JP7415059B2 - Resin, resist composition, and method for producing resist pattern - Google Patents

Description

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

特許文献２には、下記構造単位の組合せからなる樹脂が記載されている。

Patent Document 1 describes a resin consisting of a combination of the following structural units.

Patent Document 2 describes a resin consisting of a combination of the following structural units.

WO2009/078078 Japanese Patent Application Publication No. 2012-168497

A resist pattern formed from a resist composition containing the above resin may not necessarily have satisfactory CD uniformity (CDU).

［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。
Ｘは、－Ｏ－、－Ｓ－又は－ＮＲ^１１－を表す。
Ｒ^１１は水素原子又は炭素数１～６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１～４の整数を表す。
Ｒ^２は、炭素数１～６の脂肪族炭化水素基を表す。
ｕは、０～３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる
。
Ａ¹は、単結合、炭素数１～６のアルカンジイル基又は＊－Ａ²－Ｘ¹－（Ａ³－Ｘ²）_a－
（Ａ⁴）_b－を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ
－Ｏ－を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］
〔２〕Ａ¹が、単結合である〔１〕記載の樹脂。
〔３〕酸不安定基を有する構造単位が、式（ａ１－１）で表される構造単位及び式（ａ
１－２）で表される構造単位から選ばれる少なくとも１つである〔１〕又は〔２〕に記載
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た基を表す。
ｍ１は０～１４の整数を表す。
ｎ１は０～１０の整数を表す。
ｎ１’は０～３の整数を表す。］
〔４〕さらに、式（ａ３－４）で表される構造単位を含む〔１〕～〔３〕のいずれかに
記載の樹脂。

［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。
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。］
〔５〕〔１〕～〔４〕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
。
〔６〕酸発生剤が、式（Ｂ１）で表される塩である〔５〕記載のレジスト組成物。

［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、置換基を有していてもよい炭素数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、水素原子又は置換基を有していてもよい炭素数３～１８の１価の脂環式炭化水素
基を表し、該１価の脂環式炭化水素基に含まれる－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。］
〔７〕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〔
５〕又は〔６〕記載のレジスト組成物。
〔８〕さらに、フッ素原子を有する構造単位を含む樹脂を含有する〔５〕～〔７〕のい
ずれかに記載のレジスト組成物。
〔９〕（１）〔５〕～〔８〕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 resin containing a structural unit represented by formula (I) and a structural unit having an acid-labile group.

[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.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer from 0 to 3, and when u is 2 or more, a plurality of R ² 's are the same or different from each other.
A ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-A ² -X ¹ -(A ³ -X ² ) _a -
(A ⁴ ) represents _b -. * represents a bond with group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² are each independently -O-, -CO-O-, -O-CO- or -O-CO
-O- is represented.
a represents 0 or 1.
b represents 0 or 1. ]
[2] The resin according to [1], wherein A ¹ is a single bond.
[3] The structural unit having an acid-labile group is a structural unit represented by the formula (a1-1) and a structural unit having the formula (a
The resin according to [1] or [2], which is at least one structural unit selected from the structural units represented by 1-2).

[In formula (a1-1) and formula (a1-2),
L ^a1 and L ^a2 each independently represent -O- or ^* -O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer from 1 to 7, and * represents a bond with -CO- represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1' represents an integer from 0 to 3. ]
[4] The resin according to any one of [1] to [3], further comprising a structural unit represented by formula (a3-4).

[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.
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.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]
[5] A resist composition containing the resin according to any one of [1] to [4] and an acid generator.
[6] The resist composition according to [5], wherein the acid generator is a salt represented by formula (B1).

[In formula (B1),
Q ¹ and Q ² each 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 that may have a substituent,
-CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group is replaced by a fluorine atom or a hydroxyl atom. It may be substituted with a group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the monovalent alicyclic hydrocarbon group may be replaced with -O-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]
[7] Further contains a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator [
5] or the resist composition described in [6].
[8] The resist composition according to any one of [5] to [7], further containing a resin containing a structural unit having a fluorine atom.
[9] (1) Applying the resist composition according to any one of [5] to [8] onto a substrate,
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer to light;
(4) A method for producing a resist pattern, including the steps of: heating the exposed composition layer; and (5) developing the heated composition layer.

By using the resin or resist composition of the present invention, a resist pattern with good CD uniformity (CDU) can be produced.

As used herein, "(meth)acrylate" means "at least one of acrylate and methacrylate". Notations such as "(meth)acrylic acid" and "(meth)acryloyl" have the same meaning.
Furthermore, unless otherwise specified, groups that can be linear, branched, and/or cyclic, such as "aliphatic hydrocarbon groups", include any of them. "Aromatic hydrocarbon group" also includes hydrocarbon groups containing aromatic rings. If stereoisomers exist, all stereoisomers are included.
As used herein, "solid content of the resist composition" refers to the total amount of components excluding the solvent (E) described below from the total amount of the resist composition.

<Resin>
The resin of the present invention includes a structural unit represented by formula (I) (hereinafter sometimes referred to as "structural unit (I)") and a structural unit having an acid-labile group (hereinafter referred to as "resin (A )”).

［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。
Ｘは、－Ｏ－、－Ｓ－又は－ＮＲ^１１－を表す。
Ｒ^１１は水素原子又は炭素数１～６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１～４の整数を表す。
Ｒ^２は、炭素数１～６の脂肪族炭化水素基を表す。
ｕは、０～３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる
。
Ａ¹は、単結合、炭素数１～６のアルカンジイル基又は＊－Ａ²－Ｘ¹－（Ａ³－Ｘ²）_a－
（Ａ⁴）_b－を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ
－Ｏ－を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］ <Structural unit (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.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer from 0 to 3, and when u is 2 or more, a plurality of R ² 's are the same or different from each other.
A ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-A ² -X ¹ -(A ³ -X ² ) _a -
(A ⁴ ) represents _b -. * represents a bond with group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² are each independently -O-, -CO-O-, -O-CO- or -O-CO
-O- is represented.
a represents 0 or 1.
b represents 0 or 1. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Unsubstituted alkyl groups having 1 to 6 carbon atoms such as pentyl group and n-hexyl group, and trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro-sec-butyl group, Examples include haloalkyl groups having 1 to 6 carbon atoms such as perfluoro-tert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, and triiodomethyl group.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms for R ¹¹ include methyl group, ethyl group, n-propyl group,
Examples include isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group.
Preferably, one of s and v is 1.

Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms for R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group. and alkyl groups such as n-hexyl group.
R ² is preferably a methyl group or an ethyl group.
u is preferably 0 or 1.

Examples of the alkanediyl group having 1 to 6 carbon atoms for A ¹ , A ² , A ³ and A ⁴ include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-
Linear alkanediyl groups such as diyl groups and hexane-1,6-diyl groups, linear alkanediyl groups, and alkyl groups (especially alkyl groups having 1 to 4 carbon atoms, methyl groups, ethyl groups, propyl groups) , isopropyl group, butyl group, sec-butyl group, tert-butyl group, etc.), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,
3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-
Branched alkanediyl groups such as diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group are mentioned.

*-A ² -X ¹ -(A ³ -X ² ) _a -(A ⁴ ) _b - is *-A ² -O-, *-A ² -CO
-O-, *-A ² -O-CO-O-, *-A ² -CO-O-A ⁴ -, *-A ² -O-CO-,
*-A ² -CO-O-A ³ -CO-O-, *-A ² -CO-O-A ³ -CO-O-A ⁴ -, *
-A ² -O-CO-A ³ -O-, *-A ² -O-A ³ -CO-O-, *-A ² -CO-O-A ³
-O-CO-, *-A ² -O-CO-A ³ -O-CO-. Among them, *-A ²
-O-, *-A ² -CO-O- or *-A ² -O-CO-O- is preferred, *-A ² -CO
-O- or *-A ² -O-CO-O- is more preferred. * represents a bond with group X.

It is preferable that A ¹ , A ² , A ³ and A ⁴ are each independently an alkanediyl group having 1 to 6 carbon atoms.
A ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and still more preferably an alkanediyl group having 1 to 3 carbon atoms. .

The cyclic sulfoxide structure in formula (I) is preferably a structure represented by any one of formula (S-1) to formula (S-9), and any one of formula (S-1) to formula (S-3) is preferable. The structure represented by the following structure is more preferable. * is a bond with ^A1 .

The structural unit (I) corresponds to structural units represented by the following formulas (I-1) to (I-28), and R ¹ of the structural units represented by the following formulas (I-1) to (I-28). Examples include structural units in which a methyl group is replaced with a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ－１）～式（Ｉ－３）で表される構造単位が好ましい。

Among these, structural units represented by formulas (I-1) to (I-3) are preferred.

［式（Ｉ）中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］ Structural unit (I) is derived from a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)").

[In formula (I), A ¹ , R ¹ , R ³ , X, s, v and u have the same meanings as above. ]

As compound (I), compounds represented by formulas (I'-1) to (I'-28), formula (I
Examples include compounds in which the methyl group corresponding to R ¹ of the compounds represented by '-1) to (I'-28) is replaced with a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ’－１）～式（Ｉ’－３）で表される構造単位が好ましい。

Among these, structural units represented by formulas (I'-1) to (I'-3) are preferred.

［式中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、酢酸及びアセトンなどが挙げられる。
酸化剤としては、過酸化水素などが挙げられる。 <Method for producing compound (I)>
Compound (I) can be obtained by subjecting a compound represented by formula (I0-a) to an oxidation reaction in a solvent.

[In the formula, A ¹ , R ¹ , R ³ , X, s, v and u represent the same meanings as above. ]
Examples of the solvent include acetic acid and acetone.
Examples of the oxidizing agent include hydrogen peroxide.

［式中、Ａ^１、Ｒ^１、Ｒ^３、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、ジメチルホルムアミド、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、炭酸カリウム、ヨウ化カリウム、ピリジン、ジメチルアミノピリジ
ンなどが挙げられる。 Compound (I0-a) in which X is -O- is a compound represented by formula (I-a') and formula (I-
It can be obtained by reacting the compound represented by b) in a solvent in the presence of a base catalyst.

[In the formula, A ¹ , R ¹ , R ³ , s, v and u represent the same meanings as above. ]
Examples of the solvent include dimethylformamide, chloroform, tetrahydrofuran, and toluene.
Examples of the base catalyst include potassium carbonate, potassium iodide, pyridine, dimethylaminopyridine, and the like.

Examples of the compound represented by the formula (I-a') include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by formula (Ib) include compounds represented by the following formula, which are easily available on the market.

The compound represented by the formula (I0-a) in which X is -S- is a compound represented by the formula (I-a'') instead of the compound represented by the formula (I-a'). It can be obtained by carrying out the above method using.
Compound (I) in which X is -NR ¹¹ - can be obtained by the above method using a compound represented by formula (I-a''') in place of the compound represented by formula (I-a'). It can be obtained by implementing.

Examples of the compound represented by formula (Ia'') include compounds represented by the following formula.

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

The resin (A) may contain two or more types of structural units (I).
The content rate of the structural unit (I) contained in the resin (A) is based on the total structural units of the resin (A),
Usually 1 to 60 mol%, preferably 3 to 40 mol%, more preferably 4 to 35 mol%
, more preferably 5 to 30 mol%, particularly preferably 5 to 25 mol%.

In addition to the structural unit (I), the resin (A) of the present invention further has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). "Acid-labile group" refers to a structural unit that has a leaving group, which is removed by contact with an acid, and the structural unit is converted into a structural unit that has a hydrophilic group (e.g., hydroxy group or carboxy group). means a group that

［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-labile group (hereinafter sometimes referred to as "monomer (a1)").
The acid labile groups contained in the structural unit (a1) include the following groups (1) and/or groups (2).
is preferred.

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

[In formula (2), R ^a1' and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. or R ^a2' and R ^a3'
are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and -CH ₂ - contained in the hydrocarbon group and the divalent heterocyclic group are , -O- or -S-.
X represents an oxygen atom or a sulfur atom.
* represents a bond. ]

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

Examples of groups combining an alkyl group and an alicyclic hydrocarbon group include alkyl-cycloalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, and methyladamantyl group, cyclohexylmethyl group, Examples include cycloalkyl-alkyl groups such as adamantylmethyl group and norbornylmethyl group, and alkyl-cycloalkyl-alkyl groups such as methylcyclohexylmethyl group.
na is preferably 0.

-C(R ^a1 ) when R ^a1 and R ^a2 combine with each other to form a divalent alicyclic hydrocarbon group
Examples of (R ^a2 )(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 groups R ^a1' to R ^a3' include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group include those mentioned above.
Examples of aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group. and aryl groups such as phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl group.

Ｒ^a1'及びＲ^a2'のうち、少なくとも１つは水素原子であることが好ましい。 Groups formed by combining these groups include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, alkyl-cycloalkyl-alkyl groups, aralkyl groups (for example, phenylmethyl groups, 1-phenylethyl groups, 2-phenyl Ethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5- phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.), aryl-cycloalkyl group (phenyladamantyl group, phenylcyclohexyl group, etc.), and the like.
R ^a2' and R ^a3' combine with each other to form 2 together with the carbon atom to which they are bonded and X
Examples of the valent heterocyclic group include the following groups. * represents a bond.

It is preferable that at least one of R ^a1' and R ^a2' is a hydrogen atom.

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

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

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

Among (meth)acrylic monomers having acid-labile groups, preferably those having 5 to 20 carbon atoms
Examples include those having an alicyclic hydrocarbon group. 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.

In the resin (A), the content of the structural unit (a1) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, based on the total structural units of the resin (A), and Preferably it is 30 to 80 mol%.

As a structural unit derived from a (meth)acrylic monomer having a group represented by formula (1), preferably a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1) Examples include a structural unit or a structural unit represented by formula (a1-2). These may be used alone;
Two or more types may be used in combination. In this specification, the structural unit represented by formula (a1-0), the formula (a
The structural unit represented by 1-1) and the structural unit represented by formula (a1-2) are respectively referred to as structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2). , structural unit (a1-
0), a monomer that induces structural unit (a1-1), and structural unit (a1
The monomers inducing -2) may be referred to as monomer (a1-0), monomer (a1-1) and monomer (a1-2), respectively.

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

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

L ^a01 is preferably an oxygen atom or *-O-(CH ₂ ) _k01 -CO-O- (however, k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably is an oxygen atom.
Examples of the alkyl group, alicyclic hydrocarbon group, and a combination thereof for R ^a02 , R ^a03 and R ^a04 include the same groups as those listed for R ^a1 to R ^a3 in formula (1).
The alkyl groups of R ^a02 , R ^a03 and R ^a04 are preferably alkyl groups 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.
In the group that is a combination of an alkyl group and an alicyclic hydrocarbon group, the total number of carbon atoms in the combination of these alkyl groups and alicyclic hydrocarbon group is preferably 18 or less. Examples of such groups include methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, methyladamantyl group, cyclohexylmethyl group, methylcyclohexylmethyl group, adamantylmethyl group, norbornylmethyl group, etc. It will be done.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.

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

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, ethyl group, cyclohexyl group or adamantyl group.

L ^a1 and L ^a2 are preferably -O- or *-O-(CH ₂ ) _k1' -CO-O- (however, k1' is an integer from 1 to 4, preferably 1). ), more preferably -O-
It is.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group, alicyclic hydrocarbon group, and the group formed by combining these groups for R ^a6 and R ^a7 include the same groups as those listed for R ^a1 to R ^a3 in 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, more preferably 3 to 6 carbon atoms.
alicyclic hydrocarbon group or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1' is preferably 0 or 1.

As the structural unit (a1-0), for example, formulas (a1-0-1) to (a1-0-12)
Structural units represented by any of formulas (a1-0-1) to (a1-0-10) are preferred.
Structural units represented by either of these are more preferred.

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

Examples of the monomer (a1-1) include monomers described in JP-A-2010-204646. Among these, monomers represented by any of formulas (a1-1-1) to (a1-1-8) are preferred, and monomers represented by any of formulas (a1-1-1) to (a1-1-4) are preferred. Monomers represented by are more preferred.

Examples of the monomer (a1-2) include monomers represented by any of formulas (a1-2-1) to (a1-2-12); -2-4), formula (a1
-2-9) or the monomer represented by the formula (a1-2-10) is preferable, and the monomer represented by the formula (a1-2-3
) or a monomer represented by formula (a1-2-9) is more preferred.

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,
Usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 95 mol%.
~85 mol%.

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

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

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

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

Specifically, the monomer (a1-3) is 5-norbornene-2-carboxylic acid-tert
-butyl, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate,
1-Methylcyclohexyl 5-norbornene-2-carboxylate, 5-norbornene-2-
2-Methyl-2-adamantyl carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 1-(4-methylcyclohexyl)-1-methylethyl 5-norbornene-2-carboxylate, 5- 1-(4-hydroxycyclohexyl)-1-methylethyl norbornene-2-carboxylate, 1-methyl-1-5-norbornene-2-carboxylate
-(4-oxocyclohexyl)ethyl and 5-norbornene-2-carboxylic acid 1-(1
-adamantyl)-1-methylethyl and the like.

Since the resin (A) containing the structural unit (a1-3) contains a sterically bulky structural unit, the resist composition of the present invention containing such a resin (A) has a higher Resist patterns can be obtained with high resolution. Furthermore, since a rigid norbornane ring is introduced into the main chain, the resulting resist pattern tends to have excellent dry etching resistance.

When the resin (A) contains the structural unit (a1-3), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on the total structural units of the resin (A). 20-8
5 mol% is more preferred.

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

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

Examples of the alkyl group for R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group has 1 carbon number
-4 alkyl groups are preferred, methyl or ethyl groups are more preferred, and methyl groups are even more preferred.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1, 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3, 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -perfluorohexyl group, etc.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
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.
Examples of the hydrocarbon groups for R ^a34 and R ^a35 include the same groups as R ^a1' and R ^a2' in formula (2).
R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms,
Examples include aromatic hydrocarbon groups having 6 to 18 carbon atoms or groups formed by combining these groups.

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

Examples of the monomer leading to the structural unit (a1-4) include JP-A-2010-204646
Examples include monomers described in the above publication. Among them, formula (a1-4-1) to formula (a1-4
Monomers represented by formulas (a1-4-1) to (a1-4-5) are preferred.
and formula (a1-4-8)) are more preferred.

When the resin (A) has a structural unit (a1-4), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on the total structural units of the resin (A). , 20
More preferably 85 mol%.

式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲ
ン原子を表す。
Ｚ^a1は、単結合又は＊－（ＣＨ₂）_h3－ＣＯ－Ｌ⁵⁴－を表し、ｈ３は１～４の整数を表
し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
ｓ１は、１～３の整数を表す。
ｓ１’は、０～３の整数を表す。 As a structural unit derived from a (meth)acrylic monomer having a group represented by formula (2), a structural unit represented by formula (a1-5) (hereinafter referred to as "structural unit (a1-5)") ) can also be mentioned.

In formula (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 from 1 to 4, and * represents a bond with L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent -O- or -S-.
s1 represents an integer from 1 to 3.
s1' represents an integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being preferred.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group,
Examples include propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl and trifluoromethyl groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
s1 is preferably 1.
s1' is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or *-CH ₂ -CO-O-. * represents the bond with ^L51 .

Examples of the monomer leading to the structural unit (a1-5) include monomers described in JP-A No. 2010-61117. Among them, formula (a1-5-1) to formula (a1-5-
Monomers each represented by formula (a1-5-1) or formula (a1-5-2) are preferred.
) are more preferred.

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

The structural unit (a) having an acid-labile group in the resin (A) includes a structural unit (a1-0),
At least one kind selected from the group consisting of structural unit (a1-1), structural unit (a1-2) and structural unit (a1-5) is preferable, at least two or more kinds are more preferable, and structural unit (a1-1) and combination of structural unit (a1-2), combination of structural unit (a1-1) and structural unit (a1-5), combination of structural unit (a1-1) and structural unit (a1-0), structural unit ( combination of structural unit (a1-2) and structural unit (a1-0), structural unit (a1-
5) and combination of structural unit (a1-0), structural unit (a1-0), structural unit (a1-
1) and the combination of structural unit (a1-2), structural unit (a1-0), structural unit (a1-
1) and the structural unit (a1-5) are more preferable, and the combination of the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and the structural unit (a1-5) are more preferable.
A combination of these is even more preferred.

<Structural unit (s)>
The resin (A) further contains a structural unit (hereinafter "structural unit (s)" which does not have an acid-labile group, which will be described later).
), a structural unit having a halogen atom (hereinafter referred to as the "structural unit (a4)" in some cases), a structural unit having a non-eliminating hydrocarbon group (a5), and other known monomers. may contain structural units derived from Among these, it is preferable that the structural unit (s) is included. The structural unit (s) is a monomer that does not have an acid-labile group (hereinafter referred to as "monomer (s)").
”). As the monomer (s), monomers that do not have acid-labile groups and are known in the field of resists can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and not having an acid-labile group is preferable. A structural unit having a hydroxy group and not having an acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structure having a lactone ring and not having an acid-labile group By using a resin having the unit (hereinafter sometimes referred to as "structural unit (a3)") 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 that the structural unit (a2) has 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 using a high-energy beam such as an excimer laser (248 nm), an electron beam, or EUV (ultra-ultraviolet light), the structural unit (a2) is a structural unit having a phenolic hydroxy group (
It is preferable to use a2). In addition, when using ArF excimer laser (193 nm) etc., the structural unit (a2) is a structural unit having an alcoholic hydroxyl group (a2
) is preferable, and it is more preferable to use the structural unit (a2-1). The structural unit (a2) may contain one type alone or two or more types.

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

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

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

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, n
-pentyl group, n-hexyl group, etc.
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 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, n-pentyl group, n-hexyl group, n -perfluorohexyl group, etc. 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 for R ^a31 include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
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.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

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

The resin (A) containing the structural unit (a2-0) is prepared by performing 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 in a manner that does not significantly damage the acid-labile group possessed by the structural unit (a1). Examples of such protecting groups include acetyl groups and the like.

When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, its content is preferably 5 to 95 mol%, and 10 to 95 mol%, based on the total structural units of the resin (A).
80 mol% is more preferable, and 15 to 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 a structural unit represented by formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)").

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

In formula (a2-1), L ^a3 is preferably -O-, -O-(CH ₂ ) _f1 -CO-O-
(the f1 is an integer of 1 to 4), 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.

As the monomer for inducing the structural unit (a2-1), for example, JP-A-2010-2046
Examples include monomers described in Japanese Patent No. 46. Formula (a2-1-1) to formula (a2-1-6
) are preferably monomers represented by any of the formulas (a2-1-1) to (a2-1-4)
More preferred are monomers represented by either formula (a2-1-1) or formula (a2-1-
Monomers represented by 3) are more preferred.

When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on the total structural units of the resin (A). The content is preferably 1 to 35 mol%, and even more preferably 2 to 20 mol%.

<Structural unit (a3)>
The lactone ring possessed by the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a fused ring of a monocyclic lactone ring and another ring. But that's fine. The lactone ring preferably includes a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

The structural unit (a3) is preferably a formula (a3-1), a formula (a3-2), or a formula (a3-3).
Or a structural unit represented by formula (a3-4). One of these may be contained alone,
Two or more types may be contained.

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

[In formula (a3-1),
L ^a4 is -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents an integer from 1 to 7).
) represents a group represented by * 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 R ^a21s are the same or different from each other.
In formula (a3-2),
L ^a5 is -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents an integer from 1 to 7).
) represents a group represented by * 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 from 0 to 3. When q1 is 2 or more, a plurality of R ^a22s are the same or different from each other.
In formula (a3-3),
L ^a6 is -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents an integer from 1 to 7).
) represents a group represented by * 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 from 0 to 3. When r1 is 2 or more, a plurality of R ^a23s 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.
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.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]

The aliphatic hydrocarbon groups of R ^a21 , R ^a22 and R ^a23 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Can be mentioned.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group for R ^a24 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom for R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluoro Examples include hexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, and the like.

The alkanediyl groups of L ^a8 and L ^a9 include methylene group, ethylene group, propane-1,
3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1
,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane- 1,
Examples include 4-diyl group and 2-methylbutane-1,4-diyl group.

In formulas (a3-1) to (a3-3), L ^a4 to L ^a6 are each independently preferably -O- or *-O-(CH ₂ ) _k3 -CO-O-, more preferably -O- and *-O-CH ₂ -CO-O-, even more preferably an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

In formula (a3-4),
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom or a methyl group.
L ^a7 is preferably -O- or ^* -O-L ^a8 -CO-O-, more preferably,
-O-, -O-CH ₂ -CO-O- or -O-C ₂ H ₄ -CO-O-.

As monomers leading to the structural unit (a3), monomers described in JP-A-2010-204646, monomers described in JP-A-2000-122294, JP-A-201
Examples include monomers described in Publication No. 2-41274. As the structural unit (a3),
Formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4),
Formula (a3-3-1) to formula (a3-3-4) and formula (a3-4-1) to formula (a3-4-12)
) are preferably structural units represented by formula (a3-1-1) or formula (a3-1-2).
, formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-1)
2) are more preferable, and the structural units represented by formulas (a3-4-1) to (a3-4
-12) are more preferable, and the structural units represented by formulas (a3-4-1) to (a
Structural units represented by any one of 3-4-6) are even more preferred.

In the structural units represented by the following formulas (a3-4-1) to (a3-4-12), R
A compound in which the 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 the total structural units of the resin (A). , more preferably 10 to 60 mol%.
In addition, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), and the structural unit (a3-4) is relative to the total structural units of the resin (A1), respectively. 5-60
The amount is preferably mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 50 mol%.

<Other structural units (t)>
The resin (A) may contain other structural units (t) as structural units other than the structural unit (I), the structural unit (a1), and the structural unit (s). Structural units (t) include structural units that may have a halogen atom other than structural units (a2) and structural units (a3) (hereinafter referred to as "structural units (a4)" in some cases) and non-eliminated structural units. Structural unit with a separate hydrocarbon group (
s) (hereinafter sometimes referred to as "structural unit (a5)"), and the like. The resin (A) is
It may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well known in the art.

［式（ａ４－０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^４は、単結合又は炭素数１～４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフル
オロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ Examples of the structural unit (a4) include a structural unit represented by formula (a4-0).

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

Examples of the aliphatic saturated hydrocarbon group of ^L4 include methylene group, ethylene group, propane-1,3-
Diyl group, linear alkanediyl group such as butane-1,4-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methyl Branched alkanediyl groups such as propane-1,3-diyl group and 2-methylpropane-1,2-diyl group are mentioned.

The perfluoroalkanediyl group of ^L3 includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, and a perfluoropropane-1,3-
Diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-
Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2- Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7- Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2- Examples include diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group, and the like.
The perfluorocycloalkanediyl group of ^L3 includes a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group,
Examples include perfluoroadamantanediyl group.

L ⁴ is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ³ is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

Examples of the structural unit (a4-0) include the structural units shown below. The following formula (a1-
In the structural units represented by 0-1) to formula (a4-0-16), compounds in which the methyl group corresponding to R ⁵ is replaced with a hydrogen atom are also listed as specific examples of the structural unit (a4-0). be able to.

［式（ａ４－１）中、
Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^ａ４２は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水
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い。
Ａ^ａ４１は、置換基を有していてもよい炭素数１～６のアルカンジイル基又は式（ａ－
ｇ１）で表される基を表す。］

［式（ａ－ｇ１）中、
ｓは０又は１を表す。
Ａ^ａ４２及びＡ^ａ４４は、互いに独立に、置換基を有していてもよい炭素数１～５の脂
肪族炭化水素基を表す。
Ａ^ａ４３は、単結合又は置換基を有していてもよい炭素数１～５の脂肪族炭化水素基を
表す。
Ｘ^ａ４１及びＸ^ａ４２は、互いに独立に、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－
ＣＯ－を表す。
ただし、Ａ^ａ４２、Ａ^ａ４３、Ａ^ａ４４、Ｘ^ａ４１及びＸ^ａ４２の炭素数の合計は７以
下である。
＊、＊＊は結合手であり、＊＊が－Ｏ－ＣＯ－Ｒ^ａ４２との結合手である。］ Examples of the structural unit (a4) include the structural unit represented by formula (a4-1).

[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group may be replaced with -O- or -CO-. good.
A ^a41 is an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or the formula (a-
Represents a group represented by g1). ]

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

Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.
Although the chain type and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, chain type and cyclic aliphatic saturated hydrocarbon groups are preferable. The aliphatic saturated hydrocarbon group includes a linear or branched alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic group formed by combining an alkyl group and an alicyclic hydrocarbon group. Examples include group hydrocarbon groups.
Examples of chain aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group. n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Examples of cyclic aliphatic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bond). represents a hand.
) and other polycyclic alicyclic hydrocarbon groups.

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

［式（ａ－ｇ３）中、
Ｘ^ａ４３は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を
表す。
Ａ^ａ４５は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素
基を表す。
＊は結合手を表す。］ Examples of the substituent for R ^a42 include a halogen atom or a group represented by formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom.

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

Examples of the aliphatic hydrocarbon group for A ^a45 include the same groups as exemplified for R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and is an aliphatic hydrocarbon group having an alkyl group having a halogen atom and/or a group represented by formula (a-g3). It is more preferable that
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and even more preferably a carbon number A perfluoroalkyl group having 1 to 6 carbon atoms, particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), the formula (
The total number of carbon atoms in the aliphatic hydrocarbon group, including the number of carbon atoms contained in the groups represented by a to g3), is 1.
It is preferably 5 or less, more preferably 12 or less. When having a group represented by formula (a-g3) as a substituent, the number thereof is preferably one.

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

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

The aliphatic hydrocarbon group of A ^a46 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^a47 preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably A ^a47 is a cyclohexyl group or an adamantyl group.

The structure represented by *-A ^a46 -X ^a44 -A ^a47 includes the following structures.

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

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

Examples of the group (a-g1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group, or an oxycarbonyl group include the following groups. In the following examples, * and **
each represents a bond, and ** is a bond with -O-CO-R ^a42 .

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

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

Examples of the alkanediyl group of A ^f1 include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group.
Linear alkanediyl groups such as diyl group and hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-
1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-
Branched alkanediyl groups such as diyl groups are mentioned.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type, and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-
-octyl group and 2-ethylhexyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group,
Examples include cycloalkyl groups such as a cyclooctyl group and a cyclodecyl group. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1-(adamantan-1-yl)alkan-1-yl group, norbornyl group, Examples include methylnorbornyl group and isobornyl group.

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

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

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

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

Examples of the alkanediyl group for A ^f11 include the same groups as the alkanediyl group for A ^f1 .
The aliphatic hydrocarbon group of A ^f13 includes chain and cyclic aliphatic hydrocarbon groups, and divalent aliphatic hydrocarbon groups formed by combining these. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom in A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include a methylene group,
Alkanediyl groups such as ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group, etc. .
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

The aliphatic hydrocarbon group of A ^f14 includes chain and cyclic aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups formed by combining these. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Examples of chain aliphatic hydrocarbon groups that may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1 , 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, Examples include heptyl group, perfluoroheptyl group, octyl group, and perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, and a perfluoroadamantylmethyl group.

In formula (a4-3), A ^f11 is preferably an ethylene group.
The aliphatic hydrocarbon group of A ^f13 is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably an aliphatic hydrocarbon group having 2 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^f14 is preferably an aliphatic hydrocarbon group having 3 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms. Among them, A ^f1
4 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The structural unit represented by formula (a4-2) includes formulas (a4-1-1) to (a4-1-2).
Examples include the structural unit represented by 2).

The structural unit represented by formula (a4-3) includes formulas (a4-1'-1) to (a4-1'
-22), respectively.

［式（ａ４－４）中、
Ｒ^ｆ２１は、水素原子又はメチル基を表す。
Ａ^ｆ２１は、－（ＣＨ_２）_ｊ１－、－（ＣＨ_２）_ｊ２－Ｏ－（ＣＨ_２）_ｊ３－又は－（
ＣＨ_２）_ｊ４－ＣＯ－Ｏ－（ＣＨ_２）_ｊ５－を表す。
ｊ１～ｊ５は、互いに独立に、１～６の整数を表す。
Ｒ^ｆ２２は、フッ素原子を有する炭素数１～１０の炭化水素基を表す。］ The structural unit (a4) also includes a structural unit represented by formula (a4-4).

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

Examples of the hydrocarbon group having a fluorine atom for R ^f22 include the same hydrocarbon group as the hydrocarbon group for R ^f2 in formula (a4-2).
R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom;
It is more preferably an alkyl group having 10 atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

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

Examples of the structural unit represented by formula (a4-4) include the following structural units.
In the structural unit represented by the following formula, a compound in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a4-4).

When the resin (A) has a structural unit (a4), its content is preferably 1 to 20 mol%, and 2 to 15 mol%, based on the total of all structural units of the resin (A). More preferably, it is 3 to 10 mol%.

［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。
但し、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 possessed by the structural unit (a5) include linear, branched, or cyclic hydrocarbon groups. Among these, the structural unit (a5) is preferably an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by formula (a5-1).

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

The alicyclic hydrocarbon group for R ⁵² may be 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.
Examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group,
Examples include alkyl groups such as hexyl, octyl, and 2-ethylhexyl.
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, more preferably an adamantyl group, norbornyl group or cyclohexyl group.

Examples of the divalent saturated hydrocarbon group of ^L51 include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent aliphatic saturated hydrocarbon group. It will be done.
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group, and pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

Examples of groups in which a methylene group contained in a saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

［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^ｘ３Ｌ^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^ｘ６及びＬ^ｘ７の合計炭素数は、１５以下である。
式（Ｌ１－４）中、
Ｌ^ｘ８及びＬ^ｘ９は、単結合又は炭素数１～１２の２価の脂肪族飽和炭化水素基を表す
。
Ｗ^ｘ１は、炭素数３～１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^ｘ８、Ｌ^ｘ９及びＷ^ｘ１の合計炭素数は、１５以下である。］

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

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

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

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

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

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

L ⁵¹ is preferably a single bond or a group represented by formula (L1-1).
Examples of the structural unit (a5-1) include the following.

In formulas (a5-1-1) to (a5-1-18), structural units in which the methyl group corresponding to R ⁵¹ is replaced with a hydrogen atom can also be cited as specific examples of the structural unit (a5-1). can.

When the resin (A) has a structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 3 to 30 mol%, based on the total structural units of the resin (A). More preferably 15 mol%.

It is preferable that the resin (A) does not contain a structural unit having a fluorine atom. Further, the structural unit having an acid-labile group is preferably a structural unit having no fluorine atom. That is, the resin (A) is preferably a resin consisting of the structural unit (I), the structural unit (a1), and the structural unit (s), that is, the compound (I), the monomer (a1), and the monomer (s). It is a copolymer of
The structural unit (a1) preferably includes 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 type of (a1-5), more preferably structural unit (a1-1)
or structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-1).
Structural unit (a3) is preferably at least one type of structural unit represented by a γ-butyrolactone ring, a bridged ring containing a γ-butyrolactone ring structure, or an adamantane lactone ring, and more preferably represented by formula (a3-1). at least one kind selected from the structural unit represented by the formula (a3-2) and the structural unit represented by the formula (a3-4), more preferably the structural unit represented by the formula (a3-4). is the structural unit represented.

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

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and may be produced by a known polymerization method (for example, radical polymerization method) using a monomer that induces these structural units. can do. The content of each structural unit in the resin (A) can be adjusted by adjusting the amount of monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,5
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). In addition, the weight average molecular weight is
This is a value determined by gel permeation chromatography.

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter sometimes referred to as "acid generator (B)").
In addition, the resist composition contains a resin other than the resin (A), a quencher (hereinafter sometimes referred to as "quencher (C)"), and/or a solvent (hereinafter sometimes referred to as "solvent (E)"). It is preferable to do so.

<Resin other than resin (A)>
The resist composition of the present invention may contain resins other than resin (A). Such resins include resins consisting only of structural units (s) and resins containing structural units (a4) (hereinafter referred to as "resins").
X)"), etc.

<Resin (X)>
As the resin other than resin (A), resin (X) is preferable. In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more based on the total structural units of the resin (X),
The content is more preferably 45 mol% or more, and even more preferably 50 mol% or more.
Structural units that the resin (X) may further include include structural units (a1), structural units (a2), structural units (a3), structural units (a5), and structures derived from other known monomers. units, among which structural unit (a5) is preferred.
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 is the same as in the case of resin (A).
When the resist composition contains resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and The amount is preferably 1 to 40 parts by weight, particularly preferably 2 to 30 parts by weight.

The total content of resin (A) and resins other than resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. preferable. The solid content of the resist composition and the resin content relative to the solid content can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
Acid generators are classified into nonionic and ionic types, and either of them may be used as the acid generator (B) in the resist composition of the present invention. Examples of nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate,
Examples include oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone (4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane), and the like. Typical ionic acid generators include onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, and the like.

As the acid generator (B), JP-A-63-26653, JP-A-55-164824,
JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63-146029, US Patent No. 3,779,
Compounds that generate acids upon radiation, such as those described in US Pat. No. 778, US Pat. No. 3,849,137, German Pat. Moreover, you may use the compound manufactured by the well-known method. 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、置換基を有していてもよい炭素数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、水素原子又は置換基を有していてもよい炭素数３～１８の１価の脂環式炭化水素
基を表し、該１価の脂環式炭化水素基に含まれる－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, more preferably represented by formula (B1)
(hereinafter sometimes referred to as "acid generator (B1)").

[In formula (B1),
Q ¹ and Q ² each 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 that may have a substituent,
-CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group is replaced by a fluorine atom or a hydroxyl atom. It may be substituted with a group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the monovalent alicyclic hydrocarbon group may be replaced with -O-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups of Q ¹ and Q ² include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, and perfluorobutyl group. Examples include hexyl group.
Q ¹ and Q ² are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably both are 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 also be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4
-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1
,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1
, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group,
tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-
1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-
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, and 2-methylbutane-1,4-diyl group;
A monocyclic cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, or a cyclooctane-1,5-diyl group. alicyclic saturated hydrocarbon group;
norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,5-diyl group and 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。］ As the group in which -CH ₂ - contained in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO-, for example, any of formulas (b1-1) to (b1-3) Examples include groups represented by: Note that in formulas (b1-1) to (b1-3) and the specific examples below, * is -Y
Represents the bond with.

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

In formulas (b1-1) to (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbon atoms before replacement is the carbon number of the saturated hydrocarbon group. 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 bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

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 formula (b1-1) or formula (b1-3). is preferred.

［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 formula (b1-1) include groups represented by formulas (b1-4) to (b1-8), respectively.

[In formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b13 to L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b16 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, 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 formula (b1-3) include groups represented by formulas (b1-9) to (b1-11), respectively.

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

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

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

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

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

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

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

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

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

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

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

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

In other words, in Y, two hydrogen atoms contained in an alicyclic hydrocarbon group are each substituted with an oxygen atom, and the two oxygen atoms together with an alkanediyl group having 1 to 8 carbon atoms form a ketal ring. or may include a structure in which oxygen atoms are bonded to different carbon atoms. However, when constituting a spiro ring such as formulas (Y28) to (Y33), the alkanediyl group between two oxygens preferably has one or more fluorine atoms. Moreover, among the alkanediyl groups included in the ketal structure, those in which the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom are preferable.

Among these, groups represented by any of formulas (Y1) to (Y20), formula (Y30), and formula (Y31) are preferable, and more preferably groups represented by formula (Y11), formula (Y15), and formula ( Y16)
, a group represented by formula (Y19), formula (Y20), formula (Y30) or formula (Y31), more preferably a group represented by formula (Y11), formula (Y15) or formula (Y30) Examples include groups.

Substituents for the monovalent alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxy groups, alkyl groups having 1 to 12 carbon atoms, hydroxy group-containing alkyl groups having 1 to 12 carbon atoms, and 3 carbon atoms. ~16 monovalent alicyclic hydrocarbon group, alkoxy group having 1 to 12 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, aralkyl group having 7 to 21 carbon atoms, 2 to 2 carbon atoms 4 acyl group, glycidyloxy group or -(CH ₂ ) _ja -O-CO-R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, a monovalent fatty acid 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 methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group.
Monovalent aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. group, biphenyl group, phenanthryl group, 2,6-
Examples include aryl groups such as diethylphenyl group and 2-methyl-6-ethylphenyl group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of Y include the following.

Y is preferably a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and these 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, an oxoadamantyl group, or a group represented below.

As the sulfonic acid anion in the salt represented by formula (B1), formulas (B1-A-1) to
Anion represented by formula (B1-A-46) [hereinafter referred to as "anion (B1-A-46)" according to the formula number
-1)” etc. ] is preferred, and formulas (B1-A-1) to (B1-A-4)
, formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-
33), anions represented by any one of formulas (B1-A-36) to (B1-A-40) are more preferred.

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 an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
4 alkyl group, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, ethyl group, cyclohexyl group, or adamantyl group. .
L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and Q ² are the same as above.
Specifically, as the sulfonic acid anion in the salt represented by formula (B1),
Examples include anions described in Japanese Patent No. 10-204646.

Preferred sulfonic acid anions in the salt represented by formula (B1) include formula (B1a-
Examples include anions represented by formulas 1) to (B1a-22).

Among them, formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-
16), formula (B1a-18), formula (B1a-19), or formula (B1a-22).
Examples of the organic cation of Z ⁺ include organic onium cations, such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations, and preferably organic sulfonium cations or organic iodonium cations. More preferred are arylsulfonium cations.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formulas (b2-1) to (b2-4) [hereinafter referred to as "cation (b2-1)" etc. according to the formula number] There are cases where this happens. ]
It 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のアルキル基、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、該アルキル
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３～１
２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のアルキル基、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のアルキル基又は炭素数３～３
６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のアルキル基、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のアルキル基、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、該アルキル基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 formulas (b2-1) to (b2-4),
R ^b4 to R ^b6 are each independently an alkyl group having 1 to 30 carbon atoms, or 1 having 3 to 36 carbon atoms;
represents a valent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms. 3-1
2 may be substituted with a monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the monovalent alicyclic hydrocarbon group are , halogen atom, carbon number 1
It may be substituted with an alkyl group having ~18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atoms contained in the monovalent aromatic hydrocarbon group are halogen atoms, hydroxy groups, or carbon atoms It may be substituted with 1 to 12 alkoxy groups.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH ₂ - contained in the ring may be replaced with -O-, -SO- or -CO-. .
R ^b7 and R ^b8 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different; when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 are each independently an alkyl group having 1 to 36 carbon atoms or 3 to 3 carbon atoms;
6 represents a monovalent alicyclic hydrocarbon group.
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 represents a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an alkyl 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 atoms contained may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the monovalent aromatic hydrocarbon group have 1 to 12 carbon atoms. It may be substituted with an alkoxy group or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be combined to form a ring containing -CH-CO- to which they are bonded, and -CH ₂ - contained in the ring is -O-, -SO- Alternatively, it may be replaced with -CO-.
R ^b13 to R ^b18 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represent an integer from 0 to 5.
q2 and r2 each independently represent an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, multiple R ^b13s may be the same or different; when p2 is 2 or more, multiple R ^b14s may be the same or different; when q2 is 2 or more, , a plurality of R ^b15s may be the same or different; when r2 is 2 or more, a plurality of R ^b16s may be the same or different; when s2 is 2 or more, a plurality of R ^b17s are They may be the same or different, and when t2 is 2 or more, the plurality of R ^b18s may be the same or different. ]

中でも、Ｒ^ｂ９～Ｒ^ｂ１２のアルキル基の炭素数は、好ましくは３～１８であり、より
好ましくは４～１２である。 Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. It will be done. Among them, the alkyl groups of R ^b9 to R ^b12 are
Preferably it has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monovalent monovalent alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo Examples include cycloalkyl groups such as hexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

Among them, the number of carbon atoms in the alkyl group of R ^b9 to R ^b12 is preferably 3 to 18, more preferably 4 to 12.

Examples of the monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantane-2-yl group, methylnorbornyl group, and isobornyl group. Examples include groups. In a monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with a certain group, the total carbon number of the monovalent alicyclic hydrocarbon group and the alkyl group is preferably 20 or less.
Examples of the aliphatic hydrocarbon groups for R ^b7 and R ^b8 and R ^b13 to R ^b18 include the same alkyl groups, alicyclic hydrocarbon groups, and combinations thereof as described above.

Monovalent aromatic hydrocarbon groups include phenyl group, tolyl group, xylyl group, 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- Examples include aryl groups such as methyl-6-ethylphenyl group.
When the monovalent aromatic hydrocarbon group includes an alkyl group or a monovalent alicyclic hydrocarbon group, an alkyl group having 1 to 18 carbon atoms and a monovalent alicyclic carbonization having 3 to 18 carbon atoms Hydrogen groups are preferred.
Examples of the monovalent aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group and the like.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

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

The ring that R ^b4 and R ^b5 may form together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. This ring includes a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, 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 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 polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, for example,
Thiolane-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1
, 4-oxathian-4-ium ring and the like.
The ring formed by R ^b11 and R ^b12 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, such as an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring, etc. It will be done.

Among cations (b2-1) to cations (b2-4), cations (b2-1
).

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 represented by the formula (
Examples include combinations of an anion and a cation (b2-1) represented by any of B1a-1) to (B1a-3) and formulas (B1a-7) to (B1a-16).

The acid generator (B1) preferably includes those represented by formulas (B1-1) to (B1-40), preferably those represented by formula (B1-1) containing an arylsulfonium cation.
), formula (B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7
), formula (B1-11), formula (B1-12), formula (B1-13), formula (B1-14), formula (
B1-17), 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) ), formula (B1-35), formula (B1-
36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40)
The following can be mentioned.

The acid generator (B) may contain an acid generator other than the acid generator (B1).
In the resist composition of the present invention, the acid generator (B1) may contain one type alone or a plurality of types. Among these, it is preferable that the acid generator (B1) contains two or more types of acid generators. The content of the acid generator (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, based on the total amount of the acid generator (B), and It is particularly preferable to use only agent (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 40 parts by mass or less (more preferably 35 parts by mass), based on 100 parts by mass of the resin (A). (below).

<Solvent (E)>
The content of the solvent (E) in the resist composition 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. It is. The content of the solvent (E) can be measured by 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, ethyl pyruvate, etc. Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; Cyclic esters such as γ-butyrolactone; and the like. It may contain one kind of solvent (E) alone,
Two or more types may be contained.

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

<Basic nitrogen-containing organic compound>
Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine. , heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, 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)ethene, 1,2-di(4-pyridyl)ethene, 1,
3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-
pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc., and diisopropylaniline is preferred. Particularly preferred is 2,6-diisopropylaniline.

Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethyl Examples include ammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

<Salts that generate weak acids>
The acidity of a salt that generates an acid less acidic than the acid generated from the acid generator is indicated by the acid dissociation constant (pKa). A salt that generates an acid with 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 with a<7, more preferably a salt with 0<pKa<5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid inner salt represented by formula (D), and JP-A No. 2012-229206, JP-A No. 2012-6908, JP 2012-72109, JP 2011-39502, and JP 2011-19
Examples include the salts described in 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 each independently represent a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 6 carbon atoms;
alkoxy group, acyl group having 2 to 7 carbon atoms, acyloxy group having 2 to 7 carbon atoms, acyl group having 2 to 7 carbon atoms,
7 represents an alkoxycarbonyl group, a nitro group, or a halogen atom.
m' and n' each independently represent an integer from 0 to 4; when m' is 2 or more, multiple R ^D1s are the same or different; 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 formula (D) include an alkyl group,
Examples include monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and groups formed by combining these groups.
Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Examples include isobutyl group, tert-butyl group, pentyl group, hexyl group, and nonyl group.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be saturated or unsaturated. Examples include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, and cyclododecyl group, norbornyl group, and adamantyl group.
Monovalent aromatic hydrocarbon groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-naphthyl group,
-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-
Examples include aryl groups such as 6-ethylphenyl.

Groups formed by combining these groups include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, aralkyl groups (for example, phenylmethyl groups, 1-phenylethyl groups, 2-phenylethyl groups, 1-phenyl-1 -propyl group, 1-phenyl-2
-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.) , alkyl-aryl groups (e.g., 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, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aryl-
Examples thereof include a cycloalkyl group and a cycloalkyl-aryl group (eg, p-adamantylphenyl group).

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

In formula (D), R ^D1 and R ^D2 each independently represent an alkyl group having 1 to 8 carbon atoms;
A cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or A halogen atom is preferred.
m' and n' are each independently preferably an integer of 0 to 2, more preferably 0. m'
When n' is 2 or more, the plurality of R ^D1s are the same or different, and when n' is 2 or more, the plurality R ^D2 are the same or different.

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

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

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

<Other ingredients>
The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter sometimes referred to as "other components (F)"), if necessary. Other components (F) are not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. 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)
It can be prepared by mixing. The mixing order is arbitrary and is not particularly limited. The mixing temperature ranges from 10 to 40°C, depending on the type of resin and the solvent (E) for the resin.
An appropriate temperature can be selected depending on the solubility etc. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is also not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter it using a filter with a pore size of about 0.003 to 0.2 μm.

<Resist pattern manufacturing method>
The method for manufacturing a resist pattern of the present invention includes:
(1) 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) exposing the composition layer to light;
(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 using a commonly used device such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate.

By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is
For example, the solvent may be evaporated using a heating device such as a hot plate (so-called pre-baking), or a pressure reducing device may be used. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. In addition, the pressure when drying under reduced pressure is 1 to 1.
Approximately 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. Examples of exposure light sources include those that emit laser light in the ultraviolet region, such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), _F2 excimer laser (wavelength 157 nm), and solid-state laser light sources (YAG or semiconductor lasers). etc.) that converts the wavelength of laser light and emits harmonic laser light in the far ultraviolet or vacuum ultraviolet range, and uses various methods such as those that emit electron beams and ultra-ultraviolet light (EUV). Can be done. In this specification, irradiation with these radiations may be collectively referred to as "exposure." During exposure, the exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct writing without using a mask.

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

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

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 of the various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).
The alkaline developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove water remaining on the substrate and pattern.

When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. Examples include ether solvents; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole.
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 even more preferably substantially only an organic solvent.
Among these, as the organic developer, a developer containing butyl acetate and/or 2-heptanone is preferred. 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 even more preferably substantially only butyl acetate and/or 2-heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a trace amount of water.
During development, development may be stopped by replacing the organic developer with a different type of solvent.

It is preferable to wash the resist pattern after development with a rinsing liquid. As a rinse liquid,
There is no particular restriction as long as it does not dissolve the resist pattern, and any solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent.
After cleaning, it is preferable to remove the rinsing liquid remaining on the substrate and pattern.

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

The present invention will be explained in more detail with reference to Examples. In the examples, "%" and "part" representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Equipment: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0mL/min
Detector: RI detector Column temperature: 40°C
Injection volume: 100μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

The structure of the compound was determined by mass spectrometry (LC: Agilent Model 1100, MASS: A
This was confirmed by measuring the molecular peak using an LC/MSD model manufactured by Gilent. In the following examples, the value of this molecular peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物９．００部、テトラヒドロフラン４５部、ピリジン
８．２０部及びジメチルアミノピリジン０．５３部を添加し、式（Ｉ－１－ｂ）で表され
る化合物１３．３２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル２５０部を加え、５％塩酸９１部を仕込み、２３℃で３０分間攪拌した
。静置、分液することにより回収された有機層に、イオン交換水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３
回繰り返した。回収された有機層を濃縮した。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－１－ｃ）で表される化合物９．４６部を得た。

式（Ｉ－１－ｃ）で表される化合物９．４３部及び酢酸４４．４０部を添加した後、２
３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％
）６．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した
後、濃縮残に、酢酸エチル１００部及びイオン交換水１００部を加え、２３℃で３０分間
攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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－１）で表される
化合物６．４２部を得た。
ＭＳ（質量分析）：１８８．１（分子イオンピーク） Synthesis Example 1: Synthesis of compound represented by formula (I-1)

9.00 parts of the compound represented by formula (I-1-a), 45 parts of tetrahydrofuran, 8.20 parts of pyridine and 0.53 parts of dimethylaminopyridine were added, and a mixture represented by formula (I-1-b) was added. 13.32 parts of the compound described above were added. Thereafter, the mixture was stirred at 23°C for 5 hours. To the obtained reaction mixture, 250 parts of ethyl acetate was added, 91 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23°C for 30 minutes. 50 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23° C. for 30 minutes, and the organic layer was washed with water by standing and separating. 3 such washing operations
Repeated times. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n-heptane/ethyl acetate = 1/
1) By fractionating, 9.46 parts of a compound represented by formula (I-1-c) was obtained.

After adding 9.43 parts of the compound represented by formula (I-1-c) and 44.40 parts of acetic acid, 2
The mixture was stirred at 3°C for 30 minutes and cooled to 5°C. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
) was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 100 parts of ethyl acetate and 100 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23° C. for 30 minutes, allowed to stand, and separated to recover an organic layer. The collected organic layer was concentrated. By fractionating the concentrated mass through a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm, developing solvent: n-heptane/ethyl acetate = 1/1), the compound 6 represented by formula (I-1) was obtained. .42 copies were obtained.
MS (mass spectrometry): 188.1 (molecular ion peak)

式（Ｉ－２－ａ）で表される化合物６．７５部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７２部及びジメチルアミノピリジン０．７０部を添加し、式（Ｉ－２－ｂ）
で表される化合物９．２４部を添加した。その後、２３℃で５時間攪拌した。得られた反
応混合物に、酢酸エチル１００部を加え、５％塩酸５０部を仕込み、２３℃で３０分間攪
拌した。静置、分液することにより回収された有機層に、イオン交換水５０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３回繰り返した。回収された有機層を濃縮した。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－ｃ）で表される化合物６．２４部を得た。

式（Ｉ－１－ｃ）で表される化合物５．１０部及び酢酸２２．２０部を添加した後、２
３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％
）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した
。濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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
３．６８部を得た。
ＭＳ（質量分析）：２０２．１（分子イオンピーク） Synthesis Example 2: Synthesis of compound represented by formula (I-2)

6.75 parts of the compound represented by formula (I-2-a), 50 parts of tetrahydrofuran, 6.72 parts of triethylamine and 0.70 parts of dimethylaminopyridine were added, and the compound represented by formula (I-2-b) was added.
9.24 parts of the compound represented by was added. Thereafter, the mixture was stirred at 23°C for 5 hours. To the resulting reaction mixture, 100 parts of ethyl acetate was added, 50 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23°C for 30 minutes. Add 50 parts of ion-exchanged water to the organic layer recovered by standing still and separating the liquid.
The organic layer was washed with water by stirring at 3° C. for 30 minutes, leaving it to stand, and separating the layers. Such water washing operation was repeated three times. The collected organic layer was concentrated. By fractionating the concentrated mass through a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm, developing solvent: n-heptane/ethyl acetate = 1/1), the formula (I-2-c) is expressed. 6.24 parts of the compound were obtained.

After adding 5.10 parts of the compound represented by formula (I-1-c) and 22.20 parts of acetic acid, 2
The mixture was stirred at 3°C for 30 minutes and cooled to 5°C. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
) was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. The resulting reaction product was concentrated. Add 50 parts of ethyl acetate and 50 parts of ion-exchanged water to the concentrated residue, stir at 23°C for 30 minutes,
The organic layer was collected by standing still and separating the layers. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 3.68 parts of a compound represented by formula (I-2).
MS (mass spectrometry): 202.1 (molecular ion peak)

式（Ｉ－２５－ａ）で表される化合物５．９部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ－１－ｂ）で表
される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌
した。得られた混合物を静置、分液することにより回収された有機層に、イオン交換水５
０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３回繰り返した。回収された有機層を濃縮した。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－２５－ｃ）で表される化合物６
．２２部を得た。

式（Ｉ－２５－ｃ）で表される化合物４．７部及び酢酸２２．２部を添加した後、２３
℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）
３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後
、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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－２５）で表される化合
物３．１１部を得た。
ＭＳ（質量分析）：１８７．１（分子イオンピーク） Synthesis Example 3: Synthesis of compound represented by formula (I-25)

5.9 parts of the compound represented by formula (I-25-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 parts of dimethylaminopyridine were added, and a mixture represented by formula (I-1-b) was added. 9.2 parts of the compound described above were added. Thereafter, the mixture was stirred at 23°C for 5 hours. To the resulting reaction mixture, 100 parts of ethyl acetate was added, and further 50 parts of 5% hydrochloric acid were added, followed by stirring at 23°C for 30 minutes. The resulting mixture was allowed to stand and the organic layer was collected by liquid separation, and then 55% of ion-exchanged water was added.
0 part was added, stirred at 23° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass is transferred to the column (
Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n-heptane/ethyl acetate = 1/1) By fractionating, compound 6 represented by formula (I-25-c)
．． Got 22 copies.

After adding 4.7 parts of the compound represented by formula (I-25-c) and 22.2 parts of acetic acid, 23
The mixture was stirred at ℃ for 30 minutes and cooled to 5℃. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
3.00 parts were added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes.
The organic layer was collected by standing still and separating the layers. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 3.11 parts of a compound represented by formula (I-25).
MS (mass spectrometry): 187.1 (molecular ion peak)

式（Ｉ－２６－ａ）で表される化合物６．７部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ－１－ｂ）で表
される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌
した。静置、分液することにより回収された有機層に、イオン交換水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３回繰り返した。回収された有機層を濃縮した。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－２６―ｃ）で表される化合物５．９８部を得た。

式（Ｉ－２６－ｃ）で表される化合物５．１部及び酢酸２２．２部を添加した後、２３
℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）
３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後
、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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－２６）で表される化合
物３．２部を得た。
ＭＳ（質量分析）：２０１．１（分子イオンピーク） Synthesis Example 4: Synthesis of compound represented by formula (I-26)

6.7 parts of the compound represented by formula (I-26-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 parts of dimethylaminopyridine were added, and a mixture represented by formula (I-1-b) was added. 9.2 parts of the compound described above were added. Thereafter, the mixture was stirred at 23°C for 5 hours. To the obtained reaction mixture, 100 parts of ethyl acetate was added, and further 50 parts of 5% hydrochloric acid were added, followed by stirring at 23°C for 30 minutes. Add 50 parts of ion-exchanged water to the organic layer recovered by standing still and separating the liquid.23
The organic layer was washed with water by stirring at °C for 30 minutes, leaving it to stand, and separating the layers. Such water washing operation was repeated three times. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n-heptane/ethyl acetate =
1/1) fractionation to obtain 5.98 parts of a compound represented by formula (I-26-c).

After adding 5.1 parts of the compound represented by formula (I-26-c) and 22.2 parts of acetic acid, 23
The mixture was stirred at ℃ for 30 minutes and cooled to 5℃. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
3.00 parts were added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes.
The organic layer was collected by standing still and separating the layers. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 3.2 parts of a compound represented by formula (I-26).
MS (mass spectrometry): 201.1 (molecular ion peak)

Synthesis Example 5: Synthesis of compound represented by formula (I-5)

式（Ｉ－５－ｃ）で表される化合物１９．３部、式（Ｉ－１－ａ）で表される化合物１
０．４部及びアセトニトリル２００部を仕込み、２３℃で５時間攪拌した。得られた反応
物を濃縮し、クロロホルム３００部及びイオン交換水１５０部を加え、２３℃で３０分間
攪拌した。静置、分液することにより回収された有機層に、イオン交換水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。このような水
洗操作を３回繰り返した。回収された有機層を濃縮した。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：酢酸エチル）分取する
ことにより、式（Ｉ－５―ｄ）で表される化合物２２．２８部を得た。

式（Ｉ－５－ｄ）で表される化合物６．３部及び酢酸２２．２部を添加した後、２３℃
で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３
．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、
濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静
置、分液することにより有機層を回収した。回収された有機層を濃縮した。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２
．８９部を得た。
ＭＳ（質量分析）：２４６．１（分子イオンピーク） 33.5 parts of the compound represented by formula (I-5-a), 23 parts of dicyclohexylcarbodiimide
．． 9 parts and 40 parts of methylene chloride were charged, and the mixture was stirred at 23°C for 30 minutes. To the resulting mixture was added 18.83 parts of the compound represented by formula (I-5-b) at 0°C, and the mixture was stirred at 0°C for 1 hour. The temperature was raised to 23°C, and the mixture was further stirred for 30 minutes, and then filtered. The obtained filtrate was concentrated to obtain 42.2 parts of a compound represented by formula (I-5-c).

19.3 parts of compound represented by formula (I-5-c), compound 1 represented by formula (I-1-a)
0.4 parts and 200 parts of acetonitrile were charged, and the mixture was stirred at 23°C for 5 hours. The obtained reaction product was concentrated, 300 parts of chloroform and 150 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes. 150 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such water washing operation was repeated three times. The collected organic layer was concentrated. Column of concentrated mass (Kanto Chemical)
Silica gel 60N (spherical, neutral) 100-210 μm (developing solvent: ethyl acetate) was fractionated to obtain 22.28 parts of a compound represented by formula (I-5-d).

After adding 6.3 parts of the compound represented by formula (I-5-d) and 22.2 parts of acetic acid, the temperature was increased to 23°C.
The mixture was stirred for 30 minutes and cooled to 5°C. Hydrogen peroxide (purity 31%) 3
．． 00 parts were added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product,
50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23° C. for 30 minutes, allowed to stand, and separated to recover an organic layer. The collected organic layer was concentrated. Column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210μm Developing solvent: n-
By fractionating heptane/ethyl acetate = 1/1), compound 2 represented by formula (I-5)
．． Obtained 89 copies.
MS (mass spectrometry): 246.1 (molecular ion peak)

特開２００８－２０９９１７号公報に記載された方法によって得られた式（Ｂ１－２１
－ｂ）で表される化合物３０．００部、式（Ｂ１－２１－ａ）で表される塩３５．５０部
、クロロホルム１００部及びイオン交換水５０部を仕込み、２３℃で１５時間攪拌した。
得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、
このクロロホルム層にイオン交換水３０部を添加し、水洗した。この操作を５回繰り返し
た。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ－ブチルメチルエーテル１００
部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１－２１－ｃ）で表さ
れる塩４８．５７部を得た。 Synthesis Example 6 [Synthesis of salt represented by formula (B1-21)]

Formula (B1-21
-b) 30.00 parts of the compound represented by formula (B1-21-a), 35.50 parts of the salt represented by formula (B1-21-a), 100 parts of chloroform, and 50 parts of ion-exchanged water were charged, and the mixture was stirred at 23°C for 15 hours. .
The resulting reaction solution was separated into two layers, so the chloroform layer was separated and taken out, and
30 parts of ion-exchanged water was added to this chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, and tert-butyl methyl ether 100% was added to the resulting residue.
1 part, stirred at 23°C for 30 minutes, and filtered to obtain 48.57 parts of a salt represented by formula (B1-21-c).

式（Ｂ１－２１－ｃ）で表される塩２０．００部、式（Ｂ１－２１－ｄ）で表される化
合物２．８４部及びモノクロロベンゼン２５０部を仕込み、２３℃で３０分間攪拌した。
得られた混合液に、二安息香酸銅（ＩＩ）０．２１部を添加し、更に、１００℃で１時間
攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム２００部及びイ
オン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収
された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を
取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮した。得られた残渣
を、アセトニトリル５３．５１部に溶解し、濃縮した。得られた濃縮物にｔｅｒｔ－ブチ
ルメチルエーテル１１３．０５部を加えて攪拌し、ろ過することにより、式（Ｂ１－２１
）で表される塩１０．４７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３９．１

20.00 parts of the salt represented by formula (B1-21-c), 2.84 parts of the compound represented by formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23°C for 30 minutes. .
0.21 part of copper(II) dibenzoate was added to the obtained mixture, and the mixture was further stirred at 100°C for 1 hour. The resulting reaction solution was concentrated. 200 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained residue, stirred at 23°C for 30 minutes, and the organic layer was separated. 50 parts of ion-exchanged water was added to the collected organic layer, stirred at 23° C. for 30 minutes, and the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated. The obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. By adding 113.05 parts of tert-butyl methyl ether to the obtained concentrate, stirring, and filtering, formula (B1-21
) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI(-)Spectrum): M ^- 339.1

式（Ｂ１－２２－ａ）で表される塩１１．２６部、式（Ｂ１－２２－ｂ）で表される化
合物１０．００部、クロロホルム５０部及びイオン交換水２５部を仕込み、２３℃で１５
時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取
り出し、更に、このクロロホルム層にイオン交換水１５部を添加し、水洗した。この操作
を５回繰り返した。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ－ブチルメチル
エーテル５０部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１－２２
－ｃ）で表される塩１１．７５部を得た。 Synthesis Example 7 [Synthesis of salt represented by formula (B1-22)]

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

式（Ｂ１－２２－ｃ）で表される塩１１．７１部、式（Ｂ１－２２－ｄ）で表される化
合物１．７０部及びモノクロロベンゼン４６．８４部を仕込み、２３℃で３０分間攪拌し
た。得られた混合液に、二安息香酸銅（ＩＩ）０．１２部を添加し、更に、１００℃で３
０分間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム５０部及
びイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出
した。回収された有機層にイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、
分液して有機層を取り出した。この水洗操作を８回繰り返した。得られた有機層を濃縮し
た。得られた残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて攪拌し、ろ過する
ことにより、式（Ｂ１－２２）で表される塩６．８４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３２３．０

11.71 parts of the salt represented by formula (B1-22-c), 1.70 parts of the compound represented by formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged, and the mixture was heated at 23°C for 30 minutes. Stirred. 0.12 parts of copper(II) dibenzoate was added to the resulting mixed solution, and the mixture was further heated at 100°C for 3
Stirred for 0 minutes. The resulting reaction solution was concentrated. To the obtained residue, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added, stirred at 23°C for 30 minutes, and the organic layer was separated. 12.50 parts of ion-exchanged water was added to the collected organic layer and stirred at 23°C for 30 minutes.
The organic layer was separated. This water washing operation was repeated eight times. The obtained organic layer was concentrated. 50 parts of tert-butyl methyl ether was added to the resulting residue, stirred, and filtered to obtain 6.84 parts of a salt represented by formula (B1-22).
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

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

Hereinafter, these monomers will be referred to as "monomers (a1-1-3)" etc. according to their formula numbers.

Example 1 [Synthesis of resin A1]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-1), monomer (a2-1-1) and monomer (a3-4-2), and their molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (I -1):monomer (a2-1-1):monomer (a3-4-2)] is 40:9:10:2.5:38.5
1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators, respectively, based on the total monomer amount.
1 mol% and 3 mol% were added, and these were heated at 75°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered.
The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A1 with a weight average molecular weight of 8.2×10 ³ in a yield of 62%. This resin A
1 has the following structural unit.

Example 2 [Synthesis of resin A2]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-2), monomer (a2-1-1) and monomer (a3-4-2), and their molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (I -2):monomer (a2-1-1):monomer (a3-4-2)] is 40:9:10:2.5:38.5
1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators, respectively, based on the total monomer amount.
1 mol% and 3 mol% were added, and these were heated at 75°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered.
The obtained resin was again poured into a methanol/water mixed solvent to be repulped, and this resin was filtered to obtain resin A2 with a weight average molecular weight of 8.3×10 ³ in a yield of 63%. This resin A
2 has the following structural unit.

Example 3 [Synthesis of resin A3]
Monomer (a1-1-1) and monomer (I-2) are used as monomers, and mixed so that the molar ratio [monomer (a1-1-1): monomer (I-2)] is 48:52. Then, propylene glycol monomethyl ether acetate in an amount of 1.5 times the total amount of monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 0.6 mol% and 1.8 mol%, respectively, based on the total monomer amount, and these were heated at 75°C. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A3 with a weight average molecular weight of 1.6×10 ⁴ in a yield of 87%. This resin A3 has the following structural units.

Example 4 [Synthesis of resin A4]
As monomers, monomer (a1-1-2), monomer (a2-1-1), monomer (
a3-1-1) and monomer (I-1), and their molar ratio (monomer (a1-1-2)
: Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-1)) is 30
:20:40:10, and propylene glycol monomethyl ether acetate in an amount of 1.5 times the total monomer amount was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 0.8 mol% and 2.4 mol%, respectively, based on the total monomer amount, and these were heated at 75°C. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A4 (copolymer) with a weight average molecular weight of 1.0 x ¹⁰⁴ in a yield of 72%. Ta. This resin A4 has the following structural units.

Example 5 [Synthesis of resin A5]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-5), monomer (a2-1-1) and monomer (a3-4-2), and their molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (I -5):monomer (a2-1-1):monomer (a3-4-2)] is 40:9:10:2.5:38.5
1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators, respectively, based on the total monomer amount.
1 mol% and 3 mol% were added, and these were heated at 75°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered.
The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A5 with a weight average molecular weight of 7.9×10 ³ in a yield of 58%. This resin A
5 has the following structural unit.

Example 6 [Synthesis of resin A6]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-25), monomer (a2-1-1) and monomer (a3-4-2), and their molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (I -25):monomer (a2-1-1):monomer (a3-4-2)] is 40:9:10:2.5:38
．． 5, and 1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and the mixture was heated at 75°C for about 5 hours. did. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A6 with a weight average molecular weight of 8.8×10 ³ in a yield of 60%. This resin A6 has the following structural units.

Example 7 [Synthesis of resin A7]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-26), monomer (a2-1-1) and monomer (a3-4-2), and their molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (I -26):monomer (a2-1-1):monomer (a3-4-2)] is 40:9:10:2.5:38
．． 5, and 1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and the mixture was heated at 75°C for about 5 hours. did. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin A7 with a weight average molecular weight of 9.1×10 ³ in a yield of 63%. This resin A7 has the following structural units.

Synthesis Example 8 [Synthesis of resin AX1]
Monomer (a1-1-1) and monomer (IX-1) are used as monomers, and mixed so that the molar ratio [monomer (a1-1-1): monomer (IX-1)] is 48:52. Then, propylene glycol monomethyl ether acetate in an amount of 1.5 times the total amount of monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 0.6 mol% each based on the total monomer amount.
and 1.8 mol% were added, and these were heated at 75° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again poured into a methanol/water mixed solvent to be repulped, and this resin was filtered to obtain resin AX1 with a weight average molecular weight of 1.7×10 ⁴ in a yield of 87%. This resin AX1
has the following structural units.

Synthesis Example 9 [Synthesis of resin AX2]
As monomers, monomer (a1-1-2), monomer (a2-1-1), monomer (
a3-1-1) and monomer (IX-2), and their molar ratio (monomer (a1-1-2)
): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (IX-2)) were mixed in a ratio of 30:20:40:10, and 1.5 mass of the total monomer amount Two times the amount of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 0.8 mol% and 2.4 mol%, respectively, based on the total monomer amount, and these were heated at 75°C. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped by pouring it into a methanol/water mixed solvent again, and this resin was filtered to obtain resin AX with a weight average molecular weight of 1.1×10 ⁴
2 (copolymer) was obtained in a yield of 66%. This resin AX2 has the following structural units.

Synthesis Example 10 [Synthesis of Resin X1]
Using monomer (a5-1-1) and monomer (a4-0-12) as monomers,
Mix them so that the molar ratio (monomer (a5-1-1):monomer (a4-0-12)) is 50:50, add 0.6 times the mass of methyl isobutyl ketone to the total monomer amount, and make a solution. And so. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator 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 was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and this resin was filtered to obtain resin X1 with a weight average molecular weight of 1.5×10 ⁴ in a yield of 88%. This resin X1 has the following structural units.

Synthesis Example 11 [Synthesis of Resin X2]
Monomer (a4-1-7) was used as a monomer, and methyl isobutyl ketone in an amount of 1.2 times the total amount of monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and the mixture was heated at 75°C for about 5 hours. did. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was repulped in a methanol/water mixed solvent and filtered to obtain resin X2 with a weight average molecular weight of 7.8×10 ³ in a yield of 86%. This resin X2 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, a resist composition was prepared by mixing the following components and filtering the resulting mixture through a fluororesin filter with a pore size of 0.2 μm.

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２－ヘプタノン ２０部
γ－ブチロラクトン ３．５部 <Resin>
A1 to A7, X1, X2: Resin A1 to Resin A7, Resin X1, Resin X2
<Acid generator>
B1-21: Salt represented by formula (B1-21) B1-22: Salt represented by formula (B1-22) <Compound (D)>
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

<CD uniformity (CDU) evaluation (negative development)>
A silicon wafer is coated with an organic anti-reflective film composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) and baked at 205°C for 60 seconds to form an organic reflective film with a thickness of 78 nm on the wafer. A preventive film was formed. Next, the resist composition described above was applied (spin coated) onto this organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was prebaked for 60 seconds on a direct hot plate at the temperature listed in the "PB" column of Table 1 to form a composition layer. An ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3
/4Annular XY polarization), contact hole pattern (hole pitch 90n)
Using a mask for forming a hole diameter of 55 nm (hole diameter: 55 nm), exposure was performed while changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature listed in the "PEB" column of Table 1. Next, the composition layer on the silicon wafer was developed by a dynamic dispensing method at 23° C. for 20 seconds using butyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer to form a negative resist pattern. Manufactured.

In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 50 nm was defined as the effective sensitivity.

In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was calculated using a population of 400 measurements of the average hole diameter of a pattern formed using a mask with a hole diameter of 70 nm within the same wafer.
“○” if the standard deviation is 2.00 nm or less;
A case where the standard deviation was larger than 2.00 nm was judged as "x".
The results are shown in Table 2. Values in parentheses indicate standard deviation (nm).

<CD uniformity (CDU) evaluation (positive development)>
A silicon wafer is coated with an organic anti-reflective film composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) and baked at 205°C for 60 seconds to form an organic reflective film with a thickness of 78 nm on the wafer. A preventive film was formed. Next, the resist composition described above was applied (spin coated) onto this organic antireflection film so that the film thickness after drying (prebaking) was 85 nm. After coating, the silicon wafer was prebaked for 60 seconds on a direct hot plate at the temperature listed in the "PB" column of Table 1 to form a composition layer. An ArF excimer stepper for liquid immersion exposure (XT: 1900 Gi; manufactured by ASML, NA
= 1.35, 3/4Annular Note that ultrapure water was used as the immersion medium.
After exposure, the silicon wafer was heated on a hot plate at the temperature listed in the "PEB" column of Table 1 for 60 seconds (post-exposure bake treatment). Next, this silicon wafer was subjected to paddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 55 nm was defined as the effective sensitivity.

In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was calculated using a population of 400 measurements of the average hole diameter of a pattern formed using a mask with a hole diameter of 70 nm within the same wafer.
“○” if the standard deviation is 1.80 nm or less;
A case where the standard deviation was larger than 1.80 nm was judged as "x".
The results are shown in Table 3. Values in parentheses indicate standard deviation (nm).

From the above results, the resin of the present invention and the resist composition using the same have good CD.
It can be seen that a resist pattern can be manufactured with uniformity.

The resin of the present invention and the resist composition using the same are suitable for microfabrication of semiconductors because the resulting resist pattern has excellent CD uniformity.

Claims (7)

A structural unit represented by formula (I),
At least one structural unit selected from the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2),
Structural unit represented by formula (a1-0), structural unit represented by formula (a1-3), structural unit represented by formula (a1-4), structure represented by formula (a1-5) unit, a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-4), and a structural unit represented by formula (a5-1). a resin containing at least one structural unit selected from the group consisting of structural units represented by formula (I);
At least one structural unit selected from the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2),
Structural unit represented by formula (a2-0), structural unit represented by formula (a2-1), structural unit represented by formula (a3-1), structure represented by formula (a3-2) at least one structural unit selected from the group consisting of a structural unit represented by formula (a3-3) and a structural unit represented by formula (a3-4);
Structural unit represented by formula (a1-0), structural unit represented by formula (a1-3), structural unit represented by formula (a1-4), structure represented by formula (a1-5) unit, a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-4), and a structural unit represented by formula (a5-1). A resin comprising at least one structural unit selected from the group consisting of structural units,
For the total of all structural units that make up the resin,
The content of the structural unit represented by formula (I) is 1 to 60 mol%,
The total content of the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2) is 10 to 95 mol%,
When containing the structural unit represented by formula (a2-0), the content is 10 to 80 mol%,
When containing the structural unit represented by the formula (a2-1), the content is 1 to 40 mol%, and the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2) The total content when containing structural units, structural units represented by formula (a3-3), and structural units represented by formula (a3-4) is 5 to 70 mol%,
A resin in which the total content of all structural units constituting the resin is 100 mol%.
[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.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer from 0 to 3, and when u is 2 or more, a plurality of R ² 's are the same or different from each other.
A ¹ represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-A ² -X ¹ -(A ³ -X ² ) _a -(A ⁴ ) _b -. * represents a bond with group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² each independently represent -O-, -CO-O-, -O-CO- or -O-CO-O-.
a represents 0 or 1.
b represents 0 or 1. ]
[In formula (a1-1) and formula (a1-2),
L ^a1 and L ^a2 each independently represent -O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer from 1 to 7, and * represents a bond with -CO- represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.
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 formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, a plurality of R ^a31 's may be the same or different. ]
[In formula (a2-1),
L ^a3 represents -O- or *-O-(CH ₂ ) _k2 -CO-O-.
k2 represents an integer from 1 to 7. * represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group, or a hydroxy group.
o1 represents an integer from 0 to 10. ]
[In formula (a3-1),
L ^a4 represents a group represented by -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents an integer from 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 R ^a21s 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 from 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 from 0 to 3. When q1 is 2 or more, a plurality of R ^a22s are the same or different from each other.
In formula (a3-3),
L ^a6 represents a group represented by -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents an integer from 1 to 7). * represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer from 0 to 3. When r1 is 2 or more, a plurality of R ^a23s 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.
L ^a7 is -O-, ^* -O-L ^a8 -O-, ^* -O-L ^a8 -CO-O-, ^* -O-L ^a8 -CO-O-L ^a9 -CO-O-, or ^* -O-L ^a8 -O-CO-L ^a9 -O-.
* represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]
[In formula (a1-0),
L ^a01 represents an oxygen atom or *-O-(CH ₂ ) _k01 --CO-O-, k01 represents an integer from 1 to 7, and * represents a bond with a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. ]
[In formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom or -COOR ^a13 .
R ^a13 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these; The hydrogen atom contained may be substituted with a hydroxy group, and the -CH ₂ - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O- or -CO-.
R ^a10 , R ^a11 and R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these; ^a10 and R ^a11 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ]
[In formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer from 0 to 4. When la is 2 or more, a plurality of R ^a33 's may be the same or different.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other. This forms a divalent heterocyclic group having 3 to 20 carbon atoms together with C-O to which it is bonded, and -CH ₂ - contained in the hydrocarbon group and the divalent heterocyclic group is -O- or May be replaced with -S-. ]
[In formula (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 from 1 to 4, and * represents a bond with L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent -O- or -S-.
s1 represents an integer from 1 to 3.
s1' represents an integer from 0 to 3. ]
[In formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]
[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group may be replaced with -O- or -CO-. good.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1). ]
[In formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
* and ** are bonds, and ** is a bond with -O-CO-R ^a42 . ]
[In formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents -(CH ₂ ) _j1 -, -(CH ₂ ) _j2 -O-(CH ₂ ) _j3 - or -(CH ₂ ) _j4 -CO-O-(CH ₂ ) _j5 -.
j1 to j5 each independently represent an integer from 1 to 6.
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]
[In formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. You can. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] The resin according to claim 1, wherein A ¹ is a single bond. A resist composition comprising the resin according to claim 1 or 2 and an acid generator. 4. The resist composition according to claim 3, wherein the acid generator is a salt represented by formula (B1).
[In formula (B1),
Q ¹ and Q ² each 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 which may have a substituent, and -CH ₂ - contained in the divalent saturated hydrocarbon group is -O- or -CO- may be substituted, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the monovalent alicyclic hydrocarbon group may be replaced with -O-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ] 5. The resist composition according to claim 3, further comprising a salt that generates an acid less acidic than the acid generated from the acid generator. 6. The resist composition according to claim 3, further comprising a resin containing a structural unit having a fluorine atom. (1) applying the resist composition according to any one of claims 3 to 6 onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer to light;
(4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.
A method for manufacturing a resist pattern including: