JP2013007035A - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition that can produce a resist pattern that has an excellent mask error factor (MEF).SOLUTION: A compound is shown by formula (I), a resin has a structural unit that originates in the compound, and a resist composition includes the resin. In the formula (I), Rdenotes a hydrogen atom or a methyl group; r denotes an integer 1 or 2; Adenotes a group shown by formula (a-g1); s is an integer of 0-2; Adenotes an aliphatic hydrocarbon group; Adenotes a single bond or an aliphatic hydrocarbon group; and Xdenotes an oxygen atom, a carbonyl group, a carbonyloxy group, an oxycarbonyl group or oxycarbonyloxy group, wherein Ais a single bond, s=1 and Xis an oxygen atom; and Rdenotes a group that is unstable to an acid.

Description

  The present invention relates to a compound, a resin having a structural unit derived from the compound, a resist composition containing the resin, and a method for producing a resist pattern using the resist composition.

Patent Document 1 describes a resist composition containing a resin obtained by polymerizing the following compounds and triphenylsulfonium triflate as an acid generator.

WO2003 / 025676 pamphlet

  Even when a conventional compound uses a resist composition containing a resin obtained by polymerizing the compound, the mask error factor (MEF) of the produced resist pattern may not always be sufficiently satisfied.

［式（Ｉ）中、
Ｒ¹は、水素原子又はメチル基を表す。
ｒは１又は２を表す。
Ａ¹は、式（ａ−ｇ１）で表される基を表す。

（式（ａ−ｇ１）中、
ｓは０〜２の整数を表す。
Ａ^１０は、炭素数１〜５の脂肪族炭化水素基を表す。
Ａ^１１は、単結合又は炭素数１〜５の脂肪族炭化水素基を表す。
ｓが２のとき、複数存在するＡ^１０は、互いに同一であるか相異なる。
Ｘ^１０は、酸素原子、カルボニル基、カルボニルオキシ基、オキシカルボニル基又はオキシカルボニルオキシ基を表す。
但し、Ａ^１１が単結合の時、ｓ＝１かつＸ^１０は酸素原子である。
ｓが２のとき、複数存在するＸ^１０は、互いに同一であるか相異なる。）
Ｒ^２は、酸に不安定な基を表す。］
〔２〕前記式（Ｉ）のＲ^２が、単環又は多環式の酸に不安定な基である前記〔１〕記載の化合物。
〔３〕前記式（Ｉ）のＲ^２が、式（Ｉ−Ａ）又は式（Ｉ−Ｂ）で表される基である前記〔１〕又は〔２〕記載の化合物。

［式（Ｉ−Ａ）及び式（Ｉ−Ｂ）中、
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜１０の脂環式炭化水素基を表す。
ｍは０〜１４の整数を表す。
ｎは０〜１０の整数を表す。
ｌは０〜３の整数を表す。＊は、酸素原子との結合手を表す。］
〔４〕前記式（Ｉ）のＲ^１が、水素原子である前記〔１〕〜〔３〕のいずれか記載の化合物。
〔５〕前記〔１〕〜〔４〕のいずれか記載の化合物に由来する構造単位を有する樹脂。
〔６〕酸に不安定な基を有するモノマーに由来する構造単位を、さらに有する前記〔５〕記載のレジスト組成物。
〔７〕前記酸に不安定な基を有するモノマーが、式（ａ１−１）又は式（ａ１−２）で表されるモノマーである前記〔６〕記載のレジスト組成物。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜１０の脂環式炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］
〔８〕ヒドロキシアダマンチル基を有する酸安定モノマーに由来する構造単位を、さらに有する前記〔５〕〜〔７〕のいずれか記載の樹脂。
〔９〕前記ヒドロキシアダマンチル基を有する酸安定モノマーが、式（ａ２−１）で表されるモノマーである前記〔８〕記載の樹脂。

［式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］
〔１０〕ラクトン環を有する酸安定モノマーに由来する構造単位を、さらに有する前記〔５〕〜〔９〕のいずれか記載の樹脂。
〔１１〕前記ラクトン環を有する酸安定モノマーが、式（ａ３−１）、式（ａ３−２）及び式（ａ３−３）で表されるモノマーから選ばれる少なくとも１種である前記〔１０〕記載の樹脂。

［式（ａ３−１）〜式（ａ３−３）中、
Ｌ^a4〜Ｌ^a6は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a18〜Ｒ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１〜４のアルキル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４のアルキル基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上のとき、それぞれ、複数のＲ^a21、Ｒ^a22又はＲ^a23は、互いに同一であるか相異なる。］
〔１２〕前記〔５〕〜〔１１〕のいずれか記載の樹脂及び酸発生剤を含むレジスト組成物。
〔１３〕前記樹脂以外に、さらに、フッ素原子を有する酸安定モノマーに由来する構造単位を有する樹脂を含有する前記〔１２〕記載のレジスト組成物。
〔１４〕前記フッ素原子を有する酸安定モノマーが、式（ａ４−１）で表されるモノマーである前記〔１３〕記載のレジスト組成物。

［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^４１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、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。］
〔１５〕酸発生剤が、式（Ｂ１）で表される塩である前記〔１２〕〜〔１４〕のいずれか記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、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、前記アルキル基及び前記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。］
〔１６〕前記式（Ｂ１）のＹが、置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基である前記〔１５〕記載のレジスト組成物。
〔１７〕さらに、溶剤を含有する前記〔１２〕〜〔１６〕のいずれか記載のレジスト組成物。
〔１８〕（１）前記〔１２〕〜〔１７〕のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
r represents 1 or 2;
A ¹ represents a group represented by the formula (a-g1).

(In the formula (a-g1),
s represents the integer of 0-2.
A ¹⁰ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ¹¹ represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When s is 2, a plurality of A ¹⁰ are the same or different from each other.
X ¹⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group, an oxycarbonyl group or an oxycarbonyloxy group.
However, when A ¹¹ is a single bond, s = 1 and X ¹⁰ is an oxygen atom.
When s is 2, a plurality of X ¹⁰ are the same or different from each other. )
R ² represents an acid labile group. ]
[2] The compound according to [1], wherein R ^{2 in the} formula (I) is a monocyclic or polycyclic acid-labile group.
[3] The compound according to [1] or [2] above, wherein R ² in the formula (I) is a group represented by the formula (IA) or the formula (IB).

[In formula (IA) and formula (IB),
R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m represents an integer of 0 to 14.
n represents an integer of 0 to 10.
l represents an integer of 0 to 3. * Represents a bond with an oxygen atom. ]
[4] The compound according to any one of [1] to [3], wherein R ^{1 in the} formula (I) is a hydrogen atom.
[5] A resin having a structural unit derived from the compound according to any one of [1] to [4].
[6] The resist composition according to [5], further including a structural unit derived from a monomer having an acid labile group.
[7] The resist composition according to [6], wherein the monomer having an acid labile group is a monomer represented by formula (a1-1) or 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—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]
[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. ]
[10] The resin according to any one of [5] to [9], further including a structural unit derived from an acid-stable monomer having a lactone ring.
[11] The acid-stable monomer having a lactone ring is at least one selected from monomers represented by formula (a3-1), formula (a3-2) and formula (a3-3) [10] The resin described.

[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 or different from each other. ]
[12] A resist composition comprising the resin according to any one of [5] to [11] and an acid generator.
[13] The resist composition according to [12], further containing a resin having a structural unit derived from an acid stable monomer having a fluorine atom in addition to the resin.
[14] The resist composition according to [13], wherein the acid-stable monomer having a fluorine atom is a monomer represented by the formula (a4-1).

[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 ⁴¹ each independently represent 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 the C1-C18 aliphatic hydrocarbon group which may have a substituent. ]
[15] The resist composition according to any one of [12] to [14], wherein the acid generator is a salt 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, and the alkyl group and the above 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. ]
[16] The resist composition as described in [15] above, wherein Y in the formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
[17] The resist composition according to any one of [12] to [16], further containing a solvent.
[18] (1) A step of applying the resist composition according to any one of [12] to [17] 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 obtained by polymerizing the compound of the present invention is used, a resist pattern having an excellent mask error factor (MEF) can be produced.

［式（Ｉ）中、
Ｒ¹は、水素原子又はメチル基を表す。
ｒは１又は２を表す。
Ａ¹は、式（ａ−ｇ１）で表される基を表す。

（式（ａ−ｇ１）中、
ｓは０〜２の整数を表す。
Ａ^１０及びＡ^１１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。
ｓが２のとき、複数存在するＡ^１０は、互いに同一であるか相異なる。
Ｘ^１０は、酸素原子、カルボニル基、カルボニルオキシ基、オキシカルボニル基又はオキシカルボニルオキシ基を表す。
ｓが２のとき、複数存在するＸ^１０は、互いに同一であるか相異なる。）
Ｒ^２は、酸に不安定な基を表す。］ <Compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”)>
The compound of the present invention is represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
r represents 1 or 2;
A ¹ represents a group represented by the formula (a-g1).

(In the formula (a-g1),
s represents the integer of 0-2.
A ¹⁰ and A ¹¹ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When s is 2, a plurality of A ¹⁰ are the same or different from each other.
X ¹⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group, an oxycarbonyl group or an oxycarbonyloxy group.
When s is 2, a plurality of X ¹⁰ are the same or different from each other. )
R ² represents an acid labile group. ]

Group (a-g1), like the X ^10, 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 (a-g1), when it is s = 0, the group (a-g1) is consistent with the ^{A 11.}
The aliphatic hydrocarbon group in A ¹¹ and A ¹⁰ may be linear or branched. Examples thereof include alkanediyl groups such as a methylene group, ethylene group, propanediyl group, propanediyl group, butanediyl group, pentanediyl group, and hexanediyl group.

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

(* Represents a bond).

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

(* Represents a bond).

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

(* 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 (a-g1),

(* Represents a bond).

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

(* Represents a bond).

The A ^1, preferably alkanediyl group having 1 to 5 carbon atoms is s = 0, -CH ₂ - is more preferable.

The “acid-labile group” of R ² is a group having a leaving group, and the leaving group is eliminated upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). means. Examples of the acid labile group include a group represented by the formula (I-1) and a group represented by the formula (I-2).

［式（Ｉ−１）中、Ｒ^５〜Ｒ^７は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜２０の脂環式炭化水素基を表すか、Ｒ^５及びＲ^６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。］

[In Formula (I-1), R ^{5 to} R ⁷ each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ⁵ and R ^6. Combine with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

アルキル基で置換された脂環式炭化水素基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。
式（Ｉ−１）では、脂環式炭化水素基は、好ましくは炭素数３〜１６である。 Examples of the alkyl group of R ^{5 to} R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

Examples of the alicyclic hydrocarbon group substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
In the formula (I-1), the alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms.

Examples of the —C (R ⁵ ) (R ⁶ ) (R ⁷ ) group in the case where R ⁵ and R ⁶ are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms.

Examples of the acid-labile group represented by the formula (I-1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{5 to} R ⁷ are alkyl groups in the formula (I-1), Preferably a tert-butoxycarbonyl group), a 2-alkyladamantan-2-yloxycarbonyl group (in formula (I-1), R ⁵ , R ⁶ and a carbon atom form an adamantyl group, and R ⁷ is an alkyl group. A group) and 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (I-1), R ⁵ and R ⁶ are alkyl groups, and R ⁷ is an adamantyl group), etc. Is mentioned.

［式（Ｉ−Ａ）及び式（Ｉ−Ｂ）中、
「及びＲ^４は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜１０の脂環式炭化水素基を表す。
ｍは０〜１４の整数を表す。
ｎは０〜１０の整数を表す。
ｌは０〜３の整数を表す。＊は、酸素原子との結合手を表す。］ The compound represented by the formula (I) is preferably such that the acid labile group has a monocyclic or polycyclic alicyclic hydrocarbon group having 5 to 20 carbon atoms. If a resin obtained by polymerizing a monomer having a bulky structure such as a monocyclic or polycyclic alicyclic hydrocarbon group is used, the resolution of the resist pattern can be improved. The bulky structure of the acid labile group is preferably a group represented by the formula (IA) or a group represented by the formula (IB).

[In formula (IA) and formula (IB),
“And R ⁴ each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m represents an integer of 0 to 14.
n represents an integer of 0 to 10.
l represents an integer of 0 to 3. * Represents a bond with an oxygen atom. ]

  Examples of the alkyl group and alicyclic hydrocarbon group are the same as those exemplified in Formula (I-1).

R ¹ is preferably a hydrogen atom.

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

  Of these, compounds represented by formula (I-1) to formula (I-9), formula (I-19) or formula (I-20) are preferred, and formula (I-1) to formula (I-6) are preferred. Or a compound represented by formula (I-19) is more preferred, and is represented by formula (I-1), formula (I-2), formula (I-4), formula (I-6) or formula (I-19). ) Is more preferable.

式（ＩＡ−ａ）で表される化合物は、市販されているもののいずれを用いてもよい。例えば、２−クロロエタンスルホニルクロライドなどが挙げられる。式（ＩＡ−ｂ）で表される化合物も市販されているもののいずれを用いてもよい。例えば、以下で表される化合物などが挙げられる。

In compound (I), compound (IA) wherein r = 1 is obtained by reacting, for example, a compound represented by formula (IA-a) and a compound represented by formula (IA-b) under a base catalyst. By making it, it can manufacture. This reaction is usually performed in the presence of a solvent. As the solvent, dichloroethane or the like can be used. Examples of the base catalyst include pyridine.

Any commercially available compound may be used as the compound represented by the formula (IA-a). For example, 2-chloroethane sulfonyl chloride etc. are mentioned. As the compound represented by the formula (IA-b), any commercially available compound may be used. For example, the compounds represented by the following can be mentioned.

まず、式（ＩＡ）で表される化合物を、酸存在下、反応させて、式（ＩＢ−ａ）で表される化合物を製造する。この反応は通常、溶媒の存在下で行われる。溶媒としては、クロロホルムなどが使用できる。酸としては、トリフルオロ酢酸などが挙げられる。
次いで、式（ＩＢ−ａ）で表される化合物とカルボニルジイミダゾールとを反応させることにより、式（ＩＢ−ｂ）で表される化合物を製造する。
さらに、得られた式（ＩＢ−ｂ）で表される化合物と式（ＩＢ−ｃ）で表される化合物とを反応させることにより、化合物（ＩＢ）を製造することができる。この反応は通常、溶媒の存在下で行われる。溶媒としては、クロロホルムなどが使用できる。 In addition, for example, in compound (I), compound (IB) in which r = 1 and R ² is a 2-methyladamantyl-2-yl group can be produced, for example, by the following method.

First, a compound represented by the formula (IA) is reacted in the presence of an acid to produce a compound represented by the formula (IB-a). This reaction is usually performed in the presence of a solvent. As the solvent, chloroform or the like can be used. Examples of the acid include trifluoroacetic acid.
Next, the compound represented by the formula (IB-b) is produced by reacting the compound represented by the formula (IB-a) with carbonyldiimidazole.
Furthermore, compound (IB) can be produced by reacting the compound represented by formula (IB-b) with the compound represented by formula (IB-c). This reaction is usually performed in the presence of a solvent. As the solvent, chloroform or the like can be used.

<Resin (hereinafter sometimes referred to as “resin (A)”)>
The resin (A) of the present invention contains a structural unit derived from the compound represented by the formula (I).
The resin (A) preferably further has a structural unit derived from a monomer having an acid labile group. Moreover, 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.
Here, the “acid-labile group” refers to a group having a leaving group and leaving the leaving group upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). means. 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”. .
The resin which becomes alkali-soluble by the action of such an acid includes a compound represented by the formula (I) and a monomer having an acid labile group (hereinafter referred to as “monomer having an acid labile group (a1)). In some cases). As the monomer (a1) having an acid labile group, one type may be used alone, or two or more types may be used in combination.

  The content of the structural unit derived from the compound represented by the formula (I) in the resin (A) is usually 1 to 60 mol%, preferably 3 to 50 mol% in all the structural units of the resin (A). More preferably, it is 5 to 40 mol%.

<Monomer (a1) having an acid labile group>
Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

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

［式（２）中、Ｒ^a1'及びＲ^a2'は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a3'は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a2'及びＲ^a3'は互いに結合して炭素数２〜２０の２価の炭化水素基を形成し、前記炭化水素基及び２価の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。］

In Expression (1), R ^a1 ~R ^a3 each independently represent a cycloaliphatic hydrocarbon radical of the alkyl group or 3 to 20 carbon atoms having 1 to 8 carbon atoms, R ^a1 and R ^a2 are each Bonding to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

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

  These groups represented by the formula (1) are exemplified in the same manner as the above-described formula (I-1), and the same groups are exemplified.

Examples of the hydrocarbon group for R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include the same ones as exemplified in Formula (I-1).

In formula (2), preferably, at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.
Specific examples of the group represented by the formula (2) include the following groups.

  The monomer (a1) having an acid labile group is preferably a monomer having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. The resolution of the resist pattern can be improved by using a resin obtained by polymerizing the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group.

The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group (1) and a carbon-carbon double bond, more preferably an acid labile group (1). (Meth) acrylic monomer having Here, (meth) acryl represents acryl and / or methacryl.
As the (meth) acrylic monomer having an acid labile group and an alicyclic hydrocarbon group, a monomer represented by the formula (a1-1) or a monomer represented by the formula (a1-2) is preferable. It is done. Hereinafter, the monomer represented by the formula (a1-1) and the monomer represented by the formula (a1-2) may be referred to as a monomer (a1-1) and a monomer (a1-2), respectively. These may be used alone or in combination of two or more.

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

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

ｍ１は、好ましくは０〜３の整数、より好ましくは０又は１である。
ｎ１は、好ましくは０〜３の整数、より好ましくは０又は１である。
ｎ１’は、好ましくは０又は１である。 L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, more preferably —O—. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
^Examples of the alkyl group for R ^a6 and R ^a7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms. The alicyclic hydrocarbon group preferably has 8 or less carbon atoms, more preferably 6 or less.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. . In this case, the carbon number of the alicyclic hydrocarbon group is 10 or less including the carbon number of the alkyl group. Examples of the monocyclic alicyclic hydrocarbon group which may be substituted with an alkyl group include, for example, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Of the cycloalkyl group. Examples of the polycyclic saturated hydrocarbon group which may be substituted with an alkyl group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups.

m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Monomers represented by the following formulas (a1-1-1) to (a1-1-8) are preferred, and monomers represented by the following formulas (a1-1-1) to (a1-1-4) are more preferred. .

Examples of the monomer (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptan-1-yl (meth). Examples include acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, and 1-isopropylcyclopentan-1-yl (meth) acrylate. Monomers represented by the following formulas (a1-2-1) to (a1-2-12) are preferred, and the following formulas (a1-2-3), (a1-2-4), (a1-2-9) And monomers represented by (a1-2-10) are more preferred, and monomers represented by the following formulas (a1-2-3) and (a1-2-9) are more preferred.

  When the resin (A) includes structural units derived from the monomer (a1-1) and / or the monomer (a1-2), the total content thereof is usually 10 to 10 in all structural units of the resin (A). It is 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 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^１は、単結合又は＊−［ＣＨ₂］_k４−ＣＯ−Ｌ^４−基を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^１との結合手を表す。
Ｌ^１、Ｌ^２、Ｌ^３及びＬ^４は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 As the other acid labile monomer (a1), for example, a monomer represented by the formula (a1-5) (hereinafter sometimes referred to as “monomer (a1-5)”) may be used.

In 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 ¹ represents a single bond or a * — [CH ₂ ] _k ⁴ —CO—L ⁴ — group. Here, k4 represents an integer of 1 to 4. * Represents a bond to ^{L 1.}
L ¹ , L ² , L ³ and L ⁴ each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ¹ is preferably an oxygen atom.
One of L ² and L ³ is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ¹ is preferably a single bond or * —CH ₂ —CO—O—.

As a monomer (a1-5), the following monomers are mentioned, for example.

  When the resin (A) has a structural unit derived from the monomer (a1-5), the content thereof is preferably in the range of 1 to 50 mol% with respect to all the structural units of the resin (A). The range of 45 mol% is more preferable, and the range of 5 to 40 mol% is more preferable.

  Resin (A) preferably has a content of structural units derived from a monomer having an adamantyl group (particularly monomer (a1-1) having an acid labile group) having a monomer having an acid labile group ( It is 15 mol% or more with respect to a1). When the ratio of the monomer having an adamantyl group is increased, the dry etching resistance of the resist is improved.

<Acid stable monomer>
Resin (A) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as “acid-stable monomer”) in addition to the structural unit derived from the compound represented by formula (I). It preferably contains a structural unit.
More preferably, the resin (A) does not have a structural unit derived from the compound represented by the formula (I), a monomer (a1) having an acid-labile group, and an acid-labile group. It is a copolymer with a monomer (hereinafter sometimes referred to as “acid-stable monomer”). An acid stable monomer may be used individually by 1 type, and may use 2 or more types together.

  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 resolution of the resist pattern and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for KrF excimer laser exposure (248 nm), irradiation with high energy rays such as an electron beam or EUV light, the acid-stable monomer (a2) having a hydroxy group is preferably a phenol which is a hydroxystyrene. Acid-stable monomer (a2-0) having a functional hydroxy group is used. When used for short wavelength ArF excimer laser exposure (193 nm) or the like, the acid stable monomer (a2) having a hydroxy group is preferably an acid stable monomer having a hydroxyadamantyl group represented by the formula (a2-1) Is used. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

  Examples of the monomer (a2-0) having a phenolic hydroxy group include styrene monomers such as p- or m-hydroxystyrene represented by the formula (a2-0).

［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、アクリロイル基又はメタクリロイル基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一であるか相異なる。］

[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 acryloyl group, or methacryloyl. Represents a group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 are the same as or different from each other. ]

Examples of the halogen atom in R ^a30 and R ^a31 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group which may have a halogen atom of 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 copolymer resin having a structural unit derived from a monomer having a phenolic hydroxy group is obtained by radical polymerization of acetyloxystyrenes corresponding to those obtained by replacing the phenolic hydroxy group with an acetyloxy group and a monomer to be copolymerized. Thereafter, it can be produced by deacetylation with a base.
As a monomer which has a phenolic hydroxy group, the monomer described in Unexamined-Japanese-Patent No. 2010-204634 is mentioned, for example. Monomers represented by the following formulas (a2-0-1) and (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) includes a structural unit derived from the 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%.

  Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。

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

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

As an acid stable monomer (a2-1) which has a hydroxyadamantyl group, the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Monomers represented by the following formulas (a2-1-1) to (a2-1-6) are preferred, and monomers represented by the following formulas (a2-1-1) to (a2-1-4) are more preferred. A monomer represented by the following formula (a2-1-1) or (a2-1-3) is more preferable.

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

<Acid-stable monomer having a lactone ring (a3)>
The lactone ring possessed by the acid stable monomer (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a monocyclic lactone ring and other rings The condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring or a condensed ring of γ-butyrolactone ring and another ring is preferable.

  The acid-stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). These 1 type may be used independently and may use 2 or more types together.

式（ａ３−１）〜式（ａ３−３）中、
Ｌ^a4〜Ｌ^a6は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a18〜Ｒ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１〜４のアルキル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４のアルキル基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上のとき、それぞれ、複数のＲ^a21、Ｒ^a22又はＲ^a23は、互いに同一であるか相異なる。

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

In Formula (a3-1) to Formula (a3-3), L ^{a4 to} La ⁶ are each independently preferably —O— or ^* —O— (CH ₂ ) _k3 —CO—O—. More preferably, it is —O—. k3 is preferably an integer of 1 to 4, more preferably 1.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1 to r1 are each independently preferably 0 to 2, more preferably 0 or 1.

Examples of the acid-stable monomer (a3) having a lactone ring include monomers described in JP 2010-204646 A. In the following formulas (a3-1-1) to (a3-1-4), (a3-2-1) to (a3-2-4), (a3-3-1) to (a3-3-4) Monomers represented by the following formulas (a3-1-1) to (a3-1-2) and (a3-2-3) to (a3-2-4) are more preferred, A monomer represented by formula (a3-1-1) or (a3-2-3) is more preferable.

When the resin (A) includes 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 all the structural units of the resin (A). , Preferably it is 10-65 mol%, More preferably, it is 10-60 mol%.
Moreover, when resin (A) contains the structural unit derived from the acid stable monomer (a3) which has a lactone ring, the total content rate is 5-70 mol% normally in all the structural units of resin (A). , Preferably it is 10-65 mol%, More preferably, it is 10-60 mol%.

［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^４１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、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。］ <Other monomer (a4)>
The resin may have a structural unit derived from another known monomer (a4) other than the above-mentioned monomers.
For example, the compound etc. which are represented by the formula (a4-1) which has a fluorine atom are mentioned.

[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 ⁴¹ each independently represent 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 the C1-C18 aliphatic hydrocarbon group which may have a substituent. ]

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 it is ss = 0, the group (a4-g1) ^is consistent with ^{A 41.}
The aliphatic hydrocarbon group for A ⁴¹ may be linear or branched. Examples thereof include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, and hexanediyl group.
A ⁴¹ is preferably an alkanediyl group having 1 to 6 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).

アルキル基及び脂環式炭化水素基を組み合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。 The aliphatic hydrocarbon group for R ⁴² may partially have a carbon-carbon unsaturated bond, but may be a saturated aliphatic hydrocarbon group having no carbon-carbon unsaturated bond (aliphatic saturated carbon Hydrogen group) is preferred. 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.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and groups shown below.

Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

（式（ａ−ｇ３）中、
Ｘ¹²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。
Ａ¹⁴は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。）
なかでも、Ｒ^４２は、ハロゲン原子を有する脂肪族炭化水素基であるか、以下の式（ａ−ｇ２）で表される基であることが好ましい。

（式（ａ−ｇ２）中、
Ａ¹³は、ハロゲン原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ¹²は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ¹⁴は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。） The aliphatic hydrocarbon group for R ⁴² preferably has a substituent.
Examples of the substituent of the aliphatic hydrocarbon group include a halogen atom and a group represented by the formula (a-g3).

(In the formula (a-g3),
X ¹² represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. )
Among these, R ⁴² is preferably an aliphatic hydrocarbon group having a halogen atom or a group represented by the following formula (a-g2).

(In the formula (a-g2),
A ¹³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom.
X ¹² represents a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. )

Examples of the aliphatic hydrocarbon group having a halogen atom for A ¹³ and A ¹⁴ include an alkyl group having a halogen atom and an alicyclic hydrocarbon group having a halogen atom (preferably a cycloalkyl group having a halogen atom). . The alkyl group having a halogen atom is one in which part or all of the hydrogen atoms contained in the alkyl group are substituted with a halogen atom, and the alicyclic hydrocarbon group having a halogen atom is an alicyclic hydrocarbon group A part or all of the hydrogen atoms contained in is substituted with a halogen atom. Among them, a fluorine atom is preferable as the halogen atom.

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) And the compounds represented.

The aliphatic hydrocarbon group having a halogen 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, or all of the hydrogen atoms in the cycloalkyl group are substituted with fluorine atoms. More preferred are perfluorocycloalkyl groups.
The compound in which R ⁴² is a perfluoroalkyl group or a perfluorocycloalkyl group ((a4-1) is a compound represented by the formula (a4-1-3), the formula (a4-1-4), the formula (A4-1-7), Formula (a4-1-8), Formula (a4-1-11), Formula (a4-1-12), Formula (a4-1-15), Formula (a4-1-1-) 16), a compound represented by any one of formula (a4-1-19), formula (a4-1-20), formula (a4-1-21) and formula (a4-1-22).
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.

R ⁴² may have one or more groups represented by the formula (a-g3), but includes the number of carbon atoms contained in the group represented by the formula (a-g3). The total carbon number of the aliphatic hydrocarbon group is preferably 15 or less, and more preferably 12 or less. For this reason, an aliphatic hydrocarbon group having one group represented by the formula (a-g3) is preferable.

［式（ａ４−１’）中、
Ａ¹³は、ハロゲン原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ¹²は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ¹⁴は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
その他の符号はいずれも、前記と同義である。］ The compound (a4-1) in which R ⁴² is an aliphatic hydrocarbon group having one group represented by the formula (a-g3) is specifically represented by the following formula (a4-1 ′). (Hereinafter, referred to as “compound (a4-1 ′)” in some cases).

[In the formula (a4-1 ′),
A ¹³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom.
X ¹² represents a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
All other symbols are as defined above. ]

  This compound (a4-1 ′) is a useful and novel compound as a raw material for producing the resin (A) contained in the resist composition, and the present invention relates to the compound (a4-1 ′). including.

In the compound (a4-1 ′), both A ¹³ and A ¹⁴ may have a halogen atom, but A ¹³ is an aliphatic hydrocarbon group having a halogen atom, or A ¹⁴ has a halogen atom. Those having an aliphatic hydrocarbon group are preferred. Further, it is preferable that A ¹³ is an aliphatic hydrocarbon group having a halogen atom, among them, A ¹³ is more preferable alkanediyl group having a fluorine atom, and more preferred is a perfluoro alkanediyl group . The “perfluoroalkanediyl group” refers to an alkanediyl group in which all of the hydrogen atoms are substituted with fluorine atoms.

Compounds (a4-1 ′) in which R ⁴² is a perfluoroalkanediyl group and A ⁴¹ is an ethylene group are represented by the following formulas (a4-1′-1) to (a4-1′-22). The compound which is made is mentioned.

Although the number of carbon atoms of A ¹³ and A ¹⁴ are selected arbitrarily, the number of carbon atoms of A ¹³ are members preferably 1-6, 1-3 is more preferable.
On the other hand, 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.

このような構造を有する化合物（ａ４−１’）は、上述した式（ａ４−１’−９）〜式（ａ４−１’−２０）で表される化合物が該当する。 Preferred examples of * -A ¹³ -X ¹² -A ¹⁴ (* is a bond to a carbonyl group) include the following structures.

The compound (a4-1 ′) having such a structure corresponds to the compounds represented by the above formula (a4-1′-9) to formula (a4-1′-20).

  When the resin (A) includes a structural unit derived from the compound (a4-1), the content 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.

The resin (A) may be a copolymer obtained by polymerizing the structural unit derived from the compound represented by the formula (I) and the monomer (a1) having an acid labile group, preferably , At least a structural unit derived from the compound represented by formula (I), a monomer (a1) having an acid-labile group, an acid-stable monomer (a2) having a hydroxy group, and / or an acid-stable having a lactone ring It is a copolymer obtained by polymerizing the monomer (a3). 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 is preferably an acid-stable monomer (a2-1) having a hydroxyadamantyl group, and a lactone ring More preferably, the acid-stable monomer (a3) having a γ-butyrolactone ring and an acid-stable monomer (a3-1) having a condensed ring of a γ-butyrolactone ring and a norbornane ring are used. At least one.
Resin (A) can be manufactured by a well-known polymerization method (for example, radical polymerization method).

As a preferred composition ratio of the structural unit of the resin (A), a structural unit derived from the compound (I): a structural unit derived from the monomer (a1) having an acid labile group: an acid stable monomer having a hydroxy group ( Structural unit derived from a2) and / or structural unit derived from acid-stable monomer (a3) having lactone ring = 1-60: 20-60: 30-70, preferably 3-40: 25-55 : 35-65, More preferably, it is 5-35: 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 (I): the structural unit derived from the monomer (a1) having an acid labile group: the acid stable monomer having a hydroxy group Structural unit derived from (a2): Structural unit derived from acid-stable monomer (a3) having a lactone ring = 1-60: 20-60: 3-35: 25-65, preferably 3-50: It is 25-55: 4-30: 30-65, More preferably, it is 5-40: 25-50: 5-25: 35-60.

  Examples of the resin (A) include the following resins (A-1) to (A-88).

  The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less).

<Resist composition>
The resist composition of the present invention contains the resin (A) described above and an acid generator.
Moreover, it is preferable that the resist composition of this invention contains a solvent and a basic compound further.

<resin>
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.

<Resin (X)>
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 an acid stable monomer having a fluorine atom. Here, as an acid stable monomer which has a fluorine atom, the compound represented by the formula (a4-1) which has a fluorine atom mentioned above is mentioned. Resin (X) can be used as an acid-stable additive resin in the resist composition.

  When the resin (X) contains a structural unit derived from the compound (a4-1), the content thereof is preferably 80 to 100 mol%, and preferably 85 to 100 mol% with respect to all the structural units of the resin (X). Is more preferable, and 90-100 mol% is further more preferable.

  For example, when resin (X) is used as an acid-stable additive resin, the structural unit of resin (X) is compound (a4-1) other than compound (a4-1 ′): compound (a4-1 ′) ) = 80 to 100: 0 to 20 mol%, preferably 90 to 100: 0 to 10, more preferably 95 to 100: 0 to 5.

  The resin (A) used in combination when the resin (X) is contained in the resist composition includes the compound represented by the formula (I), the monomer (a1) having an acid labile group, and a hydroxy group. A copolymer obtained by polymerizing the acid-stable monomer (a2) and / or the acid-stable monomer (a3) having a lactone ring is preferable.

  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.

<Acid generator (hereinafter sometimes referred to as “acid generator (B)”)>
The acid generator (B) is preferably a sulfonate represented by the formula (B1).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、単結合又は２価の炭素数１〜１７の飽和炭化水素基を表し、前記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、前記アルキル基及び前記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, and the alkyl group and the above 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 trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group.
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.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group;
An alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group); For example, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane- Branched alkanediyl groups such as 1,4-diyl group, 2-methylbutane-1,4-diyl group, 1-methylpentane-1,4-diyl group;
Monocyclic fats which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group A cyclic hydrocarbon group;
And polycyclic alicyclic hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like. It is done.

Examples of the group in which the methylene group contained in the saturated hydrocarbon group represented by L ^b1 is replaced with an oxygen atom or a carbonyl group include formulas (b1-1) to (b1-6). The formula (b1-1) to the formula (b1-6) are described in accordance with the formula (B1) on the left and right sides, and bonded to the carbon atom of C (Q ¹ ) (Q ² ) — on the left side. Bonds to -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

式（ｂ１−１）〜式（ｂ１−６）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の２価の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の炭素数上限は１３である。
Ｌ^b5は、炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b6及びＬ^b7は、それぞれ独立に、炭素数１〜１５の２価の飽和炭化水素基を表す。但しＬ^b6及びＬ^b7の炭素数上限は１６である。
Ｌ^b8は、炭素数１〜１４の２価の飽和炭化水素基を表す。
Ｌ^b9及びＬ^b10は、それぞれ独立に、炭素数１〜１１の２価の飽和炭化水素基を表す。但しＬ^ｂ９及びＬ^ｂ１０の炭素数上限は１２である。
中でも、Ｌ^b1は、好ましくは式（ｂ１−１）〜式（ｂ１−４）のいずれか、より好ましくは式（ｂ１−１）又は式（ｂ１−２）、さらに好ましくは式（ｂ１−１）で表される２価の基である。特に、好ましくは、Ｌ^b2が単結合又は−ＣＨ_２−である式（ｂ１−１）で表される２価の基である。

In formula (b1-1) to formula (b1-6),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b6 and L ^b7 each independently represent a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent a divalent saturated hydrocarbon group having 1 to 11 carbon atoms. However, the upper limit of the carbon number of L ^b9 and L ^b10 is 12.
Among them, L ^b1 is preferably any one of formula (b1-1) to formula (b1-4), more preferably formula (b1-1) or formula (b1-2), and still more preferably formula (b1-1). ) Represented by a divalent group. Particularly preferred is a divalent group represented by the formula (b1-1) wherein L ^b2 is a single bond or —CH ₂ —.

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

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

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

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

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

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

As an alkyl group of Y, Preferably, a C1-C6 alkyl group is mentioned.
Examples of the alicyclic hydrocarbon group for Y include groups represented by the following formulas (Y1) to (Y11).
Examples of the group in which the methylene group contained in the alicyclic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group, or a carbonyl group include groups represented by the following formulas (Y12) to (Y26).

  Especially, it is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably represented by formula (Y11), formula (Y14), formula (Y15) or formula (Y19). And more preferably a group represented by formula (Y11) or formula (Y14).

Examples of the substituent of the alkyl group and the alicyclic hydrocarbon group include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 to 16 carbon atoms. An alicyclic hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _j2 —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a group having 6 to 18 carbon atoms. Represents an aromatic hydrocarbon group, j2 represents an integer of 0 to 4, and the like. The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Examples of the substituent here include an alkyl group, a halogen atom, and 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, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, 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.

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

  Y is preferably an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group optionally having a substituent, and more preferably an adamantyl group. A group, a hydroxyadamantyl group or an oxoadamantyl group.

The sulfonate anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (b1-1-1) to the formula (b1-1-9). In the following formulas, the definitions of the symbols have the same meaning as described above, and the substituents 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 cation contained in the acid generator (B) include organic onium cations such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations, and preferably organic sulfonium cations. Or it is an organic iodonium cation, More preferably, it is an aryl sulfonium cation.

Z ⁺ in formula (B1) is preferably a cation represented by any one of formula (b2-1) to formula (b2-4).

In these formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 each independently represents an alkyl 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. R ^b4 and R ^b5 may be combined to form a ring having a sulfur atom. The hydrogen atom contained in the alkyl group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group. The hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group is It may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is an integer of 2 or more, the plurality of R ^b7 are the same or different from each other. When n2 is an integer of 2 or more, the plurality of R ^b8 are the same or different from each other.

R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R ^b9 and R ^b10 are a sulfur atom to which they are bonded. Together with each other to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring). The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
The alkyl group of R ^{b9 to} R ^b11 preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
R ^b12 represents an alkyl 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. The hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkyl group having 1 to 12 carbon atoms. , May be substituted with 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.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded, and methylene contained in these rings The group may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.

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

The alkyl group is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Is mentioned.
A benzyl group etc. are mentioned as an alkyl group (aralkyl group) by which the aromatic hydrocarbon group was substituted.
Preferred examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, an adamantyl group, and a norbornyl group.
Examples of the alicyclic hydrocarbon group substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group.
The aromatic hydrocarbon group is preferably a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a 4-methoxyphenyl group, or a biphenylyl group. And a naphthyl group.

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

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

Examples of the ring formed by R ^b9 and R ^b10 together with the sulfur atom include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. Can be mentioned.
Examples of the ring formed by R ^b11 and R ^b12 together with —CH—CO— include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferable, and the cation represented by the formula (b2-1-1) is more preferable. Are triphenylsulfonium cations (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cations (in formula (b2-1-1), v2 = w2 = 0, x2 = 1 And R ^b21 is a methyl group.) Or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl. Group.)

式（ｂ２−１−１）中、
Ｒ^b19〜Ｒ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１８のアルキル基、炭素数３〜１８の脂環式炭化水素基又は炭素数１〜１２のアルコキシ基を表す。Ｒ^b19〜Ｒ^b21から選ばれる２つが一緒になって硫黄原子を有する環を形成してもよい。
アルキル基は、好ましくは炭素数１〜１２であり、脂環式炭化水素基は、好ましくは炭素数４〜１８である。
ｖ２〜ｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。ｖ２〜ｘ２のいずれかが２以上のとき、それぞれ、複数のＲ^b19〜Ｒ^b21のいずれかは、互いに同一であるか相異なる。
なかでも、Ｒ^b19〜Ｒ^b21は、それぞれ独立に、好ましくは、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基であり、より好ましくは、ヒドロキシ基又は炭素数１〜４のアルキル基である。

In formula (b2-1-1),
R ^{b19 to} R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or 1 to 1 carbon atoms. 12 alkoxy groups are represented. ^{Two members} selected from R ^b19 to R ^b21 may be combined to form a ring having a sulfur atom.
The alkyl group preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms.
v2 to x2 each independently represents an integer of 0 to 5 (preferably 0 or 1). When any one of v2 to x2 is 2 or more, each of the plurality of R ^{b19 to} R ^b21 is the same as or different from each other.
Among them, R ^{b19 to} R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, More preferably, it is a hydroxy group or an alkyl group having 1 to 4 carbon atoms.

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

  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 (b1-1-3) to (b1-1-5) and a cation (b2-3) may be mentioned.

  The acid generator (B1) is preferably a salt represented by any of the formulas (B1-1) to (B1-20), more preferably a triphenylsulfonium cation or a tolylsulfonium cation. Which are acid generators containing formula (B1-1), formula (B1-2), formula (B1-3), formula (B1-6), formula (B1-7), formula (B1-11), Examples thereof include salts represented by formula (B1-12), formula (B1-13) and formula (B1-14).

The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).
In the resist composition of the present invention, the acid generator (B) may contain a single acid generator or a plurality of acid generators.

<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. Preferred examples of the basic compound (C) include compounds represented by the formulas (C1) to (C8) and the formula (C1-1), and more preferred are compounds represented by the formula (C1-1). Is mentioned.

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

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

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

[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 ^c4 are the same or different from each other. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアルカノイル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は、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 alkanoyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different from each other. ]

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

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

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

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

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

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

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

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

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

<Solvent (sometimes referred to as "solvent (D)")
The resist composition of the present invention may contain a solvent (D). The content of the solvent (D) is, for example, 90% by mass or more in the resist composition, preferably 92% by mass or more, more preferably 94% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. It is.
The content rate of a solvent (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 And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (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 other component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

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

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

  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 The temperature in this case is preferably about 50 to 200 ° C., for example. The pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) 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”.

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 an alkali developer using a developing device.
The alkaline developer used here may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).
After development, it is preferable to rinse with ultrapure water to remove water remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is 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, particularly a liquid. It is suitable as a resist composition for immersion exposure and useful 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 structure of the compound was confirmed by mass spectrometry (LC; Agilent 1100 type, MASS; Agilent LC / MSD type).
The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard product.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

式（Ｉ１９−１）で表される化合物１６．３０部、式（Ｉ１９−２）で表される化合物１５．８６部及びジクロロエタン５００部を仕込み、２３℃で３０分間攪拌し、０℃に冷却した。得られた混合マスに、ピリジン１７．３８部を１時間かけて滴下し、２３℃まで昇温し、更に、２３℃で３時間攪拌した。得られた反応溶液に１０％炭酸ナトリウム水溶液２５０部を加え、２３℃で３０分間攪拌した。攪拌後、静置・分液することにより回収された有機層に、イオン交換水２５０部を仕込み２３℃で３０分間攪拌し、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回行った。回収された有機層を濃縮し、得られた残渣を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ−１９）で表される化合物１５．８４部を得た。
ＭＳ：２２２．１（分子イオンピーク） Example 1 Synthesis of Compound Represented by Formula (I-19)

16.30 parts of the compound represented by the formula (I19-1), 15.86 parts of the compound represented by the formula (I19-2) and 500 parts of dichloroethane were charged, stirred at 23 ° C. for 30 minutes, and cooled to 0 ° C. did. To the obtained mixed mass, 17.38 parts of pyridine was dropped over 1 hour, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 3 hours. To the obtained reaction solution, 250 parts of a 10% aqueous sodium carbonate solution was added and stirred at 23 ° C. for 30 minutes. After stirring, 250 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and then the organic layer was washed with water. Such water washing operation was performed 5 times. The collected organic layer is concentrated, and the obtained residue is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., developing solvent: ethyl acetate) to obtain the formula (I-19 ) Was obtained.
MS: 222.1 (molecular ion peak)

式（Ｉ−１９）で表される化合物１０．２３部及びクロロホルム１００部を仕込み、２３℃で３０分間攪拌し、トリフルオロ酢酸１００部を滴下した。滴下後の混合物を２３℃で１時間攪拌した。得られた反応混合物を濃縮した。濃縮物に、クロロホルム２０部を添加・攪拌し、その後、濃縮した。回収された濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ１−１）で表される化合物４．８６部を得た。 Example 2 [Synthesis of Compound Represented by Formula (I-1)]

10.23 parts of a compound represented by the formula (I-19) and 100 parts of chloroform were charged, stirred at 23 ° C. for 30 minutes, and 100 parts of trifluoroacetic acid was added dropwise. The mixture after dropping was stirred at 23 ° C. for 1 hour. The resulting reaction mixture was concentrated. To the concentrate, 20 parts of chloroform was added and stirred, and then concentrated. The collected concentrate is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: ethyl acetate), whereby compound 4. represented by formula (I1-1) is obtained. 86 parts were obtained.

式（Ｉ１−１）で表される化合物１．３３部及びクロロホルム６．６３部を仕込み、２３℃程度で３０分間攪拌した。その後、カルボニルジイミダゾール１．５４部を添加し、８０℃まで昇温し、同温度で１時間攪拌することで、式（Ｉ１−２）で表される化合物を含む反応溶液を得た。得られた反応溶液に、式（Ｉ１−３）で表される化合物１．５８部をアセトニトリル４．７３部に溶解した溶液を１時間かけて滴下した。さらに、８０℃程度で１時間攪拌し、反応混合物を濃縮した。得られた濃縮物に、クロロホルム５０部及びイオン交換水１０部を加え、２３℃で３０分間攪拌した。その後、静置・分液して有機層を得た。このような水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた残渣を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ−１）で表される化合物１．１１部を得た。
ＭＳ：３１４．１（分子イオンピーク）

1.33 parts of the compound represented by the formula (I1-1) and 6.63 parts of chloroform were charged and stirred at about 23 ° C. for 30 minutes. Thereafter, 1.54 parts of carbonyldiimidazole was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain a reaction solution containing a compound represented by the formula (I1-2). A solution prepared by dissolving 1.58 parts of the compound represented by the formula (I1-3) in 4.73 parts of acetonitrile was added dropwise to the obtained reaction solution over 1 hour. Furthermore, it stirred at about 80 degreeC for 1 hour, and concentrated the reaction mixture. To the obtained concentrate, 50 parts of chloroform and 10 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and the organic layer was obtained. Such water washing operation was further repeated 5 times. The collected organic layer is concentrated, and the resulting residue is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., developing solvent: ethyl acetate) to obtain the formula (I-1 ) Was obtained 1.11 parts.
MS: 314.1 (Molecular ion peak)

式（Ｉ２−１）で表される化合物１．３３部及びクロロホルム６．６３部を仕込み、２３℃程度で３０分間攪拌した。その後、カルボニルジイミダゾール１．５４部を添加し、８０℃まで昇温し、同温度で１時間攪拌することで、式（Ｉ２−２）で表される化合物を含む反応溶液を得た。得られた反応溶液に、式（Ｉ２−３）で表される化合物１．７１部をアセトニトリル５．１３部に溶解した溶液を１時間かけて滴下した。さらに、８０℃程度で１時間攪拌し、反応混合物を濃縮した。得られた濃縮物に、クロロホルム５０部及びイオン交換水１０部を加え、２３℃で３０分間攪拌した。その後、静置・分液して有機層を得た。このような水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた残渣を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ−２）で表される化合物１．２２部を得た。
ＭＳ：３２８．１（分子イオンピーク） Example 3 [Synthesis of Compound Represented by Formula (I-2)]

1.33 parts of the compound represented by the formula (I2-1) and 6.63 parts of chloroform were charged and stirred at about 23 ° C. for 30 minutes. Thereafter, 1.54 parts of carbonyldiimidazole was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain a reaction solution containing a compound represented by the formula (I2-2). A solution prepared by dissolving 1.71 parts of the compound represented by the formula (I2-3) in 5.13 parts of acetonitrile was dropped into the obtained reaction solution over 1 hour. Furthermore, it stirred at about 80 degreeC for 1 hour, and concentrated the reaction mixture. To the obtained concentrate, 50 parts of chloroform and 10 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and the organic layer was obtained. Such water washing operation was further repeated 5 times. The recovered organic layer is concentrated, and the resulting residue is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., developing solvent: ethyl acetate) to obtain the formula (I-2 ) Was obtained.
MS: 328.1 (molecular ion peak)

式（Ｉ４−１）で表される化合物１．３３部及びクロロホルム６．６３部を仕込み、２３℃程度で３０分間攪拌した。その後、カルボニルジイミダゾール１．５４部を添加し、８０℃まで昇温し、同温度で１時間攪拌することで、式（Ｉ４−２）で表される化合物を含む反応溶液を得た。得られた反応溶液に、式（Ｉ４−３）で表される化合物１．２２部をアセトニトリル３．６６部に溶解した溶液を１時間かけて滴下した。さらに、８０℃程度で１時間攪拌し、反応混合物を濃縮した。得られた濃縮物に、クロロホルム５０部及びイオン交換水１０部を加え、２３℃で３０分間攪拌した。その後、静置・分液して有機層を得た。このような水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた残渣を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ−４）で表される化合物０．９７部を得た。
ＭＳ：２７６．１（分子イオンピーク） Example 4 [Synthesis of Compound Represented by Formula (I-4)]

1.33 parts of a compound represented by the formula (I4-1) and 6.63 parts of chloroform were charged and stirred at about 23 ° C. for 30 minutes. Thereafter, 1.54 parts of carbonyldiimidazole was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain a reaction solution containing a compound represented by the formula (I4-2). A solution prepared by dissolving 1.22 parts of the compound represented by the formula (I4-3) in 3.66 parts of acetonitrile was added dropwise to the obtained reaction solution over 1 hour. Furthermore, it stirred at about 80 degreeC for 1 hour, and concentrated the reaction mixture. To the obtained concentrate, 50 parts of chloroform and 10 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and the organic layer was obtained. Such water washing operation was further repeated 5 times. The collected organic layer is concentrated, and the resulting residue is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., developing solvent: ethyl acetate) to obtain the formula (I-4 ) Was obtained.
MS: 276.1 (molecular ion peak)

式（Ｉ６−１）で表される化合物１．３３部及びクロロホルム６．６３部を仕込み、２３℃程度で３０分間攪拌した。その後、カルボニルジイミダゾール１．５４部を添加し、８０℃まで昇温し、同温度で１時間攪拌することで、式（Ｉ６−２）で表される化合物を含む反応溶液を得た。得られた反応溶液に、式（Ｉ６−３）で表される化合物１．０９部をアセトニトリル３．２７部に溶解した溶液を１時間かけて滴下した。さらに、８０℃程度で１時間攪拌し、反応混合物を濃縮した。得られた濃縮物に、クロロホルム５０部及びイオン交換水１０部を加え、２３℃で３０分間攪拌した。その後、静置・分液して有機層を得た。このような水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた残渣を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）することにより、式（Ｉ−６）で表される化合物０．８８部を得た。
ＭＳ：２６２．１（分子イオンピーク） Example 5 [Synthesis of Compound Represented by Formula (I-6)]

1.33 parts of the compound represented by the formula (I6-1) and 6.63 parts of chloroform were charged and stirred at about 23 ° C. for 30 minutes. Thereafter, 1.54 parts of carbonyldiimidazole was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain a reaction solution containing a compound represented by the formula (I6-2). A solution prepared by dissolving 1.09 parts of the compound represented by the formula (I6-3) in 3.27 parts of acetonitrile was added dropwise to the obtained reaction solution over 1 hour. Furthermore, it stirred at about 80 degreeC for 1 hour, and concentrated the reaction mixture. To the obtained concentrate, 50 parts of chloroform and 10 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and the organic layer was obtained. Such water washing operation was further repeated 5 times. The collected organic layer is concentrated, and the resulting residue is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., developing solvent: ethyl acetate) to obtain the formula (I-6 ) Was obtained.
MS: 262.1 (molecular ion peak)

(Synthesis of resin (A))
The compounds used are shown below.

Example 6 [Synthesis of Resin A1]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( I-19) and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): Monomer (I-19)) was mixed at 24: 10: 6: 20: 30: 10, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.2. × 10 ⁴ of the resin A1 (copolymer) was obtained in 76% yield. This resin A1 has the following structural units.

Example 7 [Synthesis of Resin A2]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( I-1) and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): The monomer (I-1)) was mixed so as to be 24: 10: 6: 20: 30: 10, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.9. × 10 ⁴ of the resin A2 (copolymer) was obtained in 68% yield. This resin A2 has the following structural units.

Example 8 [Synthesis of Resin A3]
As the monomer, the monomer (a1-1-2), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (I-1) are used, and their molar ratio (monomer (a1-1-2) ): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-1)) is mixed so as to be 30: 20: 40: 10, and the total monomer amount is 1.5 mass. Double dioxane was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.6. × 10 ³ of the resin A3 (copolymer) was obtained in 68% yield. This resin A3 has the following structural units.

Synthesis Example 1 [Synthesis of Resin A4]
As the monomer, monomer (a1-1-2), monomer (a2-1-1), monomer (a3-1-1) and monomer (J) are used, and the molar ratio thereof (monomer (a1-1-2): Monomer (a2-1-1): monomer (a3-1-1): monomer (J)) is mixed so as to be 30: 20: 40: 10, and 1.5 mass times dioxane of the total monomer amount is added. In addition, a solution was obtained. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice, and a weight average molecular weight of 8.0. × 10 ³ of the resin A4 (copolymer) was obtained in 61% yield. This resin A4 has the following structural units.

Example 9 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( I-1) and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): Monomer (I-1)) was mixed so as to be 24: 10: 6: 30: 20: 10, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.9. × afford 10 ⁴ resin A5 (copolymer) in 78% yield. This resin A5 has the following structural units.

Example 10 [Synthesis of Resin A6]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( I-2), the molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): The monomer (I-2)) was mixed so as to be 24: 10: 6: 30: 20: 10, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and the weight average molecular weight was 8.1. A × 10 ⁴ resin A6 (copolymer) was obtained in a yield of 80%. This resin A6 has the following structural units.

Example 11 [Synthesis of Resin A7]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( I-4), the molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): The monomer (I-4)) was mixed so as to be 24: 10: 6: 30: 20: 10, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.3. × 10 ⁴ resin A7 (copolymer) was obtained in 82% yield. This resin A7 has the following structural units.

Example 12 [Synthesis of Resin A8]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and monomer ( 1-6), and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3) -2-3): Monomer (I-6)) was mixed at 24: 10: 6: 30: 20: 10, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and the weight average molecular weight was 8.1. × 10 ⁴ resin A8 (copolymer) was obtained in 84% yield. This resin A8 has the following structural units.

Synthesis Example 2 [Synthesis of Resin X1]
Monomer (a4-1-7) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 0.7 mol% and 2.1 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), respectively, as initiators were added with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 1.8. A × 10 ⁴ resin X1 was obtained with a yield of 77%. This resin X1 has the following structural units.

(Preparation of resist composition)
As shown in Table 1, a chemically amplified photoresist composition was prepared by filtering a mixture obtained by mixing and dissolving the following components through a fluororesin filter having a pore size of 0.2 μm.

Ｂ２：トリフェニルスルホニウムトリフレート（和光純薬工業（株）製） <Resin>
A1 to A8: Resin A1 to Resin A8
<Acid generator>
B1: Synthesis according to the example of JP 2010-152341 A

B2: Triphenylsulfonium triflate (manufactured by Wako Pure Chemical Industries, Ltd.)

<Basic compound: Quencher>
C1: 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Solvent>
Propylene glycol monomethyl ether acetate 265 parts 2-heptanone 20.0 parts Propylene glycol monomethyl ether 20.0 parts γ-butyrolactone 3.5 parts

(Manufacture of resist pattern)
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying was 85 nm.
The obtained silicon wafer was pre-baked (PB) for 60 seconds on the direct hot plate at the temperature described in the “PB” column of Table 1. Using the ArF excimer stepper for immersion exposure [XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] on the wafer on which the resist composition film is formed in this manner, the exposure amount is stepwise. The line and space pattern was subjected to immersion exposure. Note that ultrapure water was used as the immersion medium.
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 to obtain a resist pattern.

  In the obtained resist pattern, the exposure amount at which the line width and the space width of the 50 nm line-and-space pattern were 1: 1 was defined as the effective sensitivity.

<Evaluation of mask error factor (MEF)>
The line pattern exposed with a line and space pattern (1: 1) mask with a pitch width of 100 nm (the mask size of the line pattern is 50 nm) is exposed at an exposure amount that the line width of the line pattern is 50 nm, and the mask size of the line pattern is 48 nm and 50 nm. Each pattern was formed using a 52 nm mask. The mask size is plotted on the horizontal axis, and the line width of the line pattern formed using each mask pattern is plotted on the vertical axis. The slope of the straight line
◎ less than 2.5
○ over 2.5 and under 3.0
What exceeded 3.0 was set as x.
These results are shown in Table 2. Numerical values in parentheses indicate MEF values.

  If a resist composition containing a resin obtained by polymerizing the compound of the present invention is used, a resist pattern having an excellent mask error factor (MEF) can be produced, which is useful for fine processing of semiconductors.

Claims (18)

A compound represented by formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
r represents 1 or 2;
A ¹ represents a group represented by the formula (a-g1).

(In the formula (a-g1),
s represents the integer of 0-2.
A ¹⁰ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ¹¹ represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When s is 2, a plurality of A ¹⁰ are the same or different from each other.
X ¹⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group, an oxycarbonyl group or an oxycarbonyloxy group.
However, when A ¹¹ is a single bond, s = 1 and X ¹⁰ is an oxygen atom.
When s is 2, a plurality of X ¹⁰ are the same or different from each other. )
R ² represents an acid labile group. ] The compound according to claim 1, wherein R ^{2 in the} formula (I) is a monocyclic or polycyclic acid-labile group. The compound according to claim 1 or 2, wherein R ² in the formula (I) is a group represented by the formula (IA) or the formula (IB).

[In formula (IA) and formula (IB),
R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m represents an integer of 0 to 14.
n represents an integer of 0 to 10.
l represents an integer of 0 to 3. * Represents a bond with an oxygen atom. ] The compound according to any one of claims 1 to 3, wherein R ^{1 in the} formula (I) is a hydrogen atom.   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. The resin according to claim 6, wherein the monomer having an acid labile group is a monomer represented by formula (a1-1) or 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—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
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. ]   The resin according to any one of claims 5 to 9, further comprising a structural unit derived from an acid-stable monomer having a lactone ring. The resin according to claim 10, wherein the acid-stable monomer having a lactone ring is at least one selected from monomers represented by formula (a3-1), formula (a3-2), and formula (a3-3).

[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 or different from each other. ]   A resist composition comprising the resin according to claim 5 and an acid generator.   The resist composition according to claim 12, further comprising a resin having a structural unit derived from an acid-stable monomer having a fluorine atom. The resist composition according to claim 13, wherein the acid-stable monomer having a fluorine atom is a monomer represented by the formula (a4-1).

[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 ⁴¹ each independently represent 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 the C1-C18 aliphatic hydrocarbon group which may have a substituent. ] The resist composition according to claim 12, wherein the acid generator is a salt 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, and the alkyl group and the above 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. ]   16. The resist composition according to claim 15, wherein Y in the formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.   Furthermore, the resist composition of any one of Claims 12-16 containing a solvent. (1) The process of apply | coating the resist composition in any one of Claims 12-17 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: