JP2017095444A - Compound, resin, resist composition and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which makes it possible to produce a resist pattern with excellent focus margin (DOF), and a resin and a resist composition comprising the same.SOLUTION: The present invention provides a compound represented by formula (I), a resin and a resist composition, where Ris halogen, H or C1-6 alkyl substituted/unsubstituted with halogen; Rs independently represent a group comprising a cyclic ether structure or H; Ais a single bond, or a group having one or two alkadiyl group having an ester bond, an ether bond or a carbonate bond; Ad is an adamantanediyl group or adamantanetriyl group; n is 1 or 2, where if n is 2, at least one of Rs is a group comprising a cyclic ether structure.SELECTED DRAWING: None

Description

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

Patent Document 1 describes a resist composition containing a resin composed of a structural unit derived from the following compound.

JP 2008-255188 A

  In the resist composition using the above compound, the focus margin (DOF) may not always be satisfied.

［式（Ｉ）中、
Ｒ^０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。
Ａ^１は、単結合、^＊−Ａ^２−ＣＯ−Ｏ−Ａ^３−、^＊−Ａ^４−Ｏ−ＣＯ−Ａ^５−、^＊−Ａ^６−Ｏ−Ａ^７−又は^＊−Ａ^８−Ｏ−ＣＯ−Ｏ−Ａ^９−を表す。＊は酸素原子との結合手を表す。
Ａ^２、Ａ^４、Ａ^６及びＡ^８は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。
Ａ^３、Ａ^５、Ａ^７及びＡ^９は、それぞれ独立に、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｄは、アダマンタンジイル基又はアダマンタントリイル基を表す。
Ａ^１０は、単結合又は炭素数１〜６のアルカンジイル基を表す。
ｎは１又は２を表す。ｎが２の時、２つのＲ^１は、同一でも異なっていてもよい。
Ｒ^１は、それぞれ独立に、環状エーテル構造を含む基又は水素原子を表す。但し、ｎが２である場合、Ｒ^１の少なくとも１つは、環状エーテル構造を含む基を表す。］
〔２〕Ａ^１が、単結合又は^＊−ＣＨ_２−ＣＯ−Ｏ−である〔１〕記載の化合物。
〔３〕Ｒ^１の環状エーテル構造を含む有機基が、式（ＩＡ）で表される１価の基又は式（ＩＢ）で表される２価の基である〔１〕又は〔２〕記載の化合物。

［式（ＩＡ）及び式（ＩＢ）中、
ｓ３、ｓ４及びｓ５は、０又は１の整数を表す。ただし、ｓ３及びｓ４の和は１以上である。
＊は結合手を表す。］
〔４〕〔１〕〜〔３〕のいずれかに記載の化合物に由来する構造単位を含む樹脂。
〔５〕さらに、酸不安定基を有する構造単位を含む〔４〕記載の樹脂。
〔６〕酸不安定基を有する構造単位が、式（ａ１−１）又は式（ａ１−２）で表される構造単位である〔５〕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−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］
〔７〕〔４〕〜〔６〕のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物。
〔８〕酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する〔７〕に記載のレジスト組成物。
〔９〕（１）〔７〕又は〔８〕記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In the formula (I),
R ⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —CO—O—A ³ —, ^* —A ⁴ —O—CO—A ⁵ —, ^* —A ⁶ —O—A ⁷ — or ^* —A ⁸ —O. —CO—O—A ⁹ — is represented. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantanediyl group or an adamantanetriyl group.
A ¹⁰ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. When n is 2, two R ¹ may be the same or different.
R ¹ independently represents a group containing a cyclic ether structure or a hydrogen atom. However, when n is 2, at least one of R ¹ represents a group containing a cyclic ether structure. ]
[2] The compound according to [1], wherein A ¹ is a single bond or ^* —CH ₂ —CO—O—.
[3] The organic group containing a cyclic ether structure of R ¹ is a monovalent group represented by the formula (IA) or a divalent group represented by the formula (IB) [1] or [2] Compound.

[In Formula (IA) and Formula (IB),
s3, s4, and s5 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
* Represents a bond. ]
[4] A resin containing a structural unit derived from the compound according to any one of [1] to [3].
[5] The resin according to [4], further comprising a structural unit having an acid labile group.
[6] The resin according to [5], wherein the structural unit having an acid labile group is a structural unit represented by formula (a1-1) or formula (a1-2).

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]
[7] A resist composition comprising the resin according to any one of [4] to [6] and an acid generator.
[8] The resist composition according to [7], further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.
[9] (1) A step of applying the resist composition according to [7] or [8] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  By using a resist composition containing a resin using the compound of the present invention, a resist pattern can be produced with a good focus margin (DOF).

In the present specification, unless otherwise specified, in the description of the structural formula of a compound, “aliphatic hydrocarbon group” means a linear or branched hydrocarbon group, and “alicyclic hydrocarbon group” means an aliphatic group. A group obtained by removing a number of hydrogen atoms corresponding to the valence from the ring of a cyclic hydrocarbon. The “aromatic hydrocarbon group” also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included.
In the present specification, "(meth) acrylic monomer" means at least one monomer having a "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " structure of To do. In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning. Moreover, in the group described in the present specification, any group that can take both a linear structure and a branched structure may be used.

［式（Ｉ）中、
Ｒ^０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。
Ａ^１は、単結合、^＊−Ａ^２−ＣＯ−Ｏ−Ａ^３−、^＊−Ａ^４−Ｏ−ＣＯ−Ａ^５−、^＊−Ａ^６−Ｏ−Ａ^７−又は^＊−Ａ^８−Ｏ−ＣＯ−Ｏ−Ａ^９−を表す。＊は酸素原子との結合手を表す。
Ａ^２、Ａ^４、Ａ^６及びＡ^８は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。
Ａ^３、Ａ^５、Ａ^７及びＡ^９は、それぞれ独立に、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｄは、アダマンタンジイル基又はアダマンタントリイル基を表す。
Ａ^１０は、単結合又は炭素数１〜６のアルカンジイル基を表す。
ｎは１又は２を表す。ｎが２の時、２つのＲ^１は、同一でも異なっていてもよい。
Ｒ^１は、それぞれ独立に、環状エーテル構造を含む基又は水素原子を表す。但し、ｎが２である場合、Ｒ^１の少なくとも１つは、環状エーテル構造を含む基を表す。］ [Compound (I)]
The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).

[In the formula (I),
R ⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —CO—O—A ³ —, ^* —A ⁴ —O—CO—A ⁵ —, ^* —A ⁶ —O—A ⁷ — or ^* —A ⁸ —O. —CO—O—A ⁹ — is represented. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantanediyl group or an adamantanetriyl group.
A ¹⁰ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. When n is 2, two R ¹ may be the same or different.
R ¹ independently represents a group containing a cyclic ether structure or a hydrogen atom. However, when n is 2, at least one of R ¹ represents a group containing a cyclic ether structure. ]

Examples of the alkyl group for R ⁰ 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, they are a methyl group and an ethyl group.
Examples of the halogen atom for R ⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having a halogen atom of R ⁰ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a perchloromethyl group, a perbromomethyl group, a periododomethyl group, etc. are mentioned.
R ⁰ is preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms of A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ include a methylene group, an ethylene group, and propane-1,3. A linear alkanediyl group such as a diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group, or a linear alkanediyl group, an alkyl group (Especially those having a side chain of an alkyl group having 1 to 4 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, etc.), ethane-1, 1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1 , 4-diyl group and 2-methylbutane-1 And branched alkanediyl groups such as 4-diyl group.
A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ are preferably a methylene group or an ethylene group, and more preferably a methylene group.
A ¹ is preferably a single bond or ^* —A ² —CO—O—A ³ —, and more preferably a single bond or ^* —CH ₂ —CO—O—.
The two or three bonds of the adamantanediyl group or adamantanetriyl group of Ad can be at any position.

R ¹ represents a group containing a cyclic ether structure. The cyclic ether structure is preferably a cyclic ether structure having 2 to 5 carbon atoms.
Examples of the cyclic ether structure include a structure including an oxirane ring, a structure including an oxetane ring, a structure including a 5-membered ether ring having 4 carbon atoms, and a structure including a 6-membered ether ring having 5 carbon atoms. A 3-membered ether ring having 2 carbon atoms (oxirane ring) or a 4-membered ether ring having 3 carbon atoms (oxetane ring) is preferable, and a 3-membered ether having 2 carbon atoms (oxirane ring) is more preferable.

［式（ＩＡ’）、式（ＩＢ’）、式（ＩＣ’）及び式（ＩＤ’）中、
ｓ３、ｓ４及びｓ５は、０又は１の整数を表す。ただし、ｓ３及びｓ４の和は１以上である。
Ｚ及びＫは、それぞれ独立して、−ＣＨ_２−又は−Ｏ−を表す。
ｓ１１は、１〜４の整数を表す。ｔ１１は、０〜２の整数を表す。ｔ１１が２以上である場合、複数のＺは同じであっても異なっていてもよい。
ｓ１２は、１〜４の整数を表す。ｔ１２は、０〜２の整数を表す。ｔ１２が２以上である場合、複数のＫは同じであっても異なっていてもよい。
但し、ｓ１２＋ｔ１２は、１〜４である。
＊は結合手を表す。］
結合手は、任意の位置とすることができるが、式（ＩＡ’）及び式（ＩＢ’）では、３位にあることが好ましく、式（ＩＣ’）及び式（ＩＤ’）では、４位にあることが好ましい。 Examples of the cyclic ether structure having 2 or 3 carbon atoms include a monovalent group represented by the formula (IA ′), a divalent group represented by the formula (IB ′), and 1 represented by the formula (IC ′). And a divalent group represented by the formula (ID ′).

[In Formula (IA ′), Formula (IB ′), Formula (IC ′) and Formula (ID ′),
s3, s4, and s5 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
Z and K each independently represent —CH ₂ — or —O—.
s11 represents an integer of 1 to 4. t11 represents an integer of 0 to 2. When t11 is 2 or more, the plurality of Z may be the same or different.
s12 represents an integer of 1 to 4. t12 represents an integer of 0 to 2. When t12 is 2 or more, the plurality of K may be the same or different.
However, s12 + t12 is 1-4.
* Represents a bond. ]
The bond can be in any position, but is preferably in the 3-position in Formula (IA ′) and Formula (IB ′), and in the 4-position in Formula (IC ′) and Formula (ID ′). It is preferable that it exists in.

Among these, as the cyclic ether structure, a monovalent group represented by the formula (IA) and a divalent group represented by the formula (IB ′) are preferable.

［＊は結合の手を表す。］ Examples of the monovalent group represented by the formula (IA) include the following groups.

[* Represents a binding hand. ]

［＊は結合の手を表す。］ Examples of the divalent group represented by the formula (IB) include the following groups.

[* Represents a binding hand. ]

［式（ＩＡａ）、式（ＩＢａ）及び式（ＩＣａ）中、
ｓ３、ｓ４及びｓ５は、０又は１の整数を表す。ただし、ｓ３及びｓ４の和は１以上である。
＊は結合手を表す。
Ｒ^４は、炭素数１〜１８の炭化水素基を表し、該炭化水素基に含まれる水素原子は、ニトロ基、水酸基、ハロゲン原子、で置換されていてもよく、前記炭化水素基に含まれるメチレン基は、酸素原子で置き換わっていてもよい。
ｕ１は、０〜５の整数を表し、ｕ１が２以上である場合、複数のＲ^４は同じであっても異なっていてもよい。
Ｚ及びＫは、それぞれ独立して、炭素原子又は酸素原子を表す。
Ｒ⁴⁵は、水酸基、ハロゲン基、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１〜６のヒドロキシアルキル基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアシルアミノ基又はグリシジル基を表し、Ｒ⁴⁵の２つが互いに結合して環を形成してもよい。
ｕ２は、０〜１６の整数を表し、ｕ２が２以上である場合、複数のＲ⁴⁵は同じであっても異なっていてもよい。
ｓ１１は、１〜４の整数を表す。ｔ１１は、０〜２の整数を表す。ｔ１１が２以上である場合、複数のＺは同じであっても異なっていてもよい。
ｓ１２は、１〜４の整数を表す。ｔ１２は、０〜２の整数を表す。ｔ１２が２以上である場合、複数のＫは同じであっても異なっていてもよい。
但し、ｓ１２＋ｔ１２は、１〜４である。
＊は結合手を表す。］ In the group containing the cyclic ether structure of R ^1, the cyclic ether structure may have a substituent. That is, the monovalent group represented by the formula (IA ′) or the divalent group represented by the formula (IB ′) is represented by the monovalent group represented by the formula (IAa) or the formula (IBa). The group represented by the formula (ICa) may be used.

[In formula (IAa), formula (IBa) and formula (ICa),
s3, s4, and s5 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
* Represents a bond.
R ⁴ represents a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a nitro group, a hydroxyl group, or a halogen atom, and is contained in the hydrocarbon group. The methylene group may be replaced with an oxygen atom.
u1 represents an integer of 0 to 5, when u1 is 2 or more, plural R ⁴ may be different even in the same.
Z and K each independently represent a carbon atom or an oxygen atom.
R ⁴⁵ is a hydroxyl group, a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, or 2 to 2 carbon atoms. 7 an acyloxy group, an acylamino group having 2 to 7 carbon atoms, or a glycidyl group, and two of R ⁴⁵ may be bonded to each other to form a ring.
u2 represents an integer of 0 to 16, and when u2 is 2 or more, the plurality of R ⁴⁵ may be the same or different.
s11 represents an integer of 1 to 4. t11 represents an integer of 0 to 2. When t11 is 2 or more, the plurality of Z may be the same or different.
s12 represents an integer of 1 to 4. t12 represents an integer of 0 to 2. When t12 is 2 or more, the plurality of K may be the same or different.
However, s12 + t12 is 1-4.
* Represents a bond. ]

炭素数１〜６のアルキル基としては、メチル基が挙げられる。 Examples of the hydrocarbon group for R ⁴ include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining them. The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group. Especially, as a hydrocarbon group, Preferably, it is a C1-C12 saturated hydrocarbon group or a C6-C18 aromatic hydrocarbon group.
As a C1-C12 saturated hydrocarbon group, a C1-C12 alkyl group or a C3-C12 saturated cyclic hydrocarbon group is mentioned, A C1-C12 alkyl group and C3-C3 are mentioned. -CH ₂ - contained in the saturated cyclic hydrocarbon group of 12 - may be replaced by -O-.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.
-CH ₂ - As the alkyl group having 1 to 12 carbon atoms which may be replaced by -O-, include methoxyethoxyethyl group.
Examples of the saturated cyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the saturated cyclic hydrocarbon group having 3 to 12 carbon atoms in which —CH ₂ — may be replaced by —O— include the following groups.

A methyl group is mentioned as a C1-C6 alkyl group.

  s3 is preferably 1, s4 is preferably 0 or 1, and s1 + t1 is preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁴⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the alkoxy group having 1 to 6 carbon atoms in R ⁴⁵ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Can be mentioned.
Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R ⁴⁵ include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group.
Examples of the acyl group having 2 to 7 carbon atoms in R ⁴⁵ include an acetyl group, a propionyl group, a butyryl group, and a benzoyl group.
Examples of the acyloxy group having 2 to 7 carbon atoms in R ⁴⁵ include an acetyloxy group, a propionyloxy group, a butyryloxy group, and a benzoyloxy group.
Examples of the acylamino group having 2 to 7 carbon atoms for R ⁴⁵ include an acetylamino group, a propionylamino group, a butyrylamino group, and a benzoylamino group.

s12 + t12 is preferably 1 or 2.
Z and K are preferably carbon atoms.
In the formula (IAa) and formula (IBa), 3-position of the cyclic ether structure is preferred that the carbon atoms of (according to the formula) is bound to the ^{A 10,} in the formula (ICa), the cyclic ether structure 4-position it is preferred that the carbon atoms of (according to the formula) binds to a ^10.

Examples of R ¹ include the following groups.

In the compound (I), when R ¹ is 1, R ¹ may be a hydrogen atom or a group containing a cyclic ether structure, but the latter is preferred. When two R ^{1 s} are present, one R ¹ may be a hydrogen atom, and the other R ¹ may be a group containing a cyclic ether structure, or both may be any group containing a cyclic ether structure.

Examples of compound (I) include the following.

In the compounds represented by formula (I-1) to formula (I-47), compounds in which the methyl group corresponding to R ⁰ is replaced by a hydrogen atom can also be given as specific examples of compound (I).

［式中、Ｒ^０、Ｒ^１及びＡｄは、上記と同じ意味を表す。］
溶媒としては、ジメチルホルムアミド、メチルイソブチルケトン、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、例えば、炭酸カリウム、ヨウ化カリウム、トリエチルアミン、ピリジン、Ｎ−メチルピペリジン、Ｎ−メチルピロリジンなどが挙げられる。
式（Ｉ１−ａ）で表される化合物としては、下記式で表される塩等が挙げられ、市場より容易に入手することができる。

<Method for Producing Compound (I)>
The compound represented by the formula (I1) in which A ¹ of the compound (I) is * —CH ₂ —CO—O— (* represents a bonding position with O) is represented by the formula (I1-a). And a compound represented by the formula (I1-b) in the presence of a base catalyst in a solvent.

[Wherein, R ⁰ , R ¹ and Ad represent the same meaning as described above. ]
Examples of the solvent include dimethylformamide, methyl isobutyl ketone, chloroform, tetrahydrofuran and toluene.
Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine, pyridine, N-methylpiperidine, N-methylpyrrolidine and the like.
Examples of the compound represented by the formula (I1-a) include a salt represented by the following formula, and can be easily obtained from the market.

［式中、Ｒ^０、Ｒ^１及びＡｄは、上記と同じ意味を表す。］
溶剤としては、テトラヒドロフラン、クロロホルムなどが挙げられる。
塩基触媒としては、炭酸カリウム、ヨウ化カリウム、トリエチルアミンなどが挙げられる。 The compound represented by the formula (I1-b) is obtained by reacting the compound represented by the formula (I1-c) with the compound represented by the formula (I1-d) in the presence of a base catalyst in a solvent. Can be obtained.

[Wherein, R ⁰ , R ¹ and Ad represent the same meaning as described above. ]
Examples of the solvent include tetrahydrofuran and chloroform.
Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine and the like.

［式中、Ｒ^１、Ａ^１０、ｎ及びＡｄは、上記と同じ意味を表す。］
溶剤としては、アセトン、クロロホルムなどが挙げられる。
触媒としては、塩基触媒（例えば、ピリジン、ジメチルアミノピリジン）及び公知のエステル化触媒（例えば、酸触媒やカルボジイミド触媒など）などが挙げられ、塩基触媒及び公知のエステル化触媒を共存させてもよい。
式（Ｉ１−ｅ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、市場より容易に入手できる。

式（Ｉ１−ｆ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、市場より容易に入手できる。

カルボジイミド触媒としては、下記式で表される塩等が挙げられ、市場より容易に入手することができる。

The compound represented by the formula (I1-c) is obtained by reacting the compound represented by the formula (I1-e) with the compound represented by the formula (I1-f) in a solvent in the presence of a catalyst. Can be obtained.

[Wherein R ¹ , A ¹⁰ , n and Ad represent the same meaning as described above. ]
Examples of the solvent include acetone and chloroform.
Examples of the catalyst include a base catalyst (for example, pyridine, dimethylaminopyridine) and a known esterification catalyst (for example, an acid catalyst, a carbodiimide catalyst, etc.), and a base catalyst and a known esterification catalyst may coexist. .
Examples of the compound represented by the formula (I1-e) include compounds represented by the following, and can be easily obtained from the market.

Examples of the compound represented by the formula (I1-f) include compounds represented by the following, and can be easily obtained from the market.

Examples of the carbodiimide catalyst include salts represented by the following formulas and can be easily obtained from the market.

溶媒としては、ジメチルホルムアミド、メチルイソブチルケトン、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、例えば、炭酸カリウム、ヨウ化カリウム、トリエチルアミン、ピリジン、Ｎ−メチルピペリジン、Ｎ−メチルピロリジンなどが挙げられる。
式（Ｉ２−ａ）で表される化合物としては、下記式で表される塩等が挙げられ、市場より容易に入手することができる。

The compound represented by the formula (I2) in which A ¹ of the compound (I) is a single bond is obtained by baseing the compound represented by the formula (I1-a) and the compound represented by the formula (I1-b). It can be obtained by reacting in a solvent in the presence of a catalyst.

Examples of the solvent include dimethylformamide, methyl isobutyl ketone, chloroform, tetrahydrofuran and toluene.
Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine, pyridine, N-methylpiperidine, N-methylpyrrolidine and the like.
Examples of the compound represented by the formula (I2-a) include salts represented by the following formula, and can be easily obtained from the market.

[Resin (A)]
The resin of the present invention is a resin containing a structural unit derived from compound (I) (hereinafter sometimes referred to as “structural unit (I)”) (hereinafter sometimes referred to as “resin (A)”).
Resin (A) may be a copolymer containing two or more structural units (I).
In the resin (A), the content of the structural unit (I) is preferably from 1 to 50 mol%, more preferably from 2 to 30 mol%, more preferably from 3 to 10 mol%, based on all the structural units of the resin (A). Is more preferable.

The resin (A) may be composed only of the structural unit (I), but preferably further contains an acid labile group, and includes a structural unit other than the structural unit (I). More preferred. As the structural unit other than the structural unit (I), a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a)”) is preferable. Here, the acid labile group means a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid.
The resin (A) further includes a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”), a structural unit other than the structural unit (a1) and the structural unit (s), and others. May contain structural units derived from monomers known in the art.

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。
ｎａは、０又は１を表す。
＊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’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の複素環基を形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a)>
Examples of the acid labile group contained in the structural unit (a) include a group represented by the formula (1) and a group represented by the formula (2).

[In the formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination of these, or R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
* 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 heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and are included in the hydrocarbon group and the heterocyclic group − CH ₂ — may be replaced by —O— or —S—.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

アルキル基と脂環式炭化水素基とを組み合わせた基としては、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基、アダマンチルメチル基等が挙げられる。
ｎａは、好ましくは０である。 ^Examples of the alkyl group for R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
The alicyclic hydrocarbon group for R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and an adamantylmethyl group.
na is preferably 0.

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

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

Ｒ^a1'及びＲ^a2'のうち、少なくとも１つは水素原子であることが好ましい。 Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
^{Examples of the} divalent heterocyclic group formed together with the carbon atom and X to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X include the following groups. * Represents a bond.

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

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

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

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

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

［式（ａ１−０）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。］

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. ]

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

L ^a01 is preferably an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, and more preferably an oxygen atom. k01 is preferably an integer of 1 to 4, more preferably 1.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and a group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group for R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 preferably has 8 or less carbon atoms, more preferably 6 or less.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^a1 and L ^a2 are preferably —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 of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and a group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, more preferably 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any one of the formulas (a1-0-1) to (a1-0-12) is preferable, and the structural units (a1-0-1) to (a1-0-1) The structural unit represented by any one of formulas (a1-0-10) is more preferable.

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

  The content of the structural unit represented by the formula (a1-0) is preferably 3 to 60 mol%, more preferably 4 to 55 mol% with respect to all the structural units of the resin (A).

As a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

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

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

式（ａ１−３）中、
Ｒ^a9は、ヒドロキシ基を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基、水素原子又は−ＣＯＯＲ^a13を表す。
Ｒ^a13は、炭素数１〜８の脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、又はこれらを組み合わせることにより形成される基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表すか、Ｒ^a10及びＲ^a11は互いに結合して、それらが結合する炭素原子とともに炭素数２〜２０の２価の炭化水素基を形成する。 Furthermore, examples of the structural unit (a1) having the group (1) include a structural unit represented by the formula (a1-3). The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Moreover, the monomer which derives the structural unit (a1-3) may be referred to as a monomer (a1-3).

In formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom, or —COOR ^a13 .
R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by a combination thereof, the aliphatic hydrocarbon group and the The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group, and —CH ₂ — contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is —O— or -CO- may be substituted.
R ^a10 , R ^a11 and R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, or R ^a10 and R ^a11 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the carbon atom to which they are bonded.

Here, -COOR ^a13 includes a group in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group which may have a hydroxy group of R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
^Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^a13 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -Hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, etc. are mentioned.
^Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^a13 include a cyclopentyl group, a cyclopropyl group, an adamantyl group, an adamantylmethyl group, a 1-adamantyl-1-methylethyl group, and 2-oxo-oxolane-3- Yl group and 2-oxo-oxolan-4-yl group.
^Examples of the alkyl group represented by R ^{a10 to} R ^a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include n-heptyl group, 2-ethylhexyl group, n-octyl group and the like.
The alicyclic hydrocarbon group for R ^{a10 to} R ^a12 may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Examples thereof include cycloalkyl groups such as a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, Examples thereof include a methylnorbornyl group and an isobornyl group.
-C (R ^a10 ) (R ^a11 ) (R ^a12 ) in the case where R ^a10 and R ^a11 are bonded to each other to form a divalent hydrocarbon group together with the carbon atom to which they are bonded, Groups are preferred.

  Specific examples of the monomer (a1-3) include 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, and 5-norbornene-2-carboxylic acid. Acid 1-methylcyclohexyl, 5-norbornene-2-carboxylic acid 2-methyl-2-adamantyl, 5-norbornene-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1- (4 -Methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4-oxo (Cyclohexyl) ethyl and 1- (1-adamantyl) -1-methyl 5-norbornene-2-carboxylate Chill, and the like.

  Since the resin (A) containing the structural unit (a1-3) includes a sterically bulky structural unit, the resist composition of the present invention containing such a resin (A) is more expensive. A resist pattern can be obtained with resolution. Further, since a rigid norbornane ring is introduced into the main chain, the resulting resist pattern tends to be excellent in dry etching resistance.

  When the resin (A) includes the structural unit (a1-3), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). 20-85 mol% is more preferable.

［式（ａ１−４）中、
Ｒ^a32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^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であっても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a36は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してそれらが結合するＣ−Ｏとともに炭素数３〜２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き換わってもよい。］ As the structural unit (a1) having a group represented by the group (2), a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”). Can be mentioned.

[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same as or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other And C—O to which they are bonded to form a divalent heterocyclic group having 3 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is —O— Alternatively, it may be replaced by -S-. ]

^Examples of the alkyl group for R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group that may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoro. Ethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro Butyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n-perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
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, and a butyryloxy group.
Examples of the hydrocarbon group R ^a34 and R ^a35, include the same groups as R ^{a1 'and} R ^a2' of formula (2).
^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. It is done.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
la is preferably 0 or 1, more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group in R ^a36 and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group in R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

As a monomer which introduce | transduces structural unit (a1-4), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, monomers represented by formula (a1-4-1) to formula (a1-4-8) are preferable, and formula (a1-4-1) to formula (a1-4-5) and formula (a1- The monomers represented by 4-8) are more preferable.

  When resin (A) has a structural unit (a1-4), the content rate is preferable with respect to all the structural units of resin (A), and 10-95 mol% is preferable, and 15-90 mol% is more preferable. 20 to 85 mol% is more preferable.

式（ａ１−５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４の整数を表し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴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 a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) Is also included).

In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents an integer of 1 to 4, and * represents a bond to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. Groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
One of L ⁵² and L ⁵³ is preferably —O— and the other is —S—.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

As a monomer which introduce | transduces structural unit (a1-5), the monomer described in Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. Among these, monomers represented by formulas (a1-5-1) to (a1-5-4) are preferable, and monomers represented by formula (a1-5-1) or formula (a1-5-2) are preferable. Is more preferable.

  When resin (A) has a structural unit (a1-5), the content rate is preferable 1-50 mol% with respect to all the structural units of resin (A), and 3-45 mol% is more preferable. 5 to 40 mol% is more preferable.

  In the resin (A), the content of the structural unit (a) is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). Preferably it is 20-85 mol%.

  Especially, as a structural unit which has an acid labile group in resin (A), the structural unit represented by Formula (a1-1) or Formula (a1-2) is preferable, and is represented by Formula (a1-1). The structural unit is more preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), and the structural unit (a1-5). , At least two or more are more preferable, a combination of the structural unit (a1-1) and the structural unit (a1-2), a combination of the structural unit (a1-1) and the structural unit (a1-5), and a structural unit (a1- 1) and a combination of structural unit (a1-0), a combination of structural unit (a1-2) and structural unit (a1-0), a combination of structural unit (a1-5) and structural unit (a1-0), and a structure Unit (a1-0), structural unit ( 1-1) and a combination of the structural unit (a1-2), a structural unit (a1-0), a structural unit (a1-1), and a combination of the structural unit (a1-5) are more preferable, and the structural unit (a1-1) ) And the structural unit (a1-2) are even more particularly preferred.

<Structural unit (s)>
The monomer for deriving the structural unit having no acid labile group is not particularly limited as long as it is a monomer having no acid labile group, and monomers known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structure having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used for the resist composition, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) is more preferable. As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

  When the resin (A) has a structural unit (a2) having a hydroxy group, the total content is preferably from 5 to 95 mol%, and from 10 to 80 mol%, based on all structural units of the resin (A). More preferably, 15-80 mol% is further more preferable.

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

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

^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom of R ^a30 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 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, n-pentyl group, n-hexyl Group, n-perfluorohexyl group and the like. R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the R ^a31 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
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, and a butyryloxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

Examples of the monomer that derives the structural unit (a2-0) include monomers described in JP 2010-204634 A.
Among them, the structural unit (a2-0) is represented by formula (a2-0-1), formula (a2-0-2), formula (a2-0-3), and formula (a2-0-4), respectively. The structural unit represented by the formula (a2-0-1) or the formula (a2-0-2) is more preferable.

  The resin (A) containing the structural unit (a2-0) is subjected to a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer that derives the structural unit (a2-0) is protected with a protective group, and then deprotected. It can be manufactured by processing. However, when the deprotection treatment is performed, the acid labile group of the structural unit (a1) needs to be not significantly impaired. Examples of such protecting groups include acetyl groups.

  When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, the content is preferably from 5 to 95 mol% with respect to all the structural units of the resin (A). 80 mol% is more preferable, and 15-80 mol% is further more preferable.

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

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

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

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

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

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But you can. Preferably, a γ-butyrolactone ring or a bridged ring containing a γ-butyrolactone ring structure is used.

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.

［式（ａ３−１）中、
Ｌ^a4は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異なる。
式（ａ３−２）中、
Ｌ^a5は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１は、０〜３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相異なる。
式（ａ３−３）中、
Ｌ^a6は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｒ１は、０〜３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相異なる。
式（ａ３−４）中、
Ｒ^a24は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a25は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
Ｌ^a7は、−Ｏ−、^＊−Ｏ−Ｌ^a8−Ｏ−、^＊−Ｏ−Ｌ^a8−ＣＯ−Ｏ−、^＊−Ｏ−Ｌ^a8−ＣＯ−Ｏ−Ｌ^a9−ＣＯ−Ｏ−又は^＊−Ｏ−Ｌ^a8−Ｏ−ＣＯ−Ｌ^a9−Ｏ−を表す。
＊はカルボニル基との結合手を表す。
Ｌ^a8及びＬ^a9は、互いに独立に、炭素数１〜６のアルカンジイル基を表す。
ｗ１は、０〜８の整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一であってもよく、異なってもよい。］

[In the formula (a3-1),
L ^a4 represents a group represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5. When p1 is 2 or more, the plurality of R ^a21 are the same or different from each other.
In formula (a3-2),
L ^a5 represents a group represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, the plurality of R ^a22 are the same or different from each other.
In formula (a3-3),
L ^a6 represents a group represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, the plurality of R ^a23 are the same or different from each other.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
* Represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, the plurality of R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. An alkyl group is mentioned.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group for R ^a24 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 methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group represented by L ^a8 and L ^a9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

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

（式中、Ｒ^ａ２４、Ｌ^a7は、上記と同じ意味を表す。） In formula (a3-4),
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, and more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H. _4- CO-O-.
R ^a25 is preferably a carboxy group, a cyano group, or a methyl group.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4) ′.

(Wherein R ^a24 and L ^a7 represent the same meaning as described above.)

As monomers for deriving the structural unit (a3), monomers described in JP 2010-204646 A, monomers described in JP 2000-122294 A, monomers described in JP 2012-41274 A are listed. Can be mentioned. As the structural unit (a3), formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4), formula (a3-3) 1) to a structural unit represented by any one of the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12), the formula (a3-1-1), It is represented by any one of formula (a3-1-2), formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-12) The structural unit represented by any one of formulas (a3-4-1) to (a3-4-12) is more preferred, and the structural unit represented by formula (a3-4-1) to formula (a3- The structural unit represented by any one of 4-6) is even more preferable.

In the structural units represented by the following formulas (a3-4-1) to (a3-4-12), compounds in which the methyl group corresponding to R ^a24 is replaced with a hydrogen atom are also structural units (a3-4). ).

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Other structural units (t)>
As the structural unit (t), in addition to the structural unit (a2) and the structural unit (a3), a structural unit represented by (a4) described later (hereinafter sometimes referred to as “structural unit (a4)”) and (a5) (Hereinafter sometimes referred to as “structural unit (a5)”).

［式（ａ４−０）中、
Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁵は、単結合又は炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数３〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
As the structural unit (a4), a structural unit represented by formula (a4-0) can be given.

[In the formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkyl cycloalkanediyl group perfluoro alkanediyl group or 3 to 12 carbon atoms having 1 to 8 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the aliphatic saturated hydrocarbon group for L ⁵ include an alkanediyl group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Having a side chain of an alkyl group (particularly, methyl group, ethyl group, etc.), ethane-1,1-diyl group, propane-1, Examples thereof include branched alkanediyl groups such as 2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
The perfluoroalkanediyl group of L ³ includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane-2,2 -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2 2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3, A 3-diyl group, a perfluorooctane-4,4-diyl group, etc. are mentioned.
Examples of the L ³ perfluorocycloalkanediyl group include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

L ⁵ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ⁵ is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a4-0).

〔式（ａ−ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44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。
Ａ^a43は、単結合又は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。
Ｘ^a41及びＸ^a42は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊は結合手であり、右側の＊が−Ｏ−ＣＯ−Ｒ^a42との結合手である。］ As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.

[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an ^optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents a single bond or a ^C1-C5 aliphatic hydrocarbon group which may have a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is a bond, and * on the right side is a bond with —O—CO—R ^a42 . ]

^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.
The chain and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, but the chain and cyclic aliphatic saturated hydrocarbon groups are preferable. The aliphatic saturated hydrocarbon group includes a straight chain or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic group formed by combining an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon group and the like.

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、ビフェニリル基、フェナントリル基及びフルオレニル基が挙げられる。 Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Cyclic aliphatic hydrocarbon groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other cycloalkyl groups; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* is a bond) And a polycyclic alicyclic hydrocarbon group such as “represents a hand.”

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group, and a fluorenyl group.

［式（ａ−ｇ３）中、
Ｘ^a43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。
Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数１〜１７の脂肪族炭化水素基を表す。
＊は結合手を表す。］ R ^a42 includes a halogen atom or a group represented by the formula (a-g3) as a substituent. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.
* Represents a bond. ]

^As the aliphatic hydrocarbon group for A ^a45, the same groups as those exemplified for R ^a42 can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). .
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the carbon number contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

［式（ａ−ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
Ｘ^a44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^a47は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合手を表す。］ The aliphatic hydrocarbon group having a group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2).

[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47, and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with a carbonyl group. ]

1-6 are preferable and, as for carbon number of the aliphatic hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of ^Aa47 , 5-12 are more preferable, and ^Aa47 has a cyclohexyl group or an adamantyl group further more preferable.

A more preferred structure of the partial structure represented by * -A ^a46 -X ^a44 -A ^a47 (* is a bond to a carbonyl group) is the following structure.

^As the alkanediyl group of ^Aa41 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, Examples include branched alkanediyl groups such as 2-methylbutane-1,4-diyl group.
^Examples of the substituent in the alkanediyl group of A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

The aliphatic hydrocarbon group of A ^a42 , A ^a43 and A ^{a44 in} the group (a-g1) may have a carbon-carbon unsaturated bond, but a linear and cyclic aliphatic saturated hydrocarbon group In addition, groups formed by combining them are preferred. The aliphatic saturated hydrocarbon group is formed by combining a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group. An aliphatic hydrocarbon group etc. are mentioned. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, Examples include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent for the aliphatic hydrocarbon group of A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

^Examples of the group (a-g1) in which X ^a42 is an oxygen atom include the following groups. In the following examples, among the two bonds represented by *, * on the right side is a bond with —O—CO—R ^a42 .

Examples of the group (a-g1) in which X ^a42 is a carbonyl group include the following groups.

Examples of the group (a-g1) in which X ^a42 is a carbonyloxy group include the following groups.

Examples of the group (a-g1) in which X ^a42 is an oxycarbonyl group include the following groups.

［式（ａ４−２）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ａ^f1は、炭素数１〜６のアルカンジイル基を表す。
Ｒ^f2は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ As the structural unit represented by the formula (a4-1), a structural unit represented by the formula (a4-2) or the formula (a4-3) is preferable.

[In the formula (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

As the alkanediyl group of A ^f1 , a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , A straight-chain alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain, a cyclic group, and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
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 either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group. And cycloalkyl groups such as dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, A methyl norbornyl group and an isobornyl group are mentioned.

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Examples of the alkyl group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl 2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2 , 2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluoro Butyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5 Fluorinated alkyl groups such as 6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl group can be mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

A ^f1 in formula (a4-2) is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
R ^f2 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

［式（ａ４−３）中、
Ｒ^f11は、水素原子又はメチル基を表す。
Ａ^f11は、炭素数１〜６のアルカンジイル基を表す。
Ａ^f13は、フッ素原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ^f12は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^f14は、フッ素原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有する脂肪族炭化水素基を表す。］

[In the formula (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

^Examples of the alkanediyl group for A ^f11 include the same groups as the alkanediyl group for A ^f1 .

The aliphatic hydrocarbon group for A ^f13 includes either a chain or a cyclic group, and a divalent aliphatic hydrocarbon group formed by combining them. The aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene Groups, perfluoroalkanediyl groups such as perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group, and the like.

As the aliphatic hydrocarbon group for A ^f14 , one of chain and cyclic groups and an aliphatic hydrocarbon group formed by combining them are included. The aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Examples of the chain aliphatic hydrocarbon group which may have a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 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, pentyl group, hexyl group, perfluorohexyl group, A heptyl group, a perfluoro heptyl group, an octyl group, a perfluorooctyl group, etc. are mentioned.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, and a perfluoroadamantylmethyl group.

In the formula (a4-3), A ^f11 is an ethylene group is preferred.
The aliphatic hydrocarbon group for A ^f13 preferably has 1 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms.
The aliphatic hydrocarbon group for A ^f14 preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Examples of the structural unit represented by the formula (a4-2) include the structural units shown below and a structural unit in which a methyl group corresponding to R ^f1 in the following structural units is replaced with a hydrogen atom.

The structural unit represented by formula (a4-3), a methyl group have structural units replaced by a hydrogen atom corresponding to R ^f11 in the structural unit and the following structural units shown below.

［式（ａ４−４）中、
Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、−（ＣＨ₂）_j1−、−（ＣＨ₂）_j2−Ｏ−（ＣＨ₂）_j3−又は−（ＣＨ₂）_j4−ＣＯ−Ｏ−（ＣＨ₂）_j5−を表す。
ｊ１〜ｊ５は、それぞれ独立に、１〜６の整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4).

[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents — (CH ₂ ) _j1 —, — (CH ₂ ) _j2 —O— (CH ₂ ) _j3 — or — (CH ₂ ) _j4 —CO—O— (CH ₂ ) _j5 —.
j1 to j5 each independently represents an integer of 1 to 6.
R ^f22 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

^Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same hydrocarbon groups as R ^f2 in formula (a4-2). R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In formula (a4-4), A ^f21 is preferably — (CH ₂ ) _j1 —, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

Examples of the structural unit represented by formula (a4-4) include structural units in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom in the following structural units and structural units represented by the following formulas. It is done.

  When the resin (A) has a structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on all structural units of the resin (A). More preferably, it is 10 mol%.

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但し、Ｌ⁵¹との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ⁵¹は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-leaving hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group. Especially, it is preferable that a structural unit (a5) is a structural unit containing an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group for R ⁵² may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups such as octyl group and 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. .
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

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

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

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

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

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

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

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

L ⁵¹ is preferably a single bond or a group represented by the formula (L1-1).

As the structural unit (a5-1), structural units shown below and structural units in which a methyl group corresponding to R ⁵¹ in the following structural units is replaced with a hydrogen atom can be mentioned.

  When the resin (A) has the structural unit (a5), the content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on all structural units of the resin (A). More preferred is ˜15 mol%.

The resin (A) is preferably a resin comprising the structural unit (I), the structural unit (a) and the structural unit (s), that is, the compound (I), the monomer (a1) and the monomer (s). It is a polymer.
The structural unit (a) is preferably a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) and a structural unit. At least one of (a1-5), more preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1).
The structural unit (a3) is preferably at least one of structural units represented by a γ-butyrolactone ring, a bridged ring containing a γ-butyrolactone ring structure, or an adamantane lactone ring.

  The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (particularly the structural unit (a1-1)) in an amount of 15 mol% or more based on the content of the structural unit (a). preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

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

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter sometimes referred to as “acid generator (B)”). The resist composition of the present invention preferably contains a resin other than the resin (A).
The resist composition of the present invention further has a weak acidity such as a solvent (hereinafter sometimes referred to as “solvent (E)”) weak acid inner salt (hereinafter also referred to as “weak acid inner salt (D)”). It preferably contains a quencher containing a salt (hereinafter sometimes referred to as “quencher (C)”).

<Resin other than resin (A)>
Examples of the resin other than the resin (A) include a resin composed only of the structural unit (s) and a resin including the structural unit (a4) (however, the structural unit (I) is not included); hereinafter, “resin (X)” In some cases).
As the structural unit that the resin (X) may further have, structural units derived from the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit (a5), and other known monomers. Units are listed. The resin (X) is preferably a resin composed only of the structural unit (t), and more preferably a resin composed of the structural unit (a4) and / or the structural unit (a5).
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more with respect to all the structural units of the resin (X). .
When the resin (X) contains the structural unit (a5), the content is preferably 40 mol% or more, more preferably 45 mol% or more, and more preferably 50 mol% or more with respect to all the structural units of the resin (X). Is more preferable.

Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do. The content rate of each structural unit which resin (X) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Preferably it is 1-40 mass parts, Most preferably, it is 2-30 mass parts.

  As for the total content rate of resin other than resin (A) and resin (A), 80 to 99 mass% is preferable with respect to solid content of a resist composition. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of the acid generators (B) of the resist composition of the present invention may be used. Nonionic acid generators include organic halides, sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. The compound which generate | occur | produces an acid by the radiation as described in 1 can be used. Moreover, you may use the compound manufactured by the well-known method. An acid generator (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＳＯ₂−又は−ＣＯ−に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic carbon group. —CH ₂ — contained in the hydrogen group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹ and Q ² include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro group. A hexyl group etc. are mentioned.
Q ¹ and Q ² are each independently preferably a fluorine atom or a trifluoromethyl group, and both Q ¹ and Q ² are 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 saturated hydrocarbon group, and these It may be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-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 and heptadecane-1,17-diyl group Alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-3) The group represented by these is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with -Y.

式（ｂ１−１）中、
Ｌ^b2は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b3は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^b2とＬ^b3との炭素数合計は、２２以下である。
式（ｂ１−２）中、
Ｌ^b4は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b5は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^b4とＬ^b5との炭素数合計は、２２以下である。
式（ｂ１−３）中、
Ｌ^b6は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
Ｌ^b7は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^b6とＬ^b7との炭素数合計は、２３以下である。

In formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total carbon number of L ^b4 and L ^b5 is 22 or less.
In formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total carbon number of L ^b6 and L ^b7 is 23 or less.

In formulas (b1-1) to (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbons before the replacement is represented by the saturated hydrocarbon group. The number of carbons.
Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.
L ^b3 is preferably a saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a C 1-8 divalent saturated hydrocarbon group, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

  Among these, a group represented by the formula (b1-1) or the formula (b1-3) is preferable.

式（ｂ１−４）中、
Ｌ^b8は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１−５）中、
Ｌ^b9は、炭素数１〜２０の２価の飽和炭化水素基を表す。
Ｌ^b10は、単結合又は炭素数１〜１９の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b9及びＬ^b10の合計炭素数は２０以下である。
式（ｂ１−６）中、
Ｌ^b11は、炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^b12は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b11及びＬ^b12の合計炭素数は２１以下である。
式（ｂ１−７）中、
Ｌ^b13は、炭素数１〜１９の２価の飽和炭化水素基を表す。
Ｌ^b14は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^b15は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b13、Ｌ^b14及びＬ^b15の合計炭素数は１９以下である。
式（ｂ１−８）中、
Ｌ^b16は、炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^b17は、炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^b18は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b16、Ｌ^b17及びＬ^b18の合計炭素数は１９以下である。 Examples of formula (b1-1) include groups represented by formula (b1-4) to formula (b1-8).

In formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b13 , L ^b14 and L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b16 , L ^b17 and L ^b18 is 19 or less.

L ^b8 is preferably a saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 preferably represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 preferably represents a ^C 1-6 divalent saturated hydrocarbon group.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

式（ｂ１−９）中、
Ｌ^b19は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b20は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b19及びＬ^b20の合計炭素数は２３以下である。
式（ｂ１−１０）中、
Ｌ^b21は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b22は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^b23は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b21、Ｌ^b22及びＬ^b23の合計炭素数は２１以下である。
式（ｂ１−１１）中、
Ｌ^b24は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b25は、炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^b26は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b24、Ｌ^b25及びＬ^b26の合計炭素数は２１以下である。 Examples of formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.

In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.

  In formulas (b1-9) to (b1-11), when a hydrogen atom contained in a divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms in the acyloxy group, The carbon number of the divalent saturated hydrocarbon group including the number of CO and O is used.

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, an oxocyclohexylcarbonyloxy group, and a hydroxycyclohexylcarbonyloxy group.

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-4) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-5) include the following.

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-6) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-7) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-8) include the following.

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

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-9) include the following.

Of the groups represented by the formula (b1-3), examples of the group represented by the formula (b1-10) include the following.

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11).
Examples of the group in which —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO— include formulas (Y12) to (Y38). The group represented by these is mentioned.

  Among them, the group represented by any one of the formulas (Y1) to (Y20), the formula (Y30), and the formula (Y31) is preferable, and the formula (Y11), the formula (Y15), and the formula (Y Y16), a group represented by formula (Y19), formula (Y20), formula (Y30) or formula (Y31), and more preferably represented by formula (Y11), formula (Y15) or formula (Y30). It is a group.

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent n-alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. , Glycidyloxy group or — (CH ₂ ) _en —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, monovalent alicyclic hydrocarbon having 3 to 16 carbon atoms) Represents a group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).
Examples of the substituent for the monovalent alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms. -16 monovalent alicyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 monovalent aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C2 4 acyl group, glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, monovalent fat having 3 to 16 carbon atoms) Represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. Groups, 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, and naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of Y include the following. In the following groups, * is a bond to L ^b1 .

In the case where Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bonding position with Y. The group —CH ₂ — is preferably replaced by —O— or —CO—. In this case, —CH ₂ — contained in the methyl group of Y is not replaced with —O— or —CO—.

  Y is preferably a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is particularly preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

As the sulfonate anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-46) [hereinafter, anion (B1 -A-1) "or the like. ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula An anion represented by any one of (B1-A-33) and formulas (B1-A-36) to (B1-A-40) is more preferable. In Formula (B1-A-5), Formula (B1-A-7), Formula (B1-A-24), Formula (B1-A-30) to Formula (B1-A-33), R ⁱ² ˜R ⁱ⁷ is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. In Formula (B1-A-32) and Formula (B1-A-33), R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, or a carbon number. A monovalent alicyclic hydrocarbon group of 5 to 12 or a group formed by a combination thereof, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Among them, examples of the sulfonate anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-22), respectively.

  As the sulfonate anion in the salt represented by the formula (B1), the formula (B1a-1) to the formula (B1a-3), the formula (B1a-7) to the formula (B1a-16), and the formula (B1a-18). An anion represented by any one of formula (B1a-19) and formula (B1a-22) is preferred.

式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^b4〜Ｒ^b6は、それぞれ独立に、炭素数１〜３０の１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜３６の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の１価の脂肪族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の１価の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０〜５の整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１〜３６の１価の脂肪族炭化水素基又は炭素数３〜３６の１価の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b11は、水素原子、炭素数１〜３６の１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数３〜１８の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素に含まれる水素原子は、炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２のアルコキシ基又は炭素数１〜１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^b11とＲ^b12とは、一緒になってそれらが結合する−ＣＨ−ＣＯ−を含む環を形成していてもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b13〜Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の１価の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^b31は、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０〜５の整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０〜４の整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数のＲ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。 Examples of the organic cation of Z ⁺ include an organic onium cation such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, and preferably an organic sulfonium cation or an organic iodonium cation. More preferably an arylsulfonium cation.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formula (b2-1) to formula (b2-4) [hereinafter referred to as “cation (b2-1)” or the like depending on the formula number, etc. There is a case. ].

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or a monovalent alicyclic carbon group having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom or a carbon number 1 to 18 Which may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom, hydroxy Group or an alkoxy group having 1 to 12 carbon atoms may be substituted.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b7 and R ^b8 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b11 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic carbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. And a hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the monovalent aromatic hydrocarbon group The hydrogen atom to be substituted may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may together form a ring containing —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —SO—. Alternatively, it may be replaced by -CO-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 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, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when q2 is 2 or more, multiple R ^b15 are the same or different , When r2 is 2 or more, a plurality of R ^b16 are the same or different, when s2 is 2 or more, a plurality of R ^b17 are the same or different, and when t2 is 2 or more, a plurality of R ^b18 are the same or different Different.

特に、Ｒ^b9〜Ｒ^b12の１価の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 Monovalent aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2 -The alkyl group of an ethylhexyl group is mentioned. In particular, the monovalent aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic, and the monocyclic monovalent alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Examples thereof include cycloalkyl groups such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

In particular, the monovalent alicyclic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

  Examples of the monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, and a methylnorbornyl group. Group, isobornyl group and the like. In the monovalent alicyclic hydrocarbon group in which the hydrogen atom is substituted with a monovalent aliphatic hydrocarbon group, the total number of carbon atoms of the monovalent alicyclic hydrocarbon group and the monovalent aliphatic hydrocarbon group Is preferably 20 or less.

Examples of the monovalent aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p- Examples thereof include aryl groups such as an adamantylphenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
When the monovalent aromatic hydrocarbon group includes a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, the monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. Alternatively, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is preferable.
Examples of the monovalent aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the monovalent aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. .

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
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 that R ^b4 and R ^b5 may form together with the sulfur atom to which they are bonded is a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. There may be. Examples of the ring include a ring having 3 to 18 carbon atoms, and a ring having 4 to 18 carbon atoms is preferable. Moreover, the ring containing a sulfur atom includes a 3-membered ring to a 12-membered ring, and preferably a 3-membered ring to a 7-membered ring. For example, the following rings are mentioned.

The ring formed by R ^b9 and R ^b10 together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Good. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
The ring formed by ^combining R ^b11 and R ^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable.
Examples of the cation (b2-1) include the following cations.

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

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

Examples of the cation (b2-4) include the following cations.

  Preferred examples of the acid generator (B1) include those represented by the formulas (B1-1) to (B1-40). Among them, the formula (B1-1) and the formula (B) containing an arylsulfonium cation are preferable. B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1) -13), formula (B1-14), formula (B1-13), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-24), formula (B1- 25), Formula (B1-26), Formula (B1-29), Formula (B1-31), Formula (B1-32), Formula (B1-33), Formula (B1-34), Formula (B1-35) ), Formula (B1-36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40), respectively. Only preferable.

The content of the acid generator (B1) is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and substantially the acid content with respect to the total amount of the acid generator (B). More preferably, it is only the generator (B1).
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, and 99.9% by mass or less, preferably 99% by mass or less in the resist composition. 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 ethyl pyruvate Esters such as acetone, methyl isobutyl ketone, ketones such as 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be contained alone, or two or more kinds may be contained.

<Quencher (C)>
The resist composition of the present invention may contain a quencher (C). The content of the quencher (C) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.

  Examples of the quencher (C) include a salt that generates an acid having a lower acidity than an acid generated from a basic nitrogen-containing organic compound or an acid generator (B). Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

  Specifically, 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, tripentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyl Cyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldinonylamine Decylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4 , 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methyl Imidazole, pyridine, 4-methylpyridine, 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'-dipicolylamine, bipyridine and the like are preferable, diisopropylaniline is preferable, and 2,6-diisopropylaniline is particularly preferable.

  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.

<Slightly acidic salt>
The acidity in a salt that generates an acid having a weaker acidity than the acid generated from the acid generator is indicated by an acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. More preferably, the salt is 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid inner salt represented by the formula (D), and JP 2012-229206 A, JP Examples include salts described in JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A, and JP 2011-191745 A.

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１〜１２の１価の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４の整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^D2は同一又は相異なる。］ <Weak acid inner salt (D)>
The weak acid inner salt (D) is a compound represented by the formula (D).

[In the formula (D),
R ^D1 and R ^D2 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, or an acyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are Same or different. ]

In the compound represented by the formula (D), the hydrocarbon groups of R ^D1 and R ^D2 are a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon. And groups formed by combining these groups.
Examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, and nonyl group.
The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be either saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, and cyclododecyl group, norbornyl group, adamantyl group, and the like.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4- Propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group , Aryl groups such as cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
Examples of the group formed by combining these include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1 -Propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6 -Phenyl-1-hexyl group, etc.).

Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, and a cyclohexanecarbonyl group.
Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (—CO—) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the formula (D), R ^D1 and R ^D2 each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. Preferred are an acyl group having 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ are each independently preferably an integer of 0 to 2, and more preferably 0. When m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are the same or different.

Examples of the weak acid inner salt (D) include the following compounds.

  The weak acid inner salt (D) can be produced by the method described in “Tetrahedron Vol. 45, No. 19, p6281-6296”. A commercially available compound can be used as the weak acid inner salt (D).

  The content of the quencher (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass in the solid content of the resist composition. % By mass.

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

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A) and an acid generator (B), and a quencher (C), a solvent (E) and other components (F) used as necessary. 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 from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (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.

  The resist composition can be applied onto the substrate by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various 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. In this specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction in the acid labile group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).
The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention includes a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly ArF. It is suitable as a resist composition for excimer laser exposure and is useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore 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 molecular peaks using mass spectrometry (LC: Agilent model 1100, MASS: Agilent LC / MSD model). In the following examples, the value of this molecular peak is indicated by “MASS”.

式（Ｉ−１−ａ）で表される化合物１０．００部、式（Ｉ−１−ｂ）で表される化合物７．７１部及びクロロホルム８０部を添加し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ−１−ｃ）で表される化合物１９．９５部を添加した後、２３℃で３８時間攪拌した。得られた反応混合物に、酢酸エチル２４０部及び５％塩酸３７部を添加撹拌し、分液して有機層を取り出した。回収された有機層に、イオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層に、１０％炭酸カリウム水溶液３０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層に、イオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｉ−１―ｆ）で表される化合物１０．４２部を得た。

式（Ｉ−１−ｄ）で表される化合物１０．００部、テトラヒドロフラン５０部及びピリジン２．６９部を添加し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、式（Ｉ−１−ｅ）で表される化合物３．８５部を添加し、３０分間撹拌し、さらに、２３℃で１時間攪拌した。得られた反応混合物に、酢酸エチル２００部及び５％塩酸３０部を添加撹拌し、分液して有機層を取り出した。回収された有機層に、イオン交換水４０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層に、１０％炭酸カリウム水溶液１５部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層に、イオン交換水６０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｉ−１）で表される化合物６．１９部を得た。
ＭＳ（質量分析）：４２０．２（分子イオンピーク） Example 1: Synthesis of compound represented by formula (I-1)

10.00 parts of the compound represented by the formula (I-1-a), 7.71 parts of the compound represented by the formula (I-1-b) and 80 parts of chloroform were added and stirred at 23 ° C. for 30 minutes. . After adding 19.95 parts of a compound represented by the formula (I-1-c) to the obtained mixed solution, the mixture was stirred at 23 ° C. for 38 hours. To the obtained reaction mixture, 240 parts of ethyl acetate and 37 parts of 5% hydrochloric acid were added and stirred, followed by liquid separation to take out the organic layer. To the collected organic layer, 50 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the collected organic layer, 30 parts of a 10% aqueous potassium carbonate solution was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the collected organic layer, 50 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated 5 times. The organic layer after washing with water was concentrated, and the resulting concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate) to obtain a formula. 10.42 parts of a compound represented by (I-1-f) was obtained.

10.00 parts of the compound represented by the formula (I-1-d), 50 parts of tetrahydrofuran and 2.69 parts of pyridine were added, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. To the obtained mixed solution, 3.85 parts of the compound represented by the formula (I-1-e) was added, stirred for 30 minutes, and further stirred at 23 ° C. for 1 hour. To the obtained reaction mixture, 200 parts of ethyl acetate and 30 parts of 5% hydrochloric acid were added and stirred, followed by liquid separation to take out the organic layer. To the recovered organic layer, 40 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the collected organic layer, 15 parts of 10% aqueous potassium carbonate solution was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the recovered organic layer, 60 parts of ion exchange water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated 5 times. The organic layer after washing with water was concentrated, and the resulting concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate) to obtain a formula. 6.19 parts of the compound represented by (I-1) were obtained.
MS (mass spectrometry): 420.2 (molecular ion peak)

式（Ｉ−１−ｃ）で表される化合物３．１２部、テトラヒドロフラン３０部及びピリジン０．８４部を添加し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、式（Ｉ−２−ａ）で表される化合物１．２０部を添加し、２３℃まで昇温した。その後、さらに、２３℃で１時間攪拌した。得られた反応混合物に、クロロホルム１００部及び５％塩酸７．７４を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機層に、１０％炭酸カリウム水溶液４．４１部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機層に、イオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を４回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−２−ｂ）で表される化合物２．８４部を得た。

式（Ｉ−２−ｃ）で表される化合物０．５０部、ジメチルホルムアミド５部及び炭酸カリウム０．４０部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−２−ｂ）で表される化合物２．４９部を添加し、５０℃で５時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水２５部を仕込み、２３℃で３０分間攪拌した。これを静置し、分液することにより有機層を水洗した。回収された有機層に、イオン交換水２５部を仕込み、２３℃で３０分間攪拌し、静置し、分液することにより有機層を回収した。このような洗浄操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｉ−２）で表される化合物２．１１部を得た。
ＭＳ（質量分析）：４７８．２（分子イオンピーク） Example 2: Synthesis of compound represented by formula (I-2)

3.12 parts of the compound represented by the formula (I-1-c), 30 parts of tetrahydrofuran and 0.84 part of pyridine were added, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. To the obtained mixed solution, 1.20 parts of the compound represented by the formula (I-2-a) was added, and the temperature was raised to 23 ° C. Thereafter, the mixture was further stirred at 23 ° C. for 1 hour. To the obtained reaction mixture, 100 parts of chloroform and 7.74 of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the obtained organic layer, 4.41 parts of 10% aqueous potassium carbonate solution was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated 4 times. The obtained organic layer was concentrated to obtain 2.84 parts of a compound represented by the formula (I-2-b).

0.50 part of the compound represented by the formula (I-2-c), 5 parts of dimethylformamide and 0.40 part of potassium carbonate were mixed with stirring at 23 ° C. for 30 minutes. To the obtained mixture, 2.49 parts of a compound represented by the formula (I-2-b) was added and stirred at 50 ° C. for 5 hours. The obtained reaction product was charged with 50 parts of chloroform and 25 parts of ion-exchanged water, and stirred at 23 ° C. for 30 minutes. The organic layer was washed with water by standing and separating. To the recovered organic layer, 25 parts of ion-exchanged water was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated, and the resulting concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate) to obtain a formula. 2.11 parts of the compound represented by (I-2) was obtained.
MS (mass spectrometry): 478.2 (molecular ion peak)

式（Ｉ−９−ａ）で表される化合物３．０７部、ジメチルホルムアミド３０部及び炭酸カリウム０．８０部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−９−ｂ）で表される化合物１．０７部を添加し、５０℃で５時間攪拌した。得られた反応混合物に、クロロホルム２００部を添加撹拌した。得られた混合物に、イオン交換水１００部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／５）することにより、式（Ｉ−９）で表される化合物２．４８部を得た。
ＭＳ（質量分析）：３２０．２（分子イオンピーク） Example 3: Synthesis of compound represented by formula (I-9)

3.07 parts of the compound represented by the formula (I-9-a), 30 parts of dimethylformamide and 0.80 part of potassium carbonate were mixed with stirring at 23 ° C. for 30 minutes. To the obtained mixture, 1.07 part of a compound represented by the formula (I-9-b) was added and stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 200 parts of chloroform was added and stirred. To the obtained mixture, 100 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated three times. The organic layer after washing with water is concentrated, and the resulting concentrate is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/5). This gave 2.48 parts of the compound represented by the formula (I-9).
MS (mass spectrometry): 320.2 (molecular ion peak)

式（Ｉ−１７−ａ）で表される化合物３．０７部、ジメチルホルムアミド３０部及び炭酸カリウム０．８０部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−９−ｂ）で表される化合物１．０７部を添加し、５０℃で５時間攪拌した。得られた反応混合物に、クロロホルム２００部を添加撹拌した。得られた混合物に、イオン交換水１００部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／５）することにより、式（Ｉ−１７）で表される化合物２．２８部を得た。
ＭＳ（質量分析）：３２０．２（分子イオンピーク） Example 4: Synthesis of compound represented by formula (I-17)

3.07 parts of the compound represented by the formula (I-17-a), 30 parts of dimethylformamide and 0.80 part of potassium carbonate were mixed with stirring at 23 ° C. for 30 minutes. To the obtained mixture, 1.07 part of a compound represented by the formula (I-9-b) was added and stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 200 parts of chloroform was added and stirred. To the obtained mixture, 100 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated three times. The organic layer after washing with water is concentrated, and the resulting concentrate is subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/5). This gave 2.28 parts of the compound represented by the formula (I-17).
MS (mass spectrometry): 320.2 (molecular ion peak)

式（Ｉ−２９−ａ）で表される化合物３．００部及びメタノール１００部を添加し、２３℃で３０分間攪拌した。得られた混合溶液に、トリエチルアミン２．７９部を添加した。その後、これに、式（Ｉ−２９−ｂ）で表される化合物２．２２部を３０分かけて滴下し、さらに、２３℃で１８時間攪拌した。得られた反応混合物に、クロロホルム２００部を添加撹拌した。得られた混合物に、イオン交換水１００部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−２９−ｃ）で表される化合物３．７５部を得た。

式（Ｉ−２９−ｃ）で表される化合物２．００部、テトラヒドロフラン３０部及式（Ｉ−２９−ｄ）で表される化合物０．９９部を添加し、２３℃で３０分間攪拌した後、６０℃で５時間撹拌することにより、式（Ｉ−２９−ｅ）で表される化合物を含む溶液を得た。

式（Ｉ−２９−ｅ）で表される化合物を含む溶液に、式（Ｉ−２９−ｆ）で表される化合物０．７９部を添加し、５０℃で５時間攪拌した。得られた反応物に、クロロホルム３０部及びイオン交換水１５部を仕込み、２３℃で３０分間攪拌した。これを静置した後、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１５部を仕込み、２３℃で３０分間攪拌し、静置し、分液することにより有機層を回収した。このような洗浄操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｉ−２９―ｇ）で表される化合物１．８８部を得た。

式（Ｉ−２９―ｇ）で表される塩０．９８部及びアセトニトリル１５部を仕込み、２３℃で３０分間攪拌した。これに、１％塩酸０．５０部を添加し、８０℃で３時間攪拌し、濃縮することにより、式（Ｉ−２９−ｈ）で表される化合物０．６８部を得た。

式（Ｉ−２９−ｈ）で表される化合物０．４６部、ジメチルホルムアミド１０部及び炭酸カリウム０．１６部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−９−ｂ）で表される化合物０．２１部を添加し、５０℃で５時間攪拌した。得られた反応混合物に、クロロホルム２０部を添加撹拌した。得られた混合物に、イオン交換水１０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−２９）で表される化合物０．３６部を得た。
ＭＳ（質量分析）：５０８．２（分子イオンピーク） Example 5: Synthesis of compound represented by formula (I-29)

3.00 parts of a compound represented by the formula (I-29-a) and 100 parts of methanol were added and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 2.79 parts of triethylamine was added. Thereafter, 2.22 parts of the compound represented by the formula (I-29-b) was added dropwise thereto over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction mixture, 200 parts of chloroform was added and stirred. To the obtained mixture, 100 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated three times. The obtained organic layer was concentrated to obtain 3.75 parts of a compound represented by the formula (I-29-c).

2.00 parts of a compound represented by the formula (I-29-c), 30 parts of tetrahydrofuran and 0.99 parts of a compound represented by the formula (I-29-d) were added and stirred at 23 ° C. for 30 minutes. Then, the solution containing the compound represented by a formula (I-29-e) was obtained by stirring at 60 degreeC for 5 hours.

To a solution containing the compound represented by the formula (I-29-e), 0.79 part of the compound represented by the formula (I-29-f) was added and stirred at 50 ° C. for 5 hours. To the obtained reaction product, 30 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. After standing still, the organic layer was washed with water by liquid separation. The recovered organic layer was charged with 15 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated, and the resulting concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate) to obtain a formula. 1.88 parts of the compound represented by (I-29-g) were obtained.

0.98 part of the salt represented by the formula (I-29-g) and 15 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. To this, 0.50 part of 1% hydrochloric acid was added, stirred at 80 ° C. for 3 hours, and concentrated to obtain 0.68 part of a compound represented by the formula (I-29-h).

0.46 part of a compound represented by the formula (I-29-h), 10 parts of dimethylformamide and 0.16 part of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. To the obtained mixture, 0.21 part of a compound represented by the formula (I-9-b) was added, and the mixture was stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 20 parts of chloroform was added and stirred. To the obtained mixture, 10 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated three times. The obtained organic layer was concentrated to obtain 0.36 parts of a compound represented by the formula (I-29).
MS (mass spectrometry): 508.2 (molecular ion peak)

式（Ｉ−２９−ｈ）で表される化合物０．４６部、ジメチルホルムアミド１０部及び炭酸カリウム０．１６部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−４６−ｂ）で表される化合物０．３１部を添加し、５０℃で５時間攪拌した。得られた反応混合物に、クロロホルム２０部を添加撹拌した。得られた混合物に、イオン交換水１０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−４６）で表される化合物０．３９部を得た。
ＭＳ（質量分析）：５９２．３（分子イオンピーク） Example 6: Synthesis of compound represented by formula (I-46)

0.46 part of a compound represented by the formula (I-29-h), 10 parts of dimethylformamide and 0.16 part of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. To the obtained mixture, 0.31 part of a compound represented by the formula (I-46-b) was added and stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 20 parts of chloroform was added and stirred. To the obtained mixture, 10 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This operation was repeated three times. The obtained organic layer was concentrated to obtain 0.39 parts of a compound represented by the formula (I-46).
MS (mass spectrometry): 592.3 (molecular ion peak)

式（Ｂ１−５−ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応器に仕込み、２３℃で３０分間攪拌し、式（Ｂ１−５−ｂ）で表される化合物１６．２７部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１−５−ｃ）で表される塩を含む溶液を得た。得られた式（Ｂ１−５−ｃ）で表される塩を含む溶液に、式（Ｂ１−５−ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加し、２３℃で１２時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、さらに、該クロロホルム層にイオン交換水８４．１５部を添加し、水洗した。この操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部を添加攪拌した後、ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１２５．８７部を添加攪拌し、濃縮した。得られた残渣に、アセトニトリル２０．６２部及びｔｅｒｔ−ブチルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌し、上澄み液を除去し、濃縮した。得られた残渣に、ｎ−ヘプタン２００部を添加、２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１−５）で表される塩６１．５４部を得た。 Synthesis Example 1: Synthesis of salt represented by formula (B1-5)

A compound represented by the formula (B1-5-b) was prepared by charging 50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform with stirring at 23 ° C for 30 minutes. 16.27 parts was dripped, and the solution containing the salt represented by a formula (B1-5-c) was obtained by stirring at 23 degreeC for 1 hour. To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water are added, The mixture was stirred at 23 ° C. for 12 hours. Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. To the obtained chloroform layer, 3.88 parts of activated carbon was added and stirred, followed by filtration. The collected filtrate was concentrated, and 125.87 parts of acetonitrile was added to the resulting residue, and the mixture was stirred and concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added and stirred at 23 ° C. for 30 minutes, and the supernatant was removed and concentrated. To the obtained residue, 200 parts of n-heptane was added, stirred at 23 ° C. for 30 minutes, and filtered to obtain 61.54 parts of the salt represented by the formula (B1-5).

MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (−) Spectrum): M ^- 339.1

Synthesis Example 2: Synthesis of salt represented by formula (B1-21)

30.00 parts of a compound represented by the formula (B1-21-b) obtained by the method described in JP-A-2008-209917, and a salt 35.50 represented by the formula (B1-21-a). Part, 100 parts of chloroform, and 50 parts of ion-exchanged water were stirred at 23 ° C. for 15 hours.
Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 30 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 100 parts of tert-butyl methyl ether was added to the resulting residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then filtered to obtain the salt 48 represented by the formula (B1-21-c). .57 parts were obtained.

式（Ｂ１−２１−ｃ）で表される塩２０．００部、式（Ｂ１−２１−ｄ）で表される化合物２．８４部及びモノクロロベンゼン２５０部を仕込み、２３℃で３０分間攪拌した。
得られた混合液に、二安息香酸銅（ＩＩ）０．２１部を添加した後、更に、１００℃で１時間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム２００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮した。得られた残渣を、アセトニトリル５３．５１部に溶解し、濃縮した。これに、ｔｅｒｔ−ブチルメチルエーテル１１３．０５部を加えて攪拌し、ろ過することにより、式（Ｂ１−２１）で表される塩１０．４７部を得た。

20.00 parts of a salt represented by the formula (B1-21-c), 2.84 parts of a compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23 ° C. for 30 minutes. .
After adding 0.21 part of copper (II) dibenzoate to the obtained liquid mixture, it stirred at 100 degreeC for further 1 hour. The resulting reaction solution was concentrated. To the obtained residue, 200 parts of chloroform and 50 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, separated, and the organic layer was taken out. 50 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated. The obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. To this, 113.05 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 10.47 parts of the salt represented by the formula (B1-21).

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (−) Spectrum): M ^- 339.1

Synthesis Example 3: Synthesis of salt represented by formula (B1-22)

  11.26 parts of a salt represented by the formula (B1-22-a), 10.00 parts of a compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of ion-exchanged water were charged at 23 ° C. For 15 hours. Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 15 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 50 parts of tert-butyl methyl ether was added to the resulting residue, and the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain the salt represented by the formula (B1-22-c) 11. 75 parts were obtained.

式（Ｂ１−２２−ｃ）で表される塩１１．７１部、式（Ｂ１−２２−ｄ）で表される化合物１．７０部及びモノクロロベンゼン４６．８４部を仕込み、２３℃で３０分間攪拌した。得られた混合液に、二安息香酸銅（ＩＩ）０．１２部を添加した後、更に、１００℃で３０分間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム５０部及びイオン交換水１２．５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この水洗操作を８回繰り返した。得られた有機層を濃縮した。得られた残渣に、ｔｅｒｔ−ブチルメチルエーテル５０部を加えて攪拌し、ろ過することにより、式（Ｂ１−２２）で表される塩６．８４部を得た。

11.71 parts of a salt represented by the formula (B1-22-c), 1.70 parts of a compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged, and the mixture was charged at 23 ° C. for 30 minutes. Stir. After adding 0.12 part of copper (II) dibenzoate to the obtained liquid mixture, it stirred at 100 degreeC for 30 minutes further. The resulting reaction solution was concentrated. To the obtained residue, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. 12.50 parts of ion-exchanged water was added to the collected organic layer, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This washing operation was repeated 8 times. The obtained organic layer was concentrated. To the obtained residue, 50 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 6.84 parts of the salt represented by the formula (B1-22).

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

以下、これらのモノマーを式番号に応じて「モノマー（ａ１−１−３）」等という。 Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Example 7 [Synthesis of Resin A1]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A1 (copolymer) having a weight average molecular weight of 8.5 × 10 ^{3 in} a yield of 58%. It was. This resin A1 has the following structural units.

Example 8 [Synthesis of Resin A2]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-2), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-2): monomer (a2-1-1): monomer (a3-4-2)]] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A2 (copolymer) having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 64%. It was. This resin A2 has the following structural units.

Example 9 [Synthesis of Resin A3]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-7), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-7): monomer (a2-1-1): monomer (a3-4-2)]] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin A3 (copolymer) having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 60%. It was. This resin A3 has the following structural units.

Example 10 [Synthesis of Resin A4]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-9), the monomer (a2-1-1) and the monomer (a3-4-2) are used and their moles are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-9): monomer (a2-1-1): monomer (a3-4-2)] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A4 (copolymer) having a weight average molecular weight of 7.8 × 10 ^{3 in} a yield of 58%. It was. This resin A4 has the following structural units.

Example 11 [Synthesis of Resin A5]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-29), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-29): monomer (a2-1-1): monomer (a3-4-2)] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A5 (copolymer) having a weight average molecular weight of 8.6 × 10 ^{3 in} a yield of 61%. It was. This resin A5 has the following structural units.

Example 12 [Synthesis of Resin A6]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-46), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-46): monomer (a2-1-1): monomer (a3-4-2)] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin A6 (copolymer) having a weight average molecular weight of 8.0 × 10 ^{3 in} a yield of 57%. It was. This resin A6 has the following structural units.

Synthesis Example 4 [Synthesis of Resin AX1]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (IX-1), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (IX-1): monomer (a2-1-1): monomer (a3-4-2)] is 38:14: The mixture was mixed to 5: 3: 40, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin AX1 (copolymer) having a weight average molecular weight of 8.1 × 10 ^{3 in} a yield of 60%. It was. This resin AX1 has the following structural units.

Synthesis Example 5 [Synthesis of Resin X1]
As the monomer, monomer (a5-1-1) and monomer (a4-0-12) were used, and the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X1 (copolymer) having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 91%. Got in. This resin X1 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was dissolved in a solvent in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition. The prepared resist composition was stored at 30 ° C. for 3 weeks, and then the resist characteristics were evaluated.

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２−ヘプタノン ２０部
γ−ブチロラクトン ３．５部 <Resin>
A1 to A6, AX1, X1: Resin A1 to Resin A6, Resin AX1, Resin X1
<Acid generator>
B1-5: salt represented by formula (B1-5) B1-21: salt represented by formula (B1-21) B1-22: salt represented by formula (B1-22) <weak acid inner salt (D)>
D1: (Tokyo Chemical Industry Co., Ltd.)

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

<Manufacture of resist pattern and its evaluation>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After the application, this silicon wafer was pre-baked on a direct hot plate at a temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer on the silicon wafer.
An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annual σ _out = 0.85 σ _in = 0.65 XY− pol. Illumination], using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the obtained resist pattern, the exposure amount at which the width of the trench pattern was 40 nm was defined as effective sensitivity.

<Focus margin evaluation (DOF)>
A negative resist pattern was manufactured in the same manner as described above except that the exposure was performed while changing the focus stepwise in terms of effective sensitivity. In the obtained resist pattern, the focus range in which the width of the trench pattern is 40 nm ± 5% (38 to 42 nm) was defined as DOF (nm). The results are shown in Table 2.

  Since the resist composition of the present invention is excellent in the focus margin (DOF) of the resist pattern to be obtained, it is suitable for semiconductor microfabrication and is extremely useful industrially.

Claims (9)

A compound represented by formula (I).

[In the formula (I),
R ⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —CO—O—A ³ —, ^* —A ⁴ —O—CO—A ⁵ —, ^* —A ⁶ —O—A ⁷ — or ^* —A ⁸ —O. —CO—O—A ⁹ — is represented. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantanediyl group or an adamantanetriyl group.
A ¹⁰ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. When n is 2, two R ¹ may be the same or different.
R ¹ independently represents a group containing a cyclic ether structure or a hydrogen atom. However, when n is 2, at least one of R ¹ represents a group containing a cyclic ether structure. ] The compound according to claim 1, wherein A ¹ is a single bond or ^* —CH ₂ —CO—O—. The compound according to claim 1 or 2, wherein the organic group containing a cyclic ether structure of R ¹ is a monovalent group represented by the formula (IA) or a divalent group represented by the formula (IB).

[In Formula (IA) and Formula (IB),
s3, s4, and s5 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
* Represents a bond. ]   Resin containing the structural unit derived from the compound in any one of Claims 1-3.   The resin according to claim 4, further comprising a structural unit having an acid labile group. 6. The resin according to claim 5, wherein the structural unit having an acid labile group is a structural unit represented by formula (a1-1) or formula (a1-2).

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]   A resist composition comprising the resin according to any one of claims 4 to 6 and an acid generator.   The resist composition according to claim 7, further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator. (1) The process of apply | coating the resist composition of Claim 7 or 8 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.