で表される化合物２．００部、Ｎ−メチルピロリジン１．８３部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｉ１１−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応マスにイオン交換水１０部を添加、攪拌後、分液水洗を行った。この水洗の操作を５回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ−１１）で表される化合物１．１１部を得た。
ＭＳ：３９２．１

2.00 parts of a compound represented by the formula (I11-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are charged, and the compound 0.77 represented by the formula (I11-g) is stirred. Part was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mass, and after stirring, the solution was washed with liquid. This washing operation was performed 5 times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.11 parts of the compound represented by the formula (I-11).
MS: 392.1

以下、これらのモノマーを、それぞれ「モノマー（ａ１−１−１）」、「モノマー（ａ１−１−２）」、「モノマー（ａ２−１−１）」、「モノマー（ａ３−１−１）」、「モノマー（Ｉ−１）」及び「モノマー（Ｉ−１１）」という。 Resin Synthesis Compounds (monomers) used in the synthesis of resins [resins (A), etc.] are shown below.

Hereinafter, these monomers are referred to as “monomer (a1-1-1)”, “monomer (a1-1-2)”, “monomer (a2-1-1)”, and “monomer (a3-1-1)”, respectively. "," Monomer (I-1) "and" monomer (I-11) ".

Example 3 [Synthesis of Resin A1]
The monomer (a1-1-1) 4.82 parts, p-acetoxystyrene 10.00 parts, monomer (a2-1-1) 2.43 parts, monomer (I-1) 4.49 parts 1,4- Dioxane (21.73 parts) was added to form a solution, and the temperature was raised to 87 ° C. To the obtained solution, 2.02 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 225.99 parts of methanol and 56.50 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 2.17 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated to reflux for 15 hours. After cooling, the reaction solution obtained was neutralized by adding 1.55 parts of glacial acetic acid, and then poured into a large amount of water to cause precipitation. The precipitated polymer was separated by filtration, dissolved in acetone, poured into a large amount of water and precipitated for 3 times, and purified to repeat a copolymer 16.41 having a weight average molecular weight of 4.5 × 10 ^3. Got a part. This copolymer comprises structural units derived from the following monomers derived from the monomer (a1-1-1), p-hydroxystyrene, monomer (a2-1-1) and monomer (I-1), respectively. This is referred to as Resin A1.

Example 4 [Synthesis of Resin A2]
5.10 parts of monomer (a1-1-2), 10.00 parts of p-acetoxystyrene, 1.21 parts of monomer (a2-1-1), 0.87 parts of monomer (a3-1-1), monomer ( I-1) 21.68 parts of 1,4-dioxane was added to 4.49 parts to make a solution, and the temperature was raised to 87 ° C. To the obtained solution, 2.02 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 225.45 parts of methanol and 56.36 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 2.17 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated to reflux for 15 hours. After cooling, the reaction solution obtained was neutralized by adding 1.54 parts of glacial acetic acid, and then poured into a large amount of water to cause precipitation. The precipitated polymer was separated by filtration, dissolved in acetone, then poured into a large amount of water and precipitated for 3 times and purified to obtain a copolymer 16.13 having a weight average molecular weight of 4.6 × 10 ^3. Got a part. This copolymer is derived from monomer (a1-1-2), p-hydroxystyrene, monomer (a2-1-1), monomer (a3-1-1) and monomer (I-1), respectively, These are structural units derived from the respective monomers, and are referred to as Resin A2.

Example 5 [Synthesis of Resin A3]
1.56 parts of 1,4-dioxane was added to 5.56 parts of monomer (a1-1-1), 10.00 parts of p-acetoxystyrene, and 4.14 parts of monomer (I-1) to form a solution, and the temperature was 87 ° C. The temperature was raised to. To the obtained solution, 1.87 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 204.85 parts of methanol and 51.21 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 1.97 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated to reflux for 15 hours. After cooling, 1.40 parts of glacial acetic acid was added to the resulting reaction solution for neutralization, and then poured into a large amount of water to cause precipitation. The precipitated polymer was separated by filtration, dissolved in acetone, then poured into a large amount of water and precipitated for 3 times, and purified to give a copolymer 15.21 having a weight average molecular weight of 4.7 × 10 ^3. Got a part. This copolymer has a structural unit derived from each of the following monomers derived from the monomer (a1-1-1), p-hydroxystyrene and the monomer (I-1). And

Example 6 [Synthesis of Resin A4]
5.10 parts of monomer (a1-1-2), 10.00 parts of p-acetoxystyrene, 1.21 parts of monomer (a2-1-1), 0.87 parts of monomer (a3-1-1), monomer ( I-11) 21.20 parts of 1,4-dioxane was added to 4.02 parts to obtain a solution, and the temperature was raised to 87 ° C. To the obtained solution, 2.02 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 240 parts of methanol and 60 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 2.17 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated to reflux for 15 hours. After cooling, the reaction solution obtained was neutralized by adding 1.54 parts of glacial acetic acid, and then poured into a large amount of water to cause precipitation. The precipitated polymer was separated by filtration, dissolved in acetone, then poured into a large amount of water and precipitated for 3 times to purify, and the copolymer 14.28 having a weight average molecular weight of 4.4 × 10 ³ was obtained. Got a part. This copolymer is derived from the monomer (a1-1-2), p-hydroxystyrene, monomer (a2-1-1), monomer (a3-1-1) and monomer (I-11), respectively, These are structural units derived from the respective monomers, and are referred to as Resin A4.

Examples 7 to 10 and Comparative Example 1
<Preparation of resist composition>
Resin A1 to Resin A5 obtained in Synthesis Examples of Examples 3 to 6 and JP2010-210796;
Acid generator B1-11 shown below;
Basic compound C1 shown below;
Each was dissolved in the solvent shown below in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

<Resin>
A1: Resin A1 obtained in Example 3
A2: Resin A2 obtained in Example 4
A3: Resin A3 obtained in Example 5
A4: Resin A4 obtained in Example 6
A5: The following resins were synthesized according to the synthesis example of JP2010-210796A.

<Acid generator>
B1-11:

<Basic compound: Quencher>
C1:

<Solvent> Electron beam resist composition Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts <Solvent> Resist composition for KrF Propylene glycol monomethyl ether acetate 47.5 parts γ-butyrolactone 2.5 Part

(Evaluation as a resist composition for electron beams)
The silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds, and the resist solution was spin-coated so that the film thickness after drying was 0.06 μm. Then, it prebaked for 60 seconds on the direct hot plate at the temperature shown in the "PB" column of Table 1. The wafer on which the resist film was formed was exposed to a line-and-space pattern using an electron beam drawing machine [“HL-800D 50 keV” manufactured by Hitachi, Ltd.] with the exposure amount being changed stepwise.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature shown in the “PEB” column of Table 1, and further paddle development was performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution.
In the formation of a resist pattern from each resist composition, the exposure amount at which the line width of a 60 nm line and space pattern was 1: 1 was defined as the effective sensitivity.

<Resolution and shape evaluation>
When the resist pattern was observed with a scanning electron microscope in terms of effective sensitivity, the resist pattern obtained from Examples 7 to 10 resolved 50 nm in a good shape, but the resist pattern obtained from Comparative Examples 1 and 2 Resolved 50 nm, but the top was round.

(Evaluation as a resist composition for KrF)
An organic antireflective coating composition [DUV-42; manufactured by Brewer Co., Ltd.] is applied onto a 4-inch silicon wafer and baked at 215 ° C. for 60 seconds. A film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 400 nm.
After applying the resist composition, the obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 1. Using the KrF excimer laser exposure machine [NSR-2250EX12B; manufactured by Nikon Corporation, NA = 0.55, 2/3 Annular], the exposure amount was changed stepwise on the wafer on which the resist composition film was formed. The line and space pattern was exposed.
After the exposure, post exposure bake (PEB) is performed on the hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed.
In each resist film, the exposure amount at which the 180 nm line and space pattern becomes an exposure amount of 1: 1 was defined as the effective sensitivity.

In manufacturing the resist pattern as described above, the following items were evaluated.
Focus margin evaluation (DOF): A range in which the line width is 180 nm ± 5% (about 171 to 189 nm) when the focus is shaken with an exposure amount at which the line width of a line and space pattern with a mask size of 180 nm is 180 nm. ) As the line width index. The results are shown in Table 2.

  If a resist composition containing a resin having a structural unit derived from the compound of the present invention is used, a resist pattern having an excellent focus margin (DOF) can be produced.

Claims (14)

A compound represented by formula (I).

[In the formula (I),
L ¹ is a single bond, * -X ^1- , * -X ² -A ^1- , * -X ³ -A ² -X ⁴ -or * -X ⁵ -A ³ -X ⁶ -A ⁴ -(* Represents a bond with O).
L ^{2 is, * - A 5 -X 7 -A} 6 -, * - A 7 -X 8 -A 8 -X 9 -, * - A 9 -X 10 -A 10 -X 11 -A 11 -, * -A < ¹² >-or * -A < ¹³ > -X < ¹² >-(* represents a bond with the ring W < ¹ >).
X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently an alkanediyl group having 1 to 6 carbon atoms. Represent.
A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ , A ¹¹ , A ¹² and A ¹³ are each independently an oxygen atom or —CO— Represents O-.
Ring ^{W 1} represents an aromatic ring having 6 to 18 carbon atoms.
Ring ^{W 2} represents a sultone ring 4 to 34 carbon atoms.
R ¹ represents a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ² represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms.
R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
s represents the integer of 0-2. When s is 2, a plurality of R ¹ may be the same as or different from each other.
t represents an integer of 0-2. When t is 2, a plurality of R ² may be the same as or different from each other. ] 2. The L ¹ is * —CHR ⁴ — or * —CH ₂ — (R ⁴ represents an alkyl group having 1 to 6 carbon atoms. * Represents a bond with O). Compound. The compound according to claim 1, wherein L ² is * —O—CH ₂ —CO—O— or * —CO—O— (* represents a bond to ring W ¹ ). The compound according to claim 1, wherein W ¹ is a benzene ring.   Resin which has a structural unit derived from the compound in any one of Claims 1-4.   The resin according to claim 5, further comprising a structural unit derived from a monomer having an acid labile group (however, not a compound represented by the formula (I)). The resin according to claim 6, wherein the monomer having an acid labile group is a monomer represented by the formula (a1-1) or a monomer represented by the formula (a1-2).

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * represents a bond with -CO-.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]   The resin according to any one of claims 5 to 7, further comprising a structural unit derived from an acid-stable monomer having a hydroxyadamantyl group. The resin according to claim 8, wherein the acid-stable monomer having a hydroxyadamantyl group is a monomer represented by the formula (a2-1).

[In the formula (a2-1),
L ^a3 represents —O— or * —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10. ]   A resist composition comprising the resin according to claim 5 and an acid generator. The resist composition according to claim 10, wherein the acid generator is 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 a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The methylene group contained in the alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 11, wherein Y in formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.   Furthermore, the resist composition in any one of Claims 10-12 containing a basic compound. (1) The process of apply | coating the resist composition in any one of Claims 10-13 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 method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.