JP6981767B2 - Compound - Google Patents

Description

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

Patent Document 1 describes a resin obtained by polymerizing the following compounds.

Patent Document 2 describes a resin obtained by polymerizing the following compounds.

Japanese Unexamined Patent Publication No. 2011-039498 Japanese Unexamined Patent Publication No. 2012-107204

With the above resist composition, CD uniformity (CDU) may not always be satisfactory.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、炭素数１〜１２の炭化水素基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜６の脂肪族炭化水素基を表す。
Ｘ^ａ及びＸ^ｂは、それぞれ独立に、酸素原子又は硫黄原子を表す。
Ｘ^１１は、フッ素原子を有してもよい２価の炭素数１〜１２の飽和炭化水素基を表す。
Ａ^１は、^＊−Ａ^２−又は^＊−Ａ^３−Ｘ^１−（Ａ^４−Ｘ^２）_ａ−Ａ^５−を表す。＊はＣ（Ｒ^３）（Ｒ^４）との結合手を表す。
Ａ^２及びＡ^３は、それぞれ独立に、単結合又は炭素数１〜１２の２価の炭化水素基を表す。
Ａ^４及びＡ^５は、それぞれ独立に、炭素数１〜１２の２価の炭化水素基を表す。
Ｘ^１及びＸ^２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。］
〔２〕Ａ^１が、単結合又は^＊−Ａ^３−Ｘ^１−Ａ^５−である〔１〕記載の化合物。
〔３〕Ａ^３が、アダマンタンジイル基である〔１〕又は〔２〕記載の化合物。
〔４〕Ｘ^１１が、フッ素原子を有してもよい２価の炭素数２〜６の飽和炭化水素基である〔１〕〜〔３〕のいずれか記載の化合物。
〔５〕〔１〕〜〔４〕のいずれか記載の化合物に由来する構造単位を含む樹脂。
〔６〕樹脂が、さらに、酸不安定基を有する構造単位（ただし、式（Ｉ）で表される化合物に由来する構造単位を含まない）を含む〔５〕記載の樹脂。
〔７〕酸不安定基を有する構造単位が、式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）で表される構造単位からなる群より選ばれる少なくとも１種である〔６〕記載の樹脂。

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a01、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^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。
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合せることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］
〔８〕樹脂が、さらに、ラクトン環を有する構造単位を含む請〔５〕〜〔７〕のいずれか記載の樹脂。
〔９〕ラクトン環を有する構造単位が、式（ａ３−１）、式（ａ３−２）、式（ａ３−３）及び式（ａ３−４）で表される構造単位からなる群より選ばれる少なくとも１種である〔８〕記載の樹脂。

［式（ａ３−１）、式（ａ３−２）、式（ａ３−３）及び式（ａ３−４）中、
Ｌ^ａ４、Ｌ^ａ５及びＬ^ａ６は、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７のいずれかの整数を表す。）で表される基を表す。
Ｌ^ａ７は、−Ｏ−、^＊−Ｏ−Ｌ^ａ８−Ｏ−、^＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−、^＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は^＊−Ｏ−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
Ｌ^ａ８及びＬ^ａ９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。
＊はカルボニル基との結合手を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、水素原子又はメチル基を表す。
Ｒ^ａ２４は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^ａ２１は炭素数１〜４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５のいずれかの整数を表す。
ｑ１は、０〜３のいずれかの整数を表す。
ｒ１は、０〜３のいずれかの整数を表す。
ｗ１は、０〜８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一であってもよく、異なってもよい。］
〔１０〕樹脂が、さらに、ヒドロキシ基を有する構造単位を含む〔５〕〜〔９〕のいずれか記載の樹脂。
〔１１〕ヒドロキシ基を有する構造単位が、式（ａ２−１）で表される構造単位である〔１０〕記載の樹脂。

［式（ａ２−１）中、
Ｌ^ａ３は、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ２−ＣＯ−Ｏ−を表し、
ｋ２は１〜７のいずれかの整数を表す。＊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のいずれかの整数を表す。］
〔１２〕〔５〕〜〔１１〕のいずれか記載の樹脂と、酸発生剤とを含むレジスト組成物。
〔１３〕さらに、フッ素原子を有する構造単位を含む樹脂（ただし、式（Ｉ）で表される化合物に由来する構造単位を含まない）を含有する〔１２〕に記載のレジスト組成物。
〔１４〕酸発生剤が、式（Ｂ１）で表される酸発生剤である〔１２〕又は〔１３〕記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子はフッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８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−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。］
〔１５〕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〔１２〕〜〔１４〕のいずれか記載のレジスト組成物。
〔１６〕（１）〔１２〕〜〔１５〕のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a hydrocarbon group having 1 to 12 carbon atoms.
R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
X ¹¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms which may have a fluorine atom.
A ¹ represents ^* -A ^2- or ^* -A ^3- X ^1- (A ^4- X ² ) _a- A ^5- . * Represents a bond with C (R ³ ) (R ^4).
A ² and A ³ independently represent a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms.
A ⁴ and A ⁵ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ¹ and X ² independently represent -O-, -CO-O-, -O-CO- or -O-CO-O-, respectively.
a represents 0 or 1. ]
[2] The compound according to [1] ^{, wherein A 1} is a single bond or ^* −A ³ −X ¹ −A ^{5 −.}
[3] A ³ is a adamantanediyl group (1) or (2) compounds according.
[4] ^{The compound according to any one of [1] to [3], wherein X 11} is a divalent saturated hydrocarbon group having 2 to 6 carbon atoms which may have a fluorine atom.
[5] A resin containing a structural unit derived from the compound according to any one of [1] to [4].
[6] The resin according to [5], wherein the resin further contains a structural unit having an acid unstable group (however, the structural unit derived from the compound represented by the formula (I) is not included).
[7] The structural unit having an acid unstable group is at least one selected from the group consisting of the structural units represented by the formula (a1-0), the formula (a1-1) and the formula (a1-2). [6] The resin according to the above.

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^{a01, L a1} and ^{L a2} each independently, -O- or _{^{* -O- (CH 2) k1 -CO}} -O- the stands, k1 represents an integer of 1-7, and * Represents a bond with −CO−.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]
[8] The resin according to any one of [5] to [7], wherein the resin further contains a structural unit having a lactone ring.
[9] The structural unit having a lactone ring is selected from the group consisting of the structural units represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4). The resin according to [8], which is at least one kind.

[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4 , ^{La 5} and ^{La 6} represent a group represented by -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 represents an integer of 1 to 7). ..
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- CO-O-L ^a9- CO-O- or ^* Represents −O−L ^a8 −O−CO−L ^a9 −O−.
L ^a8 and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5.
q1 represents any integer from 0 to 3.
r1 represents any integer from 0 to 3.
w1 represents any integer from 0 to 8.
When p1, q1, r1 and / or w1 is 2 or more, the plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different from each other. ]
[10] The resin according to any one of [5] to [9], wherein the resin further contains a structural unit having a hydroxy group.
[11] The resin according to [10], wherein the structural unit having a hydroxy group is the structural unit represented by the formula (a2-1).

[In equation (a2-1),
^La3 represents −O− or ^* −O− (CH ₂ ) _k2 −CO−O−.
k2 represents any 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 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents any integer from 0 to 10. ]
[12] A resist composition containing the resin according to any one of [5] to [11] and an acid generator.
[13] The resist composition according to [12], which further contains a resin containing a structural unit having a fluorine atom (however, it does not contain a structural unit derived from a compound represented by the formula (I)).
[14] The resist composition according to [12] or [13], wherein the acid generator is an acid generator represented by the 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, and —CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ - is -O -, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]
[15] The resist composition according to any one of [12] to [14], further containing a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[16] (1) A step of applying the resist composition according to any one of [12] to [15] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using a resist composition containing a resin having a structural unit derived from the compound of the present invention, a resist pattern can be produced with good CD uniformity (CDU).

In the present specification, unless otherwise specified, a hydrocarbon group having both a linear structure and a branched structure such as "aliphatic hydrocarbon group" in the description of the structural formula of a compound includes both of them. The "aliphatic hydrocarbon group" means a group obtained by removing a number of hydrogen atoms corresponding to a valence from the ring of an alicyclic hydrocarbon. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
As used herein, the term "(meth) acrylic monomer" means at least one of the monomers having a structure of _{"CH 2} = CH-CO-" or "CH ₂ = C (CH _{3) -CO-".} do. Similarly, "(meth) acrylate" and "(meth) acrylic acid" mean "at least one of acrylate and methacrylate" and "at least one of acrylic acid and methacrylic acid", respectively.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、炭素数１〜１２の炭化水素基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜６の脂肪族炭化水素基を表す。
Ｘ^ａ及びＸ^ｂは、それぞれ独立に、酸素原子又は硫黄原子を表す。
Ｘ^１１は、フッ素原子を有してもよい２価の炭素数１〜１２の飽和炭化水素基を表す。
Ａ^１は、^＊−Ａ^２−又は^＊−Ａ^３−Ｘ^１−（Ａ^４−Ｘ^２）_ａ−Ａ^５−を表す。＊はＣ（Ｒ^３）（Ｒ^４）との結合手を表す。
Ａ^２及びＡ^３は、それぞれ独立に、単結合又は炭素数１〜１２の２価の炭化水素基を表す。
Ａ^４及びＡ^５は、それぞれ独立に、炭素数１〜１２の２価の炭化水素基を表す。
Ｘ^１及びＸ^２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。］ [Compound (I)]
The compound of the present invention is a compound represented by the formula (I) (hereinafter, may be referred to as “compound (I)”).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a hydrocarbon group having 1 to 12 carbon atoms.
R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
X ^a and X ^b independently represent an oxygen atom or a sulfur atom, respectively.
X ¹¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms which may have a fluorine atom.
A ¹ represents ^* -A ^2- or ^* -A ^3- X ^1- (A ^4- X ² ) _a- A ^5- . * Represents a bond with C (R ³ ) (R ^4).
A ² and A ³ each independently represent a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms.
A ⁴ and A ⁵ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ¹ and X ² independently represent -O-, -CO-O-, -O-CO- or -O-CO-O-, respectively.
a represents 0 or 1. ]

Examples of the hydrocarbon group of R ² include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups.
The alkyl group may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, or a heptyl. Examples thereof include a group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a methylcyclohexyl group. , Cycloalkyl groups such as dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, cyclodecyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, and a norbornyl group. Examples thereof include a methylnorbornyl group and an isobornyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the group formed by the combination include an aralkyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group.
R ² is an alkyl group, preferably an alicyclic hydrocarbon group or a group formed by combining of these, and more preferably an alkyl group.

Examples of the aliphatic hydrocarbon group of R ³ and R ⁴ include an alkyl group, an alicyclic hydrocarbon group and a group formed by combining these, and a methyl group, an ethyl group, an n-propyl group and an isopropyl. Examples thereof include a group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group of X ¹¹ include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and among these groups. It may be a combination of two or more types.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group and other linear alkanediyl groups;
A linear alkanediyl group and an alkyl group (particularly, an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, etc.) Those having a side chain of, for example, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Branched alkanediyl groups such as groups, 2-methylbutane-1,4-diyl groups;
Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, 1-methylcyclohexane-1,2-diyl group, cyclohexane-1,4-diyl group, cyclo A monocyclic divalent alicyclic saturated hydrocarbon group which is a cycloalkanediyl group such as an octane-1,2-diyl group and a cyclooctane-1,5-diyl group;
Polycyclic compounds such as norbornane-2,3-diyl group, norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. Examples thereof include a divalent alicyclic saturated hydrocarbon group.
Further, the divalent alicyclic hydrocarbon group may be a group obtained by removing any one hydrogen atom from the alicyclic hydrocarbon group described later.
The hydrogen atom contained in the saturated hydrocarbon group may be replaced with a fluorine atom. However, it is preferable that the hydrogen atom contained in the carbon atom adjacent to ^{X a} and X ^{b is not replaced by the fluorine atom.}

It is preferable that both X ^a and X ^{b are oxygen atoms.}
The ^{ring containing X 11} , X ^a and X ^b is preferably a 4- to 12-membered ring, more preferably a 4- to 10-membered ring, still more preferably a 5 to 10-membered ring, and particularly preferably a 5- to 10-membered ring. It is a 9-membered ring.

As the ^{divalent hydrocarbon group having 1 to 12 carbon atoms of A 2} , A ³ , A ⁴ and A ^5, a linear or branched alkanediyl group, a monocyclic or polycyclic divalent oil ring Examples thereof include a saturated hydrocarbon group and an aromatic hydrocarbon group, and two or more of these groups may be combined.
Examples of the linear or branched alkanediyl group, include the same straight-chain or branched alkanediyl group in X ^11.
The monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group include the same divalent alicyclic saturated hydrocarbon group having a monocyclic or polycyclic in X ^11.
Examples of the aromatic hydrocarbon group include a phenylene group, a tosilene group, a naphthylene group, a biphenylene group, a xylylene group, an anthrasenylene group and the like.

^* −A ³ −X ¹ − (A ⁴ −X ² ) _a −A ⁵ − is ^* −A ³ −O ^{−A 5} −, ^* −A ³ −CO−O−A ⁵⁻ , ^* −A ^3- O-CO-A ^5- , ^* -A ^3- O-CO-O-A ^5- , ^* -A ^3- CO-O-A ^4- CO-O-A ^5- , ^* -A ^3- O-CO-A ^4- O-A ^5- , ^* -A ^3- O-CO-O-A ^4- O-A ^5- , ^* -A ^3- O-A ^4- CO-O-A ^5- , ^* -A ^3- CO-O-A ^4- O-CO-A ^5- , ^* -A ^3- O-CO-A ^4- O-CO-A ^5- . Of these, ^* -A ^3- CO-O-A ^5- or ^* -A ^3- O-CO-O-A ^5- is preferable. * Represents a bond with C (R ³ ) (R ^4).

A ² and A ³ are independent, preferably single-bonded, alkanediyl groups having 1 to 6 carbon atoms or polycyclic divalent alicyclic saturated hydrocarbon groups, and more preferably single-bonded. be.
A ⁴ and A ⁵ are independent, preferably an alkanediyl group having 1 to 6 carbon atoms or a polycyclic divalent alicyclic saturated hydrocarbon group.
A ¹ is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms or ^* −A ³ −X ¹ −A ⁵ −, and is a single bond or ^* −A ³ −X ¹ −A ⁵ −. Is more preferable. When A ¹ is an alkanediyl group having 1 to 4 carbon atoms, a methylene group or an ethylene group is more preferable. When A ¹ is ^* -A ^3- X ^1- A ^5- , A ³ is an adamantandiyl group, X ¹ is -CO-O- or -O-CO-O-, and A ⁵ is. It is more preferably a divalent hydrocarbon group having 1 to 3 carbon atoms, preferably -Ad-CO-O-CH _2- , -Ad-CO-OC (CH ₃ ) _2- or -Ad-O-. It is more preferably CO-O-CH _2- (Ad represents an adamantandiyl group).

Examples of the compound (I) include compounds represented by the following.

式（Ｉ−１）〜式（Ｉ−３９）でそれぞれ表される化合物において、Ｒ^１に相当するメチル基が水素原子で置き換わった化合物も、化合物（Ｉ）の具体例として挙げることができる。

In each compound represented by formula (I-1) ~ formula (I-39), compound methyl group corresponding to R ¹ is substituted with a hydrogen atom, may be mentioned as specific examples of the compound (I).

上記式においては、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ａ^１、Ｘ^ａ、Ｘ^ｂ及びＸ^１１は、上記と同じ意味を表す。
式（Ｉ−ａ）で表される化合物は、例えば、以下で表される化合物等が挙げられる。

<Method for producing compound (I)>
The compound (I) can be produced by reacting the compound represented by the formula (Ia) with the compound represented by the formula (Ib) in a solvent under basic medium conditions. Examples of the solvent include tetrahydrofuran, acetonitrile and the like. Examples of the base include pyridine, dimethylaminopyridine and the like. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually 0.5 to 12 hours.

In the above equation, R ¹ , R ² , R ³ , R ⁴ , A ¹ , X ^a , X ^b, and X ¹¹ have the same meanings as described above.
Examples of the compound represented by the formula (Ia) include compounds represented by the following.

式（Ｉ−ｃ）で表される化合物は、例えば、以下で表される化合物等が挙げられる。

式（Ｉ−ｄ）で表される化合物としては、エチレングリコール、プロピレングリコール、２，２，３，３−テトラフルオロ−１，４−ブタンジオール等が挙げられる。 The compound represented by (Ib) is prepared by reacting a compound represented by the formula (Ic) with a compound represented by the formula (Id) in a solvent under acid catalyst conditions. Can be manufactured. Examples of the solvent include chloroform and the like. Examples of the catalyst include sulfuric acid and p-toluenesulfonic acid. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually 0.5 to 12 hours.

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

Examples of the compound represented by the formula (Id) include ethylene glycol, propylene glycol, 2,2,3,3-tetrafluoro-1,4-butanediol and the like.

A ¹ is ^* -A ^3- X ^1- A ^5- (* represents a bond with C (R ³ ) (R ⁴ )), and X ¹ is **-CO-O- (*. ** represents a bond to ^{a 3.),} compound (I1) includes a compound represented by by the formula (I-a) with a compound represented by formula (I1-b), in a solvent, It can be produced by reacting under basic medium conditions. Examples of the solvent include tetrahydrofuran, acetonitrile and the like. Examples of the base include pyridine, dimethylaminopyridine and the like. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually 0.5 to 12 hours.

The compound represented by (I1-b) is prepared by reacting a compound represented by the formula (I1-c) with a compound represented by the formula (Id) in a solvent under acid catalyst conditions. Can be manufactured. Examples of the solvent include chloroform and the like. Examples of the catalyst include sulfuric acid and p-toluenesulfonic acid. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually 0.5 to 12 hours.

式（Ｉ１−ｅ）で表される化合物は、例えば、以下で表される化合物等が挙げられる。

式（Ｉ１−ｆ）で表される化合物は、例えば、以下で表される化合物等が挙げられる。

The compound represented by (I1-c) is reacted with the compound represented by the formula (I1-f) after reacting the compound represented by the formula (I1-e) with carbonyldiimidazole in a solvent. It can be manufactured by letting it. Examples of the solvent include chloroform and the like. The reaction temperature is usually 0 to 80 ° C., and the reaction time is usually 0.5 to 12 hours.

Examples of the compound represented by the formula (I1-e) include compounds represented by the following.

Examples of the compound represented by the formula (I1-f) include compounds represented by the following.

〔resin〕
The resin of the present invention is a resin containing a structural unit derived from compound (I) (hereinafter, may be referred to as “structural unit (I)”) (hereinafter, may be referred to as “resin (A)”). The resin (A) may contain a structural unit other than the structural unit (I).
The content of the structural unit (I) in the resin (A) of the present invention is preferably 2 to 40 mol%, more preferably 2 to 40 mol%, based on the total of all the structural units of the resin (A) of the present invention. It is 35 mol%, more preferably 3 to 30 mol%, and particularly preferably 5 to 25 mol%.

The resin (A) preferably contains an acid unstable group in addition to the structural unit (I), and may contain a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). It is preferable to have. Here, the acid unstable group means a group having a leaving group, and the leaving group is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group).
It is preferable that the resin (A) further contains a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”) and other structural units (hereinafter, “structural unit (t)””. In some cases), etc.

［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合せた基を表すか、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−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”).
The acid unstable group contained in the resin (A) is preferably a group represented by the formula (1) and / or a group represented by the formula (2).

[In the formula (1), R ^{a1 to} R ^a3 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these, or R. ^a1 and ^Ra2 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
* Represents a bond. ]

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, 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 atom and X to which they are bonded, and the hydrocarbon group and the divalent complex are formed. _{The −CH 2−} contained in the ring group may be replaced with −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合せた基としては、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、シクロヘキシルメチル基、アダマンチルメチル基、ノルボルニルエチル基等が挙げられる。
ｎａは、好ましくは０である。 ^Examples of the alkyl group of R ^{a1 to} R a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group and the like.
The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 may be either a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably an alicyclic hydrocarbon group having 3 to 16 carbon atoms.

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

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

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

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

Of R ^{a1 'and R a2',} it is preferable that at least one is a hydrogen atom.

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

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

Among the (meth) acrylic monomers having an acid unstable group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. 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.

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a01、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^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。
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合せることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］ As the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1), the structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). Examples thereof include a structural unit or a structural unit represented by the formula (a1-2). These may be used alone or in combination of two or more. In the present specification, the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1), and the structural unit represented by the formula (a1-2) are each structural unit (a1). -0), structural unit (a1-1) and structural unit (a1-2).

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^{a01, L a1} and ^{L a2} each independently, -O- or _{^{* -O- (CH 2) k1 -CO}} -O- the stands, k1 represents an integer of 1-7, and * Represents a bond with −CO−.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]

L ^a01 , ^{La 1} and ^{La 2} are preferably an oxygen atom or ^* -O- (CH ₂ ) _k01- CO-O- (where k01 is preferably an integer of 1 to 4, more preferably. Is 1), more preferably an oxygen atom.
R ^a4 and R ^a5 are preferably methyl groups.
The alkyl groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 , the alicyclic hydrocarbon group and the group combining these are the same as the groups listed in ^{R a1 to} R ^{a3 of the formula (1).} The group is mentioned.
The alkyl groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 4 to 18 in which these alkyl groups and the alicyclic hydrocarbon group are combined. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like. Be done.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1'is preferably 0 or 1.

構造単位（ａ１−１）としては、例えば、特開２０１０−２０４６４６号公報に記載されたモノマーに由来する構造単位が挙げられる。中でも、式（ａ１−１−１）〜式（ａ１−１−４）のいずれかで表される構造単位が好ましい。

As the structural unit (a1-0), for example, a structural unit represented by any one of the formulas (a1-0-1) to (a1-0-12) and ^{a methyl group corresponding to R a01} are used as hydrogen atoms. Examples thereof include the replaced structural units, and structural units represented by any of the formulas (a1-0-1) to (a1-0-10) are preferable.

Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Above all, the structural unit represented by any of the formulas (a1-1-1) to (a1-1-4) is preferable.

上記の構造単位において、式（ａ１−０）、式（ａ１−１）又は式（ａ１−２）におけるＲ^ａ０１、Ｒ^ａ４、Ｒ^ａ５に相当するメチル基が水素原子に置き換わった構造単位も、上記構造単位の具体例として挙げられる。 The structural unit (a1-2) preferably includes a structural unit represented by any of the formulas (a1-2-1) to (a1-2-6), and more preferably the formula (a1-2). -2) and the structural unit represented by the formula (a1-2-5) are preferable.

^{In the above structural unit, the structural unit in which the methyl group corresponding to R a01} , R ^a4 , R ^a5 in the formula (a1-0), the formula (a1-1) or the formula (a1-2) is replaced with a hydrogen atom is also used. A specific example of the structural unit is given.

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). It is usually 10 to 95 mol%, preferably 15 to 90 mol%, and more preferably 20 to 85 mol% with respect to the total of the units.

樹脂（Ａ）が上記構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１０〜９５モル％が好ましく、１５〜９０モル％がより好ましく、２０〜８５モル％がさらに好ましい。 Further, examples of the structural unit (a1) having the group (1) include structural units represented by the following structural unit equations (a1-3-1) to (a1-3-7).

When the resin (A) contains the above structural units, the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, and 20 to 85 mol% with respect to all the structural units of the resin (A). % Is more preferable.

樹脂（Ａ）が上記構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１０〜９５モル％が好ましく、１５〜９０モル％がより好ましく、２０〜８５モル％がさらに好ましい。 Further, as the structural unit (a1) having a group (2), it is bonded to the main chain of the following structural unit and the structural unit represented by the formulas (a1-4-1) to (a1-4-8). Examples thereof include structural units in which a hydrogen atom is replaced with a methyl group.

When the resin (A) contains the above structural units, the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, and 20 to 85 mol% with respect to all the structural units of the resin (A). % Is more preferable.

［式（ａ１−５）中、
Ｒ^ａ８は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^ａ１は、単結合又は＊−（ＣＨ_２）_ｈ３−ＣＯ−Ｌ^５４−を表し、ｈ３は１〜４のいずれかの整数を表し、＊は、Ｌ^５１との結合手を表す。
Ｌ^５１、Ｌ^５２、Ｌ^５３及びＬ^５４は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３のいずれかの整数を表す。
ｓ１’は、０〜３のいずれかの整数を表す。］ Further, as the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2), the structural unit represented by the formula (a1-5) (hereinafter, “structural unit (a1-5)””. In some cases).

[In equation (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or _{* - (CH 2) h3 -CO} -L 54 - represents, h3 represents an integer of 1 to 4, * ^represents a bond to ^{L 51.}
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ independently represent -O- or -S-, respectively.
s1 represents any integer of 1 to 3.
s1'represents an integer of 0 to 3. ]

Examples of the halogen atom include a fluorine atom and a chlorine atom, and preferably a fluorine atom. Alkyl groups having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. The group is mentioned.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
Of L ⁵² and L ⁵³ , it is preferable that one is −O− and the other is −S−.
s1 is preferably 1.
It is preferable that s1'is an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH _2- CO-O-.

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

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

<Structural unit (a3)>
The resin (A) of the present invention may further have a structural unit having a lactone ring (hereinafter, may be referred to as "structural unit (a3)") in addition to the structural unit (I) and the structural unit (a1). preferable.
The lactone ring of the structural unit (a3) may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a fused ring of a monocyclic lactone ring and another ring. But it may be. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

［式（ａ３−１）、式（ａ３−２）、式（ａ３−３）及び式（ａ３−４）中、
Ｌ^ａ４、Ｌ^ａ５及びＬ^ａ６は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７のいずれかの整数を表す。）で表される基を表す。
Ｌ^ａ７は、−Ｏ−、^＊−Ｏ−Ｌ^ａ８−Ｏ−、^＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−、^＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は^＊−Ｏ−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
Ｌ^ａ８及びＬ^ａ９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。
＊はカルボニル基との結合手を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２４は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^ａ２１は炭素数１〜４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５のいずれかの整数を表す。
ｑ１は、０〜３のいずれかの整数を表す。
ｒ１は、０〜３のいずれかの整数を表す。
ｗ１は、０〜８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一であってもよく、異なってもよい。］ The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). One of these may be contained alone, or two or more thereof may be contained.

[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4 , ^{La 5} and ^{La 6} are independently represented by -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 represents an integer of 1 to 7). Represents a group.
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- CO-O-L ^a9- CO-O- or ^* Represents −O−L ^a8 −O−CO−L ^a9 −O−.
L ^a8 and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5.
q1 represents any integer from 0 to 3.
r1 represents any integer from 0 to 3.
w1 represents any integer from 0 to 8.
When p1, q1, r1 and / or w1 is 2 or more, the plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different from each other. ]

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ^a21 , Ra ²² and Ra ²³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Can be mentioned.
^{Examples of the halogen atom of Ra24} include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^Examples of the alkyl group of R a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
^{Alkyl groups having a halogen atom of Ra24} include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The ^{alkanediyl groups of La8} and ^La9 include 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, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include 4-diyl group and 2-methylbutane-1,4-diyl group.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In the formula (a3-1) ~ formula ^(a3-4), L a4 ^{~L a6} are each independently preferably -O- or, k3 is a integer of 1 to 4 * -O- ( CH ₂ ) _{A group represented by k3-} CO-O-, more preferably -O- and * -O-CH _2- CO-O-, and even more preferably an oxygen atom.
L ^a7 is preferably a single bond or ^{* -La8-} CO-O-, more preferably a single bond, -CH _2- CO-O- or -C ₂ H _4- CO-O-.
R ^{a18 to} R ^a21 are preferably methyl groups.
^Ra24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
R ^a22 , R ^a23 and R ^a25 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1, r1 and w1 are each independently, preferably an integer of 0 to 2, and more preferably 0 or 1.
The formula (a3-4) is particularly preferably the formula (a3-4)'.

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

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

上記構造単位では、式（ａ３−１）、式（ａ３−２）、式（ａ３−３）又は式（ａ３−４）中のＲ^ａ１８、Ｒ^ａ１９、Ｒ^ａ２０及びＲ^ａ２４に相当するメチル基が水素原子に置き換わった化合物も、構造単位（ａ３）の具体例として挙げられる。

In the above structural unit, the methyl group corresponding to ^{R a18} , R ^a19 , R ^a20 and R ^a24 in the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). A compound in which a hydrogen atom is replaced with a hydrogen atom is also given as a specific example of the structural unit (a3).

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 of all the structural units of the resin (A). It is more preferably 10 to 60 mol%.
Further, the contents of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) and the structural unit (a3-4) are the total of all the structural units of the resin (A), respectively. On the other hand, it is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 50 mol%.

<Structural unit (a2)>
It is preferable that the resin (A) of the present invention further has a structural unit having a hydroxy group and no acid unstable group (hereinafter, may be referred to as “structural unit (a2)”).

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

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

［式（ａ２−１）中、
Ｌ^ａ３は、−Ｏ−又は^＊−Ｏ−（ＣＨ_２）_ｋ２−ＣＯ−Ｏ−を表し、
ｋ２は１〜７のいずれかの整数を表す。＊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のいずれかの整数を表す。］ Examples of the structural unit (a2) having an alcoholic hydroxy group include structural units represented by the formula (a2-1) (hereinafter, may be referred to as “structural unit (a2-1)”).

[In equation (a2-1),
^La3 represents −O− or ^* −O− (CH ₂ ) _k2 −CO−O−.
k2 represents any 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 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents any integer from 0 to 10. ]

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

上記構造単位においては、式（ａ２−１）中のＲ^ａ１４に相当するメチル基が水素原子に置き換わった化合物も、上記構造単位の具体例として挙げられる。
樹脂（Ａ）が構造単位（ａ２−１）を含む場合、その含有率は、樹脂（Ａ）の全構造単位の合計に対して、通常１〜４５モル％であり、好ましくは１〜４０モル％であり、より好ましくは１〜３５モル％であり、さらに好ましくは２〜２０モル％である。 Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646, preferably formulas (a2-1-1) to (a2-). Examples thereof include structural units represented by any one of 1-3), and more preferably structural units represented by any of the formulas (a2-1-1) to (a2-1-2).

In the above structural units, compounds methyl group corresponding to R ^a14 in the formula (a2-1) is replaced by a hydrogen atom, be mentioned as specific examples of the structural units.
When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on the total of all the structural units of the resin (A). %, More preferably 1 to 35 mol%, still more preferably 2 to 20 mol%.

<Structural unit (t)>
The structural unit (t) includes a structural unit that may have a halogen atom (hereinafter, sometimes referred to as “structural unit (a4)”) and a structural unit that has a non-desorbed hydrocarbon group (hereinafter, “structural unit”). (A5) ”) and the like.

［式（ａ４−０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^５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 the formula (a4-0).

[In equation (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a 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 L ^5, include alkanediyl group having 1 to 4 carbon atoms, e.g., methylene group, ethylene group, propane-1,3-diyl, butane-1,4-diyl group , Etc., a linear alkanediyl group, a linear alkanediyl group having a side chain of an alkyl group (particularly, a methyl group, an ethyl group, etc.), an ethane-1,1-diyl group, a propane-1, Examples thereof include branched alkanediyl groups such as 2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

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

L ⁵ represents 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 perfluoro alkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoro alkanediyl group having 1 to 3 carbon atoms.

Examples of the structural unit (a4-0) include the structural units shown below.

上記の構造単位において、式（ａ４−０）中のＲ⁵に相当するメチル基が水素原子に置き換わった構造単位も、構造単位（ａ４−０）の具体例として挙げることができる。

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

［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、それぞれ独立に、置換基を有していてもよい炭素数１〜５の２価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２価の脂肪族炭化水素基を表す。
Ｘ^ａ４１及びＸ^ａ４２は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ただし、Ａ^ａ４２、Ａ^ａ４３、Ａ^ａ４４、Ｘ^ａ４１及びＸ^ａ４２の炭素数の合計は７以下である。
＊で表される２つの結合手のうち、右側の＊が−Ｏ−ＣＯ−Ｒ^ａ４２との結合手である。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-1).

[In equation (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.
^Aa41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). ]

[In the formula (a-g1),
s represents 0 or 1.
^Aa42 and ^Aa44 each independently represent a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
^Aa43 represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 independently represent -O-, -CO-, -CO-O- or -O-CO-, respectively.
However, the total number of carbon atoms of ^{A a42} , A ^a43 , A ^a44 , X ^a41 and X ^{a42 is 7 or less.}
Of the two bonds represented by *, the * on the right side is the bond with -O-CO-R ^a42 . ]

^Examples of the hydrocarbon group of R a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups.
Chain and cyclic aliphatic hydrocarbon groups may have carbon-carbon unsaturated bonds, but are formed by chain and cyclic aliphatic saturated hydrocarbon groups and their combination. Groups are preferred. The aliphatic saturated hydrocarbon group is a fat formed by combining a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group. Examples include group hydrocarbon groups.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基が挙げられる。 Chain-type 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 and n-decyl. Examples include a group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. Cyclic aliphatic hydrocarbon groups include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* is a bond). Examples thereof include polycyclic alicyclic hydrocarbon groups such as).

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 of R a42 include a halogen atom or a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
^Aa45 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 of A ^{a45 include} the same groups as those exemplified in ^{R a42.}
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and is an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). Is more preferable.
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, R ^a42 is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably. It is a perfluoroalkyl group having 1 to 6 carbon atoms, and 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 (ag3), the aliphatic hydrocarbon includes the number of carbon atoms contained in the group represented by the formula (ag3). The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

A more preferable structure of the group represented by the formula (ag3) is the following structure.

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

^{The aliphatic hydrocarbon group of A a42} , A ^a43 and A ^{a44 in} the group (a-g1) may have a carbon-carbon unsaturated bond, but is preferably an aliphatic saturated hydrocarbon group.
As the aliphatic saturated hydrocarbon group, an alkyl group (the alkyl group may be linear or branched) and an alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group are combined. Examples thereof include an aliphatic hydrocarbon group formed by the above. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent of the aliphatic hydrocarbon group of A a42, A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

^{Examples of the group (ag1) 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 ** represent a bond, respectively, and ** is a bond with -O-CO-R ^a42 .

Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the following and a structural unit in which the methyl group corresponding to ^{Ra41 is replaced with a hydrogen atom in the formula (a4-1).}

［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、それぞれ独立に、１〜６のいずれかの整数を表す。
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) may be a structural unit represented by the formula (a4-4).

[In equation (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 of 1 to 6.
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

^Examples of the hydrocarbon group having a fluorine atom of R f22 include an alkyl group having 1 to 10 carbon atoms having a fluorine atom and an alicyclic hydrocarbon group having 3 to 10 carbon atoms having a fluorine atom. Specifically, 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-hexa Fluorobutyl 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 , 2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,4,4,5,5,6-dodecafluorohexyl group, perfluoro Examples thereof include a pentylmethyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and a perfluoroadamantyl group. It is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.

In the formula (a4-4), as A ^f21 , − (CH ₂ ) _j1 − is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

樹脂（Ａ）が、構造単位（ａ４）を有する場合、その含有率は、樹脂（Ａ）の全構造単位の合計に対して、１〜２０モル％であることが好ましく、２〜１５モル％であることがより好ましく、３〜１０モル％であることがさらに好ましい。 Examples of the structural unit represented by the formula (a4-4) include the following structural unit and the structural unit ^{in which the methyl group corresponding to R f21} is replaced with a hydrogen atom in the formula (a4-4).

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

［式（ａ５−１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。
但し、Ｌ^５５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^５５は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or a hydroxy group having 1 to 8 carbon atoms. May be.
However, ^{the hydrogen atom bonded to the carbon atom at the bonding position with L 55} is not substituted with the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

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

Examples of the divalent saturated hydrocarbon group of L ^55, a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably mentioned is a divalent aliphatic saturated hydrocarbon group Be done.
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include the groups described below. In the following formula, * represents a bond with an oxygen atom.

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

When the resin (A) has the structural unit (a5), the content thereof is preferably 1 to 30 mol%, preferably 2 to 20 mol%, based on the total of all the structural units of the resin (A). Is more preferable, and 3 to 15 mol% is further preferable.

The resin (A) is preferably a resin composed of a structural unit (I) and a structural unit (a1), and a resin composed of a structural unit (I), a structural unit (a1), and a structural unit having no acid unstable group. , A resin consisting of a structural unit (I), a structural unit (a1), a structural unit having no acid unstable group, and a structural unit (t), a resin consisting of only the structural unit (I), or a structural unit (I). ), A resin consisting only of the structural unit (t), and more preferably a resin composed of the structural unit (I), the structural unit (a1), and the structural unit having no acid unstable group, the structural unit (I). It is a resin consisting of only structural units, or a resin consisting of only structural units (I) and structural units (t).

The structural unit (a1) is preferably at least selected from the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group). One kind, more preferably at least two kinds selected from a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group). Is. The structural unit (a1) is a structural unit other than the structural unit derived from the formula (I).
The structural unit having no acid unstable group is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably selected from the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4). At least one kind.
The structural unit (t) is preferably a structural unit containing fluorine other than the structural unit derived from the compound represented by the formula (I), and is, for example, the structural unit (a4).

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 30,000 or more). 15,000 or less).
In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography. Gel permeation chromatography can be measured according to the analytical conditions described in the examples.

[Resist composition]
The resist composition of the present invention preferably contains the resin (A) and an acid generator known in the resist field (hereinafter, may be referred to as "acid generator (B)").
The resist composition of the present invention preferably further contains a resin other than the resin (A).
The resist composition of the present invention preferably contains a quencher (hereinafter, may be referred to as "citrate (C)") such as a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. , A solvent (hereinafter, may be referred to as "solvent (E)") is preferably contained.

<Resin other than resin (A)>
The resin other than the resin (A) may be a resin that does not contain the structural unit (I). Examples of such a resin include a resin obtained by removing the structural unit (I) from the resin (A) (hereinafter, may be referred to as “resin (A2)”), and a resin containing the structural unit (t) (hereinafter, resin (hereinafter, resin (hereinafter, resin)). X) may be referred to) and the like.

The resin (A2) has a resin containing only a structural unit having an acid unstable group, a resin containing a structural unit having an acid unstable group and a structural unit having no acid unstable group, and an acid unstable group. Examples thereof include a resin containing a structural unit, a structural unit having no acid unstable group, and a structural unit (t).
The resin (A2) is preferably a resin containing a structural unit having an acid unstable group (hereinafter, may be referred to as a resin (A2')).

As the resin (X), a resin containing the structural unit (a4) (however, not including the structural unit (I)) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, based on the total of all the structural units of the resin (X). , 50 mol% or more is more preferable.
Examples of the structural unit that the resin (X) may further include include a structural unit (a1), a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers. Among them, the resin (X) is preferably a resin from only the structural unit (t), more preferably a resin consisting of the structural unit (a4) and / or the structural unit (a5), and the structural unit (a4). It is more preferable that the resin is made of.

Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weights of the resin (A2) and the resin (X) are independently, preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less), respectively. be. The means for measuring the weight average molecular weight of the resin (A2) and the resin (X) is the same as that of the resin (A).
When the resist composition of the present invention contains the resin (A2), the content thereof is usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) with respect to 100 parts by mass of the resin (A). be.
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably 1 to 40 parts by mass, particularly preferably 2 to 30 parts by mass, and particularly preferably 2 to 8 parts by mass.

When the resin (A) in the resist composition of the present invention is a resin containing only the structural unit (I) or a resin containing no structural unit having an acid unstable group other than the structural unit (I), the resin (A) It is preferable to use a resin other than the above, and it is more preferable to use a resin containing a structural unit having an acid unstable group and / or a resin containing a structural unit having a fluorine atom, and a resin (A2') and / or a resin. It is more preferable to use (X) together.

The content of the resin (A) in the resist composition, and when the resin other than the resin (A) is contained, the total content of the resin (A) and the resin other than the resin (A) is the solid content of the resist composition. On the other hand, it is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 to 99% by mass. In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
As the acid generator (B), either a nonionic type or an ionic type may be used. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like can be mentioned. As the ionic acid generator, an onium salt containing an onium cation (for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt) is typical. Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

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

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８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−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter, may be 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, and −CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ - is, -O -, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]

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

Examples of the divalent saturated hydrocarbon group of L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more kinds of groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decane-1,10-Diyl group, Undecan-1,11-Diyl group, Dodecan-1,12-Diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. The group etc. can be mentioned.

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

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

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

In the formulas (b1-1) to (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbon atoms before the replacement is the carbon of the saturated hydrocarbon group. Let it be a number.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of ^{L b1.}

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

The _{group in which −CH 2} − contained in the divalent saturated hydrocarbon group of ^{L b1} is replaced with −O− or −CO− is a group represented by the formula (b1-1) or the formula (b1-3). Is preferable.

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

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

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

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

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

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

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

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

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

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

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

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

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

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

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

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

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
_{When -CH 2-} contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. .. Examples of such a group include groups represented by the formulas (Y12) to (Y35).

Among them, it is preferably a group represented by any one of the formulas (Y1) to (Y20), formula (Y30) and formula (Y31), and more preferably the formula (Y11), formula (Y15) and formula (Y11). Y16), a group represented by the formula (Y20), the formula (Y30) or the formula (Y31), and more preferably a group represented by the formula (Y11), the formula (Y15) or the formula (Y30).
When Y constitutes a spiro ring of the formulas (Y28) to (Y33) and the like, the alkanediyl group between the two oxygens preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, those in which the fluorine atom is not substituted in the methylene group adjacent to the oxygen atom are preferable.

As the substituent of the methyl group represented by Y, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group or-( CH ₂ ) _ja- O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group. Ja represents an integer of 0 to 4) and the like.
The substituent of the alicyclic hydrocarbon group represented by Y includes an alkyl group having 1 to 12 carbon atoms and an alicyclic group having 3 to 16 carbon atoms which may be substituted with a halogen atom, a hydroxy group or a hydroxy group. Hydrocarbon groups, alkoxy groups with 1 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, acyl groups with 2 to 4 carbon atoms, glycidyloxy groups or-(CH) ₂ ) _ja- O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms. Represents a hydrogen group. Ja represents an integer of 0 to 4) and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group and a p-adamantylphenyl group; a trill group, a xylyl group, a cumenyl group and a mesityl group. , Biphenyl group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl and the like.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group and a heptyl group, 2 -Ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like can be mentioned.
Examples of the alkyl group substituted with the hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and the like.

Examples of Y include the following.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon group at the bond position with Y It is preferable that −CH ₂₋ is replaced with −O− or −CO−.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent, and is said to be an alicyclic hydrocarbon. The methylene group constituting the hydrogen group or the adamantyl 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 by the following.

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-54) [hereinafter, "anion (B1)" according to the formula number. -A-1) "and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. (B1-A-33), formula (IA-36) to formula (IA-40), formula (B1-A-47) to formula (B1-A-54). Anions are more preferred.

ここでＲ^ｉ２〜Ｒ^ｉ７は、例えば、炭素数１〜４のアルキル基、好ましくはメチル基又はエチル基である。Ｒ^ｉ８は、例えば、炭素数１〜１２の脂肪族炭化水素基、好ましくは炭素数１〜４のアルキル基、炭素数５〜１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^４は、単結合又は炭素数１〜４のアルカンジイル基である。
Ｑ^１及びＱ^２は、上記と同じである。
式（Ｂ１）で表される塩におけるスルホン酸アニオンとしては、具体的には、特開２０１０−２０４６４６号公報に記載されたアニオンが挙げられる。

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 formed, for example, by an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. Group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ⁴ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and ^{Q 2} are the same as above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

Examples of the sulfonic acid anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-30).

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). )-Anion represented by any of the formulas (B1a-30) is preferable.

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

［式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^ｂ４〜Ｒ^ｂ６は、それぞれ独立に、炭素数１〜３０の脂肪族炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜３６の芳香族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該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の脂肪族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、該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、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０〜５のいずれかの整数を表す。
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、それぞれ独立に、炭素数１〜３６の脂肪族炭化水素基又は炭素数３〜３６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の脂肪族炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１〜１２の脂肪族炭化水素基、炭素数３〜１８の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表し、該脂肪族炭化水素に含まれる水素原子は、炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２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、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^ｂ３１は、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０〜５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０〜４のいずれかの整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b7 and R ^b8 independently represent a hydroxy group, an 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, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the aliphatic hydrocarbon group. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or 1 to 12 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
The R ^b11 and ^{R b12,} together may form a ring containing a -CH-CO- which they are bond, _-CH 2 contained in the ring - is, -O -, - SO- Alternatively, it may be replaced with −CO−.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an 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 of 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, a plurality of R ^b13s may be the same or different, when p2 is 2 or more, a plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , A plurality of R ^b15s may be the same or different, and when r2 is 2 or more, a plurality of R ^b16s may be the same or different, and when s2 is 2 or more, a plurality of R ^b17s may be present. It may be the same or different, and when t2 is 2 or more, a plurality of R ^b18s may be the same or different. ]

The aliphatic hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. Alkyl group of. In particular, ^{the aliphatic hydrocarbon group of R b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclo. Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

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

Examples of the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group and an isobornyl group. The group etc. can be mentioned. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include phenyl group, trill group, xsilyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group and p-adamantylphenyl group. , Biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and other aryl groups.
When the aromatic hydrocarbon group contains an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms may be used. preferable.
Examples of the aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the aliphatic hydrocarbon group in which the hydrogen atom is replaced with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.

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

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

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

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

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

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

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

The acid generator (B1) is a combination of the above-mentioned sulfonic acid anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably an anion and a cation (b2) represented by any of the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16). -1) or a combination with a cation (b2-3) can be mentioned.

Examples of the acid generator (B1) are preferably those represented by the formulas (B1-1) to (B1-48), among which the formulas (B1-1) to the formula (B1) containing an aryl sulfonium cation are included. -3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-20), formula (B1-21), formula (B1-1). 22), formula (B1-23) to formula (B1-26), formula (B1-29), formula (B1-31), formula (B1-32), formula (B1-33), formula (B1-34). ), Equation (B1-35), Equation (B1-36), Equation (B1-37), Equation (B1-38), Equation (B1-39), Equation (B1-40), Equation (B1-41). , Formula (B1-42), formula (B1-43), formula (B1-44), formula (B1-45), formula (B1-46), formula (B1-47) or formula (B1-48). The ones represented by each are particularly preferable.

In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less, based on 100 parts by mass of the resin (A). (More preferably, 25 parts by mass or less). The resist composition of the present invention may contain one kind of the acid generator (B) alone or may contain a plurality of kinds.

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, and 99.9% by mass or less, preferably 99% by mass or less in the resist composition. Is. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.

Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. Esters; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One type of solvent (E) may be contained alone, or two or more types may be contained.

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

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

Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine. , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine , Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, Triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4) -Pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethen, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyl) Oxy) ethane, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. , Preferably diisopropylaniline, and particularly preferably 2,6-diisopropylaniline.

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

<Salt that produces acid with weak acidity>
The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. It is more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid intramolecular salt represented by the formula (D) described in JP-A-2015-147926, and a special case. Examples thereof include the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-390502 and JP-A-2011-191745.

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１〜１２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のいずれかの整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。］
Ｒ^D1及びＲ^D2の炭化水素基としては、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基及びこれらの組み合わせることにより形成される基等が挙げられる。
脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ノニル基等のアルキル基が挙げられる。
脂環式炭化水素基としては、単環式及び多環式のいずれでもよく、飽和及び不飽和のいずれでもよい。シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロノニル基、シクロドデシル基等のシクロアルキル基、ノルボニル基、アダマンチル基等が挙げられる。
芳香族炭化水素基としては、フェニル基、１−ナフチル基、２−ナフチル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−エチルフェニル基、４−プロピルフェニル基、４−イソプロピルフェニル基、４−ブチルフェニル基、４−ｔ−ブチルフェニル基、４−ヘキシルフェニル基、４−シクロヘキシルフェニル基、アントリル基、ｐ−アダマンチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、ビフェニル基、フェナントリル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル等のアリール基等が挙げられる。
これらを組み合わせることにより形成される基としては、アルキル−シクロアルキル基、シクロアルキル−アルキル基、アラルキル基（例えば、フェニルメチル基、１−フェニルエチル基、２−フェニルエチル基、１−フェニル−１−プロピル基、１−フェニル−２−プロピル基、２−フェニル−２−プロピル基、３−フェニル−１−プロピル基、４−フェニル−１−ブチル基、５−フェニル−１−ペンチル基、６−フェニル−１−ヘキシル基等）等が挙げられる。
アルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。
アシル基としては、アセチル基、プロパノイル基、ベンゾイル基、シクロヘキサンカルボニル基等が挙げられる。
アシルオキシ基としては、上記アシル基にオキシ基（−Ｏ−）が結合した基等が挙げられる。
アルコキシカルボニル基としては、上記アルコキシ基にカルボニル基（−ＣＯ−）が結合した基等が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１０のシクロアルキル基、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、炭素数２〜４のアルコキシカルボニル基、ニトロ基又はハロゲン原子が好ましい。
ｍ’及びｎ’は、それぞれ独立に、０〜２のいずれかの整数であることが好ましく、０であることがより好ましい。ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。

[In formula (D),
R ^D1 and R ^D2 independently have a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, and a carbon number of carbon atoms. Represents 2-7 alkoxycarbonyl groups, nitro groups or halogen atoms.
m'and n'independently represent an integer of 0 to 4, and when m'is 2 or more, a plurality of R ^D1s may be the same or different, and n'is 2 or more. In the case of, a plurality of R ^D2s may be the same or different. ]
Examples of the hydrocarbon group of R ^D1 and R ^D2 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining them.
Examples of the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and a nonyl group.
The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and may be saturated or unsaturated. Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group, norbonyl group, adamantyl group and the like can be mentioned.
Examples of the aromatic hydrocarbon group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group and 4-propylphenyl group. , 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group , Mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl and the like.
Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, and an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 1-phenyl-1 group. -Propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6 -Phenyl-1-hexyl group, etc.) and the like.
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, a cyclohexanecarbonyl group and the like.
Examples of the acyloxy group include a group in which an oxy group (—O−) is bonded to the above acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (−CO−) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
R ^D1 and R ^D2 independently have 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, and a carbon number of carbon atoms. A acyloxy group of 2 to 4, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom is preferable.
It is preferable that m'and n'are independently an integer of 0 to 2, and more preferably 0. When m'is 2 or more, the plurality of R ^D1s may be the same or different, and when n'is 2 or more, the plurality of R ^D2s may be the same or different.

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

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

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (A) and the acid generator (B) of the present invention, and if necessary, the resin (A2), the resin (X), the quencher (C), and the solvent (E). And other components (F) can be prepared by mixing. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can be selected from 10 to 40 ° C., depending on the type of the resin or the like and the solubility of the resin or the like in the solvent (E). As the mixing time, an appropriate time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing or the like can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Manufacturing method of resist pattern>
The method for producing a resist pattern of the present invention is
(1) A step of applying the resist composition of the present invention onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
It includes (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

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

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

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

The exposed composition layer is heat treated (so-called post-exposure bake) to promote the deprotection reaction at the acid unstable group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

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

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.

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

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

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

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

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

The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100 type, MASS: Agilent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by "MASS".

式（Ｉ−１−ａ）で表される化合物２５部、式（Ｉ−１−ｂ）で表される化合物６０．７８部及びクロロホルム１２５部を仕込み、２３℃で３０分間攪拌した後、硫酸２．４０部を仕込み、モレキュラーシーブ存在下、６０℃で６時間還流した後、２３℃まで冷却した。得られた反応マスに、酢酸エチル４５０部及び１０％炭酸カリウム水溶液３５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液した。回収された有機層に、イオン交換水１４０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝２０／１）分取することにより、式（Ｉ−１−ｃ）で表される化合物１４．９９部を得た。

式（Ｉ−１−ｃ）で表される化合物１４．９９部、テトラヒドロフラン１５０部、ピリジン１２．１６部及びジメチルアミノピリジン０．６３部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物１０．７２部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン８．７３部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル３５０部及び５％塩酸３７．４３部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水１１０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−１）で表される化合物５．０３部を得た。 Example 1: Synthesis of a compound represented by the formula (I-1)

25 parts of the compound represented by the formula (I-1-a), 60.78 parts of the compound represented by the formula (I-1-b) and 125 parts of chloroform were charged, stirred at 23 ° C. for 30 minutes, and then sulfuric acid. 2.40 parts were charged, refluxed at 60 ° C. for 6 hours in the presence of a molecular sieve, and then cooled to 23 ° C. To the obtained reaction mass, 450 parts of ethyl acetate and 35 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and the liquid was separated. 140 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 20/1). As a result, 14.99 parts of the compound represented by the formula (I-1-c) was obtained.

14.99 parts of the compound represented by the formula (I-1-c), 150 parts of tetrahydrofuran, 12.16 parts of pyridine and 0.63 parts of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 10.72 parts of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 8.73 parts of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 350 parts of ethyl acetate and 37.43 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 110 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 5.03 parts of the compound represented by the formula (I-1) was obtained.

MASS: 214.1

式（Ｉ−１−ａ）で表される化合物６．３９部、式（Ｉ−１３−ｂ）で表される化合物１５．２２部及びクロロホルム１００部を仕込み、２３℃で３０分間攪拌した後、硫酸０．６１部を仕込み、モレキュラーシーブ存在下、６０℃で６時間還流した後、２３℃まで冷却した。得られた反応物に、１０％炭酸カリウム水溶液６５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液した。回収された有機層に、イオン交換水６０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−１３−ｃ）で表される化合物１２．２１部を得た。

式（Ｉ−１３−ｃ）で表される化合物８．４１部、テトラヒドロフラン５０部、ピリジン４．０５部及びジメチルアミノピリジン０．２１部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物３．５７部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン２．９１部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル１５０部及び５％塩酸１２．４８部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水７０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−１３）で表される化合物５．７８部を得た。 Example 2: Synthesis of the compound represented by the formula (I-13)

After charging 6.39 parts of the compound represented by the formula (I-1-a), 15.22 parts of the compound represented by the formula (I-13-b) and 100 parts of chloroform, and stirring at 23 ° C. for 30 minutes. , 0.61 part of sulfuric acid was charged, refluxed at 60 ° C. for 6 hours in the presence of a molecular sieve, and then cooled to 23 ° C. To the obtained reaction product, 65 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and the liquid was separated. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 12.21 parts of the compound represented by the formula (I-13-c) was obtained.

8.41 parts of the compound represented by the formula (I-13-c), 50 parts of tetrahydrofuran, 4.05 parts of pyridine and 0.21 parts of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 3.57 parts of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 2.91 parts of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 150 parts of ethyl acetate and 12.48 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 70 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 5.78 parts of the compound represented by the formula (I-13) was obtained.

MASS: 314.1

式（Ｉ−３３−ａ）で表される化合物２．９８部及びアセトニトリル１５部を仕込み、２３℃で３０分間攪拌した。その後、これに、カルボニルジイミダゾール２．１３部を仕込み、さらに、５０℃で２時間撹拌し、２３℃まで冷却した。得られた反応物に、式（Ｉ−１−ｃ）で表される化合物２．２９部を加え、２３℃で３０分間攪拌し、さらに、５０℃で１０時間撹拌した。得られた反応物を濃縮し、濃縮残に、クロロホルム３０部及びイオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。回収された有機層に、イオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ−３３−ｂ）で表される化合物４．１２部を得た。

式（Ｉ−３３−ｂ）で表される化合物１．２５部、テトラヒドロフラン３０部、ピリジン０．４１部及びジメチルアミノピリジン０．０２部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物０．３６部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン０．２９部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１．２５部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水３０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−３３）で表される化合物０．８９部を得た。 Example 3: Synthesis of the compound represented by the formula (I-33)

2.98 parts of the compound represented by the formula (I-33-a) and 15 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. Then, 2.13 parts of carbonyldiimidazole was added thereto, and the mixture was further stirred at 50 ° C. for 2 hours and cooled to 23 ° C. To the obtained reaction product, 2.29 parts of the compound represented by the formula (I-1-c) was added, and the mixture was stirred at 23 ° C. for 30 minutes and further at 50 ° C. for 10 hours. The obtained reaction product was concentrated, 30 parts of chloroform and 15 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. Fifteen parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 4.12 parts of the compound represented by the formula (I-33-b) was obtained.

1.25 parts of the compound represented by the formula (I-33-b), 30 parts of tetrahydrofuran, 0.41 part of pyridine and 0.02 part of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 0.36 part of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 0.29 part of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 50 parts of ethyl acetate and 1.25 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 30 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 0.89 part of the compound represented by the formula (I-33) was obtained.

MASS: 434.3

式（Ｉ−３３−ａ）で表される化合物２．９８部及びアセトニトリル１５部を仕込み、２３℃で３０分間攪拌した。その後、これに、カルボニルジイミダゾール２．１３部を仕込み、さらに、５０℃で２時間撹拌し、２３℃まで冷却した。得られた反応物に、式（Ｉ−１３−ｃ）で表される化合物３．８６部を加え、２３℃で３０分間攪拌し、さらに、５０℃で１０時間撹拌した。得られた反応物を濃縮し、濃縮残に、クロロホルム３０部及びイオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。回収された有機層に、イオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ−３６−ｂ）で表される化合物４．６８部を得た。

式（Ｉ−３６−ｂ）で表される化合物１．５９部、テトラヒドロフラン３０部、ピリジン０．４１部及びジメチルアミノピリジン０．０２部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物０．３６部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン０．２９部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１．２５部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水３０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−３６）で表される化合物１．０２部を得た。 Example 4: Synthesis of compound represented by formula (I-36)

2.98 parts of the compound represented by the formula (I-33-a) and 15 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. Then, 2.13 parts of carbonyldiimidazole was added thereto, and the mixture was further stirred at 50 ° C. for 2 hours and cooled to 23 ° C. 3.86 parts of the compound represented by the formula (I-13-c) was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and further at 50 ° C. for 10 hours. The obtained reaction product was concentrated, 30 parts of chloroform and 15 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. Fifteen parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 4.68 parts of the compound represented by the formula (I-36-b) was obtained.

1.59 parts of the compound represented by the formula (I-36-b), 30 parts of tetrahydrofuran, 0.41 part of pyridine and 0.02 part of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 0.36 part of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 0.29 part of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 50 parts of ethyl acetate and 1.25 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 30 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 1.02 parts of the compound represented by the formula (I-36) was obtained.

MASS: 534.3

式（Ｉ−２６−ａ）で表される化合物１８．１３部、式（Ｉ−１−ｂ）で表される化合物６０．７８部及びクロロホルム１２５部を仕込み、２３℃で３０分間攪拌した後、硫酸２．４０部を仕込み、モレキュラーシーブ存在下、６０℃で６時間還流した後、２３℃まで冷却した。得られた反応マスに、酢酸エチル４５０部及び１０％炭酸カリウム水溶液３５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液した。回収された有機層に、イオン交換水１４０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝２０／１）分取することにより、式（Ｉ−２６−ｃ）で表される化合物１５．２２部を得た。

式（Ｉ−３３−ａ）で表される化合物２．９８部及びアセトニトリル１５部を仕込み、２３℃で３０分間攪拌した。その後、これに、カルボニルジイミダゾール２．１３部を仕込み、さらに、５０℃で２時間撹拌し、２３℃まで冷却した。得られた反応物に、式（Ｉ−２６−ｃ）で表される化合物１．８５部を加え、２３℃で３０分間攪拌し、さらに、５０℃で１０時間撹拌した。得られた反応物を濃縮し、濃縮残に、クロロホルム３０部及びイオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。回収された有機層に、イオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ−２６−ｄ）で表される化合物３．５８部を得た。

式（Ｉ−２６−ｄ）で表される化合物１．１５部、テトラヒドロフラン３０部、ピリジン０．４１部及びジメチルアミノピリジン０．０２部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物０．３６部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン０．２９部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１．２５部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水３０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−２６）で表される化合物０．８５部を得た。 Example 5: Synthesis of the compound represented by the formula (I-26)

After charging 18.13 parts of the compound represented by the formula (I-26-a), 60.78 parts of the compound represented by the formula (I-1-b) and 125 parts of chloroform, and stirring at 23 ° C. for 30 minutes. , 2.40 parts of sulfuric acid was charged, refluxed at 60 ° C. for 6 hours in the presence of a molecular sieve, and then cooled to 23 ° C. To the obtained reaction mass, 450 parts of ethyl acetate and 35 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and the liquid was separated. 140 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 20/1). As a result, 15.22 parts of the compound represented by the formula (I-26-c) was obtained.

2.98 parts of the compound represented by the formula (I-33-a) and 15 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. Then, 2.13 parts of carbonyldiimidazole was added thereto, and the mixture was further stirred at 50 ° C. for 2 hours and cooled to 23 ° C. To the obtained reaction product, 1.85 parts of the compound represented by the formula (I-26-c) was added, and the mixture was stirred at 23 ° C. for 30 minutes and further at 50 ° C. for 10 hours. The obtained reaction product was concentrated, 30 parts of chloroform and 15 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. Fifteen parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.58 parts of the compound represented by the formula (I-26-d) was obtained.

1.15 parts of the compound represented by the formula (I-26-d), 30 parts of tetrahydrofuran, 0.41 part of pyridine and 0.02 part of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 0.36 part of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 0.29 part of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 50 parts of ethyl acetate and 1.25 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 30 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 0.85 part of the compound represented by the formula (I-26) was obtained.

MASS: 406.2

式（Ｉ−２６−ａ）で表される化合物４．６３部、式（Ｉ−１３−ｂ）で表される化合物１５．２２部及びクロロホルム１００部を仕込み、２３℃で３０分間攪拌した後、硫酸０．６１部を仕込み、モレキュラーシーブ存在下、６０℃で６時間還流した後、２３℃まで冷却した。得られた反応物に、１０％炭酸カリウム水溶液６５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液した。回収された有機層に、イオン交換水６０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−２９−ｃ）で表される化合物１０．１８部を得た。

式（Ｉ−３３−ａ）で表される化合物２．９８部及びアセトニトリル１５部を仕込み、２３℃で３０分間攪拌した。その後、これに、カルボニルジイミダゾール２．１３部を仕込み、さらに、５０℃で２時間撹拌し、２３℃まで冷却した。得られた反応物に、式（Ｉ−２９−ｃ）で表される化合物３．４１部を加え、２３℃で３０分間攪拌し、さらに、５０℃で１０時間撹拌した。得られた反応物を濃縮し、濃縮残に、クロロホルム３０部及びイオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。回収された有機層に、イオン交換水１５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ−２９−ｄ）で表される化合物３．９８部を得た。

式（Ｉ−２９−ｄ）で表される化合物１．４９部、テトラヒドロフラン３０部、ピリジン０．４１部及びジメチルアミノピリジン０．０２部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−１−ｄ）で表される化合物０．３６部を仕込み、２３℃で３０分間攪拌した後、Ｎ−メチルピロリジン０．２９部を加え、２３℃で６時間撹拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１．２５部を加え、２３℃で３０分間攪拌した後、静置し、分液した。回収された有機層に、イオン交換水３０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−２９）で表される化合物０．７８部を得た。 Example 6: Synthesis of the compound represented by the formula (I-29)

After charging 4.63 parts of the compound represented by the formula (I-26-a), 15.22 parts of the compound represented by the formula (I-13-b) and 100 parts of chloroform, and stirring at 23 ° C. for 30 minutes. , 0.61 part of sulfuric acid was charged, refluxed at 60 ° C. for 6 hours in the presence of a molecular sieve, and then cooled to 23 ° C. To the obtained reaction product, 65 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and the liquid was separated. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 10.18 parts of the compound represented by the formula (I-29-c) was obtained.

2.98 parts of the compound represented by the formula (I-33-a) and 15 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. Then, 2.13 parts of carbonyldiimidazole was added thereto, and the mixture was further stirred at 50 ° C. for 2 hours and cooled to 23 ° C. To the obtained reaction product, 3.41 part of the compound represented by the formula (I-29-c) was added, and the mixture was stirred at 23 ° C. for 30 minutes and further at 50 ° C. for 10 hours. The obtained reaction product was concentrated, 30 parts of chloroform and 15 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. Fifteen parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.98 parts of the compound represented by the formula (I-29-d) was obtained.

1.49 parts of the compound represented by the formula (I-29-d), 30 parts of tetrahydrofuran, 0.41 part of pyridine and 0.02 part of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then up to 5 ° C. Cooled. To the obtained mixture, 0.36 part of the compound represented by the formula (I-1-d) was charged, stirred at 23 ° C. for 30 minutes, then 0.29 part of N-methylpyrrolidin was added, and 6 at 23 ° C. Stir for hours. To the obtained reaction product, 50 parts of ethyl acetate and 1.25 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 30 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 0.78 part of the compound represented by the formula (I-29) was obtained.

MASS: 506.2

Synthesis of Resin (A) The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds will be referred to as "monomer (a1-1-2)" or the like according to the formula number.

Example 7: Synthesis of resin A1-1 As the monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-1) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-1)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtering, to obtain a resin A1-1 of weight average molecular weight 7.6 × 10 ³ in 68% yield rice field. This resin A1-1 has the following structural units.

Example 8: Synthesis of resin A1-2 As the monomers, a monomer (a1-1-3), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-1) is used, and its molar ratio [monomer (a1-1-3): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer ( I-1)] was mixed in the same manner as in Example 2 except that the mixture was made so that 24:35: 2.5: 28.5: 10, and the resin A1-2 having ^{a weight average molecular weight of 7.9 × 10 3 was added.} Obtained with a yield of 63%. This resin A1-2 has the following structural units.

Example 9: Synthesis of resin A1-3 As a monomer, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer Using (I-1), the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer ( The same procedure as in Example 2 was carried out except that I-1)] was mixed so as to be 24:35: 2.5: 28.5: 10, and the resin A1-3 having ^{a weight average molecular weight of 8.5 × 10 3 was added.} It was obtained with a yield of 88%. This resin A1-3 has the following structural units.

Example 10: Synthesis of resin A1-4 As the monomer, the monomer (a1-1-3), the monomer (a1-2-11)), the monomer (a2-1-3), the monomer (a3-4-2) and Monomer (I-1) is used and its molar ratio [monomer (a1-1-3): monomer (a1-2-11): monomer (a2-1-3): monomer (a3-4-2): monomer (I-1)] was mixed in the same manner as in Example 2 except that the mixture was made so that the ratio was 10:49: 2.5: 28.5: 10, and the resin A1-4 ^{having a weight average molecular weight of 8.1 × 10 3 was used.} Was obtained in a yield of 70%. This resin A1-4 has the following structural units.

Example 11 [Synthesis of Resin A1-5]
As the monomer, a monomer (a1-1-2), a monomer (a2-1-1), a monomer (a3-1-1), a monomer (a3-2-3) and a monomer (I-1) are used, and the molars thereof are used. The ratio (monomer (a1-1-2): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3): monomer (I-1)) is 40:10: The same procedure as in Example 2 was carried out except that the mixture was mixed so as to be 17:30: 3, and ^{a resin A1-5 having a weight average molecular weight of 8.1 × 10 3} was obtained in a yield of 78%. This resin A1-5 has the following structural units.

Example 12 [Synthesis of Resin A1-6]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-3), a monomer (a2-1-1), a monomer (a3-1-1) and a monomer (I-1) are used, and the molars thereof are used. The ratio (monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (I-1)) is 32: 7: The same procedure as in Example 2 was carried out except that the mixture was mixed so as to be 14:38: 9, and ^{a resin A1-6 having a weight average molecular weight of 7.6 × 10 3} was obtained in a yield of 60%. This resin A1-6 has the following structural units.

Example 13: Synthesis of resin A1-7 As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-13) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-13)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A1-7 having ^{a weight average molecular weight of 8.2 × 10 3 in a yield of 65%.} rice field. This resin A1-7 has the following structural units.

Example 14: Synthesis of resin A1-8 As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-26) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-26)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtering, to obtain a resin A1-8 of weight average molecular weight 8.0 × 10 ³ in 62% yield rice field. This resin A1-8 has the following structural units.

Example 15: Synthesis of resin A1-9 As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-29) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-29)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A1-9 having ^{a weight average molecular weight of 8.4 × 10 3 in a yield of 59%.} rice field. This resin A1-9 has the following structural units.

Example 16: Synthesis of resin A1-10 As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-33) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-33)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A1-10 having ^{a weight average molecular weight of 8.1 × 10 3 in a yield of 60%.} rice field. This resin A1-10 has the following structural units.

Example 17: Synthesis of resin A1-11 As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), and a monomer (A3-4-2) and the monomer (I-36) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer ( a2-1-3): Monomer (a3-4-2): Monomer (I-36)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is adjusted. 1.5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A1-11 having ^{a weight average molecular weight of 8.5 × 10 3 in a yield of 59%.} rice field. This resin A1-11 has the following structural units.

Synthesis Example 1 [Synthesis of Resin AX-1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-3), a monomer (a2-1-1), a monomer (a3-1-1) and a monomer (IX-1) are used, and their molars are used. The ratio (monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (IX-1)) is 32: 7: The same procedure as in Example 2 was carried out except that the mixture was mixed so as to be 14:38: 9, and ^{a resin AX-1 having a weight average molecular weight of 7.3 × 10 3} was obtained in a yield of 60%. This resin AX-1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin AX-2]
As the monomer, a monomer (a1-1-2), a monomer (a2-1-1), a monomer (a3-1-1), a monomer (a3-2-3) and a monomer (IX-2) are used, and their molars are used. The ratio (monomer (a1-1-2): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3): monomer (IX-2)) is 40:10: The same procedure as in Synthesis Example 1 was carried out except that the mixture was mixed so as to be 17:30: 3, and ^{a resin AX-2 having a weight average molecular weight of 7.9 × 10 3} was obtained in a yield of 63%. This resin AX-2 has the following structural units.

Synthesis Example 3: Synthesis of Resin X1 A monomer (a5-1-1) and a monomer (a4-0-12) are used as the monomer, and the molar ratio thereof [monomer (a5-1-1): monomer (a4-0-). 12)] was mixed so that the ratio was 50:50, and methyl isobutyl ketone 1.2% by mass of the total amount of the monomers was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 3 mol% based on the total amount of monomers, and the mixture was heated at 70 ° C. for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, to obtain a resin X having a weight-average molecular weight 1.0 × 10 ⁴ in 91% yield. This resin X1 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, each of the following components was mixed, and the obtained mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜化合物（Ｄ）＞
Ｄ１：（東京化成工業（株）製）

＜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>
A1-1 to A1-11, AX-1, AX-2, X1: Resin A1-1 to Resin A1-6, Resin AX-1, Resin AX-2, Resin X1
<Acid generator>
B1-21: Salt represented by the formula (B1-21) (synthesized according to an example of JP2012-224611A)
B1-22: Salt represented by the formula (B1-22) (synthesized according to an example of JP2012-224611A)

<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

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

In the resist pattern obtained after development, the exposure amount having a hole diameter of 50 nm formed by using the mask was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of the pattern formed by the mask having a hole diameter of 55 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained by measuring the average hole diameter of a pattern formed by a mask with a hole diameter of 55 nm in the same wafer at 400 points as a population.
"○" when the standard deviation is 2.00 nm or less,
When the standard deviation was larger than 2.00 nm, it was judged as “x”.
The results are shown in Table 2. The numbers in parentheses indicate the standard deviation (nm).

The salt of the present invention and the resist composition containing the salt are suitable for microfabrication of semiconductors and are industrially useful because a resist pattern having good CD uniformity can be obtained.

Claims (2)

A compound represented by the formula (I').

[In formula (I'),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a hydrocarbon group having 1 to 12 carbon atoms.
R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
X ¹¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms which may have a fluorine atom.
A ^{1 'is} a single bond or ^* -A ³ -X ¹ -A ⁵ - represents a. * Represents a bond with C (R ³ ) (R ^4).
A ³ represents a single bond or a divalent hydrocarbon group having 1 to 12 carbon atoms.
A ⁵ represents a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ¹ represents -O-, -CO-O-, -O-CO- or -O-CO-O-. ] A ³ is The compound according to claim 1, wherein an adamantane-diyl group.