JP6163708B2 - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Description

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

  In recent years, as a semiconductor microfabrication technique, an optical lithography technique using short-wavelength light such as an ArF excimer laser (wavelength: 193 nm) as an exposure source has been actively studied. The resist composition used in such a photolithography technique contains a resin whose solubility in an alkaline aqueous solution is changed by the action of an acid and an acid generator.

For example, in Patent Document 1, a structural unit represented by a monomer (a1-1-2), a structural unit represented by a monomer (a2-1-1), and a monomer (a3-1-1) are represented. A resist composition containing a resin represented by the following structural units is described.

JP 2007-161707 A

  In conventional resist compositions, the mask error factor (MEF) of the resulting pattern may not always be satisfactory.

［式（Ｉ）中、
Ｔ^１は、単結合又は炭素数６〜１４の芳香族炭化水素基を表す。
Ｌ^１は、２価の炭素数１〜１７の飽和炭化水素基を表し、該飽和炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
ｍは０又は１を表す。
Ｌ^２及びＬ^３は、それぞれ独立に、単結合又は２価の炭素数１〜６の飽和炭化水素基を表し、該飽和炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
環Ｗ^１及び環Ｗ^２は、互いに独立に、炭素数３〜３６の炭化水素環を表す。
Ｒ^１及びＲ^２は、互いに独立に、水素原子、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^５は、水素原子又はメチル基を表す。
ｔは、０〜２の整数を表す。ｔが２のとき、複数存在するＲ^３は、互いに同一であっても異なっていてもよい。
ｕは、０〜２の整数を表す。ｕが２のとき、複数存在するＲ^４は、互いに同一であっても異なっていてもよい。］
〔２〕前記Ｔ^１が、単結合である前記〔１〕記載の化合物。
〔３〕前記ｍが、０である前記〔１〕又は〔２〕記載の化合物。
〔４〕前記Ｌ^２が、カルボニル基である前記〔１〕〜〔３〕のいずれか記載の化合物。
〔５〕前記Ｌ^３が、単結合又はメチレン基である前記〔１〕〜〔４〕のいずれか記載の化合物。
〔６〕前記Ｌ^３が、メチレン基である前記〔１〕〜〔４〕のいずれか記載の化合物。
〔７〕前記〔１〕〜〔６〕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。
〔８〕酸に不安定な基を有するモノマー（但し、式（Ｉ）で表される化合物ではない）に由来する構造単位を、さらに有する前記〔７〕記載の樹脂。
〔９〕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〔８〕記載の樹脂。

［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−を表す。ここで、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数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。
ｎ２は０〜３の整数を表す。］
〔１０〕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〔７〕〜〔９〕のいずれか記載の樹脂。
〔１１〕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〔１０〕記載の樹脂。

［式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表す。ここで、ｋ２は１〜７の整数を表し、＊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。］
〔１２〕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〔７〕〜〔１１〕のいずれか記載の樹脂。
〔１３〕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〔１２〕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。ここで、ｋ３は１〜７の整数を表し、＊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。ｐ１が２以上のとき、複数存在するＲ^a21は、互いに同一であっても異なっていてもよい。
Ｒ^a22は、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は０〜３の整数を表す。ｑ１が２以上のとき、複数存在するＲ^a22は、互いに同一であっても異なっていてもよい。
Ｒ^a23は、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。
ｒ１は０〜３の整数を表す。ｒ１が２以上のとき、複数存在するＲ^a23は、互いに同一であっても異なっていてもよい。］
〔１４〕前記〔７〕〜〔１３〕のいずれか記載の樹脂、酸発生剤及び溶剤を含むレジスト組成物。
〔１５〕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、さらに含有する前記〔１４〕記載のレジスト組成物。
〔１６〕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〔１５〕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）

（式（ａ４−ｇ１）中、
ｓｓは０〜２の整数を表す。
Ａ^４０及びＡ^４３は、それぞれ独立に、炭素数１〜５の脂肪族炭化水素基を表す。
ｓｓが２のとき、複数存在するＡ^４０は、互いに同一であっても異なっていてもよい。
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、互いに同一であっても異なっていてもよい。）
で表される基を表す。
Ｒ^4２は、フッ素原子を有する炭素数１〜１８の脂肪族炭化水素基を表す。該脂肪族炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。］
〔１７〕酸発生剤が、式（Ｂ１）で表される塩である前記〔１４〕〜〔１６〕のいずれか記載のレジスト組成物。
〔１８〕式（Ｂ１）における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〔１７〕記載のレジスト組成物。
〔１９〕（１）前記〔１４〕〜〔１８〕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] to [19].
[1] A compound represented by the formula (I).

[In the formula (I),
T ¹ represents a single bond or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
m represents 0 or 1;
L ² and L ³ each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and the methylene group constituting the saturated hydrocarbon group is an oxygen atom or a carbonyl group. It may be replaced.
Ring W ¹ and ring W ² each independently represent a hydrocarbon ring having 3 to 36 carbon atoms.
R ¹ and R ² each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ⁵ represents a hydrogen atom or a methyl group.
t represents an integer of 0-2. When t is 2, a plurality of R ³ may be the same as or different from each other.
u represents an integer of 0 to 2. When u is 2, a plurality of R ⁴ may be the same as or different from each other. ]
[2] The compound according to [1], wherein T ¹ is a single bond.
[3] The compound according to [1] or [2], wherein m is 0.
[4] The compound according to any one of [1] to [3], wherein L ² is a carbonyl group.
[5] The compound according to any one of [1] to [4], wherein L ³ is a single bond or a methylene group.
[6] The compound according to any one of [1] to [4], wherein L ³ is a methylene group.
[7] A resin having a structural unit derived from the compound according to any one of [1] to [6].
[8] The resin according to [7], further comprising a structural unit derived from a monomer having an acid labile group (however, not a compound represented by the formula (I)).
[9] The resin according to [8] above, 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—. Here, k1 represents an integer of 1 to 7, and * represents a bond with -CO-.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms 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.
n2 represents an integer of 0 to 3. ]
[10] The resin according to any one of [7] to [9], further including a structural unit derived from an acid-stable monomer having a hydroxyadamantyl group.
[11] The resin according to [10], 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—. Here, k2 represents an integer of 1 to 7, and * 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. ]
[12] The resin according to any one of [7] to [11], further including a structural unit derived from an acid-stable monomer having a lactone ring.
[13] The above [12] description, 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) Resin.

[In Formula (a3-1)-Formula (a3-3),
L ^{a4 to} L ^a6 each independently represent —O— or * —O— (CH ₂ ) _k3 —CO—O—. Here, k3 represents an integer of 1 to 7, and * 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. When p1 is 2 or more, a plurality of R ^a21 may be the same or different from each other.
R ^a22 represents a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of R ^a22 may be the same as or different from each other.
R ^a23 represents a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of R ^a23 may be the same as or different from each other. ]
[14] A resist composition comprising the resin according to any one of [7] to [13], an acid generator, and a solvent.
[15] The resist composition according to [14], further including a resin having a structural unit derived from an acid-stable monomer having a fluorine atom.
[16] The resist composition according to [15], 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 is the formula (a4-g1)

(In the formula (a4-g1),
ss represents an integer of 0-2.
A ⁴⁰ and A ⁴³ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When ss is 2, a plurality of A ⁴⁰ may be the same as 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 may be the same as or different from each other. )
Represents a group represented by
R ⁴² represents a C 1-18 aliphatic hydrocarbon group having a fluorine atom. The methylene group constituting the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]
[17] The resist composition according to any one of [14] to [16], wherein the acid generator is a salt represented by the formula (B1).
[18] The resist composition according to [17], wherein Y in formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent.
[19] (1) A step of applying the resist composition according to any one of [14] to [18] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

  If the resist composition of this invention is used, the resist pattern excellent in mask error factor (MEF) can be manufactured.

［式（Ｉ）中、
Ｔ^１は、単結合又は炭素数６〜１４の芳香族炭化水素基を表す。
Ｌ^１は、２価の炭素数１〜１７の飽和炭化水素基を表し、該飽和炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
ｍは０又は１を表す。
Ｌ^２及びＬ^３は、それぞれ独立に、単結合又は２価の炭素数１〜６の飽和炭化水素基を表し、該飽和炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
環Ｗ^１及び環Ｗ^２は、互いに独立に、炭素数３〜３６の炭化水素環を表す。
Ｒ^１及びＲ^２は、互いに独立に、水素原子、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、ヒドロキシ基又は炭素数１〜６のアルキル基を表す。
Ｒ^５は、水素原子又はメチル基を表す。
ｔは、０〜２の整数を表す。ｔが２のとき、複数存在するＲ^３は、互いに同一であっても異なっていてもよい。
ｕは、０〜２の整数を表す。ｕが２のとき、複数存在するＲ^４は、互いに同一であっても異なっていてもよい。］ <Resin (A)>
The resin of the present invention (hereinafter sometimes referred to as “resin (A)”) has a structural unit derived from a compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”).

[In the formula (I),
T ¹ represents a single bond or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
m represents 0 or 1;
L ² and L ³ each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and the methylene group constituting the saturated hydrocarbon group is an oxygen atom or a carbonyl group. It may be replaced.
Ring W ¹ and ring W ² each independently represent a hydrocarbon ring having 3 to 36 carbon atoms.
R ¹ and R ² each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ⁵ represents a hydrogen atom or a methyl group.
t represents an integer of 0-2. When t is 2, a plurality of R ³ may be the same as or different from each other.
u represents an integer of 0 to 2. When u is 2, a plurality of R ⁴ may be the same as or different from each other. ]

T ¹ represents a single bond or an aromatic hydrocarbon group having 6 to 14 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group. T ¹ is preferably a single bond.

L ¹ represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. Examples of such saturated hydrocarbon groups include linear alkanediyl groups, branched alkanediyl groups, and cyclic saturated hydrocarbon groups.
Examples of the linear alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and hexane-1,6-diyl. Group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1 , 12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group Is mentioned.
Examples of the branched alkanediyl group include an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group) to the linear alkanediyl group. , Tert-butyl group and the like).
Examples of the divalent cyclic saturated hydrocarbon group include a cycloalkanediyl group (for example, cyclohexanediyl group) and a divalent bridged cyclic hydrocarbon group (for example, adamantanediyl group).
L ¹ may be a combination of two or more of these groups.

［式（Ｌ１−Ａ）中、Ｌ^１１は炭素数１〜１６の飽和炭化水素基を表す。＊は結合手を表し、左側の結合手は酸素原子と、右側の結合手は環Ｗ^１と、それぞれ結合する。］ The methylene group constituting the saturated hydrocarbon group for L ¹ may be replaced with an oxygen atom or a carbonyl group. L ¹ is preferably represented by the formula (L1-A).

[In the formula (L1-A), L ¹¹ represents a saturated hydrocarbon group having 1 to 16 carbon atoms. * Represents a bond, the bond on the left is bonded to an oxygen atom, and the bond on the right is bonded to ring W ¹ . ]

L ¹¹ is preferably —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₈ — or — (CH ₂ ) ₁₂ —.

L ² and L ³ each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. Examples of the saturated hydrocarbon group include a linear alkanediyl group or a branched alkanediyl group.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 A linear alkanediyl group such as, 6-diyl group; and an alkyl group (preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, having 1 to 4 carbon atoms such as a tert-butyl group), for example, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2 -Branched alkanediyl groups such as methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group;

Examples of the group in which the methylene group in the divalent saturated hydrocarbon group having 1 to 6 carbon atoms represented by L ² and L ³ is replaced by an oxygen atom or a carbonyl group include a carbonyl group (—CO—), —CO _-O-CH 2 -CO- and the like.
L ² is preferably a single bond, a methylene group or a carbonyl group, more preferably a single bond or a carbonyl group, and even more preferably a carbonyl group.
L ³ is preferably a single bond, a methylene group or a carbonyl group, more preferably a single bond or a methylene group, and even more preferably a methylene group.

The hydrocarbon ring having 3 to 36 carbon atoms represented by the ring W ¹ and the ring W ² refers to a ring composed of only carbon atoms and hydrogen atoms. Examples of the hydrocarbon ring include aromatic rings and saturated hydrocarbon rings such as a cyclohexane ring and an adamantane ring, and an adamantane ring is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, A pentyl group, a hexyl group, etc. are mentioned.

R ¹ and R ² are preferably a hydrogen atom, a hydroxy group, a methyl group or an ethyl group, more preferably a hydrogen atom, a hydroxy group or a methyl group, and even more preferably a hydrogen atom.
R ³ and R ⁴ are preferably a hydroxy group, a methyl group or an ethyl group, and more preferably a hydroxy group or a methyl group.

［式（Ｉ−Ａ）中、Ｒ^３、環Ｗ^１及びｔは、それぞれ上記と同じ意味を表す。＊は結合手を表す。］
で表される基としては、例えば、下記の基等が挙げられる。 In the formula (I), the following formula (IA)

[In formula (IA), R ³ , ring W ¹ and t each have the same meaning as described above. * Represents a bond. ]
Examples of the group represented by the following include the following groups.

In the formula (I), examples of the ring W ² include the following groups.

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

In the compound (I) represented by the formula (I-1) to the formula (I-58) shown here, the partial structure M shown below is replaced with the partial structure A shown below. Specific examples can be given.

（式中、環Ｗ^１、環Ｗ^２、Ｌ^３、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、ｔ及びｕは、それぞれ前記と同義である。） Next, the manufacturing method of compound (I) is demonstrated. For example, a method for producing a compound represented by the formula (IA) in which T ¹ is a single bond, m is 0, and L ² is a carbonyl group in the formula (I) is shown below.

(In the formula, ring W ¹ , ring W ² , L ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , t, and u are as defined above.)

［上式中、環Ｗ^１、環Ｗ^２、Ｌ^３、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、ｔ及びｕは、それぞれ前記と同義である。Ｘ^１は、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］
式（ＩＡ−ａ）で表される化合物としては、以下で表される化合物などが挙げられる。

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

By reacting the compound represented by the formula (IA-a) and the compound represented by the formula (IA-b) in a solvent in the presence of a base catalyst, the compound is represented by the formula (IA-c). A compound can be obtained. Examples of the solvent include N, N-dimethylformamide. Examples of the base catalyst include triethylamine.

[In the above formula, ring W ¹ , ring W ² , L ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , t and u are as defined above. X ¹ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]
Examples of the compound represented by the formula (IA-a) include compounds represented by the following.

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

［上式中、Ｒ^１’は、Ｒ^１で表されるアルキル基から水素原子を１つ除いたアルキリデン基を表す。
環Ｗ^１、環Ｗ^２、Ｒ^２、Ｒ^３、Ｌ^３及びｔは、それぞれ前記と同義である。］
式（ＩＡ−ｂ´）で表される化合物としては、以下で表される化合物等が挙げられる。

In addition, the compound represented by the formula (IA-c) is obtained by combining the compound represented by the formula (IA-a) and the compound represented by the formula (IA-b ′) in a solvent in the presence of an acid catalyst. It can also be obtained by reacting. Examples of the solvent include chloroform. Examples of the acid catalyst include camphorsulfonic acid.

[In the above formula, R ^{1 ′} represents an alkylidene group obtained by removing one hydrogen atom from the alkyl group represented by R ¹ .
Ring W ¹ , Ring W ² , R ² , R ³ , L ³ and t are as defined above. ]
Examples of the compound represented by the formula (IA-b ′) include compounds represented by the following.

式（ＩＡ−ａ１）で表される化合物としては、以下で表される化合物等が挙げられる。

It replaces with the compound represented by a formula (IA-a), and after performing the said reaction using the compound represented by a formula (IA-a1), it represents with a formula (IA-c) by reducing. Compounds can also be obtained.

Examples of the compound represented by the formula (IA-a1) include compounds represented by the following.

［上式中、環Ｗ^１、環Ｗ^２、Ｌ^３、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、ｔ及びｕは、それぞれ前記と同義である。Ｘ^１は、ハロゲン原子又は（メタ）アクリロイルオキシ基を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］
式（ＩＡ−ｄ）で表される化合物としては、（メタ）アクリル酸クロライド、（メタ）アクリル酸無水物等が挙げられる。
なお、本明細書において、「（メタ）アクリロイル」「（メタ）アクリル」並びに「（メタ）アクリレート」なる記載は、それぞれ「アクリロイル及びメタクリロイルの総称」「アクリル及びメタクリルの総称」並びに「アクリレート及びメタクリレートの総称」をそれぞれ意味する。 The compound represented by the formula (IA) is obtained by reacting the compound represented by the formula (IA-c) with the compound represented by the formula (IA-d) in a solvent in the presence of a catalyst. be able to. Here, as a catalyst, N-methylpyrrolidine is preferable. As the solvent, methyl isobutyl ketone and N, N-dimethylformamide are preferable.

[In the above formula, ring W ¹ , ring W ² , L ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , t and u are as defined above. X ¹ represents a halogen atom or a (meth) acryloyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]
Examples of the compound represented by the formula (IA-d) include (meth) acrylic acid chloride and (meth) acrylic anhydride.
In this specification, the descriptions “(meth) acryloyl”, “(meth) acryl” and “(meth) acrylate” are “generic name for acryloyl and methacryloyl”, “generic name for acryl and methacryl”, and “acrylate and methacrylate”, respectively. "Generic name".

  In the resin (A), the content ratio of the structural unit derived from the compound represented by the formula (I) with respect to all the structural units (100 mol%) of the resin (A) is preferably in the range of 1 to 50 mol%. The range of -40 mol% is more preferable, and the range of 5-30 mol% is more preferable.

Resin (A) is derived from a monomer having an acid labile group (but not a compound represented by formula (I)) in addition to the structural unit derived from the compound represented by formula (I) It is preferable to contain the structural unit which does.
As such a monomer having an acid labile group (hereinafter sometimes referred to as “monomer having an acid labile group (a1)”), one type may be used alone, or two or more types may be used in combination. May be.

［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する。前記の各炭化水素基を構成するメチレン基は、酸素原子又は硫黄原子に置き換わっていてもよい。＊は結合手を表す。］ <Monomer (a1) having an acid labile group>
“Acid labile group” means a group having a leaving group that can be converted into a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group upon contact with an acid. . Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

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. The methylene group constituting each hydrocarbon group may be replaced with an oxygen atom or a sulfur atom. * Represents a bond. ]

^Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and dimethylcyclohexane. Examples thereof include cycloalkyl groups such as hexyl group, cycloheptyl group, and cyclooctyl group. Examples of the polycyclic saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups (in the formula, * represents a bond). It is done. In the formula (1), the alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms.

When R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group, examples of the * -C (R ^a1 ) (R ^a2 ) (R ^a3 ) group include the following groups (in the formula, * Represents a bond.). The divalent hydrocarbon group preferably has 3 to 12 carbon atoms.

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

Examples of the hydrocarbon group for R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above for R ^{a1 to} R ^a3 .
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 of R ^{a1 ′ to} R ^{a3 ′} include a group in which one hydrogen atom has been removed from the hydrocarbon group.

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) is preferably a monomer having an acid labile group and a carbon-carbon double bond, more preferably a (meth) acrylic monomer having an acid labile group.

  Of the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferred. If a resin obtained by polymerizing the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used, the resolution of the resist pattern can be improved.

［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−を表す。ここで、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数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。
ｎ２は０〜３の整数を表す。］ As the (meth) acrylic monomer having an acid labile group and an alicyclic hydrocarbon group, a monomer represented by the formula (a1-1) or a monomer represented by the formula (a1-2) is preferably used. Can be mentioned. 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.

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * represents a bond with -CO-.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms 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.
n2 represents an integer of 0 to 3. ]

脂環式炭化水素基は、好ましくは炭素数８以下、より好ましくは６以下である。
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。 L ^a1 and L ^a2 are preferably —O— or * —O— (CH ₂ ) _k1 —CO—O—, and 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 for R ^a6 and R ^a7 may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, Examples thereof include cycloalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, and cyclooctyl group. Examples of the polycyclic saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups.

The alicyclic hydrocarbon group preferably has 8 or less carbon atoms, more preferably 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.

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 (a1-1) include 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, and 2-isopropyladamantan-2-yl (meth) acrylate. Preferred examples include 2-methyladamantan-2-yl methacrylate, 2-ethyladamantan-2-yl methacrylate, and 2-isopropyladamantan-2-yl methacrylate.

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-methylcyclopentan-1-yl (meth) acrylate, and 1-isopropylcyclopentan-1-yl (meth) acrylate. Monomers represented by the following formulas (a1-2-1) to (a1-2-10) are preferred, and monomers represented by the following formulas (a1-2-3) to (a1-2-4) are more preferred. A monomer represented by the following formula (a1-2-3) is more preferable.

  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 with respect to all the structural units of the resin (A). It is -95 mol%, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

  Further, the content of the structural unit derived from the monomer having an adamantyl group (particularly the monomer (a1-1) having an acid labile group) is preferably relative to the monomer (a1) having an acid labile group. 15 mol% or more. When the ratio of the monomer having an adamantyl group is increased, the dry etching resistance of the resist is improved.

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］_k1−ＣＯ−Ｌ^４−基を表す。ここで、ｋ１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 ] _k1 —CO—L ⁴ — group. Here, k1 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.

<Monomer not having acid labile group>
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.
The resin (A) is more preferably a copolymer of a monomer (a1) having an acid labile group and an 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. Derived from an acid stable monomer having a hydroxy group (hereinafter referred to as “acid stable monomer having a hydroxy group (a2)”) or an acid stable monomer having a lactone ring (hereinafter referred to as “acid stable monomer having a lactone ring (a3)”) If a resin having a structural unit to be used is used, the resolution of the resist 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), electron beam or EUV or other high energy beam exposure, the acid-stable monomer (a2) having a hydroxy group is preferably a phenolic hydroxy group which is a hydroxystyrene. An acid stable monomer (a2-0) having When using 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). use. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

［式（ａ２−０）中、
Ｒ^a30は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は同一であっても異なってもよい。］ 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).

[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 may be the same or different. ]

Examples of the halogen atom for R ^a30 and R ^a31 include fluorine, chlorine, bromine and iodine atoms.
^Examples of the alkyl group for 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. Preferably, it is a C1-C4 alkyl group, More preferably, it is a C1-C2 alkyl group, Most preferably, it is a methyl group.
Examples of the alkoxy group for R ^a31 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 an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 or 2 carbon atoms, and particularly preferably a methoxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
ma is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

When obtaining a copolymer resin having a structural unit derived from a monomer having such a phenolic hydroxy group, acetyloxystyrenes corresponding to those obtained by replacing the phenolic hydroxy group with an acetyloxy group and a monomer to be copolymerized are used. After radical polymerization, 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%.

［式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表す。ここで、ｋ２は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］ Examples of the acid stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1).

[In the formula (a2-1),
L ^a3 represents —O— or * —O— (CH ₂ ) _k2 —CO—O—. Here, k2 represents an integer of 1 to 7, and * 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) includes a structural unit derived from the monomer represented by the formula (a2-1), the content thereof 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 3-20 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.

［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。ここで、ｋ３は１〜７の整数を表し、＊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。ｐ１が２以上のとき、複数存在するＲ^a21は、互いに同一であっても異なっていてもよい。
Ｒ^a22は、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は０〜３の整数を表す。ｑ１が２以上のとき、複数存在するＲ^a22は、互いに同一であっても異なっていてもよい。
Ｒ^a23は、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。
ｒ１は０〜３の整数を表す。ｒ１が２以上のとき、複数存在するＲ^a23は、互いに同一であっても異なっていてもよい。］ 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.

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

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are preferably each independently —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 thereof 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%.

［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）

（式（ａ４−ｇ１）中、
ｓｓは０〜２の整数を表す。
Ａ^４０及びＡ^４３は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の脂肪族炭化水素基を表す。
ｓｓが２のとき、複数存在するＡ^４０は、互いに同一であっても異なっていてもよい。
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、互いに同一であっても異なっていてもよい。）
で表される基を表す。
Ｒ^4２は、フッ素原子を有する炭素数１〜１８の脂肪族炭化水素基を表す。該脂肪族炭化水素基を構成しているメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。］ <Other monomer (a4)>
Resin (A) may have a structural unit derived from other known monomers (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 is the formula (a4-g1)

(In the formula (a4-g1),
ss represents an integer of 0-2.
A ⁴⁰ and A ⁴³ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
When ss is 2, a plurality of A ⁴⁰ may be the same as 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 may be the same as or different from each other. )
Represents a group represented by
R ⁴² represents a C 1-18 aliphatic hydrocarbon group having a fluorine atom. The methylene group constituting the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The aliphatic hydrocarbon group for A ⁴⁰ and A ⁴³ is typically an alkanediyl group having 1 to 5 carbon atoms. The alkanediyl group may be linear or branched, and specific examples thereof include methylene group, ethylene group, propanediyl group, propanediyl group, butanediyl group and pentanediyl group. It is done. And the hydrogen atom which comprises this alkanediyl group may be substituted by the substituent. Examples of the substituent include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
X ⁴⁰ is a divalent group containing an atom or an atomic group of an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl 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).

A ⁴¹ is preferably an aliphatic hydrocarbon group, more preferably an aliphatic hydrocarbon group having no substituent, further preferably an alkanediyl group having 1 to 4 carbon atoms, and particularly preferably an ethylene group.

The aliphatic hydrocarbon group having a fluorine atom of R ⁴² includes either a chain or a cyclic group, and a combination of these chain and cyclic aliphatic hydrocarbon groups having a fluorine atom. To do. Moreover, although you may have a carbon-carbon unsaturated bond, the aliphatic hydrocarbon group which has a saturated fluorine atom is preferable.
Examples of the aliphatic hydrocarbon group having a chain fluorine atom include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl. Group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group and Examples include 1,1,1,2,2,3,3,4,4-nonafluoropentyl group.
The alicyclic hydrocarbon group having a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group having a fluorine atom such as a perfluorocyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include a perfluoroadamantyl group.

[式（ａ４−ｇ２）中、
Ａ^１３は、フッ素原子を有していてもよい２価の炭素数１〜１５の脂肪族炭化水素基を表す。
Ｘ^１２ａは、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^１４ａは、フッ素原子を有していてもよい１価の炭素数１〜１５の脂肪族炭化水素基を表す。
ただし、Ａ^１３及びＡ^１４ａの炭素数の合計は１６以下であり、それらのいずれかはフッ素原子を有している。] Examples of the group in which the methylene group constituting the aliphatic hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by the following formula (a4-g2).

[In the formula (a4-g2),
A ¹³ represents a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a fluorine atom.
X ^12a represents a carbonyloxy group or an oxycarbonyl group.
A ^14a represents a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a fluorine atom.
However, the total number of carbon atoms of A ¹³ and A ^14a is 16 or less, they either have a fluorine atom. ]

A ¹³ includes any one of a chain and a ring, and a combination of these chain and cyclic divalent aliphatic hydrocarbon groups which may have a fluorine atom. Moreover, although it may have a carbon-carbon unsaturated bond, the bivalent aliphatic hydrocarbon group which may have a saturated fluorine atom is preferable. Examples of the divalent aliphatic hydrocarbon group which may have a chain fluorine atom include methylene group, difluoromethylene group, ethylene group, perfluoroethylene group, propanediyl group, perfluoropropanediyl group, butanediyl group, perfluoro Examples include butanediyl group, pentanediyl group, and perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent alicyclic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

A ^14a includes any of a chain type and a cyclic type and a combination of these aliphatic hydrocarbon groups which may have a linear or cyclic fluorine atom. Moreover, although it may have a carbon-carbon unsaturated bond, the aliphatic hydrocarbon group which may have a saturated fluorine atom is preferable.
Examples of the aliphatic hydrocarbon group which may have a chain fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1 , 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group and pentyl group, hexyl group, perfluorohexyl group, A heptyl group, a perfluoro heptyl group, an octyl group, a perfluorooctyl group, etc. are mentioned.
The alicyclic hydrocarbon group which may have a fluorine atom may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclohexyl group and a perfluorocyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group, a norbornyl group, a perfluoroadamantyl group, and the like.
In the formula (a4-g2), A ¹³ and A ^14a preferably have a total carbon number of 15 or less. The number of carbon atoms of A ¹³ are members is preferably in the range of 1 to 6, more preferably in the range 2-3. The carbon number of A ^14a is preferably in the range of 5 to 12, and more preferably in the range of 6 to 10.
Among them, A ^14a is preferably an alicyclic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a cyclohexyl group, a norbornyl group, and an adamantyl group.

As group represented by a formula (a4-g2), the following groups are preferable, for example.

As a compound represented by a formula (a4-1), the compound represented by the following formula | equation (a4-1-1)-a formula (a4-1-22) is mentioned, for example.

  Among them, formula (a4-1-3), formula (a4-1-4), formula (a4-1-7), formula (a4-1-8), formula (a4-1-11), formula ( a4-1-12), formula (a4-1-15), formula (a4-1-16), formula (a4-1-19), formula (a4-1-20), formula (a4-1-21) ) And the compound represented by formula (a4-1-22) are preferable.

  The resin (A) is preferably a monomer (a1) having at least a structural unit derived from the compound represented by the formula (I) and an acid-labile group different from the compound represented by the formula (I) , A copolymer obtained by polymerizing an acid-stable monomer (a2) having a hydroxy group and / or an acid-stable monomer (a3) having a lactone ring. In the copolymer, the monomer (a1) having an acid labile group is more preferably at least one of a monomer (a1-1) having an adamantyl group and a monomer (a1-2) having a cyclohexyl group. (More preferably, the monomer (a1-1) having an adamantyl group), and the acid-stable monomer (a2) having a hydroxy group 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.

The preferred structural ratio (molar ratio) of the structural unit of the resin (A) is a structural unit derived from the compound represented by the formula (I): an acid-labile group different from the compound represented by the formula (I) Monomer (a1) having: acid-stable monomer (a2) having a hydroxy group and / or acid-stable monomer (a3) having a lactone ring: other monomers (a4) = (1-50): (20-60): (30-70) :( 1-20) (more preferably (3-40) :( 25-55) :( 35-65) :( 2-15), more preferably (5-30): (25-50) :( 35-65) :( 3-10)).
A more preferred structural ratio (molar ratio) of the structural unit of the resin (A) is a structural unit derived from the compound represented by the formula (I): unstable to an acid different from the compound represented by the formula (I) Group-containing monomer (a1): acid-stable monomer (a2) having a hydroxy group and / or acid-stable monomer having a lactone ring (a3) = (1-50): (20-60): (30-70) ( More preferably, it is (3-40) :( 25-55) :( 35-65), Most preferably, it is (5-30) :( 25-50) :( 35-65)).
A more preferable structural ratio (molar ratio) of the structural unit of the resin (A) is a structural unit derived from the compound represented by the formula (I): which is unstable to an acid different from the compound represented by the formula (I). Monomer having group (a1): acid-stable monomer having hydroxy group (a2): acid-stable monomer having lactone ring (a3) = (1-50) :( 20-60) :( 3-35) :( 25 ~ 65) (more preferably (3-40) :( 25-55) :( 4-30) :( 30-65), particularly preferably (5-30) :( 25-50) :( 5 -25): (35-60)).

More preferable specific examples of the resin (A) include the following resins (A-1) to (A-72).

Resin (A) can be manufactured by a well-known polymerization method (for example, radical polymerization method).
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).
The content of the resin (A) is preferably 80% by mass or more in the solid content of the composition. The content of the resin (A) is preferably 99% by mass or less in the solid content of the composition.
In addition, "solid content in a composition" means the sum total of the resist composition component except the solvent (E) mentioned 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.

<Resist composition>
The resist composition of the present invention comprises the above-described resin (A), acid generator (hereinafter sometimes referred to as “acid generator (B)”) and solvent (hereinafter also referred to as “solvent (E)”). Including.
The resist composition of the present invention preferably further contains a resin having a structural unit derived from an acid stable monomer having a fluorine atom (hereinafter sometimes referred to as “resin (D)”). The resin (D) is different from the resin (A). The resist composition of the present invention more preferably further contains a basic compound (hereinafter sometimes referred to as “basic compound (C)”).

<Acid generator (B)>
The acid generator (B) is classified into a nonionic type and an ionic type. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonate), sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

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

［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、該飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該アルキル基及び該脂環式炭化水素基を構成するメチレン基は、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。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a sulfonate 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 constituting the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The methylene group constituting 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 (preferably 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, or a tert-butyl group) on the linear alkylene side Having a chain, for example, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl A branched alkanediyl group such as a 2-methylbutane-1,4-diyl group;
A simple cycloalkanediyl group such as cyclobutane-1,3-diyl group, 1,3-cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. A cyclic divalent alicyclic hydrocarbon group;
Polycyclic divalent alicyclic rings such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, 1,5-adamantane-1,5-diyl group, adamantane-2,6-diyl group Formula hydrocarbon group; and the like.

Examples of the group in which the methylene group constituting the saturated hydrocarbon group of L ^b1 is replaced with an oxygen atom or a carbonyl group include formula (b1-1) to formula (b1-6). L ^b1 is preferably any one of formulas (b1-1) to (b1-4), more preferably formula (b1-1) or formula (b1-2). Incidentally, the formula (b1-1) ~ formula (b1-6) has its left and right are described in accordance with the formula (B1), the left ^{C (Q 1) (Q 2} ) - of the attached to a carbon atom Bond to -Y on the right. 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.

Examples of the alkyl group for Y include a methyl group, an ethyl group, a 1-methylethyl group (isopropyl group), a 1,1-dimethylethyl group (tert-butyl group), a 2,2-dimethylethyl group, a propyl group, 1-methylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-propylbutyl group, pentyl group, 1-methyl Pentyl group, hexyl group, 1,4-dimethylhexyl group, heptyl group, 1-methylheptyl group, octyl group, methyloctyl group, methylnonyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Or a linear or branched alkyl group. Especially, a C1-C6 alkyl group is preferable.
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 constituting the alkyl group and the alicyclic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group include, for example, the methylene group constituting the alkyl group described above is replaced with an oxygen atom or a carbonyl group. And 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 for the alkyl group and alicyclic hydrocarbon group in Y include, for example, 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 3 carbon atoms. 16 alicyclic hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 21 carbon atoms, acyl groups having 2 to 4 carbon atoms, 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 6 to 6 carbon atoms). Represents an aromatic hydrocarbon group of 18. j2 represents an integer of 0 to 4). 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 fluorine, chlorine, bromine and iodine atoms.
Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, 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 alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and more preferably an adamantyl group. A group, a hydroxyadamantyl group or an oxoadamantyl group.

Preferred examples of the anion in the salt represented by the formula (B1) include anions represented by the formulas (b1-1-1) to (b1-1-9). In the following formulas, the definitions of the symbols have the same meaning as described above, and 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 anion in the salt represented by the formula (B1) include 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 cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, and preferably organic sulfonium cation. Or it is an organic iodonium cation, More preferably, it is an aryl sulfonium cation.

Z ⁺ in formula (B1) is preferably represented by any 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 that may have a hetero atom. 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 the alicyclic hydrocarbon group has a halogen atom or a carbon number. The aromatic hydrocarbon group may be substituted with an acyl group of 2 to 4 or a glycidyloxy group, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alicyclic group having 3 to 18 carbon atoms. It may be substituted with a hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. R ^b4 and R ^b5 may be combined to form a ring that may have a hetero atom.

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 represents an integer of 0 to 5, and when m2 is 2 or more, a plurality of R ^b7 may be the same or different. When n2 is 2 or more, a plurality of R ^b8 are the same. But it may be different.

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.
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 aromatic hydrocarbon group is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 1 to 12 carbon atoms. May be substituted.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with —CH—CO— to which they are bonded. . The methylene group contained in the ring 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 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more, the plurality of R ^b15 is When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 may be the same or different, and t2 is 2 or more. Sometimes, the plurality of R ^b18 may be the same or different.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ｐ−アダマンチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、ビフェニル基、フェナントリル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル等のアリール基等が挙げられる。 Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. .
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and dimethylcyclohexane. Examples thereof include a cycloalkyl group such as a hexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups. * Represents a bond with an adamantane ring or a cyclohexane ring. Preferably, they are a cyclopentyl group and a cyclohexyl group.

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 alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the 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.

The alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl. A group, hexyl group, octyl group and 2-ethylhexyl group are more preferred.
The alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cyclodecyl group, a 2-alkyl-2-adamantyl group, a 1- (1-adamantyl) -1-alkyl group, and an isobornyl group are more preferable.
The aromatic hydrocarbon group for R ^b12 includes a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a 4-methoxyphenyl group, a biphenylyl group, and A naphthyl group is preferred.
A group in which an aromatic hydrocarbon group of R ^b12 and an alkyl group are bonded is typically an aralkyl group.

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

Among cation (b2-1) to cation (b2-4), cation (b2-1) and cation (b2-2) are preferable, and cation (b2-1) is more preferable. Is a cation (b2-1) in which any of R ^{b4 to} R ^b6 is an aromatic hydrocarbon group, and particularly preferably a cation represented by the formula (b2-1-1). Among them, triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cation (in formula (b2-1-1), v2 = w2 = 0, x2 = 1 and R ^b21 is a methyl group) or a tolylsulfonium cation (in the formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all Methyl group) is preferred.

式（ｂ２−１−１）中、
Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１８のアルキル基、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つが一緒になってヘテロ原子を有してもよい環を形成してもよい。
ｖ２、ｗ２及びｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。
ｖ２が２以上のとき、複数のＲ^b19は同一又は相異なり、ｗ２が２以上のとき、複数のＲ^b20は同一又は相異なり、ｘ２が２以上のとき、複数のＲ^b21は同一又は相異なる。

In formula (b2-1-1),
R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or carbon. The number 1-12 alkoxy group is represented. ^{Two members} selected from R ^b19 to R ^b21 may be combined to form a ring which may have a hetero atom.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, the plurality of R ^b19 are the same or different, when w2 is 2 or more, the plurality of R ^b20 are the same or different, and when x2 is 2 or more, the plurality of R ^b21 are the same or different. .

The alkyl group of R ^{b19 to} R ^b21 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms.
Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is.

  Specific examples of the cation represented by 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 (C)>
The basic compound (C) contained in the resist composition of the present invention acts as a quencher. The basic compound (C) is a compound capable of capturing an acid, particularly an acid generated from an acid generator upon exposure.
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably a compound represented by the formula (C1) to a compound represented by the formula (C8), more preferably a compound represented by the formula (C1-1). It is done.

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

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

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

[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, a plurality of R ^{c4 s} may be the same as 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、互いに同一でも異なってもよい。］
アルカノイル基としては、アセチル基、２−メチルアセチル基、２，２−ジメチルアセチル基、プロピオニル基、ブチリル基、イソブチリル基、ペンタノイル基、２，２−ジメチルプロピオニル基等が挙げられる。

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

［式（Ｃ５）及び式（Ｃ６）中、Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に０〜３の整数を表し、ｏ３が２以上であるとき、複数のＲ^c1４は同一又は相異なり、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のアルキレン基、−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 a C 1-6 alkylene group, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

［式（Ｃ７）及び式（Ｃ８）中、Ｒ^c18、Ｒ^c19及びＲ^c20は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｑ３、ｒ３及びｓ３は、それぞれ独立に０〜３の整数を表し、ｑ３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のアルキレン基、−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 alkylene group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In the formulas (C1) to (C8), examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, and the alkanediyl group are the same as those described above.
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 still more preferably based on the solid content of the resist composition. It is about 0.01-1 mass%.

<Resin (D)>
The resin (D) is a resin having a structural unit derived from an acid stable monomer having a fluorine atom. As this resin, what homopolymerized or copolymerized the acid stable monomer chosen from the group which consists of said Formula (a4-1) is preferable. As described above, the resin (D) is different from the resin (A).

  The resin (D) can be produced by selecting a monomer to be homopolymerized or copolymerized and then subjecting the monomer to a known polymerization method (for example, radical polymerization method).

  The weight average molecular weight of the resin (D) is preferably from 8,000 to 80,000, more preferably from 10,000 to 60,000.

  The content of the resin (D) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and still more preferably 0.5, based on the solid content of the resist composition. ˜3 mass%.

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

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and pyruvic acid. An ester such as ethyl; a ketone such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; a cyclic ester such as γ-butyrolactone; A solvent (E) 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, for example, sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes and the like can be used.

<Method for preparing resist composition>
The resist composition of the present invention comprises a resin (A), an acid generator (B), a solvent (E), and optionally a basic compound (C), a resin (D), and other components (F). Can be prepared. 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 etc. of resin, the solubility with respect to solvent (E), 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) A step of applying the resist composition of the present invention on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

  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 the solvent using a heating device such as a hot plate (so-called pre-baking) or by using a decompression device to form a composition layer from which the solvent has been removed. 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.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do.

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) exposure, or a resist composition for EUV exposure, particularly a liquid. It is suitable as a resist composition for immersion exposure and useful for fine processing of semiconductors.

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.
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)

  The structure of the compound was confirmed by measuring the molecular peak using mass spectrometry (LC is model 1100 manufactured by Agilent, and MASS is LC / MSD manufactured by Agilent). In the following examples, the value of this molecular peak is indicated by “MASS”.

式（Ｉ１−ａ）で表される化合物５．００部及びＮ，Ｎ−ジメチルホルムアミド２５部を仕込み、２３℃で３０分間攪拌した後、トリエチルアミン３．８７部を滴下し、さらに、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ１−ｂ）で表される化合物６．５７部をＮ，Ｎ−ジメチルホルムアミド６．５７部に溶解した溶液を３０分かけて滴下し、さらに、２３℃で２時間攪拌した。得られた反応混合物に、イオン交換水２３．５０部及び酢酸エチル１４０．９９部を加え、２３℃で３０分間攪拌した後、分液し、有機層を回収した。回収された有機層に、イオン交換水７０．５０部を仕込み２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに６回行った。得られた有機層を濃縮し、得られた濃縮物に、ｎ−ヘプタン９２．２０部を添加して攪拌した後、ろ過することにより、式（Ｉ１−ｃ）で表される化合物２．８５部を得た。 Example 1: Synthesis of compound represented by formula (I-1)

5.00 parts of the compound represented by the formula (I1-a) and 25 parts of N, N-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. Then, 3.87 parts of triethylamine was added dropwise, and further at 23 ° C. Stir for 30 minutes. A solution obtained by dissolving 6.57 parts of the compound represented by the formula (I1-b) in 6.57 parts of N, N-dimethylformamide was added dropwise to the obtained mixture over 30 minutes. Stir for hours. To the resulting reaction mixture, 23.50 parts of ion-exchanged water and 140.99 parts of ethyl acetate were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. The recovered organic layer was charged with 70.50 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. This washing operation was further repeated 6 times. The obtained organic layer was concentrated, and 92.20 parts of n-heptane was added to the obtained concentrate and stirred, followed by filtration to obtain a compound 2.85 represented by the formula (I1-c). Got a part.

式（Ｉ１−ｃ）で表される化合物２．３０部、Ｎ−メチルピロリジン１．８３部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｉ１−ｄ）で表される化合物１．２８部を添加し、６０℃で２４時間攪拌した。その後、反応混合物にイオン交換水１０部、メチルイソブチルケトン２０部を添加、攪拌後、分液水洗を行った。この水洗の操作を３回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ−１）で表される化合物１．７２部を得た。
ＭＳ：４４２．３

2.30 parts of the compound represented by the formula (I1-c), 1.83 parts of N-methylpyrrolidine, and 20 parts of methyl isobutyl ketone were charged, and the compound 1.28 represented by the formula (I1-d) was stirred. Part was added and stirred at 60 ° C. for 24 hours. Thereafter, 10 parts of ion-exchanged water and 20 parts of methyl isobutyl ketone were added to the reaction mixture, followed by stirring and liquid separation washing. This washing operation was performed three times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.72 parts of a compound represented by the formula (I-1).
MS: 442.3

式（Ｉ１３−ａ）で表される化合物５．００部及びＮ，Ｎ−ジメチルホルムアミド２５部を仕込み、２３℃で３０分間攪拌した後、トリエチルアミン３．８７部を滴下し、さらに、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ１３−ｂ）で表される化合物６．５７部をＮ，Ｎ−ジメチルホルムアミド６．５７部に溶解した溶液を３０分かけて滴下し、さらに、２３℃で２時間攪拌した。得られた反応混合物に、イオン交換水２３．５０部及び酢酸エチル１４０．９９部を加え、２３℃で３０分間攪拌した後、分液し、有機層を回収した。回収された有機層に、イオン交換水７０．５０部を仕込み２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに６回行った。得られた有機層を濃縮し、得られた濃縮物に、ｎ−ヘプタン９０部を添加して攪拌した後、ろ過することにより、式（Ｉ１３−ｃ）で表される化合物３．１２部を得た。 Example 2: Synthesis of compound represented by formula (I-13)

5.00 parts of the compound represented by the formula (I13-a) and 25 parts of N, N-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. Then, 3.87 parts of triethylamine was added dropwise, and further at 23 ° C. Stir for 30 minutes. A solution obtained by dissolving 6.57 parts of the compound represented by the formula (I13-b) in 6.57 parts of N, N-dimethylformamide was added dropwise to the obtained mixture over 30 minutes. Stir for hours. To the resulting reaction mixture, 23.50 parts of ion-exchanged water and 140.99 parts of ethyl acetate were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. The recovered organic layer was charged with 70.50 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. This washing operation was further repeated 6 times. The obtained organic layer was concentrated, and 90 parts of n-heptane was added to the obtained concentrate and stirred, followed by filtration to obtain 3.12 parts of the compound represented by the formula (I13-c). Obtained.

式（Ｉ１３−ｃ）で表される化合物２．３０部、Ｎ−メチルピロリジン１．８３部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｉ１３−ｄ）で表される化合物１．２８部を添加し、６０℃で２４時間攪拌した。その後、反応混合物にイオン交換水１０部、メチルイソブチルケトン２０部を添加、攪拌後、分液水洗を行った。この水洗の操作を３回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ−１３）で表される化合物１．９８部を得た。
ＭＳ：４４２．３

2.30 parts of the compound represented by the formula (I13-c), 1.83 parts of N-methylpyrrolidine, and 20 parts of methyl isobutyl ketone were charged, and the compound 1.28 represented by the formula (I13-d) was stirred. Part was added and stirred at 60 ° C. for 24 hours. Thereafter, 10 parts of ion-exchanged water and 20 parts of methyl isobutyl ketone were added to the reaction mixture, followed by stirring and liquid separation washing. This washing operation was performed three times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.98 parts of the compound represented by the formula (I-13).
MS: 442.3

式（Ｉ４３−ａ）で表される化合物５．００部及びＮ，Ｎ−ジメチルホルムアミド２５部を仕込み、２３℃で３０分間攪拌した後、トリエチルアミン３．８７部を滴下し、さらに、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ４３−ｂ）で表される化合物６．１４部をＮ，Ｎ−ジメチルホルムアミド６．１４部に溶解した溶液を３０分かけて滴下し、さらに、２３℃で２時間攪拌した。得られた反応混合物に、イオン交換水２５部及び酢酸エチル１５０部を加え、２３℃で３０分間攪拌した後、分液し、有機層を回収した。回収された有機層に、イオン交換水７５部を仕込み２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに５回行った。得られた有機層を濃縮し、得られた濃縮物に、ｎ−ヘプタン９２．２０部を添加して攪拌した後、ろ過することにより、式（Ｉ４３−ｃ）で表される化合物２．６９部を得た。 Example 3: Synthesis of compound represented by formula (I-43)

5.00 parts of the compound represented by the formula (I43-a) and 25 parts of N, N-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. Then, 3.87 parts of triethylamine was added dropwise, and further at 23 ° C. Stir for 30 minutes. A solution obtained by dissolving 6.14 parts of the compound represented by the formula (I43-b) in 6.14 parts of N, N-dimethylformamide was added dropwise to the obtained mixture over 30 minutes. Stir for hours. To the obtained reaction mixture, 25 parts of ion-exchanged water and 150 parts of ethyl acetate were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover an organic layer. The recovered organic layer was charged with 75 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated. To the obtained concentrate, 92.20 parts of n-heptane was added and stirred, followed by filtration to obtain a compound 2.69 represented by the formula (I43-c). Got a part.

式（Ｉ４３−ｃ）で表される化合物２．２１部、Ｎ−メチルピロリジン１．８３部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｉ４３−ｄ）で表される化合物１．２８部を添加し、６０℃で２４時間攪拌した。その後、反応混合物にイオン交換水１０部、メチルイソブチルケトン２０部を添加、攪拌後、分液水洗を行った。この水洗の操作を３回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ−４３）で表される化合物１．５９部を得た。
ＭＳ：４２８．３

A compound represented by formula (I43-c): 2.21 parts; N-methylpyrrolidine: 1.83 parts; methyl isobutyl ketone: 20 parts; Part was added and stirred at 60 ° C. for 24 hours. Thereafter, 10 parts of ion-exchanged water and 20 parts of methyl isobutyl ketone were added to the reaction mixture, followed by stirring and liquid separation washing. This washing operation was performed three times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.59 parts of a compound represented by the formula (I-43).
MS: 428.3

式（Ｉ５３−ａ）で表される化合物５．００部及びクロロホルム３５部を仕込み、２３℃で３０分間攪拌した後、カンファースルホン酸０．００１２部及びクロロホルム０．５９８８部の混合溶液を仕込み、さらに、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ５３−ｂ）で表される化合物５．１７部をクロロホルム１０．３４部に溶解した溶液を３０分かけて滴下し、さらに、２３℃で１７時間攪拌した。得られた反応混合物に、トリエチルアミン０．０３部を添加、攪拌後、２％炭酸水素ナトリウム水溶液２１．６３部をを加え、２３℃で３０分間攪拌した後、分液し、有機層を回収した。回収された有機層に、回収された有機層に、イオン交換水２２．６７部を仕込み、２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに５回行った。得られた有機層を濃縮することにより、式（Ｉ５３−ｃ）で表される化合物８．４９部を得た。 Example 4: Synthesis of compound represented by formula (I-53)

After charging 5.00 parts of the compound represented by the formula (I53-a) and 35 parts of chloroform and stirring at 23 ° C. for 30 minutes, a mixed solution of 0.0012 part of camphorsulfonic acid and 0.5988 parts of chloroform was prepared. Furthermore, it stirred at 23 degreeC for 30 minutes. A solution obtained by dissolving 5.17 parts of the compound represented by the formula (I53-b) in 10.34 parts of chloroform was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 17 hours. To the obtained reaction mixture, 0.03 part of triethylamine was added, stirred, 21.63 parts of 2% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to recover the organic layer. . The recovered organic layer was charged with 22.67 parts of ion-exchanged water, and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated to obtain 8.49 parts of a compound represented by the formula (I53-c).

式（Ｉ５３−ｃ）で表される化合物８．４８部及びアセトニトリル４２．３２部を仕込み、２３℃で３０分間攪拌した後、５℃に冷却した。水素化ホウ素ナトリウム０．４２部及びイオン交換水６．２３部を仕込み、さらに、５℃で２時間攪拌した。得られた反応混合物に、酢酸エチル２２９．７７部及びイオン交換水７６．５９部を仕込み、２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに５回行った。得られた有機層を濃縮し、得られた濃縮物に、ｎ−ヘプタン４８．４５部を添加して攪拌した後、ろ過することにより、式（Ｉ５３−ｄ）で表される化合物７．０６部を得た。

8.48 parts of the compound represented by the formula (I53-c) and 42.32 parts of acetonitrile were charged, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. 0.42 part of sodium borohydride and 6.23 parts of ion-exchanged water were added, and the mixture was further stirred at 5 ° C. for 2 hours. The obtained reaction mixture was charged with 229.77 parts of ethyl acetate and 76.59 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, and then separated to recover an organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated, and to the obtained concentrate, 48.45 parts of n-heptane was added and stirred, followed by filtration to give compound 7.06 represented by the formula (I53-d). Got a part.

式（Ｉ５３−ｄ）で表される化合物２．３９部、Ｎ−メチルピロリジン１．８３部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｉ５３−ｅ）で表される化合物１．２８部を添加し、６０℃で２４時間攪拌した。その後、反応混合物にイオン交換水１０部、メチルイソブチルケトン２０部を添加、攪拌後、分液水洗を行った。この水洗の操作を３回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｉ−５３）で表される化合物１．６６部を得た。
ＭＳ：４５６．３

2.39 parts of a compound represented by the formula (I53-d), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone were charged, and the compound 1.28 represented by the formula (I53-e) was stirred. Part was added and stirred at 60 ° C. for 24 hours. Thereafter, 10 parts of ion-exchanged water and 20 parts of methyl isobutyl ketone were added to the reaction mixture, followed by stirring and liquid separation washing. This washing operation was performed three times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.66 parts of a compound represented by the formula (I-53).
MS: 456.3

以下、これらのモノマーを、それぞれ「モノマー（ａ１−１−２）」、「モノマー（ａ２−１−１）」、「モノマー（ａ３−１−１）」、「モノマー（ａ３−２−３）」、「モノマー（ａ１−２−３）」、「モノマー（Ｉ−１）」、「モノマー（Ｉ−１３）」、「モノマー（Ｉ−４３）」、「モノマー（Ｉ−５３）」及び「モノマー（ａ４−１−７）」という。 Resin Synthesis Compounds (monomers) used in the synthesis of resins [resins (A), etc.] are shown below.

Hereinafter, these monomers are respectively referred to as “monomer (a1-1-2)”, “monomer (a2-1-1)”, “monomer (a3-1-1)”, “monomer (a3-2-3)”. "," Monomer (a1-2-3) "," Monomer (I-1) "," Monomer (I-13) "," Monomer (I-43) "," Monomer (I-53) "and" Monomer (a4-1-7) ".

Example 5 [Synthesis of Resin A1]
As the monomer, monomer (a1-1-2), monomer (1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( I-1) and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3) -1-1): The monomer (I-1)) was mixed so as to be 30: 6: 8: 20: 30: 6, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 7 × 10 ³ resin A1 (copolymer) was obtained with a yield of 71%. This resin A1 has the following structural units.

Example 6 [Synthesis of Resin A2]
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 35: 25: 25: 15, and 1.5 mass of the total monomer amount. Double dioxane was added to make a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 6 × 10 ³ resin A2 (copolymer) was obtained in a yield of 73%. This resin A2 has the following structural units.

Example 7 [Synthesis of Resin A3]
As the monomer, monomer (a1-1-2), monomer (1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( I-13) and the molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3) -1-1): The monomer (I-13)) was mixed so as to be 30: 6: 8: 20: 30: 6, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 8 × 10 ³ resin A3 (copolymer) was obtained in a yield of 73%. This resin A3 has the following structural units.

Example 8 [Synthesis of Resin A4]
As the monomer, the monomer (a1-1-2), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (I-13) were used, and the molar ratio (monomer (a1-1-2) ): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-13)) were mixed so as to be 35: 25: 25: 15, and 1.5 mass of the total monomer amount. Double dioxane was added to make a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice, and the weight average molecular weight was 8. 0 × 10 ³ resin A4 (copolymer) was obtained in a yield of 76%. This resin A4 has the following structural units.

Synthesis Example 1 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) were used, and the molar ratio (monomer (a1-1-2): monomer (a2-1) -1): The monomer (a3-1-1)) was mixed so as to be 50:25:25, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, based on the total monomer amount, and these are heated at 80 ° C. for about 8 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 9. 2 × 10 ³ resin A5 (copolymer) was obtained with a yield of 60%. This resin A5 has the following structural units.

Example 9 [Synthesis of Resin A6]
As the monomer, monomer (a1-1-2), monomer (1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( I-43) and its molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3) -1-1): The monomer (I-43)) was mixed so as to be 30: 6: 8: 20: 30: 6, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice, and the weight average molecular weight was 8. 2 × 10 ³ resin A6 (copolymer) was obtained with a yield of 85%. This resin A6 has the following structural units.

Example 10 [Synthesis of Resin A7]
As the monomer, monomer (a1-1-2), monomer (1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( I-53) and the molar ratio (monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3) -1-1): Monomer (I-53)) was mixed so as to be 30: 6: 8: 20: 30: 6, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice, and the weight average molecular weight was 8. 1 × 10 ³ resin A1 (copolymer) was obtained with a yield of 81%. This resin A7 has the following structural units.

Synthesis Example 2 [Synthesis of Resin D1]
Monomer (a4-1-7) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of 0.7 mol% and 2.1 mol%, respectively, with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice to perform the reprecipitation operation twice. 8 × 10 ⁴ resin A6 (copolymer) was obtained with a yield of 77%. This resin D1 has the following structural units.

Examples 7 to 15 and Comparative Example 1
<Preparation of resist composition>
Resins A1 to A7 and Resins D1 obtained in Examples 5 to 10 and Synthesis Examples 1 and 2;
Acid generators B1 to B2 shown below;
Basic compound C1 shown below;
Each was dissolved in the solvent shown below in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

Ｂ２：

<Resin>
A1 to A7: Resin A1 to Resin A7
D1: Resin D1
<Acid generator>
B1:

B2:

<Basic compound: Quencher>
C1: 2,6-diisopropylaniline <solvent>
Propylene glycol monomethyl ether acetate 265.0 parts Propylene glycol monomethyl ether 20.0 parts 2-heptanone 20.0 parts γ-butyrolactone 3.5 parts

<Manufacture of resist pattern and its evaluation>
The resist compositions of Examples and Comparative Examples were subjected to defect evaluation and mask error factor (MEF) evaluation by immersion exposure as follows. Hereinafter, the resist compositions of Examples and Comparative Examples may be collectively referred to as “resist compositions”.

<Immersion exposure evaluation of resist composition>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Co., Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 780 mm. 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.
After applying the resist composition, the obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 1. Using the 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 space width of the 50 nm line-and-space pattern were 1: 1 was defined as effective sensitivity.

(Mask error factor (MEF) evaluation)
The line pattern mask size is 48 nm, 50 nm, and 52 nm with an exposure amount at which the line width of the line pattern exposed to a line and space pattern (1: 1) mask with a pitch width of 100 nm (line pattern mask size is 50 nm) is 50 nm The resist pattern was formed by performing exposure using the above mask (pitch width 100 nm). 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
2.3 or less ◎,
○ over 2.3 and under 3.0
What exceeded 3.0 was set as x.
These results are shown in Table 2. The numerical value in parentheses in the MEF column represents the obtained slope value.

  Resist patterns obtained using the resist compositions of the present invention (Examples 11 to 23) are excellent in mask error factor (MEF). On the other hand, in the resist composition of Comparative Example 1, the mask error factor (MEF) at the time of producing the resist pattern was poor.

  The resist composition of the present invention can be used for fine processing of semiconductors.

Claims (7)

A structural unit derived from the compound represented by formula (I),
A resin comprising a structural unit derived from a monomer having two or more types of acid labile groups and a structural unit derived from an acid stabilizing group monomer having two or more types of lactone rings.

[In the formula (I),
T ¹ represents a single bond or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
m represents 0 or 1;
L ² and L ³ each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and the methylene group constituting the saturated hydrocarbon group is an oxygen atom or a carbonyl group. It may be replaced.
Ring W ¹ and ring W ² each independently represent a hydrocarbon ring having 3 to 36 carbon atoms.
R ¹ and R ² each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydroxy group or an alkyl group having 1 to 6 carbon atoms.
R ⁵ represents a hydrogen atom or a methyl group.
t represents an integer of 0-2. When t is 2, a plurality of R ³ may be the same as or different from each other.
u represents an integer of 0 to 2. When u is 2, a plurality of R ⁴ may be the same as or different from each other. ] A resist composition comprising the resin according to claim 1 , an acid generator, and a solvent. The resist composition according to claim 2 , further comprising a resin having a structural unit derived from an acid-stable monomer having a fluorine atom. The resist composition according to claim 3 , 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 is the formula (a4-g1)

(In the formula (a4-g1),
ss represents an integer of 0-2.
A ⁴⁰ and A ⁴³ each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When ss is 2, a plurality of A ⁴⁰ may be the same as 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 may be the same as or different from each other.
) Represents a group represented by
R ⁴² represents a C 1-18 aliphatic hydrocarbon group having a fluorine atom. The methylene group constituting the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] The resist composition according to claim 2 , 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 constituting the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. The methylene group constituting the alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group.
Z ⁺ represents an organic cation. ] 6. The resist composition according to claim 5 , wherein Y in formula (B1) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. (1) The process of apply | coating the resist composition in any one of Claims 2-6 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: