JP2021178964A - Compound, resin, resist composition and method for producing resist pattern - Google Patents

Abstract

To provide a resin and a resist composition which make it possible to produce a resist pattern with excellent focus margin (DOF).SOLUTION: The present invention discloses a compound represented by the formula (I), a resin and a resist composition [where R0 is H or a halogen atom or the like. A1 is a single bond, *-A2-CO-O-A3- or the like. * is a bond to an oxygen atom. A2 is a C1-6 alkanediyl group. A3 is a single bond or a C1-6 alkanediyl group. Ad is an adamantanediyl group or the like. A10 is a single bond or a C1-6 alkanediyl group. n is 1 or 2. R1 is a group having a cyclic ether structure or H].SELECTED DRAWING: None

Description

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

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

Japanese Unexamined Patent Publication No. 2008-255188

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

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

［式（ＩＡ）及び式（ＩＢ）中、
ｓ３、ｓ４及びｓ５は、０又は１の整数を表す。ただし、ｓ３及びｓ４の和は１以上で
ある。
＊は結合手を表す。］
〔４〕〔１〕〜〔３〕のいずれかに記載の化合物に由来する構造単位を含む樹脂。
〔５〕さらに、酸不安定基を有する構造単位を含む〔４〕記載の樹脂。
〔６〕酸不安定基を有する構造単位が、式（ａ１−１）又は式（ａ１−２）で表される
構造単位である〔５〕記載の樹脂。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表
し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環
式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］
〔７〕〔４〕〜〔６〕のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物
。
〔８〕酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する〔
７〕に記載のレジスト組成物。
〔９〕（１）〔７〕又は〔８〕記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In formula (I),
^R0 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* -A ^2- CO-O-A ^3- , ^* -A ^4- O-CO-A ^5- , ^* -A
^6- O-A ⁷ -or ^* -A ^8- O-CO-O-A ⁹ -represents. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represent a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantandiyl group or an adamantane triyl group.
A ¹⁰ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. when n is 2, the two R ¹ may be the same or different.
R ¹ independently represents a group or a hydrogen atom containing a cyclic ether structure. However, when n is 2, ^{at least one of R 1} represents a group containing a cyclic ether structure. ]
[2] The compound according to [1] ^{, wherein A 1} is a single bond or ^* -CH _2-CO-O-.
[3] The ^{organic group containing the cyclic ether structure of R 1} is a monovalent group represented by the formula (IA) or a divalent group represented by the formula (IB) [1] or [2]. Compound.

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

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent −O− or ^* −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents a bond with −CO−. Represent a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ]
[7] A resist composition containing the resin and acid generator according to any one of [4] to [6].
[8] Further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator [8]
7] The resist composition according to.
[9] (1) A step of applying the resist composition according to [7] or [8] 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 using the compound of the present invention, a resist pattern can be produced with a good focus margin (DOF).

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, "aliphatic hydrocarbon group" means a linear or branched hydrocarbon group, and "aliphatic hydrocarbon group" means fat. It means a group obtained by removing a number of hydrogen atoms corresponding to a valence from the ring of a cyclic hydrocarbon. "Aromatic hydrocarbon groups"
Also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "(meth) acrylic monomer" means "CH ₂ = CH-CO-".
Alternatively, it means at least one kind of monomer having a structure of "CH ₂ = C (CH _{3) -CO-".} Further, in the present specification, "(meth) acrylate" means "at least one of acrylate and methacrylate", respectively. "(Meta) acrylic acid" and "(meta)"
Notations such as "acryloyl" have the same meaning. In addition, any of the groups described in the present specification that can have both a linear structure and a branched structure may be used.

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

[In formula (I),
^R0 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* -A ^2- CO-O-A ^3- , ^* -A ^4- O-CO-A ^5- , ^* -A
^6- O-A ⁷ -or ^* -A ^8- O-CO-O-A ⁹ -represents. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represent a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantandiyl group or an adamantane triyl group.
A ¹⁰ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. when n is 2, the two R ¹ may be the same or different.
R ¹ independently represents a group or a hydrogen atom containing a cyclic ether structure. However, when n is 2, ^{at least one of R 1} represents a group containing a cyclic ether structure. ]

The alkyl group of R ⁰ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like.
Examples thereof include an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group and a methyl group. It is an ethyl group.
^{Examples of the halogen atom of R0} include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^{Alkyl groups having a halogen atom of R0} include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a perchloromethyl group, a perbromomethyl group and a periodomethyl group.
^R0 is preferably a hydrogen atom or a methyl group.

The ^{alkanediyl groups having 1 to 6 carbon atoms of A 2} , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ include a methylene group, an ethylene group, and a propane-1,3. -Diyl group, butane-
A linear alkanediyl group such as a 1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group, a linear alkanediyl group, and an alkyl group (particularly, 1 carbon number). ~ 4
Alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-
Butyl group, tert-butyl group, etc.), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1 ， 3-
Diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2
-A branched alkanediyl group such as a methylbutane-1,4-diyl group can be mentioned.
A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ are preferably methylene groups or ethylene groups, and more preferably methylene groups.
A ¹ is preferably a single bond or ^* -A ^2- CO-O-A ^3- , and is preferably a single bond or ^*.
It is more preferably −CH _{2 −CO−O−.}
Two or three bonds of the adamantandiyl group or the adamantantriyl group of Ad
It can be in any position.

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

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

[In formula (IA'), formula (IB'), formula (IC') and formula (ID'),
s3, s4 and s5 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
Z and K independently _{represent −CH 2-} or −O−, respectively.
s11 represents an integer of 1 to 4. t11 represents an integer of 0 to 2. When t11 is 2 or more, the plurality of Zs may be the same or different.
s12 represents an integer of 1 to 4. t12 represents an integer of 0 to 2. When t12 is 2 or more, the plurality of Ks may be the same or different.
However, s12 + t12 is 1 to 4.
* Represents a bond. ]
The bond can be at any position, but in equations (IA') and (IB'), 3
It is preferably in the 4-position, and in the formula (IC') and the formula (ID'), it is preferably in the 4-position.

Among them, the cyclic ether structure includes a monovalent group represented by the formula (IA) and the formula (IB'.
) Is preferred.

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

[* Represents a bond hand. ]

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

[* Represents a bond hand. ]

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

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

炭素数１〜６のアルキル基としては、メチル基が挙げられる。 Hydrocarbon groups of R ⁴ include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups and groups formed by combining them. Aliphatic hydrocarbon groups are carbon-
It may have a carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group. Among them, the hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 12 carbon atoms or 6 carbon atoms.
~ 18 aromatic hydrocarbon groups.
The saturated hydrocarbon group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms or 3 carbon atoms.
Saturated cyclic hydrocarbon groups of ~ 12 are mentioned, and alkyl groups having 1 to 12 carbon atoms and 3 to 1 carbon atoms are mentioned.
_{-CH 2-} contained in the saturated cyclic hydrocarbon group of 2 may be replaced with -O-.
Alkyl groups having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples include a pentyl group and a hexyl group.
As an alkyl group having 1 to 12 carbon atoms in which _{−CH 2 − may be replaced by −O −,}
Examples thereof include a methoxyethoxyethyl group.
Examples of the saturated cyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclopropyl group and a cyclobutyl group.
Cyclopentyl group, cyclohexyl group, adamantyl group can be mentioned.
Examples of the saturated cyclic hydrocarbon group having 3 to 12 carbon atoms in which −CH _{2 − may be replaced by −O − include the following groups.}

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group.

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

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

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

Examples of R ¹ include the following groups.

Note that when in the compound (I) R ¹ is one, to R ¹ may be a hydrogen atom, may be any group containing a cyclic ether structure, the latter is preferred. When there are two ^{R 1 , one R 1} may be a hydrogen atom and the other R ¹ may be a group containing a cyclic ether structure, or both may be a group containing a cyclic ether structure.

Examples of the compound (I) include the following.

Among the compounds represented by the formulas (I-1) to (I-47), the compound in which ^{the methyl group corresponding to R0} is replaced with a hydrogen atom can also be mentioned as a specific example of the compound (I).

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

<Method for producing compound (I)>
^{Formula (* represents a binding site with O) in which A 1} of compound (I) is * -CH _2- CO-O- (* represents a binding site with O).
The compound represented by I1) is obtained by reacting the compound represented by the formula (I1-a) with the compound represented by the formula (I1-b) in the presence of a base catalyst in a solvent. be able to.

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

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

[In the formula, R ⁰ , R ¹ and Ad have the same meanings as described above. ]
Examples of the solvent include tetrahydrofuran, chloroform and the like.
Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine and the like.

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

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

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

The compounds represented by the formula (I1-c) are the compound represented by the formula (I1-e) and the compound represented by the formula (I1-e).
It can be obtained by reacting the compound represented by f) in a solvent in the presence of a catalyst.

[In the formula, R ¹ , A ¹⁰ , n and Ad have the same meanings as described above. ]
Examples of the solvent include acetone and chloroform.
Examples of the catalyst include a base catalyst (for example, pyridine, dimethylaminopyridine) and a known esterification catalyst (for example, an acid catalyst, a carbodiimide catalyst, etc.), and the base catalyst and a known esterification catalyst may coexist. ..
Examples of the compound represented by the formula (I1-e) include compounds represented by the following.
Easily available on the market.

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

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

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

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

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

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

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

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３
〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに
結合してそれらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を
形成する。
ｎａは、０又は１を表す。
＊は結合手を表す。］

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１〜１２の
炭化水素基を表し、Ｒ^a3’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a2’及びＲ^a3’
は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の複素環基を
形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き
換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a)>
Examples of the acid unstable group contained in the structural unit (a) include a group represented by the formula (1) and a group represented by the formula (2).

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

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

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

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, an adamantylmethyl group and the like.
na is preferably 0.

^{-C (R a1} ) (R ^a2 ) when R ^a1 and R a ² are bonded to each other to form a divalent hydrocarbon group.
) (R ^a3 ) includes the following groups. The divalent hydrocarbon group preferably has 3 carbon atoms.
~ 12. * Represents a bond with -O-.

The group represented by the formula (1) is a 1,1-dialkylalkoxycarbonyl group (formula (1).
), R ^{a1 to} R ^a3 are alkyl groups, preferably tert-butoxycarbonyl group), 2-alkyladamantane-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- (adamantane-1-yl) -1-alkylalkoxycarbonyl group (formula (formula).
1) Among the ^{groups, 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',} for example, an alkyl group, an alicyclic hydrocarbon group, and a group formed by combining an aromatic hydrocarbon group and thereof.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group, mesityl group and biphenyl. Examples thereof include an aryl group such as a group, a phenanthryl group, a 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl.
R ^a2'and R ^a3' bond to each other and form with the carbon atoms and X to which they bond 2
Examples of the valence heterocyclic group include the following groups. * Represents a bond.

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 leading to the structural unit (a) is preferably a monomer having an acid unstable group and an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer having an acid unstable group.

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

As the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1), the structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). Examples thereof include a structural unit or a structural unit represented by the formula (a1-2). These may be used alone
Two or more kinds may be used together. In the present specification, the structural unit represented by the formula (a1-0), the formula (a).
The structural unit represented by 1-1) and the structural unit represented by the formula (a1-2) are referred to as a structural unit (a1-0), a structural unit (a1-1), and a structural unit (a1-2), respectively. , Structural unit (a1-
Monomer for inducing 0), monomer for inducing structural unit (a1-1) and structural unit (a1)
The monomer that induces -2) may be referred to as a monomer (a1-0), a monomer (a1-1), and a monomer (a1-2), respectively.

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

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

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

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

^La01 is preferably an oxygen atom or ^* -O- (CH ₂ ) _k01- CO-O-, and more preferably an oxygen atom. k01 is preferably an integer of 1 to 4, more preferably 1.
Examples of the alkyl group of R ^a02 , R ^a03 and R ^a04 , the alicyclic hydrocarbon group and the group combining these groups include the same groups as those mentioned in ^{R a1 to} R ^{a3 of the formula (1).}
The alkyl groups of R ^a02 , R ^a03 and R ^a04 preferably have 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 preferably has 8 or less carbon atoms, and more preferably 6 or less carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group and the like.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are preferably −O− or ^* −O− (CH ₂ ) _k1 −CO−O−.
More preferably, it is −O−. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
As ^{the alkyl group of R a6} and R ^a7 , the alicyclic hydrocarbon group and the group combining these,
^Examples thereof include the same groups as those mentioned in ^{R a1 to} R a3 of the formula (1).
The alkyl groups of R ^a6 and R ^a7 preferably have 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, and more preferably 6 or less carbon atoms.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1'is preferably 0 or 1.

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

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

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

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

Examples of the monomer (a1-2) include 1-ethylcyclopentane-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcyclopentane-1-yl (meth) acrylate, and the like. 1-Methylcyclopentane-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-isopropylcyclopentane-1-yl (meth) acrylate, 1-isopropylcyclohexane-1-yl (1-isopropylcyclohexane-1-yl (meth) acrylate) Meta) Acrylate and the like can be mentioned. Equations (a1-2-1) to Equations (a1-)
The monomer represented by 2-12) is preferable, and it is represented by the formulas (a1-2-3) to (a1-2-4) or the formulas (a1-2-9) to (a1-2-10). Monomers are more preferred, the formula (
Monomers represented by a1-2-3) or the formula (a1-2-9) are more preferable.

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

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

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

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

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

Specifically, the monomer (a1-3) is 5-norbornene-2-carboxylic acid-tert.
-Butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl,
5-Norbornene-2-carboxylic acid 1-methylcyclohexyl, 5-norbornene-2-
2-Methyl-2-adamantyl carboxylate, 5-norbornen-2-carboxylate 2-ethyl-2-adamantyl, 5-norbornen-2-carboxylate 1- (4-methylcyclohexyl) -1-methylethyl, 5- Norbornen-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornen-2-carboxylic acid 1-methyl-1
-(4-oxocyclohexyl) ethyl and 5-norbornene-2-carboxylic acid 1- (1)
-Adamantyl) -1-methylethyl and the like can be mentioned.

Since the resin (A) containing the structural unit (a1-3) contains a three-dimensionally bulky structural unit, it is higher than the resist composition of the present invention containing such a resin (A). The resist pattern can be obtained at the resolution. Further, since a rigid norbornane ring is introduced into the main chain, the obtained resist pattern tends to have excellent dry etching resistance.

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

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

[In equation (a1-4),
R ^a32 may have a hydrogen atom, a halogen atom, or a halogen atom and has 1 to 6 carbon atoms.
Represents the alkyl group of.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or the like. Represents a methacryloyloxy group.
la represents an integer from 0 to 4. When la is 2 or more, a plurality of Ra ^33s may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms,
R ^a36 is either a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are the divalent heterocyclic group having 3 to 20 carbon atoms to form together with the C-O to which they are attached, _{, -CH 2-} contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with -O- or -S-.
]

^Examples of the alkyl group of R a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like. The alkyl group has 1 carbon atom.
Alkyl groups of ~ 4 are preferred, methyl or ethyl groups are more preferred, and methyl groups are even more preferred.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group that may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,
1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1
, 2,2-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2
, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group,
1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-
Examples thereof include a hexyl group and an n-perfluorohexyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon group R ^a34 and R ^a35, include the same groups as R ^{a1 'and} R ^a2' of formula (2).
R ^a36 includes an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
Examples thereof include aromatic hydrocarbon groups having 6 to 18 carbon atoms or groups formed by combining them.

In the formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and even more preferably a methoxy group.
For la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms and 3 to 1 carbon atoms.
It is an alicyclic aliphatic hydrocarbon group of 8 or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R ^{a36 are preferably unsubstituted.} When ^{the aromatic hydrocarbon group in Ra36} has a substituent, an aryloxy group having 6 to 10 carbon atoms is preferable as the substituent.

As the monomer for deriving the structural unit (a1-4), for example, Japanese Patent Application Laid-Open No. 2010-204646
Examples thereof include the monomers described in the publication. Above all, equations (a1-4-1) to equations (a1-4)
The monomers represented by -8) are preferable, and the formulas (a1-4-1) to (a1-4-5) are preferable.
) And the monomers represented by the formulas (a1-4-8), respectively, are more preferable.

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

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

In equation (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or * − (CH ₂ ) _h3 −CO−L ⁵⁴ −, h3 represents an integer of 1 to 4, and * represents a bond with ^{L 51.}
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ independently represent -O- or -S-, respectively.
s1 represents an integer of 1 to 3.
s1'represents an integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group and an ethyl group.
Examples thereof include 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.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
1 is preferable for s1.
s1'is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH _2- CO-O-.

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

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

In the resin (A), the content of the structural unit (a) is higher than that of all the structural units of the resin (A).
It is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%.

Among them, the structural unit having an acid unstable group in the resin (A) is preferably the structural unit represented by the formula (a1-1) or the formula (a1-2), and is represented by the formula (a1-1). The structural unit to be formed is more preferable, and at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2) and the structural unit (a1-5) is preferable. , At least two or more are more preferable, a combination of structural units (a1-1) and structural units (a1-2), a combination of structural units (a1-1) and structural units (a1-5), structural units (a1-). 1
) And the combination of the structural unit (a1-0), the structural unit (a1-2) and the structural unit (a1-).
Combination of 0), combination of structural unit (a1-5) and structural unit (a1-0), combination of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2), structure The combination of the unit (a1-0), the structural unit (a1-1) and the structural unit (a1-5) is further preferable, and the combination of the structural unit (a1-1) and the structural unit (a1-2) is even more preferable. ..

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

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

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

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

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

^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom of R a30 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group and 1 , 1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl Groups, n-perfluorohexyl group and the like can be mentioned. R ^a3
0 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkoxy group of R a31 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
The ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

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

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

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

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

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

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

Examples of the monomer for inducing the structural unit (a2-1) include JP-A-2010-2046.
Examples thereof include the monomers described in Japanese Patent Publication No. 46. Equations (a2-1-1) to (a2-1-6)
) Is preferable, and formulas (a2-1-1) to (a2-1-4) are preferable.
The monomer represented by any of the above is more preferable, and the formula (a2-1-1) or the formula (a2-1-1) is preferable.
The monomer represented by 3) is more preferable.

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

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

The structural unit (a3) is preferably the formula (a3-1), the formula (a3-2), and the formula (a3-3).
Alternatively, it is a structural unit represented by the formula (a3-4). One of these may be contained alone.
It may contain two or more kinds.

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

[In equation (a3-1),
L ^a4 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In formula (a3-2),
L ^a5 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of ^Ra22s are the same or different from each other.
In formula (a3-3),
L ^a6 represents −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of ^Ra23s are the same or different from each other.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- C
Represents O-O-L ^a9- CO-O- or ^* -O-L ^a8- O-CO-L ^a9- O-.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other.
w1 represents an integer from 0 to 8. When w1 is 2 or more, the plurality of Ra ^25s may be the same or different from each other. ]

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

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

In the formula (a3-1) ~ formula (a3-3), L ^a4 ~L ^a6 are each independently preferably, -O- or, k3 is an integer of from 1 to 4 * -O- (CH ₂ ) _{A group represented by k3-} CO-O-, more preferably -O- and * -O-CH _2- CO-O-, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably integers of 0 to 2, and more preferably 0 or 1.

（式中、Ｒ^ａ２４、Ｌ^a7は、上記と同じ意味を表す。） In formula (a3-4)
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
L ^a7 is preferably −O− or ^* −OL ^a8 −CO—O−, and more preferably.
-O-, -O-CH ₂ -CO-O- or -O-C ₂ H ₄ -CO-O-.
^Ra25 is preferably a carboxy group, a cyano group or a methyl group.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4)'.

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

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

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

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

<Other structural units (t)>
The structural unit (t) will be described later (a) in addition to the structural unit (a2) and the structural unit (a3).
Examples thereof include a structural unit represented by 4) (hereinafter sometimes referred to as “structural unit (a4)”) and a structural unit represented by (a5) (hereinafter sometimes referred to as “structural unit (a5)”). ..

［式（ａ４−０）中、
Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁵は、単結合又は炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数３〜１２のペルフル
オロシクロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
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 an alkanediyl group having 1 to 4 carbon atoms.
For example, a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a linear alkanediyl group, and an alkyl group (particularly, a methyl group, Those having a side chain of (ethyl group, etc.), ethane-1,1-diyl group, propane-1,2
-Diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2
Examples thereof include branched alkanediyl groups such as −methylpropane-1,2-diyl group.
Examples of the perfluoroalkanediyl group of L ³ include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, and a perfluoropropane-1,3-.
Diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-
Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2- Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7- Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctanoic acid-1,8-diyl group, perfluorooctanoic acid-2,2- Examples thereof include a diyl group, a perfluorooctane-3,3-diyl group, and a perfluorooctane-4,4-diyl group.
Examples of the perfluorocycloalkanediyl group of L ³ include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, and a perfluorocycloheptanediyl group.
Examples thereof include a perfluoroadamantandiyl group.

L ⁵ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

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

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

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

[In the formula (a-g1),
s represents 0 or 1.
A a ⁴² and A a ⁴⁴ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 are independently -O-, -CO-, -CO-O- or -O-CO, respectively.
Represents-.
However, the total number of carbon atoms of ^{A a42} , A ^a43 , A ^a44 , X ^a41 and X ^{a42 is 7 or less.} ]
* Is a bond, and * on the right is a bond with -O-CO-R ^a42 . ]

The hydrocarbon groups of R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like.
In addition, a group formed by combining these can be mentioned.
The chain and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups are preferable. 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. The cyclic aliphatic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* is a bond). Represent a hand.
) Etc., a polycyclic alicyclic hydrocarbon group can be mentioned.

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 R a42 include a halogen atom or a group represented by the formula ( ^{ag3) as a substituent.} Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
It is preferably a fluorine atom.

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

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

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

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

Partial structure represented by * -A ^a46- X ^a44- A ^a47 (* is a bond with a carbonyl group)
A more preferable structure of the above is the following structure.

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

^{The aliphatic hydrocarbon groups A a42} , A ^a43 and A ^{a44 in} the group (a-g1) may have a carbon-carbon unsaturated bond, but are chain and cyclic aliphatic saturated hydrocarbon groups. In addition, a group formed by combining these is preferable. The aliphatic saturated hydrocarbon group includes
Examples thereof include a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining an alkyl group and an alicyclic hydrocarbon group.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2
-Diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-
Examples thereof include a methylpropane-1,3-diyl group and a 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 is an oxygen atom include the following groups. In the following examples, of the two bonds represented by *, * on the right side is -O-CO-R ^a42.
It is a bond with.

^{Examples of the group (ag1) in} which X a42 is a carbonyl group include the following groups.

^{Examples of the group (ag1) in} which X a42 is a carbonyloxy group include the following groups.

^{Examples of the group (ag1) in} which X a42 is an oxycarbonyl group include the following groups.

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

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

The ^{alkanediyl group of A f1} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexine-1,6-diyl group and other linear alkanediyl groups; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1
, 2-Diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
Examples of 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, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl 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 the like.
Examples thereof include a norbornyl group, a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
As the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,
1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1-(
Trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,
2-Tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,
1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1
-Bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group,
Perfluoropentyl group, 1,1,2,2,3,3,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3-3 Pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3,4,4,5
, 5-Decafluorohexyl group, 1,1,2,2,3,4,4,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group and other fluorinated alkyl The group is mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorocycloalkyl group such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

^{As A f1} in the formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.
As R ^f2 , an alkyl fluoride group having 1 to 6 carbon atoms is preferable.

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

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

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

The aliphatic hydrocarbon group of A ^f13 includes either a chain type or a cyclic type, and a divalent aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon is
It may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The ^{aliphatic hydrocarbon group which may have a fluorine atom of A f13} is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain-type aliphatic hydrocarbon group which may have a fluorine atom include a methylene group.
Alcandiyl groups such as ethylene group, propanediyl group, butandyl group and pentandiyl group; perfluoroalkandyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutandyl group and perfluoropentanediyl group can be mentioned. ..
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantandiyl group, a norbornanediyl group, and a perfluoroadamantandiyl group.

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

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

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

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

［式（ａ４−４）中、
Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、−（ＣＨ₂）_j1−、−（ＣＨ₂）_j2−Ｏ−（ＣＨ₂）_j3−又は−（ＣＨ₂）_j4−
ＣＯ−Ｏ−（ＣＨ₂）_j5−を表す。
ｊ１〜ｊ５は、それぞれ独立に、１〜６の整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ The structural unit (a4) also includes 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 is − (CH ₂ ) _j1 −, − (CH ₂ ) _j2 −O− (CH ₂ ) _j3 − or − (CH ₂ ) _j4 −
Represents 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 the same hydrocarbon group ^{of R f2 in the formula (a4-2).} R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom. Preferably, it has 1 to 6 carbon atoms having a fluorine atom.
Alkyl groups of are more preferred.

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.

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 structural unit represented by the following formula. Be done.

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

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水
素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但
し、Ｌ⁵¹との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化
水素基で置換されない。
Ｌ⁵¹は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基
に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-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 structural unit containing 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 having 1 to 8 carbon atoms or a hydroxy group. May be. However, ^{the hydrogen atom bonded to the carbon atom at the bonding position with L 51} is not replaced by the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

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

Examples of the divalent saturated hydrocarbon group of L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent aliphatic saturated hydrocarbon group is preferable. ..
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

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

In formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total number of carbon atoms of ^{L x 1} and L ^{x 2 is 16 or less.}
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total number of carbon atoms of ^{L x3} and L ^{x4 is 17 or less.}
In formula (L1-3),
L ^{x 5} represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of ^{L x5} , L ^x6 and L ^{x7 is 15 or less.}
In equation (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^{x 1} represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of ^{L x8} , L ^x9 and W ^{x1 is 15 or less.}

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

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

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

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

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

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

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

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

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

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

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500).
00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30)
000 or less, more preferably 15,000 or less).

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter, may be referred to as "acid generator (B)"). The resist composition of the present invention preferably contains a resin other than the resin (A).
The resist composition of the present invention further has a weak acidity such as a solvent (hereinafter sometimes referred to as "solvent (E)") and a weak acid intramolecular salt (hereinafter sometimes referred to as "weak acid intramolecular salt (D)"). It is preferable to contain a citrate containing a salt (hereinafter, may be referred to as "citrate (C)").

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

Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer 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 weight of the resin (X) is preferably 6,000 or more (more preferably 7.0).
00 or more), 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further, with respect to 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, and particularly preferably 2 to 30 parts by mass.

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

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of them may be used in the acid generator (B) of the resist composition of the present invention. Nonionic acid generators include organic halides, sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like are included. The ionic acid generator is typically an onium salt containing an onium cation (for example, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt). 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, and JP-A-55-164824.
Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,
Compounds that generate acid by radiation as described in 778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used alone or in combination of two or more.

The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably the formula (B1).
It is a salt represented by (hereinafter, may be referred to as "acid generator (B1)").

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル
基を表す。
Ｌ^b1は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含
まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化
水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１
８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる−ＣＨ₂−は
、−Ｏ−、−ＳＯ₂−又は−ＣＯ−に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and −CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y may have a methyl group or a substituent which may have a substituent, and may have 3 to 1 carbon atoms.
Represents a monovalent alicyclic hydrocarbon group of 8, even if −CH ₂ − contained in the monovalent alicyclic hydrocarbon group is replaced with −O −, −SO _{2− or −CO−.} good.
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.
For Q ¹ and Q ² , respectively, a fluorine atom or a trifluoromethyl group is preferable, and Q ¹
Fluorine atoms are more preferable for both and Q ^2.

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. 2 of the groups
It may be a group formed by combining seeds or more.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4
-Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1
, 7-Diyl group, Octane-1,8-Diyl group, Nonane-1,9-Diyl group, Decane-1
, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group,
Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-
1,15-Diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-
Linear alkanediyl groups such as diyl groups;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-
Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples thereof include a polycyclic divalent alicyclic saturated hydrocarbon group such as a 1,5-diyl group and an adamantane-2,6-diyl group.

_{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 saturated hydrocarbon group. The number of carbon atoms in.
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 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11).
_{-CH 2-} contained in the monovalent alicyclic hydrocarbon group represented by Y is -O-, -SO _{2- or-}
Examples of the group replaced by CO- include groups represented by the formulas (Y12) to (Y38).

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 (Y19), the formula (Y20), the formula (Y30) or the formula (Y31), more preferably a group represented by the formula (Y11), the formula (Y15) or the formula (Y30). be.

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

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

Examples of Y include the following. In the following group, * is a bond with ^{L b1.}

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bond position with Y is used. The base −CH ₂₋ is
It is preferably replaced with −O− or −CO−. _{In this case, −CH 2} − contained in the methyl group of Y is not replaced with −O − or −CO−.

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

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include the formulas (B1-A-1) to
Anion represented by the formula (B1-A-46) [hereinafter, "anion (B1-A)" according to the formula number.
-1) ”and so on. ] Is preferable, and the formulas (B1-A-1) to (B1-A-4)
, Formula (B1-A-9), Formula (B1-A-10), Formulas (B1-A-24) to Formulas (B1-A-)
33), the anion represented by any of the formulas (B1-A-36) to (B1-A-40) is more preferable. Further, the formula (B1-A-5), the formula (B1-A-7), the formula (B1-A-24)
, In the formulas (B1-A-30) to (B1-A-33), 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. Equation (B1-A-32)
And in the formula (B1-A-33), R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and a monovalent fat having 5 to 12 carbon atoms. A cyclic hydrocarbon group or a group formed by combining these groups, more preferably a methyl group or an ethyl group,
It is a cyclohexyl group or an adamantyl group. L ⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Specifically, the sulfonic acid anion in the salt represented by the formula (B1) is JP-A-20.
Examples thereof include the anions described in JP-A-10-204646.

Among them, the sulfonic acid anion in the salt represented by the preferable formula (B1) is the formula (
Examples thereof include anions represented by the formulas (B1a-1) to (B1a-22).

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include formulas (B1a-1) to (B1a-3), formulas (B1a-7) to formulas (B1a-16), and formulas (B1a-18). ,formula(
An anion represented by either B1a-19) or the formula (B1a-22) is preferable.

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

In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 are monovalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms and 3 carbon atoms, respectively.
Represents a monovalent alicyclic hydrocarbon group of ~ 36 or a monovalent aromatic hydrocarbon group of 6 to 36 carbon atoms.
The hydrogen atom contained in the monovalent aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted with a monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group may be substituted.
It may be substituted with a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and is contained in the monovalent aromatic hydrocarbon group. The hydrogen atom 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 with the sulfur atom to which they are bonded, and −CH ₂ − contained in the ring may be replaced with −O−, −SO− or −CO−. ..
R ^b7 and R ^b8 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 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 a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring with the sulfur atom to which they are bonded, and −CH ₂ − contained in the ring may be replaced with −O−, −SO− or −CO−. ..
R ^b11 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, and 1 having 3 to 36 carbon atoms.
It represents a valent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 comprises a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the monovalent aromatic hydrocarbon group. The hydrogen atom may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be combined to form a ring containing −CH—CO— to which they are bound, and −CH ₂₋ contained in the ring is −O−, −SO−. Alternatively, it may be replaced with −CO−.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represent an integer 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 are the same or different, when p2 is 2 or more, a plurality of R ^b14s are the same or different, and when q2 is 2 or more, a plurality of R ^b15s are the same or different. , R2
When is 2 or more, plural R ^b16 same or different, when s2 is 2 or more, plural R ^b17 same or different, when t2 is 2 or more, plural R ^b18 same or different.

特に、Ｒ^b9〜Ｒ^b12の１価の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好
ましくは炭素数４〜１２である。 The monovalent aliphatic hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and 2 -Alkyl groups of ethylhexyl groups can be mentioned. Especially, R ^b9 ~ R ^b12
The monovalent aliphatic hydrocarbon group of No. 1 preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic monovalent alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group and a cyclopentyl group.
Cycloalkyl groups such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

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

As a monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, for example,
Methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantane-2-
Examples thereof include an yl group, a methylnorbornyl group and an isobornyl group. In a monovalent alicyclic hydrocarbon group in which a hydrogen atom is replaced with a monovalent aliphatic hydrocarbon group, the total number of carbon atoms of the monovalent alicyclic hydrocarbon group and the monovalent aliphatic hydrocarbon group Is preferably 20 or less.

Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, and a cumenyl group.
Mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group, biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group, 2- Aryl groups such as a methyl-6-ethylphenyl group can be mentioned.
When the monovalent aromatic hydrocarbon group contains a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, it is a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. Or 1 of 3 to 18 carbon atoms
Valuable alicyclic hydrocarbon groups are preferred.
Examples of the monovalent aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the monovalent aliphatic hydrocarbon group in which the hydrogen atom is replaced with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group. ..

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

The ring that R ^b4 and R ^b5 may form with the sulfur atom to which they are bonded is monocyclic,
It may be a polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. Examples of this ring include a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, the following ring may be mentioned.

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. This ring is 3
A member ring to a 12-membered ring is mentioned, and a 3-membered ring to a 7-membered ring is preferable. For example, Thioran-1-
Examples thereof include an ion ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
The ^{ring formed by R b11} and R ^b12 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. This ring may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring and the like can be mentioned.

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

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

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

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

Preferred examples of the acid generator (B1) include those represented by the formulas (B1-1) to (B1-40), among which the formula (B1-1) containing an aryl sulfonium cation is included.
), Equation (B1-2), Equation (B1-3), Equation (B1-5), Equation (B1-6), Equation (B1-7)
), Equation (B1-11), Equation (B1-12), Equation (B1-13), Equation (B1-14), Equation (
B1-13), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-2)
4), formula (B1-25), formula (B1-26), formula (B1-29), formula (B1-31), formula (B1-32), formula (B1-33), formula (B1-34) ), Equation (B1-35), Equation (B1-
36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40)
Those represented by are particularly preferable.

The content of the acid generator (B1) is 30% by mass or more and 100 with respect to the total amount of the acid generator (B).
It is preferably 5% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and further preferably substantially only the acid generator (B1).
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). (Below).

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

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

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

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

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

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

<Salt with weak acidity>
The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pK.
It is a salt of a <7, more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid intramolecular salt represented by the formula (D), and JP-A-2012-229206, JP-A. 2012-6908, 2012-72109, 2011-39502 and 2011-19
Examples thereof include the salt described in Japanese Patent Publication No. 1745.

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

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

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

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

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

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

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

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

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

<Preparation of resist composition>
The resist composition of the present invention is prepared by mixing a resin (A) and an acid generator (B), and a quencher (C), a solvent (E) and other components (F) used as necessary. Can be prepared. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can 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. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying
For example, it is carried out by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or by using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is 1 to 1.
About 0 × 10 ⁵ Pa is preferable.

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

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

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

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

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

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

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

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

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

式（Ｉ−１−ａ）で表される化合物１０．００部、式（Ｉ−１−ｂ）で表される化合物
７．７１部及びクロロホルム８０部を添加し、２３℃で３０分間攪拌した。得られた混合
溶液に、式（Ｉ−１−ｃ）で表される化合物１９．９５部を添加した後、２３℃で３８時
間攪拌した。得られた反応混合物に、酢酸エチル２４０部及び５％塩酸３７部を添加撹拌
し、分液して有機層を取り出した。回収された有機層に、イオン交換水５０部を加えて２
３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層に、１０％炭酸
カリウム水溶液３０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。
回収された有機層に、イオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有
機層を取り出した。この操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮
物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシ
ュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｉ−１―ｆ）で表され
る化合物１０．４２部を得た。

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

10.00 parts of the compound represented by the formula (I-1-a), 7.71 parts of the compound represented by the formula (I-1-b) and 80 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. .. To the obtained mixed solution, 19.95 parts of the compound represented by the formula (I-1-c) was added, and then the mixture was stirred at 23 ° C. for 38 hours. To the obtained reaction mixture, 240 parts of ethyl acetate and 37 parts of 5% hydrochloric acid were added and stirred, and the mixture was separated to take out the organic layer. Add 50 parts of ion-exchanged water to the recovered organic layer for 2
The mixture was stirred at 3 ° C. for 30 minutes and separated to remove the organic layer. To the recovered organic layer, 30 parts of a 10% potassium carbonate aqueous solution was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer.
50 parts of ion-exchanged water was added to the recovered organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. This operation was repeated 5 times. The organic layer after washing with water was concentrated, and the obtained concentrate was subjected to column preparative (column preparative conditions, stationary phase: Merck & Co. silica gel 60-200 mesh developing solvent: n-heptane / ethyl acetate). 10.42 parts of the compound represented by (I-1-f) was obtained.

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

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

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

3.12 parts of the compound represented by the formula (I-1-c), 30 parts of tetrahydrofuran and 0.84 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes and then cooled to 5 ° C. 1.20 parts of the compound represented by the formula (I-2-a) was added to the obtained mixed solution, and the temperature was raised to 23 ° C.
Then, the mixture was further stirred at 23 ° C. for 1 hour. Chloroform 100 is added to the obtained reaction mixture.
A portion and 5.74 5% hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. To the obtained organic layer, 4.41 parts of a 10% potassium carbonate aqueous solution was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. Add 50 parts of ion-exchanged water to the obtained organic layer for 2
The mixture was stirred at 3 ° C. for 30 minutes and separated to remove the organic layer. This operation was repeated 4 times. By concentrating the obtained organic layer, 2.84 parts of the compound represented by the formula (I-2-b) was obtained.

0.50 parts of the compound represented by the formula (I-2-c), 5 parts of dimethylformamide and 0.40 parts of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. In the resulting mixture, formula (I-2-
2.49 parts of the compound represented by b) was added, and the mixture was stirred at 50 ° C. for 5 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes. This was allowed to stand, and the organic layer was washed with water by separating the liquid. Twenty-five parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. Such a cleaning operation was repeated 5 times. The organic layer after washing with water is concentrated, and the obtained concentrate is subjected to column preparative (column preparative conditions, stationary phase: Merck silica gel 60-200 mesh).
The developing solvent: n-heptane / ethyl acetate) gave 2.11 parts of the compound represented by the formula (I-2).
MS (Mass Spectrometry): 478.2 (Molecular Ion Peak)

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

3.07 parts of the compound represented by the formula (I-9-a), 30 parts of dimethylformamide and 0.80 parts of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. In the resulting mixture, formula (I-9)
1.07 parts of the compound represented by −b) was added, and the mixture was stirred at 50 ° C. for 5 hours. 200 parts of chloroform was added to the obtained reaction mixture and stirred. Ion-exchanged water 100 in the obtained mixture
The portion was added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. This operation was repeated 3 times. The organic layer after washing with water is concentrated, and the obtained concentrate is subjected to column preparative (column preparative conditions, stationary phase: Merck & Co. silica gel 60-200 mesh developing solvent: n-heptane / ethyl acetate = 1/5). As a result, 2.48 parts of the compound represented by the formula (I-9) was obtained.
MS (Mass Spectrometry): 320.2 (Molecular Ion Peak)

式（Ｉ−１７−ａ）で表される化合物３．０７部、ジメチルホルムアミド３０部及び炭
酸カリウム０．８０部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−
９−ｂ）で表される化合物１．０７部を添加し、５０℃で５時間攪拌した。得られた反応
混合物に、クロロホルム２００部を添加撹拌した。得られた混合物に、イオン交換水１０
０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰
り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取（カラム分取条件
固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エ
チル＝１／５）することにより、式（Ｉ−１７）で表される化合物２．２８部を得た。
ＭＳ（質量分析）：３２０．２（分子イオンピーク） Example 4: Synthesis of compound represented by formula (I-17)

3.07 parts of the compound represented by the formula (I-17-a), 30 parts of dimethylformamide and 0.80 parts of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. In the resulting mixture, formula (I-
1.07 parts of the compound represented by 9-b) was added, and the mixture was stirred at 50 ° C. for 5 hours. 200 parts of chloroform was added to the obtained reaction mixture and stirred. Ion-exchanged water 10 in the obtained mixture
0 part was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. This operation was repeated 3 times. The organic layer after washing with water is concentrated, and the obtained concentrate is subjected to column sorting (column sorting conditions).
Fixed phase: Merck & Co., Ltd. silica gel 60-200 mesh Developing solvent: n-heptane / ethyl acetate = 1/5) to obtain 2.28 parts of the compound represented by the formula (I-17).
MS (Mass Spectrometry): 320.2 (Molecular Ion Peak)

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

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

式（Ｉ−２９−ｅ）で表される化合物を含む溶液に、式（Ｉ−２９−ｆ）で表される化
合物０．７９部を添加し、５０℃で５時間攪拌した。得られた反応物に、クロロホルム３
０部及びイオン交換水１５部を仕込み、２３℃で３０分間攪拌した。これを静置した後、
分液することにより有機層を水洗した。回収された有機層に、イオン交換水１５部を仕込
み、２３℃で３０分間攪拌し、静置し、分液することにより有機層を回収した。このよう
な洗浄操作を５回繰り返した。水洗後の有機層を濃縮し、得られた濃縮物を、カラム分取
（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ
−ヘプタン／酢酸エチル）することにより、式（Ｉ−２９―ｇ）で表される化合物１．８
８部を得た。

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

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

3.00 parts of the compound represented by the formula (I-29-a) and 100 parts of methanol were added, and 2
The mixture was stirred at 3 ° C. for 30 minutes. 2.79 parts of triethylamine was added to the obtained mixed solution. Then, 2.22 parts of the compound represented by the formula (I-29-b) was added dropwise thereto over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. 200 parts of chloroform was added to the obtained reaction mixture and stirred. To the obtained mixture, 100 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. This operation was repeated 3 times. By concentrating the obtained organic layer, 3.75 parts of the compound represented by the formula (I-29-c) was obtained.

2.00 parts of the compound represented by the formula (I-29-c), 30 parts of tetrahydrofuran and the formula (I).
After adding 0.99 parts of the compound represented by −29−d) and stirring at 23 ° C. for 30 minutes, 60
Stirring at ° C. for 5 hours gave a solution containing the compound represented by the formula (I-29-e).

To a solution containing the compound represented by the formula (I-29-e), 0.79 part of the compound represented by the formula (I-29-f) was added, and the mixture was stirred at 50 ° C. for 5 hours. Chloroform 3 is added to the obtained reaction product.
0 parts and 15 parts of ion-exchanged water were charged and stirred at 23 ° C. for 30 minutes. After letting this stand still
The organic layer was washed with water by separating the liquids. Fifteen parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. Such a cleaning operation was repeated 5 times. The organic layer after washing with water is concentrated, and the obtained concentrate is collected by column preparative (column preparative conditions, stationary phase: 60-200 mesh of silica gel manufactured by Merck & Co., Inc. developing solvent: n.
-Heptane / ethyl acetate), the compound represented by the formula (I-29-g) 1.8
I got 8 copies.

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

0.46 parts of the compound represented by the formula (I-29-h), 10 parts of dimethylformamide and 0.16 parts of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. In the resulting mixture, formula (I-
0.21 part of the compound represented by 9-b) was added, and the mixture was stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 20 parts of chloroform was added and stirred. To the obtained mixture, 10 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. This operation was repeated 3 times. By concentrating the obtained organic layer, the compound represented by the formula (I-29) is 0.36.
I got a part.
MS (Mass Spectrometry): 508.2 (Molecular Ion Peak)

式（Ｉ−２９−ｈ）で表される化合物０．４６部、ジメチルホルムアミド１０部及び炭
酸カリウム０．１６部を、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ−
４６−ｂ）で表される化合物０．３１部を添加し、５０℃で５時間攪拌した。得られた反
応混合物に、クロロホルム２０部を添加撹拌した。得られた混合物に、イオン交換水１０
部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を３回繰り
返した。得られた有機層を濃縮することにより、式（Ｉ−４６）で表される化合物０．３
９部を得た。
ＭＳ（質量分析）：５９２．３（分子イオンピーク） Example 6: Synthesis of the compound represented by the formula (I-46)

0.46 parts of the compound represented by the formula (I-29-h), 10 parts of dimethylformamide and 0.16 parts of potassium carbonate were stirred and mixed at 23 ° C. for 30 minutes. In the resulting mixture, formula (I-
0.31 part of the compound represented by 46-b) was added, and the mixture was stirred at 50 ° C. for 5 hours. To the obtained reaction mixture, 20 parts of chloroform was added and stirred. Ion-exchanged water 10 in the obtained mixture
The portion was added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. This operation was repeated 3 times. By concentrating the obtained organic layer, compound 0.3 represented by the formula (I-46) is obtained.
I got 9 copies.
MS (Mass Spectrometry): 592.3 (Molecular Ion Peak)

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

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

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

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

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

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

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

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

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

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

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

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged and charged at 23 ° C. for 30 minutes. Stirred. After adding 0.12 parts of copper (II) dibenzoate to the obtained mixed solution, the temperature was further increased to 100 ° C.
Was stirred for 30 minutes. The obtained reaction solution was concentrated. Chloroform 50 in the obtained residue
After adding parts and 12.50 parts of ion-exchanged water and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. 12.50 parts of ion-exchanged water was added to the recovered organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. This washing operation was repeated 8 times. The obtained organic layer was concentrated. To the obtained residue, 50 parts of tert-butylmethyl ether was added and stirred.
By filtration, 6.84 parts of a salt represented by the formula (B1-22) was obtained.

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

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

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

Example 7 [Synthesis of resin A1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-1), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof is [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -1): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 mol each based on the total amount of monomers.
% And 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The resulting reaction mixture,
A large amount of methanol / water mixed solvent was poured to precipitate the resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A1 (copolymer) having ^{a weight average molecular weight of 8.5 × 10 3 in a yield of 58%.} rice field. This resin A1 has the following structural units.

Example 8 [Synthesis of resin A2]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-2), the monomer (a2-1-1) and the monomer (a3-4-2) are used, and the molar ratio thereof [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -2): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 mol each based on the total amount of monomers.
% And 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The resulting reaction mixture,
A large amount of methanol / water mixed solvent was poured to precipitate the resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A2 (copolymer) having ^{a weight average molecular weight of 8.8 × 10 3 in a yield of 64%.} rice field. This resin A2 has the following structural units.

Example 9 [Synthesis of resin A3]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-7), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof is [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -7): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 mol each based on the total amount of monomers.
% And 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The resulting reaction mixture,
A large amount of methanol / water mixed solvent was poured to precipitate the resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A3 (copolymer) having ^{a weight average molecular weight of 8.2 × 10 3 in a yield of 60%.} rice field. This resin A3 has the following structural units.

Example 10 [Synthesis of resin A4]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-9), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof is [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -9): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 mol each based on the total amount of monomers.
% And 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The resulting reaction mixture,
A large amount of methanol / water mixed solvent was poured to precipitate the resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A4 (copolymer) having ^{a weight average molecular weight of 7.8 × 10 3 in a yield of 58%.} rice field. This resin A4 has the following structural units.

Example 11 [Synthesis of resin A5]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-29), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof is [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -29): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 m each based on the total amount of monomers.
ol% and 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A5 (copolymer) having ^{a weight average molecular weight of 8.6 × 10 3 in a yield of 61%.} rice field. This resin A5 has the following structural units.

Example 12 [Synthesis of Resin A6]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
I-46), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio thereof is [monomer (a1-1-3): monomer (a1-2-9): monomer (I). -46): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 m each based on the total amount of monomers.
ol% and 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a mixed methanol / water solvent to repulp, and the resin is filtered to obtain a resin A6 (copolymer) having ^{a weight average molecular weight of 8.0 × 10 3 in a yield of 57%.} rice field. This resin A6 has the following structural units.

Synthesis Example 4 [Synthesis of resin AX1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (
IX-1), monomer (a2-1-1) and monomer (a3-4-2) are used, and their molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (IX). -1): Monomer (a2-1-1): Monomer (a3-4-2)] is mixed so as to be 38: 14: 5: 3: 40, and propylene is 1.5 times by mass of the total amount of the monomer. Glycolmonomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 1 m each based on the total amount of monomers.
ol% and 3 mol% were added and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin AX1 (copolymer) having ^{a weight average molecular weight of 8.1 × 10 3 in a yield of 60%.} rice field.
This resin AX1 has the following structural units.

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

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

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２−ヘプタノン ２０部
γ−ブチロラクトン ３．５部 <Resin>
A1 to A6, AX1, X1: Resin A1 to Resin A6, Resin AX1, Resin X1
<Acid generator>
B1-5: Salt represented by the formula (B1-5) B1-21: Salt represented by the formula (B1-21) B1-22: Salt represented by the formula (B1-22) <Weak acid intramolecular salt (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>
A composition for an organic antireflection film [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to a thickness of 78 n.
An organic antireflection film of m was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (prebaking) was 100 nm. After coating, place this silicon wafer on a direct hot plate, "PB" in Table 1.
The composition layer was formed on the silicon wafer by prebaking at the temperature described in the column for 60 seconds.
ArF excimer laser stepper for immersion exposure [XT: 1900Gi; ASML, NA = 1.35, Anal σ _out =
0.85 σ _in = 0.65 XY-pol. Lighting], trench pattern (pitch 12)
Using a mask for forming (0 nm / trench width 40 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 obtained resist pattern, the exposure amount at which the width of the trench pattern was 40 nm was taken as the effective sensitivity.

<Focus Margin Evaluation (DOF)>
A negative resist pattern was manufactured by performing the same operation as above except that the focus was changed stepwise for exposure in terms of effective sensitivity. In the obtained resist pattern, the focus range in which the width of the trench pattern is 40 nm ± 5% (38 to 42 nm) is set to DOF (.
nm). The results are shown in Table 2.

The resist composition of the present invention has a focus margin (DOF) of the obtained resist pattern.
), It is suitable for microfabrication of semiconductors and is extremely useful in industry.

Claims (9)

A compound represented by the formula (IA).

[In formula (IA),
^R0 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* -A ^2- CO-O-A ^3- , ^* -A ^4- O-CO-A ^5- , ^* -A ^6- O-A ⁷ -or ^* -A ^8- O ^{-CO-O-a 9} - represents a. * Represents a bond with an oxygen atom.
A ² , A ⁴ , A ⁶ and A ⁸ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
A ³ , A ⁵ , A ⁷ and A ⁹ each independently represent a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ad represents an adamantandiyl group or an adamantane triyl group.
A ¹⁰ represents an alkanediyl group having 1 to 6 carbon atoms.
n represents 1 or 2. When n is 2, the two R1 ^-A may be the same or different.
Each of R1 ^-A independently represents a monovalent group represented by the formula (IAa). ]

[In the formula (IAa),
s3 and s4 represent an integer of 0 or 1. However, the sum of s3 and s4 is 1 or more.
R ⁴ represents an alkyl group having 1 to 12 carbon atoms.
u1 represents 0 or 1.
* Represents a bond. ] The compound according to claim 1, wherein A ¹ is a single bond or ^* -CH _2-CO-O-. The compound according to claim 1 or 2, wherein the cyclic ether structure of R ^{1-A is a monovalent group represented by the formula (IA).}

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

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent −O− or ^* −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents a bond with −CO−. Represent a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ] A resist composition containing the resin and acid generator according to any one of claims 4 to 6. The resist composition according to claim 7, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to claim 7 or 8 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.