JP2021181443A - Compound, resin, resist composition and production method of resist pattern - Google Patents

Abstract

To provide a compound capable of producing a resist pattern of an excellent mask error factor (MEF), to provide a resin, and to provide a resist composition containing the resin.SOLUTION: There are provided: a compound represented by a formula (I); a resin derived from the compound; and a resist composition containing the resin. [In the formula, R1 represents an alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom. R2 and R3 each independently represent an alkyl group. n represents an integral number of 1-6. R represents a 1-adamantyl group which may have an alkyl group or *-CHR4R5. * represents a bonding position. R4 and R5 each independently represent a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or their combined group, or R4 and R5 are bonded each other and form a divalent alicyclic hydrocarbon group together with carbon atoms to which they are bonded.]SELECTED DRAWING: None

Description

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

特許文献２には、下記化合物に由来する構造単位を含む樹脂を含有するレジスト組成物
が記載されている。

特許文献３には、下記化合物に由来する構造単位を含む樹脂を含有するレジスト組成物
が記載されている。

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

Patent Document 2 describes a resist composition containing a resin containing a structural unit derived from the following compound.

Patent Document 3 describes a resist composition containing a resin containing a structural unit derived from the following compound.

Japanese Unexamined Patent Publication No. 2008-268740 Japanese Unexamined Patent Publication No. 11-24274 Japanese Unexamined Patent Publication No. 2014-112158

The resist pattern formed from the resist composition containing the above resin may not always be satisfied with the mask error factor (MEF).

［式（Ｉ）中、
Ｒ^１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^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
ｎは、１〜６の整数を表す。
Ｒは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４
Ｒ^５を表す。＊は結合位を表す。
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、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か、Ｒ^４及びＲ^５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３〜１８の２価の脂環式炭化水素基を形
成する。］
〔２〕Ｒは、１−アダマンチル基又はＲ^４及びＲ^５が互いに結合してそれらが結合する
炭素原子とともに炭素数３〜１２の２価の脂環式炭化水素基である〔１〕記載の化合物。
〔３〕Ｒ^２及びＲ^３は、メチル基である〔１〕又は〔２〕記載の化合物。
〔４〕ｎは、２である〔１〕〜〔３〕のいずれかに記載の化合物。
〔５〕〔１〕〜〔４〕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。
〔６〕さらに、式（Ｉ）で表される化合物に由来する構造単位とは異なる酸不安定基を
有する構造単位を含む〔５〕記載の樹脂。
〔７〕式（Ｉ）で表される化合物に由来する構造単位とは異なる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〔６〕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。］
〔８〕〔５〕〜〔７〕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
。
〔９〕酸発生剤が、式（Ｂ１）で表される塩である〔８〕記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル
基を表す。
Ｌ^b1は、炭素数１〜２４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３〜１
８の１価の脂環式炭化水素基を表し、該メチル基及び該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。］
〔１０〕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
〔８〕又は〔９〕に記載のレジスト組成物。
〔１１〕（１）〔８〕〜〔１０〕のいずれかに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 formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ² and R ³ each independently represent an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 6.
R may have an alkyl group having 1 to 8 carbon atoms as a 1-adamantyl group or * -CHR ⁴
It represents an R ^5. * Represents the binding site.
R ⁴ and R ⁵ each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 3 carbon atoms.
Represent a 18 alicyclic hydrocarbon group or a group composed of a combination of these, divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms together with the carbon atoms R ⁴ and R ⁵ which binds them combine with each other To form. ]
[2] R is 1-adamantyl group, or R ⁴ and R ⁵ are bonded to each other together with the carbon atoms to which they are attached a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms [1], wherein Compound.
[3] The compound according to [1] or [2], ^{wherein R 2} and R ^{3 are methyl groups.}
[4] n is the compound according to any one of [1] to [3], which is 2.
[5] A resin containing a structural unit derived from the compound according to any one of [1] to [4].
[6] The resin according to [5], further containing a structural unit having an acid unstable group different from the structural unit derived from the compound represented by the formula (I).
[7] A structural unit having an acid unstable group different from the structural unit derived from the compound represented by the formula (I) is a structural unit represented by the formula (a1-1) or the formula (a1-2). A resin according to [6].

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent −O− or ^* −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents a bond with −CO−. Represent 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 them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ]
[8] A resist composition containing the resin and acid generator according to any one of [5] to [7].
[9] The resist composition according to [8], wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
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 with −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 may have a methyl group or a substituent which may have a substituent, and may have 3 to 1 carbon atoms.
_{Representing a monovalent alicyclic hydrocarbon group of 8, -CH 2} − contained in the methyl group and the monovalent alicyclic hydrocarbon group becomes −O−, −SO ₂ − or −CO−. It may be replaced.
Z ⁺ represents an organic cation. ]
[10] The resist composition according to [8] or [9], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[11] (1) A step of applying the resist composition according to any one of [8] to [10] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using the resist composition of the present invention, a good mask error factor (MEF) is used.
), The resist pattern can be manufactured.

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, "aliphatic hydrocarbon group" means a linear or branched hydrocarbon group, and "aliphatic hydrocarbon group" means fat. It means a group obtained by removing a number of hydrogen atoms corresponding to a valence from the ring of a cyclic hydrocarbon. "Aromatic hydrocarbon groups"
Also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
As used herein, the term "(meth) acrylate" means "at least one of acrylate and methacrylate," respectively. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

［式（Ｉ）中、
Ｒ^１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^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
ｎは、１〜６の整数を表す。
Ｒは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４
Ｒ^５を表す。＊は結合位を表す。
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、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か、Ｒ^４及びＲ^５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３〜１８の２価の脂環式炭化水素基を形
成する。］ [Compound (I)]
The compound of the present invention is a compound represented by the formula (I) (hereinafter, may be referred to as “compound (I)”).

[In formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ² and R ³ each independently represent an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 6.
R may have an alkyl group having 1 to 8 carbon atoms as a 1-adamantyl group or * -CHR ⁴
It represents an R ^5. * Represents the binding site.
R ⁴ and R ⁵ each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 3 carbon atoms.
Represent a 18 alicyclic hydrocarbon group or a group composed of a combination of these, divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms together with the carbon atoms R ⁴ and R ⁵ which binds them combine with each other To form. ]

The alkyl group of R ¹ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like.
Examples thereof include an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group and a methyl group. It is an ethyl group.
Examples of the halogen atom of R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Alkyl groups having a halogen atom of R ¹ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a perchloromethyl group, a perbromomethyl group and a periodomethyl group.
R ¹ is preferably a hydrogen atom or a methyl group.

Examples ^{of the alkyl group of R 2} and R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec-butyl group, and an alkyl group having 1 to 3 carbon atoms is preferable. , More preferably a methyl group and an ethyl group, and even more preferably.
It is a methyl group.

n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
It is more preferably 1 or 2, and particularly preferably 2.

The alkyl group that the adamantyl group of R may have includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and n.
Examples thereof include a-pentyl group and an n-hexyl group, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group and an ethyl group.
Examples ^{of the alkyl group of R 4} and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec-butyl group, and an alkyl group having 1 to 3 carbon atoms is preferable. , More preferably a methyl group and an ethyl group, and even more preferably.
It is a methyl group.
The alicyclic hydrocarbon group of R ⁴ and R ⁵ may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group. The alicyclic hydrocarbon groups of R ⁴ and R ⁵ preferably have 3 to 12 carbon atoms.
The group formed by combining the alkyl group and the alicyclic hydrocarbon group of R ⁴ and R ^5, for example,
Examples thereof include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbornylmethyl group and the like.

なお、Ｒ^４及びＲ^５が互いに結合して形成する脂環式炭化水素基に含まれる水素原子は
、炭素数１〜８のアルキル基で置換されていてもよい。この場合、酸素原子に結合する炭
素原子にはアルキル基は置換されない。
Ｒは、好ましくは、単環のシクロアルキル基又は１−アダマンチル基であり、より好ま
しくは、シクロペンチル基、シクロヘキシル基、１−アダマンチル基である。 ^{-CHR 4} R when R ⁴ and R ⁵ are bonded to each other to form a divalent alicyclic hydrocarbon group.
^{Examples of 5} include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a monovalent cycloalkanediyl group. * Represents a bond with -O-.

The ^{hydrogen atom contained in the alicyclic hydrocarbon group formed by bonding R 4} and R ⁵ to each other may be substituted with an alkyl group having 1 to 8 carbon atoms. In this case, the alkyl group is not substituted on the carbon atom bonded to the oxygen atom.
R is preferably a monocyclic cycloalkyl group or 1-adamantyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 1-adamantyl group.

Examples of the compound (I) include a compound represented by the following formula and a compound in which ^{a methyl group corresponding to R 1} is replaced with a hydrogen atom.

溶媒としては、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、ピリジン、ジメチルアミノピリジンなどが挙げられる。
式（Ｉ−ｂ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場
より容易に入手することができる。

化合物（Ｉ−ａ）は、式（Ｉ−ｃ）で表される化合物と式（Ｉ−ｄ１）で表される化合
物又は式（Ｉ−ｄ２）で表される化合物とを、触媒の存在下、溶媒中で、反応させること
により製造することができる。

溶媒としては、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。
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（Ｉ−ｃ）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（Ｉ−ｄ１）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（Ｉ−ｄ２）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。

<Method for producing compound (I)>
Compound (I) can be produced by reacting a compound represented by the formula (Ia) with a compound represented by the formula (Ib) in the presence of a base catalyst in a solvent. .. In the following equation, R ¹ , R ² , R ³ and R have the same meanings as above.

Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
Examples of the base catalyst include pyridine, dimethylaminopyridine and the like.
Examples of the compound represented by the formula (I-b) include compounds represented by the following formula, which can be easily obtained from the market.

The compound (I-a) is a compound represented by the formula (I-c) and a compound represented by the formula (Id1) or a compound represented by the formula (Id2) in the presence of a catalyst. , Can be produced by reacting in a solvent.

Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
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 the base catalyst and a known esterification catalyst may coexist. ..
Examples of the compound represented by the formula (I-c) include compounds represented by the following, which are easily available on the market.

Examples of the compound represented by the formula (Id1) include compounds represented by the following.
Easily available on the market.

Examples of the compound represented by the formula (I-d2) include compounds represented by the following.
Easily available on the market.

Examples of the carbodiimide catalyst include salts represented by the following formulas, which 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, may be referred to as “structural unit (I)”) (hereinafter, may be referred to as “resin (A)”). Resin (A)
May be a homopolymer containing one type of structural unit (I) or a copolymer containing two or more types of structural unit (I).
The resin (A) may be composed of only the structural unit (I), or may include a structural unit other than the structural unit (I). In the resin (A), the content of the structural unit (I) is 1 to 100 mol%, preferably 3 to 60 mol%, based on all the structural units of the resin (A).
5 to 50 mol% is more preferable, and 10 to 40 mol% is even more preferable.

The resin (A) preferably contains an acid unstable group in addition to the structural unit (I), and may contain a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). It is preferably a resin having. Here, the acid unstable group means a group having a leaving group, and the leaving group is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group).

The resin (A) may be further referred to as a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”) or another structural unit (hereinafter, may be referred to as “structural unit (t)”). ) And 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。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”). As the acid unstable group contained in the structural unit (a1), the following groups (1) and / or groups (2) are preferable.

[In the formula (1), R ^{a1 to} R ^a3 are independently alkyl groups having 1 to 8 carbon atoms and 3 carbon atoms.
Represents an alicyclic hydrocarbon group of ~ 20 or a group combining these, or R ^a1 and R ^a2 are divalent alicyclic hydrocarbons having 3 to 20 carbon atoms together with carbon atoms to which they are bonded to each other. Form a group.
na represents 0 or 1.
* Represents a bond. ]

[In the 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. Represent or R ^a2'and R ^a3'
Form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the hydrocarbon group and −CH ₂ − contained in the divalent heterocyclic group are , -O- or -S- may be replaced.
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、例えば、メチルシクロヘ
キシル基、ジメチルシクロへキシル基、メチルノルボルニル基、メチルアダマンチル基、
シクロヘキシルメチル基、メチルシクロヘキシルメチル基、アダマンチルメチル基、ノル
ボルニルメチル基等が挙げられる。
ｎａは、好ましくは０である。 The alkyl groups of R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like.
Examples thereof include an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.
The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 may be either a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates 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 the alkyl group and the alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and a methyladamantyl group.
Examples thereof include a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like.
na is preferably 0.

^{-C (R a1} ) when R ^a1 and R a ² are bonded to each other to form a divalent alicyclic hydrocarbon group.
Examples of (R ^a2 ) and (R ^a3 ) include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the hydrocarbon group R ^{a1 '~R a3',} for example, an alkyl group, an alicyclic hydrocarbon group, and a group formed by combining an aromatic hydrocarbon group and thereof.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group, mesityl group and biphenyl. Examples thereof include an aryl group such as a group, a phenanthryl group, a 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl.
R ^a2'and R ^a3' bond to each other and form with the carbon atoms and X to which they bond 2
Examples of the valence heterocyclic group include the following groups. * Represents a bond.

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-Alkyl adamantan-2-yloxycarbonyl group (in formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (group) and 1- (in the formula (1)). Examples thereof include adamantan-1-yl) -1- ^{alkylalkoxycarbonyl group (in the formula (1), R a1} and R ^a2 are alkyl groups and R ^a3 is an adamantyl group).
Of R ^{a1 'and} R ^a2', it is preferable that at least one is a hydrogen atom.

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

The monomer (a1) is preferably a monomer having an acid unstable group and an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer having an acid unstable group.

Of the (meth) acrylic monomers having an acid unstable group, preferably 5 to 20 carbon atoms.
Examples thereof include those having an alicyclic hydrocarbon group of. If the resin (A) having a structural unit derived from the monomer (a1) 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 the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1), the structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). Examples thereof include a structural unit or a structural unit represented by the formula (a1-2). These may be used alone
Two or more kinds may be used together. In the present specification, the structural unit represented by the formula (a1-0), the formula (a).
The structural unit represented by 1-1) and the structural unit represented by the formula (a1-2) are referred to as a structural unit (a1-0), a structural unit (a1-1), and a structural unit (a1-2), respectively. , Structural unit (a1-
Monomer for inducing 0), monomer for inducing structural unit (a1-1) and structural unit (a1)
The monomer that induces -2) may be referred to as a monomer (a1-0), a monomer (a1-1), and a 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 equation (a1-0),
L ^a01 represents an oxygen atom or _{^{* -O- (CH 2) k01 -CO}} -O- the stands, k01 represents an integer of 1-7, * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 are independently alkyl groups having 1 to 8 carbon atoms and 3 to 3 carbon atoms, respectively.
Represents 18 alicyclic hydrocarbon groups 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。］

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent −O− or ^* −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents a bond with −CO−. Represent 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 them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ]

^La01 is preferably an oxygen atom or ^* -O- (CH ₂ ) _k01- CO-O- (where k01 is preferably an integer of 1 to 4, more preferably 1), more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03 and R ^a04 , the alicyclic hydrocarbon group and the group combining these groups include the same groups as those mentioned in ^{R a1 to} R ^{a3 of the formula (1).}
The alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 are preferably aliphatic hydrocarbon groups having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like. Be done.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and 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− (where k1 ′ is an integer of 1 to 4, preferably 1). Yes), more preferably -O-
Is.
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 the group formed by combining them include the same groups as those mentioned in ^{R a1 to} R ^{a3 of the formula (1).}
The alkyl groups of R ^a6 and R ^a7 are preferably alkyl groups having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a6 and R ^a7 preferably have 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.
It is less than or equal to the alicyclic hydrocarbon group of.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1'is preferably 0 or 1.

Examples of the structural unit (a1-0) include equations (a1-0-1) to equations (a1-0-12).
The structural unit represented by any of the above is preferable, and the formulas (a1-0-1) to (a1-0-10) are preferable.
The structural unit represented by any of the above is more preferable.

In the above structural units, structural units in which a methyl group is replaced by a hydrogen atom corresponding to R ^a01 may be mentioned as specific examples of the structural units (a1-0).

Examples of the monomer (a1-1) include the monomers described in JP-A-2010-204646. Among them, the monomers represented by any of the formulas (a1-1-1) to (a1-1-8) are preferable, and any one of the formulas (a1-1-1) to (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-methylcyclopentane-1-yl (meth) acrylate, 1-ethylcyclopentane-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, and the like. 1-Ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptane-1-yl (meth) acrylate, 1-ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentane-
Examples thereof include 1-yl (meth) acrylate and 1-isopropylcyclohexane-1-yl (meth) acrylate. Monomers represented by any of the formulas (a1-2-1) to (a1-2-12) are preferable, and formulas (a1-2-3), formulas (a1-2-4), and formulas (a1-) are preferable. 2-
9) or the monomer represented by the formula (a1-2-10) is more preferable, and the formula (a1-2-3) is preferable.
Alternatively, the monomer represented by the formula (a1-2-9) is more preferable.

When the resin (A) contains a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is the total structure of the resin (A). For the unit
It is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20.
~ 85 mol%.

Further, as the structural unit (a1), for example, the formulas (a1-3-1) to the formulas (a1-3-1) represented by the following are used.
A1-3-7), structural units represented by the formulas (a1-4-1) to (a1-4-8) can also be mentioned.

樹脂（Ａ）が上記構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対し
て、１０〜９５モル％が好ましく、１５〜９０モル％がより好ましく、２０〜８５モル％
がさらに好ましい。

When the resin (A) contains the above structural units, the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, and 20 to 85 mol% with respect to all the structural units of the resin (A). %
Is even 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。 The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2) is a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”). There is).

In equation (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms, which may have 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 with ^{L 51.}
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ independently represent -O- or -S-, respectively.
s1 represents an integer of 1 to 3.
s1'represents an integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Alkyl groups 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. The group is mentioned.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
1 is preferable for s1.
s1'is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH _2- CO-O-. * Represents a bond with ^{L 51.}

Examples of the monomer for deriving the structural unit (a1-5) include the monomers described in JP-A-2010-61117. Above all, the formulas (a1-5-1) to the formulas (a1-5-)
The monomers represented by 4) are preferable, and the formula (a1-5-1) or the formula (a1-5-2) is preferable.
) Is more preferable.

When the resin (A) has a structural unit (a1-5), the content thereof is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, based on all the structural units of the resin (A). , 5-40
Mol% is more preferred.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”). As the monomer (s), a monomer having no acid unstable group 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 unstable group is preferable. A structure having a hydroxy group and no acid unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or having a lactone ring and no acid unstable group. If a resin having a unit (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

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

［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 structural units represented by the formula (a2-0) (hereinafter, may be referred to as “structural unit (a2-0)”).

[In equation (a2-0),
R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, the plurality of Ra ^31s may be the same or different from each other. ]

Alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and n.
-Pentyl group, n-hexyl group and the like can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,1. 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 -Pelfluorohexyl group and the like can be mentioned. 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 alkoxy group of R a31 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even 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, a butyryloxy group and the like.
The ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

Examples of the monomer for inducing the structural unit (a2-0) include JP-A-2010-2046.
Examples thereof include the monomers described in Japanese Patent Publication No. 34.
Among them, the structural unit (a2-0) includes the formula (a2-0-1), the formula (a2-0-2), and the like.
Those represented by the formula (a2-0-3) and the formula (a2-0-4) are preferable, and the formula (a) is preferable.
Those represented by 2-0-1) or the formula (a2-0-2) are more preferable.

The resin (A) containing the structural unit (a2-0) undergoes a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer inducing the structural unit (a2-0) is protected with a protecting group, and then deprotected. It can be manufactured by processing. However, when performing the deprotection treatment, it is necessary to carry out the deprotection treatment so as not to significantly impair the acid unstable group possessed by the structural unit (a1). Examples of such a protecting group include an acetyl group and the like.

When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, the content thereof is preferably 5 to 95 mol% with respect to all the structural units of the resin (A), preferably 10 to 10.
80 mol% is more preferable, and 15-80 mol% is even more preferable.

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表す。
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 structural units represented by the formula (a2-1) (hereinafter, may be referred to as “structural unit (a2-1)”).

In equation (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 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O-
(The f1 is an integer of 1 to 4), and more preferably −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 structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. Equations (a2-1-1) to (a2-1-6)
) Is preferable, and equations (a2-1-1) to (a2-1-4) are preferred.
The structural unit represented by any of the above is more preferable, and the formula (a2-1-1) or the formula (a2-1-1) is preferable.
The structural unit represented by 3) is more preferable.

When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). Yes, more preferably 1 to 35 mol%, still more preferably 2 to 20 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a fused ring of a monocyclic lactone ring and another ring. But it may be. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

［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。
ｗ１は、０〜３の整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一又は
相異なる。
Ｌ^a7は、−Ｏ−、^＊−Ｏ−Ｌ^a8−Ｏ−、^＊−Ｏ−Ｌ^a8−ＣＯ−Ｏ−、^＊−Ｏ−Ｌ^a8−Ｃ
Ｏ−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。］ The structural unit (a3) is preferably the formula (a3-1), the formula (a3-2), and the formula (a3-3).
Alternatively, it is a structural unit represented by the formula (a3-4). One of these may be contained alone.
Two or more kinds may be contained.

[In equation (a3-1),
L ^a4 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * 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 from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In formula (a3-2),
L ^a5 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * 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, a plurality of ^Ra22s are the same or different from each other.
In formula (a3-3),
L ^a6 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * 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, a plurality of ^Ra23s 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.
w1 represents an integer of 0 to 3. When w1 is 2 or more, the plurality of Ra ^25s are the same or different from each other.
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- C
Represents O-O-L ^a9- CO-O- or ^* -O-L ^a8- O-CO-L ^a9- O-.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other. ]

The aliphatic hydrocarbon groups of R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group and n.
Examples thereof include alkyl groups such as -propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Examples of the halogen atom of R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^Examples of the alkyl group of R a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Alkyl groups 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 and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The ^{alkanediyl groups of La8} and ^La9 include a methylene group, an ethylene group, and a propane-1,
3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1
, 5-Diyl group, Hexane-1,6-Diyl group, Butane-1,3-Diyl group, 2-Methylpropane-1,3-Diyl group, 2-Methylpropane-1,2-Diyl group, Pentane- 1,
Examples thereof include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formula (a3-1) ~ formula (a3-3), L ^a4 ~L ^a6 are each independently preferably, -O- or, k3 is an integer of from 1 to 4 * -O- (CH ₂ ) _{A group represented by k3-} 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 independently, preferably integers of 0 to 2, and 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 further preferably a hydrogen atom or a methyl group.
L ^a7 is preferably −O− or ^* −OL ^a8 −CO—O−, and more preferably.
-O-, -O-CH ₂ -CO-O- or -O-C ₂ H ₄ -CO-O-.
RR ^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)'.

(In the formula, ^Ra24 and ^La7 have the same meanings as above.)

Examples of the monomer for deriving the structural unit (a3) include the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and JP-A-201.
Examples thereof include the monomers described in Japanese Patent Publication No. 2-41274. As a structural unit (a3),
Equations (a3-1-1) to (a3-1-4), equations (a3-2-1) to equations (a3-2-4),
Formulas (a3-3-1) to formulas (a3-3-4) and formulas (a3-4-1) to formulas (a3-4-12)
) Is preferable, and the formula (a3-1-1) and the formula (a3-1-2) are preferable.
, Formulas (a3-2-3) to formulas (a3-2-4) and formulas (a3-4-1) to formulas (a3-4-1).
The structural unit represented by any of 2) is more preferable, and the formulas (a3-4-1) to (a3-4) are more preferable.
The structural unit represented by any one of -12) is more preferable, and the formulas (a3-4-1) to (a) are more preferable.
The structural unit represented by any of 3-4-6) is even more preferable.

In the structural unit represented by the following formulas (a3-4-1) to (a3-4-12), R
^{A compound in which a methyl group corresponding to a24} is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a3-4).

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). , More preferably 10-60 mol%.
Further, the contents of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) and the structural unit (a3-4) are the respective contents with respect to all the structural units of the resin (A). Therefore, 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

<Other structural units (t)>
As the structural unit (t), a structural unit having a halogen atom in addition to the structural unit (a2) and the structural unit (a3) (hereinafter, sometimes referred to as “structural unit (a4)”) and a non-desorbed hydrocarbon group are used. Examples thereof include structural units having (hereinafter, may be referred to as “structural unit (a5)”).

［式（ａ４）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、炭素数１〜２４のフッ素原子を有する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 (a4)>
The structural unit (a4) is represented by the following.

[In equation (a4),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

脂肪族飽和炭化水素基と脂環式飽和炭化水素基とを組み合わせた基としては、アダマン
チルメチル基、ノルボルニルメチル基、ペルフルオロアダマンチルメチル基等が挙げられ
る。 ^Examples of the saturated hydrocarbon group of R a42 include an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, and a group combining these. Examples of the aliphatic saturated hydrocarbon group include linear and branched alkyl groups. Examples of the alicyclic saturated hydrocarbon group include monocyclic and polycyclic alicyclic hydrocarbon groups.
The linear and branched alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl group. , N-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.
Examples of the monocyclic aliphatic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic aliphatic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond).

Examples of the group in which the aliphatic saturated hydrocarbon group and the alicyclic saturated hydrocarbon group are combined include an adamantylmethyl group, a norbornylmethyl group, a perfluoroadamantylmethyl group and the like.

^Examples of the saturated hydrocarbon group having a fluorine atom of R a42 include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group and 2,2,2.
-Trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoro) Methyl) -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, 1,1,2,2,3,3,4,5, 5-Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2 3,3
, 4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,5,5
, 6,6-Dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group and other fluorinated alkyl groups; perfluorocyclohexyl group, perfluoroadamantyl group and other alicyclic hydrocarbon groups having a fluorine atom.

［式（ａ４−０）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ｒ^f2は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。］
Ｒ^f2の飽和炭化水素基及びフッ素原子を有する飽和炭化水素基は、Ｒ^a42で例示したも
のと同様の基が挙げられる。 The structural unit (a4) is, for example, a structural unit represented by any of the equations (a4-0) to (a4-3) (hereinafter, “structural unit (a4-0) to structural unit (a4-3)). ") Is preferable.

[In equation (a4-0),
R ^f1 represents a hydrogen atom or a methyl group.
R ^f2 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]
Examples of the saturated hydrocarbon group of R ^{f2 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified in ^{R a42.}

Examples of the structural unit (a4-0) include the structural unit shown below and the structural unit in which the methyl group corresponding to ^{R f1 is replaced with a hydrogen atom.}

［式（ａ４−１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ³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。
Ｒ^f4は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ³及びＲ^f4の合計炭素数の上限は２１である。］

[In equation (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents 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.
R ^f4 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of ^{L 3} and R ^{f 4 is 21.} ]

Examples of the divalent saturated hydrocarbon group of L ³ include an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, and a group combining these. Examples of this aliphatic saturated hydrocarbon include linear or branched alkanediyl groups. Examples of the alicyclic saturated hydrocarbon group include monocyclic and polycyclic alicyclic hydrocarbon groups.
The alkanediyl group includes a methylene group, an ethylene group, a propane-1,3-diyl group, and the like.
Propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3
-Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like can be mentioned.
Examples of the divalent alicyclic saturated hydrocarbon group include a group obtained by removing one hydrogen atom from the above-mentioned monovalent alicyclic hydrocarbon group.

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 the following groups. In the following examples, * and ** represent bonds, respectively.

Examples of the saturated hydrocarbon group of R ^{f4 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified in ^{R a42.}

Examples of the structural unit (a4-1) include the structural unit shown below and the structural unit in which the methyl group corresponding to ^{R f3 is replaced with a hydrogen atom.}

［式（ａ４−２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴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。
Ｒ^f6は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ⁴及びＲ^f6の合計炭素数の上限は２１である。］

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents 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.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of ^{L 4} and R ^{f 6 is 21.} ]

Examples of the divalent saturated hydrocarbon group of L ⁴ include the same groups as those exemplified in ^{L 3.}
Examples of the saturated hydrocarbon group of R ^{f6 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified in ^{R a42.}

The saturated hydrocarbon group of L ^4, preferably alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

Examples of the structural unit (a4-2) include the structural unit shown below and the structural unit in which the methyl group corresponding to ^{R f5 is replaced with a hydrogen atom.}

［式（ａ４−３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ⁵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２価の飽和炭化水素基を表
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の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14
の合計炭素数の上限は２０である。］

[In equation (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a divalent saturated 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 a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, ^{at least one of A f13} and A ^f14 has a fluorine atom, and L ⁵ , A ^f13 and A ^f14.
The upper limit of the total carbon number of is 20. ]

Examples of the alkanediyl group of L ⁵ include the same groups as those exemplified for the alkanediyl group in the divalent saturated hydrocarbon group of ^{L 3.}

Examples of the divalent saturated hydrocarbon group of A ^f13 include the same groups as those exemplified for the ^{divalent saturated hydrocarbon group of L 3.}
As the ^{saturated hydrocarbon group which may have a fluorine atom of A f13,} a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom are preferable. And more preferably a perfluoroalkandyl group.
Examples of the divalent aliphatic hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group;
Examples thereof include a perfluoroalkanediyl group such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantandiyl group, a norbornanediyl group, a perfluoroadamantandiyl group and the like.

Examples of the saturated hydrocarbon group of A ^{f14 and} the saturated hydrocarbon group which may have a fluorine atom include the same groups as those exemplified in ^{R a42.} Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1
, 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,
2,2-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,
2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1
, 1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group and other fluorinated alkyl Group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group Etc. are preferable.

In the formula (a4-3), L ⁵ is preferably an ethylene group.
The saturated hydrocarbon group of A ^f13 is preferably a group containing an aliphatic hydrocarbon group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aliphatic hydrocarbon group having 2 to 3 carbon atoms. Is even more preferable.
The saturated hydrocarbon group of A ^f14 is preferably a group containing an aliphatic hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aliphatic hydrocarbon group having 3 to 10 carbon atoms. And 3 carbon atoms
Groups containing 10 to 10 alicyclic hydrocarbon groups are more preferred. 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 (a4-3) include the structural unit shown below and the structural unit in which the methyl group corresponding to ^{R f7 is replaced with a hydrogen atom.}

When the resin (A) has the structural unit (a4), the content thereof is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3) with respect to all the structural units of the resin (A). 10 mol% is more preferable.

［式（ａ５−１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２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。
ただし、Ｌ^５１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。
Ｌ^５１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-eliminating hydrocarbon group of the structural unit (a5) include a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably contains an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

[In equation (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 the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or a 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 the 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 of R ⁵² may be either 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.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, and the like.
Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group,
Alkyl groups such as a hexyl group, an octyl group and a 2-ethylhexyl group can be mentioned.
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 of L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. Be done.
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl 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、互いに独立に、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^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、互いに独立に、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 the formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

[In the 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 number of carbon atoms 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 number of carbon atoms 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 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms independently of each other.
However, the total number of carbon atoms of ^{L x5 to} L ^{x7 is 15 or less.}
In equation (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms independently of each other.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total number of carbon atoms of ^{L x8} , L ^x9 and W ^{x1 is 15 or less.} ]

L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and 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, it is a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
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, and 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, it is 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, it is 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, it is a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantanediyl group.

Examples of the group represented by the formula (L1-1) include the divalent group shown below.

Examples of the group represented by the formula (L1-2) include the divalent group shown below.

Examples of the group represented by the formula (L1-3) include the divalent group shown below.

Examples of the group represented by the formula (L1-4) include the divalent group shown below.

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

Examples of the structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to ^{R 51 is replaced with a hydrogen atom.}

When the resin (A) has the structural unit (a5), the content thereof is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 3) with respect to all the structural units of the resin (A). ~ 15 mol% is more preferred.

The resin (A) is preferably a resin composed of a structural unit (I), a structural unit (a1), and a structural unit (s), that is, a copolymer of a monomer (I), a monomer (a1), and a monomer (s). It is a polymer.
The structural unit (a1) 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 a structural unit (a1-1)
Alternatively, it is a 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 a structural unit 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 (particularly, a structural unit (a1-1)) derived from a monomer having an adamantane group in an amount of 15 mol% or more based on the content of the structural unit (a1). preferable. As the content of the structural unit having an adamantyl group increases, 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 for inducing these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500).
00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30)
000 or less, more preferably 15,000 or less). The weight average molecular weight is
It is a value obtained by gel permeation chromatography.

[Resist composition]
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter, may be referred to as "acid generator (B)").
The content of the resin (A) is 80% by mass or more and 99% by mass with respect to the solid content of the resist composition.
The following is preferable. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

The resist composition of the present invention preferably contains a resin other than the resin (A).
The resist composition of the present invention may further contain a solvent (hereinafter sometimes referred to as "solvent (E)") and / or a quencher (hereinafter sometimes referred to as "quencher (C)"). preferable.

<Resin other than resin (A)>
Examples of the resin other than the resin (A) include a resin composed of only the structural unit (t). Resin containing structural unit (a4) (however, not including structural unit (I); hereinafter, "resin (resin ()
X) "may be called. ) Is preferable. The content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 50 mol% or more, based on all the structural units of the resin (X).
The structural unit that the resin (X) may further have is derived from a structural unit (a1), a structural unit (a2), a structural unit (a3), a structural unit (a5), and a compound known in the art. Examples include structural units to be used.
The resin (X) is preferably a resin from only the structural unit (t), and the structural unit (a4).
And or a resin made of the structural unit (a5) is more preferable.
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 50 mol% or more, based on all the structural units of the resin (X). ..
When the structural unit (a5) is contained in the resin (X), the content thereof is preferably 15 mol% or more, more preferably 20 mol% or more, and more preferably 25, with respect to all the structural units of the resin (X).
More preferably, mol% or more.

The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7.0).
00 or more), 80,000 or less (more preferably 60,000 or less). Resin (X)
The means for measuring the weight average molecular weight of the above is the same as in the case of 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, and further, with respect to 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, and particularly preferably 2 to 30 parts by mass.

The total content of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical 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 generator (B) of the resist composition of the present invention may be used. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, etc.).
Examples thereof include oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. As the ionic acid generator, an onium salt containing an onium cation (for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt) is typical. Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

Examples of the acid generator (B) include JP-A-63-26653 and JP-A-55-164824.
Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,
Compounds that generate acid by radiation as described in 778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used alone or in combination of two or more.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、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−ＣＨ_２−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３〜１
８の１価の脂環式炭化水素基を表し、該メチル基及び該１価の脂環式炭化水素基に含まれ
る−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−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。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably the formula (B1).
It is a salt represented by (hereinafter, may be referred to as "acid generator (B1)").

[In formula (B1),
Q ¹ and ^{Q 2} independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
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 with −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 may have a methyl group or a substituent which may have a substituent, and may have 3 to 1 carbon atoms.
_{Representing a monovalent alicyclic hydrocarbon group of 8, -CH 2-} contained in the methyl group and the monovalent alicyclic hydrocarbon group becomes -O-, -SO _2- or -CO-. It may be replaced.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl group of Q ¹ and Q ^2, a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, a perfluoro sec- butyl group, perfluoro-tert- butyl group, perfluoropentyl group, and a perfluoro A hexyl group and the like can be mentioned.
Q ¹ and Q ² each independently is preferably a fluorine atom or a trifluoromethyl group, and more preferably both fluorine atoms.

Examples of the divalent saturated hydrocarbon group of L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more kinds of 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-
Linear alkanediyl groups such as diyl groups;
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, etc. Valuable alicyclic saturated hydrocarbon group;
Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples thereof include a polycyclic divalent alicyclic saturated hydrocarbon group such as a 1,5-diyl group and an adamantane-2,6-diyl group.

［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。］ _{Examples of the group in which −CH 2} − contained in the divalent saturated hydrocarbon group of L ^b1 is replaced with −O− or −CO− are any of the formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * is -Y.
Represents a bond with.

[In equation (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-bonded or 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, and the saturated hydrocarbon group may be substituted. 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 equation (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-bonded or 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, and the saturated hydrocarbon group may be substituted. 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 b4} and L ^{b5 is 22 or less.}
In equation (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-bonded or 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, and the saturated hydrocarbon group may be substituted. 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 b6} and L ^{b7 is 23 or less.} ]

In the 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 carbon atoms before the replacement is the carbon of the saturated hydrocarbon group. Let it be a number.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of ^{L b1.}

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the 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-bonded or 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.

The _{group in which −CH 2} − contained in the divalent saturated hydrocarbon group of ^{L b1} is replaced with −O− or −CO− is 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^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^ｂ１８の合計炭素数は１９以下である。］ Examples of the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8).

[In equation (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 equation (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 equation (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 equation (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 number of carbon atoms of ^{L b13 to} L ^{b15 is 19 or less.}
In equation (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 to} L ^{b18 is 19 or less.} ]

L ^b8 is preferably a divalent 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 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and 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^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^ｂ２６の合計炭素数は２１以下である。］ Examples of the formula (b1-3) include groups represented by the formulas (b1-9) to (b1-11), respectively.

[In equation (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 good. 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 replaced with a hydroxy group.
However, the total carbon number of ^{L b19} and L ^{b20 is 23 or less.}
In equation (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 replaced with a hydroxy group.
However, the total carbon number of ^{L b21 to} L ^{b23 is 21 or less.}
In equation (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 replaced with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

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

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, and an oxocyclohexylcarbonyloxy group.
Hydroxycyclohexylcarbonyloxy group and the like can be mentioned.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-4) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-5) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-6) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-7) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-8) include the following.

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

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-9) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-10) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11).
_{When -CH 2-} contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. There may be more than one. Examples of such a group include groups represented by the formulas (Y12) to (Y38).

That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each replaced with an oxygen atom, and the two oxygen atoms are combined with an arcandyl group having 1 to 8 carbon atoms to form a ketal ring. It may contain a structure in which an oxygen atom is bonded to different carbon atoms. However, when forming a spiro ring of the formulas (Y28) to (Y33), it is preferable that the alkanediyl group between the two oxygens has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, those in which the fluorine atom is not substituted in the methylene group adjacent to the oxygen atom are preferable.

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

The substituent of the methyl group represented by Y includes a halogen atom, a hydroxy group, and 3 to 1 carbon atoms.
A monovalent alicyclic hydrocarbon group of 6, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group or a-(CH ₂ ) _ja- O-CO-R ^b1 group (in the formula, R). ^b1 represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents 0 to 0. (Representing an integer of 4) and the like.
The substituent of the monovalent alicyclic hydrocarbon group represented by Y includes a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkyl group containing a hydroxy group having 1 to 12 carbon atoms, and 3 carbon atoms. ~ 16 monovalent alicyclic hydrocarbon groups, 1 to 12 carbons alkoxy groups, 6-18 carbons monovalent aromatic hydrocarbon groups, 7-21 carbon atoms aralkyl groups, 2 to 2 carbon atoms Acylic group of 4, glycidyloxy group _{or-(CH 2} ) _ja- O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent fat having 3 to 16 carbon atoms. It represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Ja represents an integer of 0 to 4) and the like.

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
The monovalent aromatic hydrocarbon group includes phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group and mesityl. Group, biphenyl group, phenanthryl group, 2,6-
Examples thereof include an aryl group such as a diethylphenyl group and 2-methyl-6-ethylphenyl.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and the like.
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.

When 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 bond position with Y is used. It is preferable that the -CH _{2- of the} group is replaced with -O- or -CO-. _{In this case, -CH 2-} contained in the alkyl group of Y does not replace -O- or -CO-.

Y is a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may preferably 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 more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group or a group represented by the following.

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include the formulas (B1-A-1) to
Anion represented by the formula (B1-A-46) [hereinafter, "anion (B1-A)" according to the formula number.
-1) ”and so on. ] Is preferable, and the formulas (B1-A-1) to (B1-A-4)
, Formula (B1-A-9), Formula (B1-A-10), Formulas (B1-A-24) to Formulas (B1-A-)
33), the anion represented by any of the formulas (B1-A-36) to (B1-A-40) is more preferable.

Here, R ^{i2 to} R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms.
It is an alkyl group of 4, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining them, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ..
L ⁴ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and ^{Q 2} are the same as above.
Specifically, the sulfonic acid anion in the salt represented by the formula (B1) is JP-A-20.
Examples thereof include the anions described in JP-A-10-204646.

The sulfonic acid anion in the salt represented by the preferred formula (B1) is the formula (B1a-).
1) ~ Anions represented by the formulas (B1a-22) can be mentioned.

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-).
16), the anion represented by the formula (B1a-18), the formula (B1a-19), or the formula (B1a-22) is preferable.
Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodine cation. These include, more preferably aryl sulfonium cations.
^{Z +} in the formula (B1) is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" or the like according to the formula number. In some cases. ]
Is.

［式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^ｂ４〜Ｒ^ｂ６は、互いに独立に、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−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、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、互いに独立に、０〜５の整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上の
とき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、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−ＣＨ_２−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−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き
換わってもよい。
Ｒ^ｂ１３〜Ｒ^ｂ１８は、互いに独立に、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、互いに独立に、０〜５の整数を表す。
ｑ２及びｒ２は、互いに独立に、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は同一であっても異なってもよく、ｐ２が２以上
のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数の
Ｒ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一
であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異な
ってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 are independent of each other, 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 hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group represents a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, and a monovalent alicyclic hydrocarbon 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 and has 1 to 18 carbon atoms. It may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom or hydroxy. It may be substituted with a group or an alkoxy group having 1 to 12 carbon atoms.
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 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 represent integers from 0 to 5 independently of each other.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 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 hydrocarbon having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 comprises 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. The 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 may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
The R ^b11 and ^{R b12,} together may form a ring containing a -CH-CO- which they are bond, _-CH 2 contained in the ring - is, -O -, - SO- Alternatively, it may be replaced with −CO−.
R ^{b13 to} R ^b18 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 represent integers 0 to 5 independently of each other.
q2 and r2 represent integers from 0 to 4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s may be the same or different, when p2 is 2 or more, a plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , A plurality of R ^b15s may be the same or different, and when r2 is 2 or more, a plurality of R ^b16s may be the same or different, and when s2 is 2 or more, a plurality of R ^b17s may be present. It may be the same or different, and when t2 is 2 or more, a plurality of R ^b18s may be the same or different. ]

中でも、Ｒ^ｂ９〜Ｒ^ｂ１２の１価の脂環式炭化水素基の炭素数は、好ましくは３〜１８
であり、より好ましくは４〜１２である。 The monovalent aliphatic hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and 2 -Alkyl groups of ethylhexyl groups can be mentioned. Above all, R ^b9 ~ R
^{The monovalent aliphatic hydrocarbon group of b12} preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic monovalent alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclo. Cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

Above all, the carbon number of the monovalent alicyclic hydrocarbon group of ^{R b9 to} R ^{b12 is preferably 3 to 18.}
It is more preferably 4 to 12.

As a monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, for example,
Methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantane-2-
Examples thereof include an yl group, a methylnorbornyl group and an isobornyl group. In a monovalent alicyclic hydrocarbon group in which a hydrogen atom is replaced 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 a phenyl group, a tolyl group, a xylyl group, and a cumenyl group.
Mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group, biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group, 2- Aryl groups such as a methyl-6-ethylphenyl group can be mentioned.
When the monovalent aromatic hydrocarbon group contains a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, the monovalent aliphatic hydrocarbon group or carbon having 1 to 18 carbon atoms is used. A monovalent alicyclic hydrocarbon group having a number of 3 to 18 is preferable.
Examples of the monovalent aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the monovalent aliphatic hydrocarbon group in which the hydrogen atom is replaced with an aromatic hydrocarbon group include an aralkyl group 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 a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the 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, and a tert-butylcarbonyloxy group. Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.

The ^{rings that R b4} and R ^b5 may form with the sulfur atoms to which they are bonded are monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. Examples of this ring include a ring having 3 to 18 carbon atoms, and preferably a ring having 4 to 18 carbon atoms. Examples of the ring containing a sulfur atom include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and specific examples thereof include the following rings.

The ^{ring formed by R b9} and R ^b10 together with the sulfur atom to which they are bonded is monocyclic,
It may be a polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include a 3-membered ring to a 7-membered ring.
Thioran-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1
, 4-oxatian-4-ium ring and the like.
The ^{ring formed by R b11} and R ^b12 together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring. Be done.

Among the cations (b2-1) to cations (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.

The acid generator (B1) is a combination of the above-mentioned sulfonic acid anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably of the formula (
A combination of an anion represented by any of B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-15) and a cation (b2-1) or a cation (b2-3). Can be mentioned.

Examples of the acid generator (B1) preferably include those represented by the formulas (B1-1) to (B1-40), and preferably the formula (B1-1) containing an aryl sulfonium cation.
), Equation (B1-2), Equation (B1-3), Equation (B1-5), Equation (B1-6), Equation (B1-7)
), Equation (B1-11), Equation (B1-12), Equation (B1-13), Equation (B1-14), Equation (
B1-13), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-2)
4), formula (B1-25), formula (B1-26), formula (B1-29), formula (B1-31), formula (B1-32), formula (B1-33), formula (B1-34) ), Equation (B1-35), Equation (B1-
36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40)
The ones represented by are listed below.

The content of the acid generator (B1) is 30% by mass or more and 100 with respect to the total amount of the acid generator (B).
It is preferably 5% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and further preferably substantially only the acid 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). (Below). The resist composition of the present invention may contain one kind of acid generator (B) or a plurality of kinds.

<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. Is. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.

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; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One of the solvent (E) may be contained alone, and the solvent (E) may be contained alone.
Two or more kinds may be contained.

<Quencher (C)>
The resist composition of the present invention may contain a quencher (hereinafter, may be referred to as "quencher (C)"). Examples of the quencher (C) include a basic nitrogen-containing organic compound or a salt that generates an acid having a weaker acidity than the acid generator (B).

<Basic nitrogen-containing organic compounds>
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, trypentylamine, trihexylamine, Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine , Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, 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-methylimidazole, pyridine,
4-Methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl)
Ethane, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 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'-dipicorylamine, bipyridine and the like, preferably diisopropylaniline. , Particularly preferably 2,6-diisopropylaniline.

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

<Salt that produces acid with weak acidity>
The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator is indicated by the 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 <pK.
It is a salt of a <7, more preferably a salt of 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 intramolecular salt represented by the formula (D), and JP-A-2012-229206, JP-A. 2012-6908, 2012-72109, 2011-39502 and 2011-19
Examples thereof include the salt described in Japanese Patent Publication No. 1745.

［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。］

[In formula (D),
R ^D1 and R ^D2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms and 1 to 6 carbon atoms.
Alkoxy group, acyl group having 2 to 7 carbon atoms, acyloxy group having 2 to 7 carbon atoms, 2 to 7 carbon atoms
Represents an alkoxycarbonyl group, a nitro group or a halogen atom of 7.
m'and n'independently represent integers from 0 to 4, and when m'is 2 or more, multiple R ^D1s are the same or different, and when n'is 2 or more, multiple R ^D2s are. Same or different. ]

^{The hydrocarbon groups of R D1} and R ^D2 in the compound represented by the formula (D) include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Examples thereof include groups formed by combining these.
Examples of the monovalent aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and a nonyl group.
The monovalent alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and may be saturated or unsaturated. Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group, norbonyl group, adamantyl group and the like can be mentioned.
The monovalent aromatic hydrocarbon group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 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, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-
Aryl groups such as 6-ethylphenyl and the like can be mentioned.
Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, and an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 1-phenyl-1 group. -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.) And so on.

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, a cyclohexanecarbonyl group and the like.
Examples of the acyloxy group include a group in which an oxy group (—O−) is bonded to the above 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, a bromine atom and the like.

In the formula (D), R ^D1 and R ^D2 are independently alkyl groups having 1 to 8 carbon atoms, respectively.
Cycloalkyl group with 3 to 10 carbon atoms, alkoxy group with 1 to 6 carbon atoms, acyl group with 2 to 4 carbon atoms, acyloxy group with 2 to 4 carbon atoms, alkoxycarbonyl group with 2 to 4 carbon atoms, nitro group or Halogen atoms are preferred.
For m'and n', an integer of 0 to 2 is preferable, and 0 is more preferable, respectively. m'
When is 2 or more, the plurality of R ^D1s are the same or different, and when n'is 2 or more, the plurality of R ^D2s are the same or different.

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

The weak acid intramolecular salt (D) can be produced by the method described in "Tetrahedron Vol. 45, No. 19, p6281-6296". Further, as the weak acid intramolecular salt (D), a commercially available compound can be used.

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

<Other ingredients>
If necessary, the resist composition of the present invention may contain a component other than the above-mentioned components (hereinafter, may be referred to as "other component (F)"). 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 the resin (A) and the acid generator (B) of the present invention, as well as the resin (X), quencher (C), solvent (E) and other components used as necessary. (F)
Can be prepared by mixing. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing is from 10 to 40 ° C., types of resin and the like, and solvent (E) such as resin.
An appropriate temperature can be selected according to the solubility of the substance. As the mixing time, an appropriate 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 or the like 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.

<Manufacturing method of resist pattern>
The method for producing a resist pattern of the present invention is
(1) A step of applying the resist composition of the present invention onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
It includes (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 device such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. The substrate may be washed before the resist composition is applied, 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
For example, it is carried out by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or by 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 for drying under reduced pressure is 1 to 1.
About 0 × 10 ⁵ Pa is preferable.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source includes a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excima laser (wavelength 157 nm) that emits laser light in the ultraviolet region, and a solid-state laser light source (YAG or semiconductor laser). Etc.), and various ones such as those that radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, those that irradiate electron beams, super-ultraviolet light (EUV), etc. are used. Can be done. In addition, in this specification, irradiation of these radiations may be generically referred to as "exposure". At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.

The exposed composition layer is heat treated (so-called post-exposure bake) to promote the deprotection reaction at the acid unstable 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 developing device using a developing solution. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense 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 any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned.
The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.

When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, may be referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples include an ether solvent; an amide solvent such as N, N-dimethylacetamide; an aromatic hydrocarbon solvent such as anisole, and the like.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less.
It is more preferably 95% by mass or more and 100% by mass or less, and it is further preferable that it is substantially only an organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass.
It is preferably 100% by mass or more, more preferably 90% by mass or more and 100% by mass or less, and further preferably substantially only butyl acetate and / or 2-heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting with a solvent of a type different from that of the organic developer.

It is preferable to wash the resist pattern after development with a rinsing solution. As a rinse liquid,
There is no particular limitation 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 cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

In the resist composition of the present invention, the resin (X) tends to have a high distribution on the surface in the composition layer, and can suppress elution of an acid generator or the like into an immersion exposure liquid during immersion exposure. ..
Further, the above-mentioned forward contact angle and backward contact angle caused by the resin (X) exert water repellency and enable high-speed scan exposure without leaving water droplets.

<Use>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or EU.
It is suitable as a resist composition for V-exposure, particularly as a resist composition for ArF excimer laser immersion exposure, and is useful for microfabrication of semiconductors.

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicating the content or the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography under the following conditions.
Equipment: HLC-8120GPC type (manufactured by Tosoh)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh)
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)

The structure of the compound is mass spectrometry (LC is Agilent 1100 type, MASS is A.
It was confirmed by measuring the molecular peak using an Agilent LC / MSD type). In the following examples, the value of this molecular peak is indicated by "MASS".
The receding contact angle (RCA) and forward contact angle (ACA) are "DM-700" manufactured by Kyowa Interface Science Co., Ltd.
It was confirmed by measuring using.

式（Ｉ−２−ａ）で表される化合物１５部、式（Ｉ−２−ｂ）で表される化合物１４．
８９部及びクロロホルム６７．５部を添加し、２３℃で３０分間攪拌した。得られた混合
溶液を５℃まで冷却し、ピリジン１７．０９部及び式（Ｉ−２−ｃ）で表される化合物４
１．４３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反
応物に、クロロホルム１６０部及び５％塩酸１２７部を仕込み、２３℃で３０分間攪拌し
、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１１
５部を仕込み、２３℃で３０分間攪拌し、静置、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、１０％炭酸カリウム水溶液１００部を仕込み、２３℃で３０分間攪
拌し、静置、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
１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗し
た。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮
マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶
媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２−ｄ）で表さ
れる化合物２９．２２部を得た。

式（Ｉ−２−ｄ）で表される化合物２０部、テトラヒドロフラン１００部及びピリジン
８．８６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、
式（Ｉ−２−ｅ）で表される化合物１１．７１部を添加し、２３℃に昇温し、さらに、２
３℃で６時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸４１部を仕
込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収され
た有機層に、１０％炭酸カリウム水溶液４７部を仕込み、２３℃で３０分間攪拌し、静置
、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９０部を仕
込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このよう
な水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム
（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプ
タン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２）で表される化合物１９．
４２部を得た。 Example 1 [Synthesis of compound represented by formula (I-2)]

Fifteen parts of the compound represented by the formula (I-2-a), the compound represented by the formula (I-2-b) 14.
89 parts and 67.5 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 17.09 parts of pyridine and compound 4 represented by the formula (I-2-c) were used.
1.43 parts were added, the temperature was raised to 23 ° C, and the mixture was further stirred at 23 ° C for 18 hours. The obtained reaction product was charged with 160 parts of chloroform and 127 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Ion-exchanged water 11 in the recovered organic layer
Five parts were charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water.
The recovered organic layer was charged with 100 parts of a 10% potassium carbonate aqueous solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) by the formula (I-2-d). 29.22 parts of the represented compound was obtained.

20 parts of the compound represented by the formula (I-2-d), 100 parts of tetrahydrofuran and 8.86 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The resulting mixed solution was cooled to 5 ° C.
11.71 parts of the compound represented by the formula (I-2-e) was added, the temperature was raised to 23 ° C., and further, 2
The mixture was stirred at 3 ° C. for 6 hours. The obtained reaction product was charged with 300 parts of ethyl acetate and 41 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Forty-seven parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 90 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass is represented by the formula (I-2) by fractionating the column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). Compound 19.
I got 42 copies.

MS (Mass Spectrometry): 282.2 (Molecular Ion Peak)

式（Ｉ−１４−ａ）で表される化合物４０部、テトラヒドロフラン２００部及びピリジ
ン３６．４６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却
し、式（Ｉ−１４−ｂ）で表される化合物４７．０５部を添加した。その後、これを２３
℃に昇温し、さらに、２３℃で３時間攪拌し、濃縮した。得られた濃縮残に、酢酸エチル
２７５部及び５％塩酸３４０部を仕込み、２３℃で３０分間攪拌し、静置、分液すること
により有機層を洗浄した。回収された有機層に、イオン交換水１１０部を仕込み、２３℃
で３０分間攪拌し、静置、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、
１０％炭酸カリウム水溶液１９１部を仕込み、２３℃で３０分間攪拌し、静置、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１００部を仕込み、２
３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操
作を５回繰り返した。回収された有機層を濃縮することにより、式（Ｉ−１４−ｃ）で表
される化合物５１．０２部を得た。

式（Ｉ−１４−ｃ）で表される化合物４０部、テトラヒドロフラン２００部及びピリジ
ン２５．９７部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却
し、式（Ｉ−１４−ｄ）で表される化合物３４．３２部を添加した。その後、これを２３
℃に昇温し、さらに、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル６５０部
及び５％塩酸１２０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有
機層を洗浄した。回収された有機層に、１０％炭酸カリウム水溶液１４０部を仕込み、２
３℃で３０分間攪拌し、静置、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２００部を仕込み、２３℃で３０分間攪拌し、静置、分液することによ
り有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮す
ることにより、式（Ｉ−１４）で表される化合物２０．２０部を得た。
ＭＳ（質量分析）：２１４．１（分子イオンピーク） Example 2 [Synthesis of compound represented by formula (I-14)]

40 parts of the compound represented by the formula (I-14-a), 200 parts of tetrahydrofuran and 36.46 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 47.05 parts of the compound represented by the formula (I-14-b) was added. Then do this 23
The temperature was raised to ° C., and the mixture was further stirred at 23 ° C. for 3 hours to concentrate. The obtained concentrated residue was charged with 275 parts of ethyl acetate and 340 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 110 parts of ion-exchanged water was added to the recovered organic layer at 23 ° C.
The organic layer was washed with water by stirring with the mixture for 30 minutes, allowing it to stand, and separating the liquid. In the recovered organic layer,
The organic layer was washed with water by charging 191 parts of a 10% potassium carbonate aqueous solution, stirring at 23 ° C. for 30 minutes, allowing it to stand, and separating the liquids. Add 100 parts of ion-exchanged water to the recovered organic layer, and 2
The organic layer was washed with water by stirring at 3 ° C. for 30 minutes, allowing it to stand, and separating the liquids. Such a washing operation was repeated 5 times. By concentrating the recovered organic layer, 51.02 parts of the compound represented by the formula (I-14-c) was obtained.

40 parts of the compound represented by the formula (I-14-c), 200 parts of tetrahydrofuran and 25.97 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 34.32 parts of the compound represented by the formula (I-14-d) was added. Then do this 23
The temperature was raised to ° C., and the mixture was further stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 650 parts of ethyl acetate and 120 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 140 parts of a 10% potassium carbonate aqueous solution, and 2
The organic layer was washed with water by stirring at 3 ° C. for 30 minutes, allowing it to stand, and separating the liquids. 200 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 20.20 parts of the compound represented by the formula (I-14) was obtained.
MS (Mass Spectrometry): 214.1 (Molecular Ion Peak)

式（Ｉ−５−ａ）で表される化合物１５部、式（Ｉ−５−ｂ）で表される化合物２０．
９４部及びクロロホルム１００部を添加し、２３℃で３０分間攪拌した。得られた混合溶
液を５℃まで冷却し、ピリジン１７．０９部及び式（Ｉ−５−ｃ）で表される化合物４１
．４３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反応
物に、クロロホルム１５０部及び５％塩酸１２７部を仕込み、２３℃で３０分間攪拌し、
静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１５０
部を仕込み、２３℃で３０分間攪拌し、静置、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、１０％炭酸カリウム水溶液１００部を仕込み、２３℃で３０分間攪拌
し、静置、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１
５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した
。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マ
スをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒
：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−５−ｄ）で表され
る化合物３１．４８部を得た。

式（Ｉ−５−ｄ）で表される化合物２４．８６部、テトラヒドロフラン１００部及びピ
リジン８．８６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷
却し、式（Ｉ−５−ｅ）で表される化合物１１．７１部を添加し、２３℃に昇温し、さら
に、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸４１
部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回
収された有機層に、１０％炭酸カリウム水溶液４７部を仕込み、２３℃で３０分間攪拌し
、静置、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９０
部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。こ
のような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスを
カラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ
−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−５）で表される化合物
２２．４８部を得た。 Example 3 [Synthesis of compound represented by formula (I-5)]

Fifteen parts of the compound represented by the formula (I-5a), the compound represented by the formula (I-5-b) 20.
94 parts and 100 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 17.09 parts of pyridine and the compound represented by the formula (I-5-c) 41
.. Forty-three parts were added, the temperature was raised to 23 ° C, and the mixture was further stirred at 23 ° C for 18 hours. 150 parts of chloroform and 127 parts of 5% hydrochloric acid were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes.
The organic layer was washed by allowing it to stand and separating the liquid. Ion-exchanged water 150 in the recovered organic layer
The portion was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 100 parts of a 10% potassium carbonate aqueous solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Ion-exchanged water 1 in the recovered organic layer
50 parts were charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) by the formula (I-5d). 31.48 parts of the represented compound was obtained.

24.86 parts of the compound represented by the formula (I-5d), 100 parts of tetrahydrofuran and 8.86 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 11.71 part of the compound represented by the formula (I-5e) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 6 hours. The obtained reaction product contains 300 parts of ethyl acetate and 41 of 5% hydrochloric acid.
The part was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Forty-seven parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Ion-exchanged water 90 in the recovered organic layer
The portion was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was used as a column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n.
-Heptane / ethyl acetate = 1/1) fractionation gave 22.48 parts of the compound represented by the formula (I-5).

MS (Mass Spectrometry): 334.2 (Molecular Ion Peak)

式（Ｉ−２０−ａ）で表される化合物１２．９８部、式（Ｉ−２０−ｂ）で表される化
合物１４．８９部及びクロロホルム６７．５部を添加し、２３℃で３０分間攪拌した。得
られた混合溶液を５℃まで冷却し、ピリジン１７．０９部及び式（Ｉ−２０−ｃ）で表さ
れる化合物４１．４３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した
。得られた反応物に、クロロホルム１６０部及び５％塩酸１２７部を仕込み、２３℃で３
０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオ
ン交換水１１５部を仕込み、２３℃で３０分間攪拌し、静置、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、１０％炭酸カリウム水溶液１００部を仕込み、２３℃
で３０分間攪拌し、静置、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１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有
機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。
得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０
μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２
０−ｄ）で表される化合物２２．１９部を得た。

式（Ｉ−２０−ｄ）で表される化合物１８．６９部、テトラヒドロフラン１００部及び
ピリジン８．８６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで
冷却し、式（Ｉ−２０−ｅ）で表される化合物１１．７１部を添加し、２３℃に昇温し、
さらに、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸
４１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した
。回収された有機層に、１０％炭酸カリウム水溶液４７部を仕込み、２３℃で３０分間攪
拌し、静置、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
９０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した
。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マ
スをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒
：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２０）で表される
化合物１４．９８部を得た。 Example 4 [Synthesis of compound represented by formula (I-20)]

12.98 parts of the compound represented by the formula (I-20-a), 14.89 parts of the compound represented by the formula (I-20-b) and 67.5 parts of chloroform were added, and the mixture was added at 23 ° C. for 30 minutes. Stirred. The obtained mixed solution was cooled to 5 ° C., 17.09 parts of pyridine and 41.43 parts of the compound represented by the formula (I-20-c) were added, the temperature was raised to 23 ° C., and the temperature was further increased to 23 ° C. Was stirred for 18 hours. 160 parts of chloroform and 127 parts of 5% hydrochloric acid were added to the obtained reaction product, and 3 at 23 ° C.
The organic layer was washed by stirring for 0 minutes, allowing it to stand, and separating the liquid. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 100 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer at 23 ° C.
The organic layer was washed with water by stirring with the mixture for 30 minutes, allowing it to stand, and separating the liquid. In the recovered organic layer,
115 parts of ion-exchanged water was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated.
The obtained concentrated mass was used as a column (Kanto Chemical Silica Gel 60N (Spherical, Neutral) 100-210.
μm developing solvent: n-heptane / ethyl acetate = 1/1) By fractionation, the formula (I-2)
22.19 parts of the compound represented by 0-d) was obtained.

18.69 parts of the compound represented by the formula (I-20-d), 100 parts of tetrahydrofuran and 8.86 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 11.71 part of the compound represented by the formula (I-20-e) was added, and the temperature was raised to 23 ° C.
Further, the mixture was stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 300 parts of ethyl acetate and 41 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Forty-seven parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 90 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) and represented by the formula (I-20). 14.98 parts of the compound was obtained.

MS (Mass Spectrometry): 268.2 (Molecular Ion Peak)

式（Ｉ−３９−ａ）で表される化合物１７．０２部、式（Ｉ−３９−ｂ）で表される化
合物１４．８９部及びクロロホルム６７．５部を添加し、２３℃で３０分間攪拌した。得
られた混合溶液を５℃まで冷却し、ピリジン１７．０９部及び式（Ｉ−３９−ｃ）で表さ
れる化合物４１．４３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した
。得られた反応物に、クロロホルム１６０部及び５％塩酸１２７部を仕込み、２３℃で３
０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオ
ン交換水１１５部を仕込み、２３℃で３０分間攪拌し、静置、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、１０％炭酸カリウム水溶液１００部を仕込み、２３℃
で３０分間攪拌し、静置、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１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有
機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。
得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０
μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−３
９−ｄ）で表される化合物２５．４８部を得た。

式（Ｉ−３９−ｄ）で表される化合物２１．３１部、テトラヒドロフラン１００部及び
ピリジン８．８６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで
冷却し、式（Ｉ−３９−ｅ）で表される化合物１１．７１部を添加し、２３℃に昇温し、
さらに、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸
４１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した
。回収された有機層に、１０％炭酸カリウム水溶液４７部を仕込み、２３℃で３０分間攪
拌し、静置、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
９０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した
。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マ
スをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒
：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−３９）で表される
化合物１４．９１部を得た。 Example 5 [Synthesis of compound represented by formula (I-39)]

17.02 parts of the compound represented by the formula (I-39-a), 14.89 parts of the compound represented by the formula (I-39-b) and 67.5 parts of chloroform were added, and the mixture was added at 23 ° C. for 30 minutes. Stirred. The obtained mixed solution was cooled to 5 ° C., 17.09 parts of pyridine and 41.43 parts of the compound represented by the formula (I-39-c) were added, the temperature was raised to 23 ° C., and the temperature was further increased to 23 ° C. Was stirred for 18 hours. 160 parts of chloroform and 127 parts of 5% hydrochloric acid were added to the obtained reaction product, and 3 at 23 ° C.
The organic layer was washed by stirring for 0 minutes, allowing it to stand, and separating the liquid. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 100 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer at 23 ° C.
The organic layer was washed with water by stirring with the mixture for 30 minutes, allowing it to stand, and separating the liquid. In the recovered organic layer,
115 parts of ion-exchanged water was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated.
The obtained concentrated mass was used as a column (Kanto Chemical Silica Gel 60N (Spherical, Neutral) 100-210.
μm developing solvent: n-heptane / ethyl acetate = 1/1) By fractionation, the formula (I-3)
25.48 parts of the compound represented by 9-d) was obtained.

21.31 parts of the compound represented by the formula (I-39-d), 100 parts of tetrahydrofuran and 8.86 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 11.71 part of the compound represented by the formula (I-39-e) was added, and the temperature was raised to 23 ° C.
Further, the mixture was stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 300 parts of ethyl acetate and 41 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Forty-seven parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 90 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) and represented by the formula (I-39). 14.91 parts of the compound was obtained.

MS (Mass Spectrometry): 296.2 (Molecular Ion Peak)

式（Ｉ−５７−ａ）で表される化合物１５部、式（Ｉ−５７−ｂ）で表される化合物１
４．８９部及びクロロホルム６７．５部を添加し、２３℃で３０分間攪拌した。得られた
混合溶液を５℃まで冷却し、ピリジン１７．０９部及び式（Ｉ−５７−ｃ）で表される化
合物４１．４３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得ら
れた反応物に、クロロホルム１６０部及び５％塩酸１２７部を仕込み、２３℃で３０分間
攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換
水１１５部を仕込み、２３℃で３０分間攪拌し、静置、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、１０％炭酸カリウム水溶液１００部を仕込み、２３℃で３０
分間攪拌し、静置、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１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を
水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られ
た濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ
展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−５７−ｄ
）で表される化合物２１．６６部を得た。

式（Ｉ−５７−ｄ）で表される化合物２０部、テトラヒドロフラン１００部及びピリジ
ン８．８６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し
、式（Ｉ−５７−ｅ）で表される化合物１１．７１部を添加し、２３℃に昇温し、さらに
、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸４１部
を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収
された有機層に、１０％炭酸カリウム水溶液４７部を仕込み、２３℃で３０分間攪拌し、
静置、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９０部
を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この
ような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカ
ラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−
ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−５７）で表される化合物
１２．４４部を得た。 Example 6 [Synthesis of compound represented by formula (I-57)]

15 parts of the compound represented by the formula (I-57-a), compound 1 represented by the formula (I-57-b).
4.89 parts and 67.5 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 17.09 parts of pyridine and 41.43 parts of the compound represented by the formula (I-57-c) were added, the temperature was raised to 23 ° C., and the temperature was further increased to 23 ° C. Was stirred for 18 hours. The obtained reaction product was charged with 160 parts of chloroform and 127 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 100 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer, and 30 at 23 ° C.
The organic layer was washed with water by stirring for 1 minute, allowing it to stand, and separating the liquid. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was used as a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm.
Developing solvent: n-heptane / ethyl acetate = 1/1) By fractionation, the formula (I-57-d)
) Was obtained.

20 parts of the compound represented by the formula (I-57-d), 100 parts of tetrahydrofuran and 8.86 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 11.71 part of the compound represented by the formula (I-57-e) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 300 parts of ethyl acetate and 41 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 47 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes.
The organic layer was washed with water by allowing it to stand and separating the liquid. 90 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was used as a column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-
Heptane / ethyl acetate = 1/1) fractionation gave 12.44 parts of the compound represented by the formula (I-57).

MS (Mass Spectrometry): 282.2 (Molecular Ion Peak)

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 will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

Example 7 [Synthesis of resin A1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-2), the monomer (a2-1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-9): monomer (I) -2): Monomer (a2-1-1): Monomer (a3-4-2)] is 30:14:15: 2.5: 38.
The mixture was mixed so as to be 5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A1 (copolymer) having ^{a weight average molecular weight of 8.0 × 10 3 in a yield of 62%.} rice field. This resin A1 has the following structural units.

Example 8 [Synthesis of resin A2]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-2), the monomer (a2-1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-9): monomer (I) -2): Monomer (a2-1-1): Monomer (a3-4-2)] is 15:14:30: 2.5: 38.
The mixture was mixed so as to be 5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A2 (copolymer) having ^{a weight average molecular weight of 7.8 × 10 3 in a yield of 71%.} rice field. This resin A2 has the following structural units.

Example 9 [Synthesis of resin A3]
As the monomer, monomer (a1-2-9), monomer (I-2), monomer (a2-)
1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-2-9).
: Monomer (I-2): Monomer (a2-1-1): Monomer (a3-4-2)] is 14
The mixture was mixed so as to have a ratio of: 45: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A3 (copolymer) having ^{a weight average molecular weight of 8.2 × 10 3 in a yield of 78%.} rice field. This resin A3 has the following structural units.

Example 10 [Synthesis of resin A4]
As the monomer, monomer (a1-2-9), monomer (I-2), monomer (a2-)
1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-2-9).
: Monomer (I-2): Monomer (a2-1-1): Monomer (a3-4-2)] is 29
The mixture was mixed so as to have a ratio of: 30: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A4 (copolymer) having ^{a weight average molecular weight of 8.3 × 10 3 in a yield of 77%.} rice field. This resin A4 has the following structural units.

Example 11 [Synthesis of Resin A5]
As the monomer, monomer (a1-2-9), monomer (I-2), monomer (a2-)
1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-2-9).
: Monomer (I-2): Monomer (a2-1-1): Monomer (a3-4-2)] is 45
The mixture was mixed so as to have a ratio of 14: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a mixed methanol / water solvent to repulp, and the resin is filtered to obtain a resin A5 (copolymer) having ^{a weight average molecular weight of 8.0 × 10 3 in a yield of 79%.} rice field. This resin A5 has the following structural units.

実施例１３〔樹脂Ａ７の合成〕
モノマーとして、モノマー（Ｉ−２）、モノマー（ａ２−１−１）及びモノマー（ａ３
−４−２）を用い、そのモル比〔モノマー（Ｉ−２）：モノマー（ａ２−１−１）：モノ
マー（ａ３−４−２）〕が５９：２．５：３８．５となるように混合し、全モノマー量の
１．５質量倍のプロピレングリコールモノメチルエーテルアセテートを加えて溶液とした
。この溶液に、開始剤としてアゾビスイソブチロニトリル及びアゾビス（２，４−ジメチ
ルバレロニトリル）を全モノマー量に対して各々、１ｍｏｌ％及び３ｍｏｌ％添加し、こ
れらを７５℃で約５時間加熱した。得られた反応混合物を、大量のメタノール／水混合溶
媒に注いで樹脂を沈殿させ、この樹脂をろ過した。得られた樹脂を再び、メタノール／水
混合溶媒に注いでリパルプし、この樹脂をろ過することにより、重量平均分子量７．７×
１０³の樹脂Ａ７（共重合体）を収率７８％で得た。この樹脂Ａ７は、以下の構造単位を
有するものである。

Example 12 [Synthesis of Resin A6]
As the monomer, the monomer (a1-1-3), the monomer (I-2), the monomer (a2-)
1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-1-3)].
: Monomer (I-2): Monomer (a2-1-1): Monomer (a3-4-2)] is 15
The mixture was mixed so as to have a ratio of: 44: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A6 (copolymer) having ^{a weight average molecular weight of 7.4 × 10 3 in a yield of 71%.} rice field. This resin A6 has the following structural units.

Example 13 [Synthesis of Resin A7]
As the monomers, the monomer (I-2), the monomer (a2-1-1) and the monomer (a3)
-4-2) is used so that the molar ratio [monomer (I-2): monomer (a2-1-1): monomer (a3-4-2)] is 59: 2.5: 38.5. Was mixed with propylene glycol monomethyl ether acetate in an amount of 1.5% by mass of the total amount of the monomers to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent to repulp, and the resin was filtered to obtain a weight average molecular weight of 7.7 ×.
10 ^third resin A7 (copolymer) was obtained in 78% yield. This resin A7 has the following structural units.

実施例１５〔樹脂Ａ９の合成〕
モノマーとして、モノマー（Ｉ−１３）、モノマー（ａ２−１−１）及びモノマー（ａ
３−４−２）を用い、そのモル比〔モノマー（Ｉ−１３）：モノマー（ａ２−１−１）：
モノマー（ａ３−４−２）〕が５９：２．５：３８．５となるように混合し、全モノマー
量の１．５質量倍のプロピレングリコールモノメチルエーテルアセテートを加えて溶液と
した。この溶液に、開始剤としてアゾビスイソブチロニトリル及びアゾビス（２，４−ジ
メチルバレロニトリル）を全モノマー量に対して各々、１ｍｏｌ％及び３ｍｏｌ％添加し
、これらを７５℃で約５時間加熱した。得られた反応混合物を、大量のメタノール／水混
合溶媒に注いで樹脂を沈殿させ、この樹脂をろ過した。得られた樹脂を再び、メタノール
／水混合溶媒に注いでリパルプし、この樹脂をろ過することにより、重量平均分子量８．
４×１０³の樹脂Ａ９（共重合体）を収率７９％で得た。この樹脂Ａ９は、以下の構造単
位を有するものである。

Example 14 [Synthesis of Resin A8]
As the monomer, monomer (a1-2-9), monomer (I-13), monomer (a2)
-1-1) and monomer (a3-4-2) are used, and their molar ratio [monomer (a1-2-9)
): Monomer (I-13): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 29: 30: 2.5: 38.5, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators in this solution
1 mol% and 3 mol%, respectively, with respect to the total amount of monomers, and these were added at about 5 ° C. at 75 ° C.
Heated for hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to be repulped, and the resin is filtered to obtain a resin A8 ^{having a weight average molecular weight of 8.6 × 10 3.}
Copolymer) was obtained in a yield of 77%. This resin A8 has the following structural units.

Example 15 [Synthesis of Resin A9]
As the monomers, the monomer (I-13), the monomer (a2-1-1) and the monomer (a)
3-4-2) is used, and the molar ratio [monomer (I-13): monomer (a2-1-1) :.
Monomer (a3-4-2)] was mixed so as to be 59: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a weight average molecular weight of 8.
A 4 × 10 ³ resin A9 (copolymer) was obtained in a yield of 79%. This resin A9 has the following structural units.

Example 16 [Synthesis of Resin A10]
As the monomer, monomer (a1-2-9), monomer (I-5), monomer (a2-)
1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-2-9).
: Monomer (I-5): Monomer (a2-1-1): Monomer (a3-4-2)] is 29
The mixture was mixed so as to have a ratio of: 30: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A10 (copolymer) having ^{a weight average molecular weight of 8.1 × 10 3 in a yield of 75%.} rice field. This resin A10 has the following structural units.

Example 17 [Synthesis of Resin A11]
As the monomer, monomer (a1-2-9), monomer (I-20), monomer (a2)
-1-1) and monomer (a3-4-2) are used, and their molar ratio [monomer (a1-2-9)
): Monomer (I-20): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 29: 30: 2.5: 38.5, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators in this solution
1 mol% and 3 mol%, respectively, with respect to the total amount of monomers, and these were added at about 5 ° C. at 75 ° C.
Heated for hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A11 ^{having a weight average molecular weight of 7.9 × 10 3.}
(Copolymer) was obtained in a yield of 80%. This resin A11 has the following structural units.

Example 18 [Synthesis of Resin A12]
As the monomer, the monomer (a1-2-9), the monomer (I-39), and the monomer (a2)
-1-1) and monomer (a3-4-2) are used, and their molar ratio [monomer (a1-2-9)
): Monomer (I-39): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 29: 30: 2.5: 38.5, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators in this solution
1 mol% and 3 mol%, respectively, with respect to the total amount of monomers, and these were added at about 5 ° C. at 75 ° C.
Heated for hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A12 ^{having a weight average molecular weight of 8.4 × 10 3.}
(Copolymer) was obtained in a yield of 75%. This resin A12 has the following structural units.

Example 19 [Synthesis of Resin A13]
As the monomer, the monomer (a1-2-9), the monomer (I-57), and the monomer (a2)
-1-1) and monomer (a3-4-2) are used, and their molar ratio [monomer (a1-2-9)
): Monomer (I-57): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 29: 30: 2.5: 38.5, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators in this solution
1 mol% and 3 mol%, respectively, with respect to the total amount of monomers, and these were added at about 5 ° C. at 75 ° C.
Heated for hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A13 ^{having a weight average molecular weight of 8.1 × 10 3.}
(Copolymer) was obtained in a yield of 76%. This resin A13 has the following structural units.

Synthesis Example 1 [Synthesis of resin AX1]
As the monomer, the monomer (IX-1), the monomer (a2-1-1) and the monomer (a)
3-4-2) is used, and the molar ratio [monomer (IX-1): monomer (a2-1-1) :.
Monomer (a3-4-2)] was mixed so as to be 59: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a weight average molecular weight of 9.
A 4 × 10 ³ resin AX1 (copolymer) was obtained in a yield of 70%. This resin AX1 has the following structural units.

Synthesis Example 2 [Synthesis of resin AX2]
As the monomer, the monomer (IX-2), the monomer (a2-1-1) and the monomer (a)
3-4-2) is used, and the molar ratio [monomer (IX-2): monomer (a2-1-1) :.
Monomer (a3-4-2)] was mixed so as to be 59: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a weight average molecular weight of 8.
A 6 × 10 ³ resin A9 (copolymer) was obtained in a yield of 83%. This resin A9 has the following structural units.

Synthesis Example 3 [Synthesis of resin AX3]
As the monomer, the monomer (IX-3), the monomer (a2-1-1) and the monomer (a)
3-4-2) is used, and the molar ratio [monomer (IX-3): monomer (a2-1-1) :.
Monomer (a3-4-2)] was mixed so as to be 59: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a weight average molecular weight of 8.
A 6 × 10 ³ resin A9 (copolymer) was obtained in a yield of 83%. This resin A9 has the following structural units.

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

<Preparation of resist composition>
Each of the components shown below was mixed in parts by mass shown in Table 1, dissolved in a solvent, and filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜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 (A)>
A1 to A13, AX1 to AX3, X1: Resin A1 to Resin A13, Resin AX1 to Resin AX
3, resin X1
<Acid generator (B)>
B1-5: Salt represented by the formula (B1-5) (synthesized according to Examples of JP-A-2015-200886)
B1-21: Salt represented by the formula (B1-21) (synthesized according to Examples of JP-A-2015-200886)
B1-22: Salt represented by the formula (B1-22) (synthesized according to Examples of JP-A-2015-200886)
<Quencher (C)>
D1: (manufactured by 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

<Manufacturing of resist pattern and its evaluation>
An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to cause organic reflection on the wafer with a film thickness of 78 nm. An anti-reflective film was formed. Next, the above resist composition was applied (spin coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was prebaked on a direct hot plate at the temperature listed in the "PB" column of Table 1 for 60 seconds to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900Gi; ASML, NA = 1.35, 3) on a silicon wafer on which a composition layer is formed.
/ 4Annular XY polarized light) with contact hole pattern (hole pitch 90n)
Using a mask for forming m / hole diameter 55 nm), the exposure amount was changed stepwise for exposure. Ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed on a hot plate at the temperature listed in the “PEB” column of Table 1 for 60 seconds. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution at 23 ° C. for 20 seconds by the dynamic dispensing method to obtain a negative resist pattern. Manufactured.

In the resist pattern obtained after development, the exposure amount having a hole diameter of 45 nm formed by using the mask was defined as the effective sensitivity.

<Mask error factor (MEF) evaluation>
In terms of effective sensitivity, the mask hole diameter (hole diameter of the translucent part of the mask) is 5 each.
7nm, 56nm, 55nm, 54nm, 53nm (hole pitch is 90nm)
A resist pattern was formed using the mask of. The slope of the regression line when the hole diameter of the resist pattern formed (transferred) on the substrate by exposure was plotted on the vertical axis with the mask hole diameter on the horizontal axis was calculated as the MEF value.
Those with a MEF value of 5.0 or less are evaluated as having a good MEF, and are marked with ○.
Those having a MEF value of more than 5.0 were evaluated as having a poor MEF and were evaluated as x.
The results are shown in Table 2. The numbers in parentheses indicate the MEF value.

From the above results, according to the compound and resin of the present invention and the resist composition containing this resin,
It can be seen that the resist pattern can be manufactured with a good mask error factor (MEF).

The compound of the present invention, the resin, and the resist composition containing the resin can produce a resist pattern with a good mask error factor (MEF), and are therefore suitable for microfabrication of semiconductors.

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 will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

実施例１５〔樹脂Ａ９の合成〕
モノマーとして、モノマー（Ｉ−１４）、モノマー（ａ２−１−１）及びモノマー（ａ３−４−２）を用い、そのモル比〔モノマー（Ｉ−１４）：モノマー（ａ２−１−１）：モノマー（ａ３−４−２）〕が５９：２．５：３８．５となるように混合し、全モノマー量の１．５質量倍のプロピレングリコールモノメチルエーテルアセテートを加えて溶液とした。この溶液に、開始剤としてアゾビスイソブチロニトリル及びアゾビス（２，４−ジメチルバレロニトリル）を全モノマー量に対して各々、１ｍｏｌ％及び３ｍｏｌ％添加し、これらを７５℃で約５時間加熱した。得られた反応混合物を、大量のメタノール／水混合溶媒に注いで樹脂を沈殿させ、この樹脂をろ過した。得られた樹脂を再び、メタノール／水混合溶媒に注いでリパルプし、この樹脂をろ過することにより、重量平均分子量８．４×１０³の樹脂Ａ９（共重合体）を収率７９％で得た。この樹脂Ａ９は、以下の構造単位を有するものである。

Example 14 [Synthesis of Resin A8]
As the monomer, a monomer (a1-2-9), a monomer (I-14) , a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molar ratio [monomer (a1-2-9). ): Monomer (I-14) : Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 29:30: 2.5: 38.5, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A8 (copolymer) having ^{a weight average molecular weight of 8.6 × 10 3 in a yield of 77%.} rice field. This resin A8 has the following structural units.

Example 15 [Synthesis of Resin A9]
As the monomer, a monomer (I-14) , a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof [monomer (I-14) : monomer (a2-1-1) :. Monomer (a3-4-2)] was mixed so as to be 59: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. bottom. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A9 (copolymer) having ^{a weight average molecular weight of 8.4 × 10 3 in a yield of 79%.} rice field. This resin A9 has the following structural units.

Claims (10)

A compound represented by the formula (I).

[In formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ² represents an alkyl group having 2 to 4 carbon atoms.
R ³ represents an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 1 to 6.
^{R represents a 1-adamantyl group or * -CHR 4} R ⁵ which may have an alkyl group having 1 to 8 carbon atoms. * Represents the binding site.
R ⁴ and R ⁵ independently represent a hydrogen atom, 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 them, or R ⁴ and R ^{5 respectively.} Form divalent alicyclic hydrocarbon groups with 3 to 18 carbon atoms together with the carbon atoms to which they bond] R is 1-adamantyl group, or R ⁴ and a compound of claim 1, wherein together with the carbon atoms a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms R ⁵ are bonded to which they are attached to each other. The compound according to claim 1 or 2, wherein R ² and R ^{3 are methyl groups.} n is the compound according to any one of claims 1 to 3. A structural unit derived from the compound represented by the formula (I) according to any one of claims 1 to 4.
At least one selected from the group consisting of the structural unit represented by the formula (a2-0) and the structural unit represented by the formula (a2-1).
The structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), the structural unit represented by the formula (a3-3), and the structure represented by the formula (a3-4). Containing or including at least one selected from the group consisting of units
A structural unit derived from the compound represented by the formula (I) according to any one of claims 1 to 4.
At least one selected from the group consisting of the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1), and the structural unit represented by the formula (a1-2).
At least one selected from the group consisting of the structural unit represented by the formula (a2-0) and the structural unit represented by the formula (a2-1).
The structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), the structural unit represented by the formula (a3-3), and the structure represented by the formula (a3-4). A resin containing at least one selected from the group consisting of units.
For the total of all structural units of resin
The content of the structural unit derived from the compound represented by the formula (I) is 3 to 60 mol%, and the content is 3 to 60 mol%.
When at least one selected from the group consisting of the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) is included. The total content of the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) is 15 to 90 mol%. can be,
When the structural unit represented by the formula (a2-0) is included, the content of the structural unit represented by the formula (a2-0) is 10 to 80 mol%.
When the structural unit represented by the formula (a2-1) is included, the content of the structural unit represented by the formula (a2-1) is 1 to 40 mol%.
The structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), the structural unit represented by the formula (a3-3), and the structure represented by the formula (a3-4). A resin having a total unit content of 5 to 70 mol%.

[In equation (a1-0),
L ^a01 represents an oxygen atom or _{^{* -O- (CH 2) k01 -CO}} -O- the stands, k01 represents an integer of 1-7, * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups. ]

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent −O− or ^* −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents a bond with −CO−. Represent 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 them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ]

[In equation (a2-0),
R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, the plurality of Ra ^31s may be the same or different from each other. ]

In equation (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 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents an integer of 0 to 10.

[In equation (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 from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s 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, a plurality of ^Ra22s are the same or different from each other.
In formula (a3-3),
L ^a6 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * 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, a plurality of ^Ra23s 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.
w1 represents an integer of 0 to 3. When w1 is 2 or more, the plurality of Ra ^25s are the same or different from each other.
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- CO-O-L ^a9- CO-O- or ^* Represents −O−L ^a8 −O−CO−L ^a9 −O−.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other. ] The resin according to claim 5, which comprises at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2). A resist composition containing the resin and acid generator according to claim 5 or 6. The resist composition according to claim 7, wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
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 with −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 methyl group and the monovalent group thereof. _{-CH 2} − contained in the alicyclic hydrocarbon group may be replaced with −O −, −SO _{2 − or −CO−.}
Z ⁺ represents an organic cation. ] The resist composition according to claim 7 or 8, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to any one of claims 7 to 9 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.