JP2018043978A - Salt, acid generator, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a salt suitable for a resist composition capable of producing a resist pattern having good CD uniformity (CDU).SOLUTION: The salt is represented by formula (I) [where Rand Reach independently represent a C6-18 aromatic hydrocarbon group which may have a substituent; Rrepresents an acid-labile group; Xrepresents a C1-12 divalent aliphatic saturated hydrocarbon group, provided that a methylene group constituting the divalent aliphatic saturated hydrocarbon group may be substituted with an oxygen atom or a carbonyl group; and Arepresents an organic anion].SELECTED DRAWING: None

Description

  The present invention relates to a salt, an acid generator, a resist composition, and a method for producing a resist pattern.

Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator.

Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator.

JP 2010-44347 A JP2013-47209A

  An object of the present invention is to improve CD uniformity (CDU) of a resist pattern obtained using a resist composition.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有してもよい炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^３は、酸不安定基を有する基を表す。
Ｘ^１は、炭素数１〜１２の２価の脂肪族飽和炭化水素基を表し、該２価の脂肪族飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ａ⁻は、有機アニオンを表す。］
〔２〕 前記式（Ｉ）のＸ^１は、−Ｘ^１２−Ｏ−Ｘ^２２−＊（Ｘ^１２は炭素数１〜１０の２価の脂肪族炭化水素基を表し、該２価の脂肪族炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。Ｘ^２２は、炭素数１〜１０の２価の脂肪族炭化水素基を表す。ただし、Ｘ^１２及びＸ^２２の合計炭素数は１１である。＊はＲ^３との結合手を表す。）で表される基である〔１〕に記載の塩。
〔３〕 前記式（Ｉ）のＲ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよいフェニル基である〔１〕又は〔２〕に記載の塩。
〔４〕 前記式（Ｉ）のＲ^３は、酸と接触すると脱離基が脱離して、ヒドロキシ基又はカルボキシ基を形成する基である〔１〕〜〔３〕のいずれかに記載の塩。
〔５〕 前記式（Ｉ）のＲ^３は、式（１）で表される基である〔１〕〜〔４〕のいずれかに記載の塩。

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、置換基を有していてもよい炭素数１〜８のアルキル基、置換基を有していてもよい炭素数３〜２０の脂環式炭化水素基を表すか、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の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立に０又は１を表し、ｍａ及びｎａのうち少なくとも一方は１である。
＊は結合手を表す。］
〔６〕 前記式（１）のｍａは０であり、ｎａは１である〔５〕に記載の塩。
〔７〕 〔１〕〜〔６〕のいずれかに記載の塩を含有する酸発生剤。
〔８〕 酸発生剤と酸不安定基を有する構造単位を含む樹脂とを含有し、前記酸発生剤として〔１〕〜〔６〕のいずれかに記載の塩を含有するレジスト組成物。
〔９〕さらに、前記酸発生剤から発生する酸よりも酸性度の低い酸を発生する塩を含有する〔８〕に記載のレジスト組成物。
〔１０〕（１）〔８〕又は〔９〕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）組成物層を露光する工程、
（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 salt represented by the formula (I).

[In the formula (I),
R ¹ and R ² each independently represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
R ³ represents a group having an acid labile group.
X ¹ represents a C1-C12 divalent aliphatic saturated hydrocarbon group, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
A ⁻ represents an organic anion. ]
[2] X ^{1 in the} formula (I) represents —X ¹² —O—X ²² — * (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the divalent aliphatic group. methylene group constituting the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group .X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. However, X ¹² and X ²² total carbon number of 11. * salt according to a group represented by the representative.) a bond to R ³ (1).
[3] The salt according to [1] or [2], wherein R ¹ and R ^{2 in} the formula (I) are each independently a phenyl group which may have a substituent.
[4] The salt according to any one of [1] to [3], wherein R ^{3 in the} formula (I) is a group that forms a hydroxy group or a carboxy group by elimination of a leaving group upon contact with an acid. .
[5] The salt according to any one of [1] to [4], wherein R ³ in the formula (I) is a group represented by the formula (1).

[In Formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 3 to 20 carbon atoms which may have a substituent. R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represents 0 or 1, and at least one of ma and na is 1.
* Represents a bond. ]
[6] The salt according to [5], wherein ma in the formula (1) is 0 and na is 1.
[7] An acid generator containing the salt according to any one of [1] to [6].
[8] A resist composition containing an acid generator and a resin containing a structural unit having an acid labile group, and containing the salt according to any one of [1] to [6] as the acid generator.
[9] The resist composition according to [8], further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator.
[10] (1) A step of applying the resist composition according to [8] or [9] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

  If a resist composition containing the salt of the present invention as an acid generator is used, a resist pattern can be produced with good CD uniformity (CDU).

In the present specification, "(meth) acrylic monomer" means at least one monomer having a _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " structure of To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

  The resist composition of the present invention contains a resin (A) having an acid labile group and a salt represented by the formula (I) (hereinafter sometimes referred to as “salt (I)”). is there. In the resist composition, the salt (I) is included as an acid generator. The acid generator of the present invention contains a salt (I) and may contain an acid generator (B) other than the salt (I). The resist composition of the present invention comprises an acid generated from a resin (X) other than the resin (A), a solvent (E), a quencher (C), a salt (I) and an acid generator (B) as necessary. The salt which generate | occur | produces the acid of lower acidity than this, and the other component (F) are contained. Hereinafter, these will be described.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有してもよい炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^３は、酸不安定基を表す。
Ｘ^１は、炭素数１〜１２の２価の脂肪族飽和炭化水素基を表し、該２価の脂肪族飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ａ⁻は、有機アニオンを表す。］
式（Ｉ）において、脂肪族飽和炭化水素基に含まれる−ＣＨ_２−が−Ｏ−又は−Ｃ（＝Ｏ）−に置き換わっている場合、置き換わる前の炭素数を該脂肪族飽和炭化水素基の炭素数とする。 <Salt represented by formula (I)>
The salt of the present invention is a salt represented by the formula (I) (salt (I)).

[In the formula (I),
R ¹ and R ² each independently represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
R ³ represents an acid labile group.
X ¹ represents a C1-C12 divalent aliphatic saturated hydrocarbon group, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
A ⁻ represents an organic anion. ]
In the formula (I), when —CH ₂ — contained in the aliphatic saturated hydrocarbon group is replaced with —O— or —C (═O) —, the number of carbon atoms before the replacement is represented by the aliphatic saturated hydrocarbon group. The number of carbons.

これら置換基のうち、ヒドロキシ基、炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基であることが好ましく、ヒドロキシ基又は炭素数１〜１２のアルキル基であることがより好ましく、炭素数１〜１２のアルキル基であることがさらに好ましく、炭素数１〜６のアルキル基がさらにより好ましい。
Ｒ^１及びＲ^２で表される、置換基を有していてもよい炭素数６〜１８の芳香族炭化水素基は、フェニル基が好ましい。 <Cation Constructing Formula (I)>
Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹ and R ² include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and a fluorenyl group. , A naphthyl group and an anthryl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is more preferable.
Examples of the substituent that the aromatic hydrocarbon group having 6 to 18 carbon atoms of R ¹ and R ² may have include a hydroxy group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. An alkoxy group, a C3-C12 alicyclic hydrocarbon group, and the group which combined these are mentioned.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. .
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group Group, dodecyloxy group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the following groups. * Is a bond with a ring.

Among these substituents, a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms is preferable, and a hydroxy group or an alkyl group having 1 to 12 carbon atoms is more preferable, It is more preferable that it is a C1-C12 alkyl group, and a C1-C6 alkyl group is still more preferable.
The aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent represented by R ¹ and R ² is preferably a phenyl group.

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、置換基を有していてもよい炭素数１〜８のアルキル基、又は置換基を有していてもよい炭素数３〜２０の脂環式炭化水素基を表すか、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の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立に０又は１を表し、ｍａ及びｎａのうち少なくとも一方は１である。
＊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の複素環を形成し、該非芳香族炭化水素環及び該複素環に含まれるメチレン基は、酸素原子又は硫黄原子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。
ｎａ’は、０又は１を表す。
＊は結合手を表す。］ <Acid labile group>
R ³ represents an acid labile group. “Acid labile group” means a group that has a leaving group and forms a hydrophilic group (for example, a hydroxy group, a carboxy group, or an amino group) by leaving the leaving group upon contact with an acid. .
In the acid labile group represented by R ³ , the atom bonded to X ¹ is usually an oxygen atom or a carbon atom constituting a carbonyl group.
Examples of the acid labile group include a group represented by the formula (1) (hereinafter sometimes referred to as “acid labile group (1)”) and a group represented by the formula (2) (hereinafter, depending on the case). "Acid labile group (2)").

[In Formula (1), R ^<a1 > -R < ^a3 > is respectively independently the C1-C8 alkyl group which may have a substituent, or C3-C3 which may have a substituent. 20 represents an alicyclic hydrocarbon group, or R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represents 0 or 1, and at least one of ma and na is 1.
* Represents a bond. ]

[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and methylene contained in the non-aromatic hydrocarbon ring and the heterocycle The group may be replaced with an oxygen atom or a sulfur atom.
X represents an oxygen atom or a sulfur atom.
na ′ represents 0 or 1.
* Represents a bond. ]

^Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. It is done.
The alicyclic hydrocarbon group represented by R ^{a1 to} R ^a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). Carbon number of the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably 3 to 16.

As a substituent of the C1-C8 alkyl group which may have a substituent, a C3-C20 alicyclic hydrocarbon group is mentioned. As a substituent of a C3-C20 alicyclic hydrocarbon group which may have a substituent, a C1-C8 alkyl group is mentioned. More specifically, examples include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group.
Preferably, ma is 0 and na is 1.

In the case where R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring, -C (R ^a1 ) (R ^a2 ) (R ^a3 ) includes monocyclic non-aromatic hydrocarbon rings and Examples include cyclic non-aromatic hydrocarbon rings, and specific examples include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the group represented by the formula (1) include a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1) (preferably a tert-butoxycarbonyl group), and in the formula (1), R ^a1 and R ^a2 are Are bonded together to form an adamantane ring together with the carbon atoms to which they are bonded, and R ^a3 is an alkyl group, and in formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 Group in which is an adamantyl group.

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

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

Specific examples of the acid labile group (1) include the following groups. * Represents a bond.

Specific examples of the acid labile group (2) include the following groups. * Represents a bond.

The acid labile group represented by R ³ is preferably a group having an acid labile group (1), and R ^a1 and R ^a2 are bonded to each other to form a carbon atom having 3 to 3 carbon atoms together with the carbon atom to which they are bonded. More preferably, 20 non-aromatic hydrocarbon rings are formed, and R ^a1 and R ^a2 are bonded together to form a polycyclic non-aromatic hydrocarbon ring together with the carbon atoms to which they are bonded. More preferably, R ^a1 and R ^a2 are bonded to each other to form an adamantane ring together with the carbon atom to which they are bonded.

Examples of the divalent aliphatic saturated hydrocarbon group represented by X ¹ include alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and 2 of these groups. It may be a combination of more than one species.
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 Linear alkanediyl groups such as
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

The methylene group constituting the aliphatic saturated hydrocarbon group for X ¹ may be replaced with an oxygen atom or a carbonyl group. For example, an ether bond, an ester bond (—CO—O— or —O—CO—) and — It may be an aliphatic saturated hydrocarbon group replaced by O—CO—O or the like.
In the group represented by X ¹ , a methylene group is usually bonded to R ³ .
Specifically, X ¹ represents —X ¹² —O—X ²² — * (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the divalent aliphatic hydrocarbon group represents The constituting methylene group may be replaced by an oxygen atom or a carbonyl group, X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, provided that the total carbon number of X ¹² and X ²² Is 11. It is preferable that * represents a bond to R ³ .
The divalent aliphatic hydrocarbon group represented by X ¹² and X ²² is preferably an alkanediyl group, more preferably an alkanediyl group having 1 to 6 carbon atoms.

Specific examples of the organic cation constituting the salt (I) include organic cations represented by the following formulas (Ic-1) to (Ic-24).

  The cation (I) is preferably a cation represented by the formula (Ic-1) to the formula (Ic-20), represented by the formula (Ic-1) to the formula (Ic-14). The cation represented by the formula (Ic-1), the formula (Ic-2), and the formula (Ic-7) is more preferable.

［式（Ｉ−Ａ）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、該飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子はフッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。］
式（Ｉ−Ａ）において、飽和炭化水素基、脂環式炭化水素基に含まれる−ＣＨ_２−が−Ｏ−、−Ｃ（＝Ｏ）−又は−ＳＯ_２−に置き換わっている場合、置き換わる前の炭素数をそれぞれ該飽和炭化水素基、該脂環式炭化水素基の炭素数とする。 <Organic anion constituting salt (I)>
Examples of the organic anion (A ⁻ ) constituting the salt (I) include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. Among these, a sulfonate anion is preferable, and a sulfonate anion represented by the formula (IA) is more preferable.

[In the formula (IA),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—, The hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —SO ₂ — or —CO—. ]
In the formula (IA), when —CH ₂ — contained in a saturated hydrocarbon group or alicyclic hydrocarbon group is replaced by —O—, —C (═O) — or —SO ₂ —, the group is replaced. The previous carbon number is defined as the carbon number of the saturated hydrocarbon group and the alicyclic hydrocarbon group, respectively.

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoro group. A hexyl group etc. are mentioned.
Q ¹ and Q ² are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and among these groups, It may be a group formed by combining two 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-diyl group Alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

［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−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
ただし、Ｌ^ｂ２とＬ^ｂ３との合計炭素数は、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−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
ただし、Ｌ^ｂ４とＬ^ｂ５との合計炭素数は、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−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
ただし、Ｌ^ｂ６とＬ^ｂ７との合計炭素数は、２３以下である。］ Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-3) The group represented by these is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with -Y.

[In the formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
However, the total carbon number of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
However, the total carbon number of L ^b4 and L ^b5 is 22 or less.
In formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—.
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 —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—, the number of carbons before the replacement is changed to the saturated hydrocarbon. The number of carbons in the group.
Examples of the divalent saturated hydrocarbon group and the group in which —CH ₂ — and a hydrogen atom contained in the saturated hydrocarbon group may be substituted as described above include a divalent saturated hydrocarbon group represented by L ^b1. The same thing is mentioned.

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and more preferably an alkanediyl 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, more preferably carbon. It is an alkanediyl group of formulas 1-4.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.
As the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO—, a group represented by the formula (b1-1) or the formula (b1-2) In formula (b1-1), L ^b2 is a single bond, L ^b3 is an alkanediyl group having 1 to 4 carbon atoms, and in formula (b1-2), L ^b4 is 1 to 1 carbon atoms. 4 is an alkanediyl group and L ^b5 is more preferably a single bond.

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

[In the formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
^Lb9 represents a C1-C20 bivalent saturated hydrocarbon group.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a C1-C21 divalent saturated hydrocarbon group.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b13 to} L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a C1-C18 divalent saturated hydrocarbon group.
L ^b17 represents a C1- ^C18 divalent saturated hydrocarbon group.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]

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

［式（ｂ１−９）中、
Ｌ^ｂ１９は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ２０は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子はフッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニ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ルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニ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。
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ルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ２１〜Ｌ^ｂ２３の合計炭素数は２１以下である。
式（ｂ１−１１）中、
Ｌ^ｂ２４は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ２５は、炭素数１〜２１の２価の飽和炭化水素基を表し、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ルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニ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。
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ルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ２４〜Ｌ^ｂ２６の合計炭素数は２１以下である。］ Examples of the formula (b1-3) include groups represented by any of the formulas (b1-9) to (b1-11).

[In the formula (b1-9),
L ^b19 represents a single bond or a ^C1-C23 divalent saturated hydrocarbon group, 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 a hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. It may be. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a ^C1-C21 divalent saturated hydrocarbon group, 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, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. It may be. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
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 alkylcarbonyloxy group. May be. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^{b21 to} L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
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 alkylcarbonyloxy group. May be. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

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

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

Examples of the group represented by the formula (b1-4) include the following.

Examples of the group represented by the formula (b1-5) include the following.

Examples of the group represented by the formula (b1-6) include the following.

Examples of the group represented by the formula (b1-7) include the following.

Examples of the group represented by the formula (b1-8) include the following.

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

Examples of the group represented by the formula (b1-9) include the following.

Examples of the group represented by the formula (b1-10) include the following.

Examples of the group represented by the formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y in formula (IA) include groups represented by formula (Y1) to formula (Y11) and formula (Y36) to formula (Y38). Can be mentioned.
When —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO—, the number may be one, or two or more There may be multiple. Examples of such a group include groups represented by formula (Y12) to formula (Y35).

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

Examples of the substituent of the methyl group represented by Y in the formula (IA) include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, and an aromatic hydrocarbon having 6 to 18 carbon atoms. Group, glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms and monovalent alicyclic carbonization having 3 to 16 carbon atoms) Represents a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).
As a substituent of the monovalent alicyclic hydrocarbon group represented by Y in the formula (IA), a halogen atom, a hydroxy group, or an alkyl having 1 to 12 carbon atoms which may be substituted with a hydroxy group Group, alicyclic hydrocarbon group having 3 to 16 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, aralkyl group having 7 to 21 carbon atoms, 2 to 4 carbon atoms An acyl group, a glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent alicyclic ring having 3 to 16 carbon atoms) Represents a formula hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).

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

The following groups are mentioned as a C1-C18 alicyclic hydrocarbon group which may have the substituent represented by Y in Formula (IA).

In the formula (IA), when Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 24 carbon atoms, The divalent saturated hydrocarbon group —CH ₂ — is preferably replaced with —O— or —CO—.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and the alicyclic carbonization —CH ₂ — constituting the hydrogen group or adamantyl group may be replaced by —O—, —SO ₂ — or —CO—. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by the following.

  Examples of the sulfonate anion represented by the formula (IA) include anions represented by the formula (B1-A-1) to the formula (B1-A-54) [hereinafter referred to as “anion (B1 -A-1) "or the like. ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula It is represented by any one of (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-54). An anion is more preferable.

[In the formulas (B1-A-1) to (B1-A-54),
R ^{i2 to} R ⁱ⁷ represent an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. And more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.
L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and Q ² represent the same meaning as described above. ]

Examples of the sulfonate anion represented by the formula (IA) include anions represented by the formulas (B1a-1) to (B1a-30).

  Among them, the sulfonate anion is an anion represented by any one of formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-19), and (B1a-22). Is preferred.

  Specific examples of the salt represented by the formula (I) include salts obtained by arbitrarily combining the above cation and anion. Specific examples of the salt represented by the formula (I) are shown in Tables 1 to 14.

In each table, each symbol represents a symbol attached to the structure representing the above-described anion or cation. For example, the salt (I-1) is a salt composed of an anion represented by the formula (BIa-1) and a cation represented by the formula (Ic-1), and is a salt shown below.

  When using the salt (I) as the acid generator (I0) described later, the salt (I-1), the salt (I-2), the salt (I-3), the salt (I-16), the salt (I- 17), salt (I-18), salt (I-19), salt (I-22), salt (I-23), salt (I-24), salt (I-25), salt (I-38) ), Salt (I-39), salt (I-40), salt (I-41), salt (I-44), salt (I-45), salt (I-46), salt (I-47) , Salt (I-60), salt (I-61), salt (I-62), salt (I-63), salt (I-66), salt (I-133), salt (I-134), Salt (I-135), salt (I-148), salt (I-149), salt (I-150), salt (I-151) and salt (I-154) are preferably used.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
溶剤としては、アセトニトリルなどが挙げられる。
塩基触媒としては、トリエチルアミンなどが挙げられる。
反応は通常、温度１５〜９０℃の範囲で、０．５〜２４時間行われる。
式（Ｉ１−ａ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

<Method for Producing Salt Represented by Formula (I)>
In the formula (I), the salt (I) [salt (I) represented by the following formula (I1) (salt (I1))] when X ¹ and R ³ are the following groups is represented by the formula (I1- The compound represented by a) and the salt represented by the formula (I1-b) can be produced by reacting in a solvent in the presence of a base catalyst.
X1 represents —X ¹² —O—X ²² — * (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group is X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, provided that X ¹² and X ²² have 11 total carbon atoms. * Represents a bond to R ³ ).
R ³ represents a case where ma = 0 and na = 1 in the group represented by the formula (1) (* —CO—O—CR ^a1 R ^a2 R ^a3 (* represents a bond)).

[Wherein all symbols have the same meaning as described above. ]
Examples of the solvent include acetonitrile.
Examples of the base catalyst include triethylamine.
The reaction is usually carried out at a temperature in the range of 15 to 90 ° C. for 0.5 to 24 hours.
Examples of the compound represented by the formula (I1-a) include compounds represented by the following, and can be easily obtained from the market.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
触媒としては、安息香酸銅（ＩＩ）などが挙げられ、溶剤としては、モノクロロベンゼンなどが挙げられる。
反応は通常、温度２０〜１２０℃の範囲で、０．５〜２４時間行われる。 The salt represented by the formula (I1-b) is obtained by reacting the salt represented by the formula (I1-c) with the compound represented by the formula (I1-d) in a solvent in the presence of a catalyst. Can be manufactured.

[Wherein all symbols have the same meaning as described above. ]
Examples of the catalyst include copper (II) benzoate, and examples of the solvent include monochlorobenzene.
The reaction is usually carried out at a temperature in the range of 20 to 120 ° C. for 0.5 to 24 hours.

Examples of the salt represented by the formula (I1-c) include salts represented by the following, and can be easily obtained from the market.

Examples of the compound represented by the formula (I1-d) include compounds represented by the following, and are easily available from the market.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
溶剤としては、アセトニトリル、クロロホルムなどが挙げられる。
反応は通常、温度１５〜８０℃の範囲で、０．５〜２４時間行われる。
式（Ｉ２−ａ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

式（Ｉ２−ｂ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

In the formula (I), R ³ is a group represented by the formula (1) (* —CO—O—CR ^a1 R ^a2 R ^a3 (* represents a bond)), and ma = 0, na = 1 salt [I (salt (I) represented by the following formula (I2) (salt (I2))] is a solvent of the salt represented by (I2-b) and carbonyldiimidazole It can be manufactured by reacting with a compound represented by the formula (I2-a) after reacting in the reaction.

[Wherein all symbols have the same meaning as described above. ]
Examples of the solvent include acetonitrile and chloroform.
The reaction is usually carried out at a temperature in the range of 15 to 80 ° C. for 0.5 to 24 hours.
Examples of the compound represented by the formula (I2-a) include compounds represented by the following, and can be easily obtained from the market.

Examples of the compound represented by the formula (I2-b) include compounds represented by the following, and can be easily obtained from the market.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
溶剤としては、アセトニトリルなどが挙げられる。
塩基触媒としては、水酸化カリウムなどが挙げられる。
反応は通常、温度５〜８０℃の範囲で、０．５〜２４時間行われる。 In the formula (I), R ³ is a group represented by the formula (1) (* —O—CR ^a1 R ^a2 R ^a3 (* represents a bond)), and ma = 1 and na = 0. The salt (I) [salt (I) (salt (I3)) represented by the following formula (I3)] is a compound represented by the formula (I2-a) and the formula (I1-b) Can be produced by reacting in a solvent in the presence of a base catalyst.

[Wherein all symbols have the same meaning as described above. ]
Examples of the solvent include acetonitrile.
Examples of the base catalyst include potassium hydroxide.
The reaction is usually carried out at a temperature in the range of 5 to 80 ° C. for 0.5 to 24 hours.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
溶剤としては、アセトニトリルなどが挙げられる。
塩基触媒としては、トリエチルアミン、ジメチルアミノピリジンなどが挙げられる。
反応は通常、温度５〜８０℃の範囲で、０．５〜２４時間行われる。
式（Ｉ４−ａ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

In the formula (I), R ³ is a group represented by the formula (1) (* —O—CO—O—CR ^a1 R ^a2 R ^a3 (* represents a bond)), and ma = 1. , Na = 1 (salt (I) represented by the following formula (I4) (salt (I4))) is a compound represented by the formula (I4-a): It can manufacture by making the salt represented by I1-b) react in a solvent in presence of a base catalyst.

[Wherein all symbols have the same meaning as described above. ]
Examples of the solvent include acetonitrile.
Examples of the base catalyst include triethylamine and dimethylaminopyridine.
The reaction is usually carried out at a temperature in the range of 5 to 80 ° C. for 0.5 to 24 hours.
Examples of the compound represented by the formula (I4-a) include compounds represented by the following, and can be easily obtained from the market.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。］
溶剤としては、アセトニトリルなどが挙げられる。
塩基触媒としては、トリエチルアミン、ジメチルアミノピリジンなどが挙げられる。
反応は通常、温度５〜８０℃の範囲で、０．５〜２４時間行われる。
式（Ｉ５−ａ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

In the formula (I), R ³ is a group represented by the formula (2) (* —CO—O—CR ^{a1 ′} R ^{a2 ′} —X—R ^{a3 ′} (* represents a bond)), and , Na ′ = 1, the salt (I) represented by the following formula (I5) (salt (I5)) is a compound represented by the formula (I5-a): It can manufacture by making the salt represented by (I2-b) react in a solvent in presence of a base catalyst.

[Wherein all symbols have the same meaning as described above. ]
Examples of the solvent include acetonitrile.
Examples of the base catalyst include triethylamine and dimethylaminopyridine.
The reaction is usually carried out at a temperature in the range of 5 to 80 ° C. for 0.5 to 24 hours.
Examples of the compound represented by the formula (I5-a) include compounds represented by the following, and can be easily obtained from the market.

［式中、全ての符号は、それぞれ上記と同じ意味を表す。Ｒ^a２´´は、Ｒ^ａ２´から水素原子を除いた基である。］
溶剤としては、アセトニトリルなどが挙げられる。
酸触媒としては、ｐ−トルエンスルホン酸などが挙げられる。
反応は通常、温度５〜８０℃の範囲で、０．５〜２４時間行われる。
式（Ｉ６−ａ）で表される化合物は、以下で表される化合物等が挙げられ、市場より容易に入手できる。

In the formula (I), R ³ is a group represented by the formula (2) (* —O—CR ^{a1 ′} R ^{a2 ′} —X—R ^{a3 ′} (* represents a bond)), and na In the case where '= 0, the salt (I) [salt (I) represented by the following formula (I6) (salt (I6))] is a compound represented by the formula (I6-a) and the formula (I1 The salt represented by -b) can be produced by reacting in a solvent in the presence of an acid catalyst.

[Wherein all symbols have the same meaning as described above. R ^{a2 ″} is a group obtained by removing a hydrogen atom from R ^{a2 ′} . ]
Examples of the solvent include acetonitrile.
Examples of the acid catalyst include p-toluenesulfonic acid.
The reaction is usually carried out at a temperature in the range of 5 to 80 ° C. for 0.5 to 24 hours.
Examples of the compound represented by the formula (I6-a) include compounds represented by the following, and can be easily obtained from the market.

<Resist composition>
The resist composition of the present invention contains an acid generator and a resin having an acid labile group (hereinafter sometimes referred to as “resin (A)”). The resist composition contains salt (I) as an acid generator. Here, the “acid labile group” has a leaving group, the leaving group is eliminated by contact with an acid, and the structural unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). This means a group that converts to a unit.
The resist composition of the present invention preferably contains a quencher such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator (hereinafter sometimes referred to as “quencher (C)”). And a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Acid generator>
The acid generator of the present invention contains a salt (I). The acid generator of this invention contains 1 type (s) or 2 or more types among salt (I), and it is preferable to contain 2 types. Hereinafter, the salt (I) as the acid generator may be particularly referred to as “acid generator (I0)”.
The acid generator of the present invention may contain other acid generators known in the resist field other than the acid generator (I0) (hereinafter sometimes referred to as “acid generator (B)”). .
When the acid generator (I0) and the acid generator (B) are contained as the acid generator, the content of the acid generator (I0) and the acid generator (B) is expressed by mass ratio, and the acid generator (I0 ): The acid generator (B) is usually 1:99 to 99: 1, preferably 2:98 to 98: 2, more preferably 5:95 to 95: 5, still more preferably 25:75. ~ 75: 25.
In the resist composition, the content of the acid generator (I0) is preferably 1.5 to 40 parts by weight, more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the resin (A).

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

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. And the acid generators described in JP2013-68914A, JP2013-3155A, JP2013-11905A, and the like. Moreover, you may use the compound manufactured by the well-known method.

［式（Ｂ１）中、
Ｑ^１１及びＱ^１２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^Ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子はフッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙ^Ｂ１は、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ Examples of the acid generator (B) include organic sulfonates, preferably fluorine-containing acid generators, more preferably an acid generator represented by the formula (B1) (hereinafter referred to as “acid generator ( B1) ”may be mentioned).

[In the formula (B1),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^B1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—, The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y ^B1 represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group. —CH ₂ — may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group for Q ¹¹ and Q ¹² include the same groups as those described for the perfluoroalkyl group represented by Q ¹ and Q ² .
Q ¹¹ and Q ¹² are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom. More preferably, Q ¹¹ and Q ¹² are both fluorine atoms.

Examples of the divalent saturated hydrocarbon group represented by L ^B1 include the same divalent saturated hydrocarbon groups represented by L ^b1 .
The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^B1 is replaced by —O— or —CO— is contained in the divalent saturated hydrocarbon group represented by L ^b1. And the same groups as those in which —CH ₂ — is replaced by —O— or —CO—. Specific examples include groups represented by the above-described formulas (b1-1) to (b1-3). In addition, when L ^B1 is a group represented by Formula (b1-1) to Formula (b1-3), * in the group represented by Formula (b1-1) to Formula (b1-3) is Y ^B1 Represents a bond with
L ^B1 is preferably any one of groups represented by formula (b1-1) to formula (b1-3), * 2-CO—O— (CH ₂ ) _t1 —, * 2- (CH _{2) t2 -O-CO- (.} t1 is .t2 representing an integer of 0 to 6 represents an integer of any of 1 to 6 * ^{2, -C (Q 11) (Q} 12) - It is more preferable that the bond is

The monovalent alicyclic hydrocarbon group represented by Y ^B1 may be monocyclic, polycyclic, or spirocyclic. Specific examples include monovalent alicyclic hydrocarbon groups represented by Y ^B1 (groups represented by the above formula (Y1) to formula (Y38), etc.). Of the groups represented by Y ^B1 , preferred groups are the same as the preferred range of the group represented by Y.

  Examples of the anion of the salt represented by formula (B1) include formula (B1-A-1) to formula (B1-A-55). Anions represented by formula (B1-A-1) to formula (B1-A-55) [hereinafter referred to as “anions (B1-A-1)” depending on the formula number, etc.). ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), Formula (B1-A-47) to Formula (B1-A-55) An anion is more preferable.

Here, R ^{i2 to} R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. It is a group to be formed, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹¹ and Q ¹² are the same as described above.

Examples of the anion in the salt represented by the formula (B1) include anions represented by the formulas (Ia-1) to (Ia-34), respectively.

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-34) are preferable.

The cation Z ⁺ in the acid generator (B1) is preferably an organic onium cation. Examples of the organic onium cation include an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, preferably an organic sulfonium cation or an organic iodonium cation, and more preferably an arylsulfonium cation. It is.
Among these, a cation represented by any one of the formulas (b2-1) to (b2-4) (hereinafter may be referred to as “cation (b2-1)” or the like depending on the formula number) is preferable.

[In Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group which may be substituted is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may together form a ring containing a sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O— or —S (═O) —. Alternatively, -C (= O)-may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different from each other. When n2 is 2 or more, the plurality of R ^b8 may be the same or different from each other.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may together form a ring containing a sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O—, —S (═O) —. Alternatively, -C (= O)-may be substituted.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the aliphatic hydrocarbon. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may together form a ring containing —CH—C (═O) — to which they are bonded, and —CH ₂ — contained in the ring is —O— , -S (= O)-or -C (= O)-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different from each other. When p2 is 2 or more, the plurality of R ^b14 may be the same or different from each other, and q2 is When two or more, the plurality of R ^b15 may be the same or different from each other. When r2 is two or more, the plurality of R ^b16 may be the same or different from each other, and s2 is two or more. In this case, the plurality of R ^b17 may be the same or different from each other, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different from each other. ]

特に、Ｒ^b9〜Ｒ^b12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。 An aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl alkyl groups. Can be mentioned.
In particular, the chain hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. Examples thereof include cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

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

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

As aromatic hydrocarbon group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group , Aryl groups such as a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
In addition, when the aromatic hydrocarbon group includes a chain hydrocarbon group or an alicyclic hydrocarbon group, the chain hydrocarbon group having 1 to 18 carbon atoms and the alicyclic hydrocarbon having 3 to 18 carbon atoms. Groups are preferred.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the alkylcarbonyl 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.
As the alkylcarbonyloxy group, methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group Hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

The ring formed by combining R ^b4 and R ^b5 together with the sulfur atom to which they are bonded is monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may be Examples of the ring include a ring having 3 to 18 carbon atoms, and a ring having 4 to 18 carbon atoms is preferable. Moreover, the ring containing a sulfur atom includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include the following rings.

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

  Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable.

Examples of the cation (b2-1) include the following cations.

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

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

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

  Among them, formulas (b2-c-1), (b2-c-10), (b2-c-12), (b2-c-14), (b2-c-27), (b2-c-30) And a cation represented by (b2-c-31) is preferable.

  Examples of the acid generator (B) include organic sulfonic acids, organic sulfonium salts, and the like. For example, acid generation described in JP2013-68914A, JP2013-3155A, and JP2013-11905A Agents and the like. Specific examples include those represented by any one of formulas (B1-1) to (B1-48). Among them, those containing an arylsulfonium cation are preferable. Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14) ), Formula (B1-17), Formula (B1-20) to Formula (B1-26), Formula (B1-29), Formula (B1-31) to Formula (B1-48). A salt is more preferred.

<Structural unit of resin (A)>
The resin (A) has a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) preferably further contains a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”), other structural unit (hereinafter referred to as “structural unit (t)”). In some cases).

<Structural unit (a1) having acid labile group>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”). Here, the “acid labile group” means a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. To do.
<Acid labile group>
In the resin (A), examples of the acid labile group contained in the structural unit (a1) include a group represented by the above formula (1) and a group represented by the formula (2).

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

  Among the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. If the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

<Specific example of structural unit (a1)>
The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter referred to as the structural unit (a1-0)). The structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, And may be referred to as a structural unit (a1-2).). These may be used alone or in combination of two or more.

［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のいずれかの整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。］

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

L ^a01 is preferably an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, and more preferably an oxygen atom. k01 is preferably an integer of 1 to 4, and more preferably 1.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and the group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group for R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

［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のいずれかの整数を表し、＊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のいずれかの整数を表す。
ｎ１は、０〜１０のいずれかの整数を表す。
ｎ１’は、０〜３のいずれかの整数を表す。］

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

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _{k1 ′} —CO—O—, more preferably —O—. k1 ′ is an integer of 1 to 4, and is preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
^Examples of the alkyl group for R ^a6 and R ^a7 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, Examples include n-heptyl group, 2-ethylhexyl group, n-octyl group and the like.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Cycloalkyl groups such as cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkyl group, norbornyl group, methylnor A bornyl group, an isobornyl group, etc. are mentioned.
Examples of the group formed by combining the alkyl group of R ^a6 and R ^a7 and the alicyclic hydrocarbon group include an aralkyl group, and examples thereof include a benzyl group and a phenethyl group.
The number of carbon atoms of the alkyl group represented by R ^a6 and R ^a7 is preferably 6 or less.
Carbon number of the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 3-8, more preferably 3-6.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

In the above formulas (a1-0-1) to (a1-0-12), a structural unit in which a methyl group corresponding to R ^a01 is replaced with a hydrogen atom is also given as a specific example of the structural unit (a1-0). Can do.

Examples of the structural unit (a1-1) include structural units derived from monomers described in JP2010-204646A. Preferably, it is a structural unit represented by any one of formula (a1-1-1) to formula (a1-1-8).

The structural unit (a1-2) is preferably a monomer represented by any one of the formulas (a1-2-1) to (a1-2-12), more preferably the formula (a1-2-3). ), A formula (a1-2-4), a formula (a1-2-9) or a formula (a1-2-10).

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

［式（ａ１−５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４のいずれかの整数を表し、＊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のいずれかの整数を表す。
ｓ１’は、０〜３のいずれかの整数を表す。］ As the structural unit (a1) having an acid labile group, a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”) can also be used.

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

In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ⁵¹ is preferably —O—.
One of L ⁵² and L ⁵³ is preferably —O— and the other is —S—.
As s1, 1 is preferable.
As s1 ', the integer in any one of 0-2 is preferable.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

Examples of the monomer for deriving the structural unit (a1-5) include monomers described in JP 2010-61117 A. Among these, a structural unit represented by any one of formulas (a1-5-1) to (a1-5-4) is preferable, and is represented by formula (a1-5-1) or formula (a1-5-2). More preferred is a structural unit.

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

Furthermore, examples of the structural unit (a1) include the following structural units.

  When resin (A) contains the said structural unit, the content rate is 10-95 mol% with respect to all the structural units of resin (A), 15-90 mol% is more preferable, 20-85 mol % Is more preferable.

  The structural unit (a1) having an acid labile group in the resin (A) includes the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), and the structural unit (a1-5). ) Is preferably at least one selected from the group consisting of, and more preferably at least two, a combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-1) and structural unit ( a1-5), a structural unit (a1-1) and a structural unit (a1-0), a structural unit (a1-2) and a structural unit (a1-0), and a structural unit (a1-5) And a combination of the structural unit (a1-0), a structural unit (a1-0), a combination of the structural unit (a1-1) and the structural unit (a1-2), a structural unit (a1-0), and a structural unit (a1- 1) and structural unit (a1-5 More preferably a combination of a combination of structural units (a1-1) and the structural unit (a1-2), the combination of the structural units (a1-1) and the structural unit (a1-5) is particularly preferred.

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

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

  Examples of the structural unit (a2) having a phenolic hydroxy group include structural units derived from monomers described in JP2010-204634A.

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

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

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

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

アルコール性ヒドロキシ基を有する構造単位（ａ２）を誘導するモノマーとしては、例えば、特開２０１０−２０４６４６号公報に記載されたモノマーが挙げられる。 Examples of the structural unit (a2-1) include those described in JP 2010-204646 A and are represented by any one of the formulas (a2-1-1) to (a2-1-6). The structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and the structural unit represented by formula (a2-1-1) or formula (a2-1) The structural unit represented by -3) is more preferable.

Examples of the monomer for deriving the structural unit (a2) having an alcoholic hydroxy group include monomers described in JP2010-204646A.

  When the resin (A) contains a structural unit (a2) having an alcoholic hydroxy group, the content is usually 1 to 45 mol%, preferably 1 to 45 mol% with respect to all the structural units of the resin (A). It is 40 mol%, More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

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

［式（ａ３−１）中、
Ｌ^ａ４は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７のいずれかの整数を表す。）で表される基を表す。＊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のいずれかの整数を表す。ｐ１が２以上のとき、複数のＲ^ａ２１は互いに同一であっても異なってもよい。
式（ａ３−２）中、
Ｌ^ａ５は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７のいずれかの整数を表す。）で表される基を表す。＊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のいずれかの整数を表す。ｑ１が２以上のとき、複数のＲ^ａ２２は互いに同一であっても異なってもよい。
式（ａ３−３）中、
Ｌ^ａ６は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７のいずれかの整数を表す。）で表される基を表す。＊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のいずれかの整数を表す。ｒ１が２以上のとき、複数のＲ^ａ２３は互いに同一であっても異なってもよい。
式（ａ３−４）中、
Ｒ^ａ２４は、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｌ^ａ７は、＊−Ｏ−、＊−Ｏ−Ｌ^ａ８−Ｏ−、＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−、＊−Ｏ−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は＊−Ｏ−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
＊はカルボニル基との結合手を表す。
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。
ｗは、０〜８のいずれかの整数を表す。
Ｌ^ａ８及びＬ^ａ９は、互いに独立に、炭素数１〜６のアルカンジイル基を表す。］ The structural unit (a3) is preferably a structural unit represented by any one of the formulas (a3-1) to (a3-4). Resin (A) may contain these 1 type individually, and may contain 2 or more types.

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

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. An alkyl group is mentioned.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group for ^Ra24 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. , Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of Ra ²⁴ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

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

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are independently of each other preferably —O— or k 3 is an integer of 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 —O—.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are independently of each other preferably a carboxy group, a cyano group or a methyl group.
p1, q1, r1 and w are each independently an integer of preferably 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 still more preferably a hydrogen atom or a methyl group. It is.
L ^a7 is preferably * —O— or * —O—L ^a8 —CO—O—, more preferably * —O—, * —O—, * —O—CH ₂ —CO—O— or * —O—C ₂ H ₄ —CO—O—.
Formula (a3-4 ′) is particularly preferably formula (a3-4 ′).

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

  Examples of the monomer for deriving the structural unit (a3) include monomers described in JP2010-204646, monomers described in JP2000-122294, and monomers described in JP2012-41274. Is mentioned. As the structural unit (a3), formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4), formula (a3-3) 1) to a structural unit represented by any one of the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12), the formula (a3-1-1), It is represented by any one of formula (a3-1-2), formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-12) The structural unit represented by any one of formulas (a3-4-1) to (a3-4-12) is more preferred, and the structural unit represented by formula (a3-4-1) to formula (a3- The structural unit represented by any one of 4-6) is even more preferable.

The structural unit (a3) may contain one kind alone or two or more kinds. Examples of the structural unit (a3) include the following structural units.

In the structural units represented by the above formulas (a3-4-1) to (a3-4-12), a compound in which a methyl group corresponding to R ^a24 is replaced with a hydrogen atom is also represented by the structural unit (a3-4). It can mention as a specific example.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Each content rate of the structural unit represented by Formula (a3-1), Formula (a3-2), Formula (a3-3), and Formula (a3-4) is based on all structural units of the resin (A). Usually, it is 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 50 mol%.

<Other structural units (t)>
The resin (A) may further contain other structural unit (t). The structural unit (t) is a structural unit other than the structural unit (a2) and the structural unit (a3) and has a halogen atom (hereinafter, sometimes referred to as “structural unit (a4)”) and non-structural unit. And a structural unit having a leaving hydrocarbon group (hereinafter sometimes referred to as “structural unit (a5)”).

［式（ａ４−０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^５は、単結合又は炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数５〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
The halogen atom in the structural unit (a4) is preferably a fluorine atom. As the structural unit (a4), a structural unit represented by formula (a4-0) can be given.

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

Examples of the aliphatic saturated hydrocarbon group for L ⁵ include an alkanediyl group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Having a side chain of an alkyl group (especially methyl group, ethyl group, etc.), ethane-1,1-diyl group, propane-1,2 -Branched alkanediyl groups such as diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

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

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

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

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

［式（ａ４−１）中、
Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ａ^a41は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１）で表される基を表す。ただし、Ａ^ａ４１及びＲ^ａ４２のうち少なくとも１つは、置換基としてハロゲン原子（好ましくはフッ素原子）を有する。

［式（ａ−ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の２価の脂肪族炭化水素基を表す。
Ａ^a43は、置換基を有していてもよい炭素数１〜５の２価の脂肪族炭化水素基又は単結合を表す。
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６以下である。
＊、＊＊は結合手であり、＊が−Ｏ−ＣＯ−Ｒ^ａ４２との結合手である。〕
ただし、Ａ^a41及びＲ^a42のうち少なくとも一方は、置換基としてハロゲン原子を有する基である。］
ｓは０が好ましい。 As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. Good.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a ^C 1-5 divalent aliphatic hydrocarbon group which may have a substituent.
A ^a43 represents a ^C 1-5 divalent aliphatic hydrocarbon group which may have a substituent or a single bond.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 6 or less.
* And ** are bonds, and * is a bond with —O—CO—R ^a42 . ]
However, at least one of A ^a41 and R ^a42 is a group having a halogen atom as a substituent. ]
s is preferably 0.

芳香族炭化水素基としては、例えば、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等が挙げられる。 ^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, pentadecyl, hexyldecyl And alkyl groups such as a heptadecyl group and an octadecyl group. Examples of the cyclic alicyclic hydrocarbon group include 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 (* Represents a bond.) And a polycyclic alicyclic hydrocarbon group.

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.

The hydrocarbon group for R ^a42 is preferably a chain or cyclic aliphatic hydrocarbon group or a group formed by combining these. These groups may have a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups and groups formed by combining them are more preferable.

［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Ｒ^a42の炭化水素基との結合手を表す。］ ^Examples of the substituent for R ^a42 include a halogen atom and a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom is mentioned.

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.
* Represents a bond with a hydrocarbon group of R ^a42 . ]

^As the aliphatic hydrocarbon group for A ^a45, the same groups as the aliphatic hydrocarbon groups exemplified for R ^a42 can be mentioned.
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). preferable.

When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.

When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the carbon number contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

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

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

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

Examples of the group represented by the formula (a-g2) include the following groups.

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

^Examples of the aliphatic hydrocarbon group represented by A ^a42 , A ^a43, and A ^{a44 in} the group represented by the formula (a-g1) (hereinafter sometimes referred to as “group (a-g1)”) include a methylene group and an ethylene group. Propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl Group, 2-methylpropane-1,2-diyl group and the like. Examples of these substituents include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

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

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

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

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

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

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

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

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

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Specifically, 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, 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, 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- (perfluoro (Ropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5- Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

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

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

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

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

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

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

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

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

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

Examples of the structural unit (a4) include the following structural units and structural units in which a methyl group bonded to the main chain is replaced with a hydrogen atom.

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

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基で置換されていてもよい。但し、Ｌ⁵⁵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。
Ｌ⁵⁵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-elimination hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group, and preferably an alicyclic hydrocarbon group. As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

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

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

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. .
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

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

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

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

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

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

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

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

^L55 is preferably a single bond, a methylene group, an ethylene group or a group represented by the formula (L1-1), more preferably a single bond or a group represented by the formula (L1-1). .

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

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

  The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well known in the art.

<Resin (A)>
The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s).
The structural unit (a1) is preferably at least one selected from the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably the structural unit ( a1-1) or the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably a structural unit represented by formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4). And at least one selected from structural units represented by formula (a3-4-1) to formula (a3-4-2).

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

<Resin (X) other than Resin (A)>
The resist composition of the present invention may contain a resin (X) that does not contain the structural unit (a1) having an acid labile group other than the resin (A). Examples of such a resin (X) include a resin containing a structural unit (t).

The resin (X) is preferably a resin containing the structural unit (a4) exemplified as the structural unit (t). In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more with respect to all the structural units of the resin (X). .
Examples of the structural unit that the resin (X) may further include include a structural unit (a2) that does not have an acid labile group, a structural unit (a3), and a structural unit derived from other known monomers. .
The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Preferably it is 1-40 mass parts, More preferably, it is 1-20 mass parts, Most preferably, it is 1.5-10 mass parts.

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

<Solvent (E)>
In the resist composition, 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 it is 99 mass% or less. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

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

<Quencher (C)>
Examples of the quencher (C) include a salt that generates an acid having a lower acidity than an acid generated from a basic nitrogen-containing organic compound or an acid generator. The content of the quencher (C) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.

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

  Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, Rudicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl Didecylamine, 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- Tyrimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2- Di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4 , 4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc., preferably diisopropylaniline, more preferably 2,6-diisopropylaniline. .

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

<Salt that generates acid with lower acidity than acid generated from acid generator>
The salt that generates an acid having a weaker acidity than the acid generated from the acid generator means that when the salt contains only the salt (I) as the acid generator, the salt has a higher acidity than the acid generated from the salt (I). A salt that generates a weak acid means salt (I) and an acid generator (B) when it contains salt (I) and an acid generator (B) that is an acid generator other than this. ) Means a salt that generates an acid having a lower acidity than the acid generated from.
The acidity in a salt that generates an acid having a lower acidity than the acid generated from the acid generator is represented by an acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. And more preferably 0 <pKa <5.
Examples of the salt that generates an acid having a lower acidity than the acid generated from the acid generator include salts represented by the following formulas, JP2012-229206A, JP2012-6908A, and JP2012. 72109, JP-A-2011-39502, and JP-A-2011-191745.

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

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A) and a salt (I) of the present invention, and, if necessary, a resin (X), an acid generator (B), a solvent (E), a quencher (C), And other components (F) can be mixed. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

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

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

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

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

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

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

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

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

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

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μL
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

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

式（Ｉ−２−ａ）で表される塩２．９８部、式（Ｉ−２−ｂ）で表される化合物０．６３部及びモノクロロベンゼン２４部を反応器に仕込み、２３℃で３０分間攪拌した。その後、式（Ｉ−２−ｃ）で表される安息香酸銅０．０３部を添加し、１００℃程度まで昇温した後、同温度で１時間攪拌した。得られた反応物を濃縮した後、得られた濃縮物に、クロロホルム４５部及びイオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作を５回繰り返した。回収された有機層をろ過した後、得られたろ液を濃縮した。得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−２―ｄ）で表される塩１．５９部を得た。

式（Ｉ−２−ｄ）で表される塩０．６３部、式（Ｉ−２−ｅ）で表される化合物０．２６部及びアセトニトリル１５部を混合し、２３℃で３０分間攪拌した。得られた混合物に、トリエチルアミン０．１２部を仕込み、７５℃で３時間攪拌した。得られた混合物を、２３℃まで冷却し、クロロホルム３０部及びイオン交換水２０部を加え、２３℃で３０分間攪拌した。得られた混合物を静置し、分液して有機層を得た。この水洗操作をさらに５回繰り返した。回収された有機層に活性炭０．５部を加えて攪拌し、ろ過した。得られたろ液を濃縮し、酢酸エチル１０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル１０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−２）で表される塩０．３３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５０７．３
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３３９．１ [Example 1] Synthesis of salt represented by formula (I-2)

2.98 parts of a salt represented by the formula (I-2-a), 0.63 part of a compound represented by the formula (I-2-b) and 24 parts of monochlorobenzene were charged into a reactor, and the mixture was charged at 23 ° C. for 30 parts. Stir for minutes. Thereafter, 0.03 part of copper benzoate represented by the formula (I-2-c) was added, the temperature was raised to about 100 ° C., and the mixture was stirred at the same temperature for 1 hour. After concentrating the obtained reaction product, 45 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was repeated 5 times. After the collected organic layer was filtered, the obtained filtrate was concentrated. 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.59 parts of the salt represented by the formula (I-2-d).

0.63 part of the salt represented by the formula (I-2-d), 0.26 part of the compound represented by the formula (I-2-e) and 15 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. . To the obtained mixture, 0.12 part of triethylamine was added and stirred at 75 ° C. for 3 hours. The obtained mixture was cooled to 23 ° C., 30 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was left still and separated to obtain an organic layer. This washing operation was further repeated 5 times. To the collected organic layer, 0.5 part of activated carbon was added, stirred and filtered. The obtained filtrate was concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 0.33 parts of the salt represented by the formula (I-2).
MASS (ESI (+) Spectrum): M ⁺ 507.3
MASS (ESI (−) Spectrum): M ^- 339.1

式（Ｉ−３−ａ）で表される塩２．９１部、式（Ｉ−２−ｂ）で表される化合物０．６３部及びモノクロロベンゼン２４部を反応器に仕込み、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−２−ｃ）で表される安息香酸銅０．０３部を添加し、１００℃程度まで昇温した後、同温度で１時間攪拌した。得られた反応物を濃縮した。得られた濃縮物に、クロロホルム４５部及びイオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作を５回繰り返した。回収された有機層をろ過した後、得られたろ液を濃縮した。得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−３―ｄ）で表される塩１．７２部を得た。

式（Ｉ−３−ｄ）で表される塩０．６１部、式（Ｉ−２−ｅ）で表される化合物０．２６部及びアセトニトリル１５部を混合し、２３℃で３０分間攪拌した。得られた混合物に、トリエチルアミン０．１２部を仕込み、７５℃で３時間攪拌した。得られた混合物を、２３℃まで冷却し、クロロホルム３０部及びイオン交換水２０部を加え、２３℃で３０分間攪拌した。得られた混合物を静置し、分液して有機層を得た。この水洗操作をさらに５回繰り返した。回収された有機層に活性炭０．５部を加えて攪拌し、ろ過した。得られたろ液を濃縮し、酢酸エチル１０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル１０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−３）で表される塩０．４２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５０７．３
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３２３．０ [Example 2] Synthesis of salt represented by formula (I-3)

2.91 parts of a salt represented by the formula (I-3-a), 0.63 part of a compound represented by the formula (I-2-b) and 24 parts of monochlorobenzene were charged into a reactor, and the mixture was stirred at 23 ° C. for 30 parts. Stir for minutes. To the obtained mixture, 0.03 part of copper benzoate represented by the formula (I-2-c) was added, and the temperature was raised to about 100 ° C., followed by stirring at the same temperature for 1 hour. The resulting reaction was concentrated. To the obtained concentrate, 45 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was repeated 5 times. After the collected organic layer was filtered, the obtained filtrate was concentrated. 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.72 parts of the salt represented by the formula (I-3-d).

0.61 part of a salt represented by the formula (I-3-d), 0.26 part of a compound represented by the formula (I-2-e) and 15 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. . To the obtained mixture, 0.12 part of triethylamine was added and stirred at 75 ° C. for 3 hours. The obtained mixture was cooled to 23 ° C., 30 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was left still and separated to obtain an organic layer. This washing operation was further repeated 5 times. To the collected organic layer, 0.5 part of activated carbon was added, stirred and filtered. The obtained filtrate was concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 0.42 parts of the salt represented by the formula (I-3).
MASS (ESI (+) Spectrum): M ⁺ 507.3
MASS (ESI (-) Spectrum): M ^- 323.0

式（Ｉ−１８−ａ）で表される塩２．９８部、式（Ｉ−２−ｂ）で表される化合物０．６３部及びモノクロロベンゼン２４部を反応器に仕込み、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−２−ｃ）で表される安息香酸銅０．０３部を添加し、１００℃程度まで昇温した後、同温度で１時間攪拌した。得られた反応物を濃縮した。得られた濃縮物に、クロロホルム４５部及びイオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作を５回繰り返した。回収された有機層をろ過した後、得られたろ液を濃縮した。得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−１８―ｄ）で表される塩１．６２部を得た。

[Example 3] Synthesis of salt represented by formula (I-18)

2.98 parts of a salt represented by the formula (I-18-a), 0.63 parts of a compound represented by the formula (I-2-b) and 24 parts of monochlorobenzene were charged into a reactor, and the mixture was stirred at 23 ° C. for 30 parts. Stir for minutes. To the obtained mixture, 0.03 part of copper benzoate represented by the formula (I-2-c) was added, and the temperature was raised to about 100 ° C., followed by stirring at the same temperature for 1 hour. The resulting reaction was concentrated. To the obtained concentrate, 45 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was repeated 5 times. After the collected organic layer was filtered, the obtained filtrate was concentrated. 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.62 parts of the salt represented by the formula (I-18-d).

0.63 part of the salt represented by the formula (I-18-d), 0.26 part of the compound represented by the formula (I-2-e) and 15 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. . To the obtained mixture, 0.12 part of triethylamine was added and stirred at 75 ° C. for 3 hours. The obtained mixture was cooled to 23 ° C., 30 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was left still and separated to obtain an organic layer. This washing operation was further repeated 5 times. To the collected organic layer, 0.5 part of activated carbon was added, stirred and filtered. The obtained filtrate was concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 0.39 parts of the salt represented by the formula (I-18).
MASS (ESI (+) Spectrum): M ⁺ 507.3
MASS (ESI (−) Spectrum): M ^- 339.1

式（Ｉ−１９−ａ）で表される塩２．９７部、式（Ｉ−２−ｂ）で表される化合物０．６３部及びモノクロロベンゼン２４部を反応器に仕込み、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−２−ｃ）で表される安息香酸銅０．０３部を添加し、１００℃程度まで昇温した後、同温度で１時間攪拌した。得られた反応物を濃縮した。得られた濃縮物に、クロロホルム４５部及びイオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水１５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作を５回繰り返した。回収された有機層をろ過した後、得られたろ液を濃縮した。得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル２０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−１９―ｄ）で表される塩１．８２部を得た。

式（Ｉ−１９−ｄ）で表される塩０．６２部、式（Ｉ−２−ｅ）で表される化合物０．２６部及びアセトニトリル１５部を混合し、２３℃で３０分間攪拌した。得られた混合物に、トリエチルアミン０．１２部を仕込み、７５℃で３時間攪拌した。得られた混合物を、２３℃まで冷却し、クロロホルム３０部及びイオン交換水２０部を加え、２３℃で３０分間攪拌した。得られた混合物を静置し、分液して有機層を得た。この水洗操作をさらに５回繰り返した。回収された有機層に活性炭０．５部を加えて攪拌し、ろ過した。得られたろ液を濃縮し、酢酸エチル１０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル１０部を加えて攪拌した。得られた上澄液を除去し、上澄液除去後の残渣をさらに濃縮した。得られた濃縮物をアセトニトリルに溶解した後、濃縮することにより、式（Ｉ−１９）で表される塩０．４４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５０７．３
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３３７．１ [Example 4] Synthesis of salt represented by formula (I-19)

A reactor was charged with 2.97 parts of the salt represented by the formula (I-19-a), 0.63 parts of the compound represented by the formula (I-2-b) and 24 parts of monochlorobenzene. Stir for minutes. To the obtained mixture, 0.03 part of copper benzoate represented by the formula (I-2-c) was added, and the temperature was raised to about 100 ° C., followed by stirring at the same temperature for 1 hour. The resulting reaction was concentrated. To the obtained concentrate, 45 parts of chloroform and 15 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was repeated 5 times. After the collected organic layer was filtered, the obtained filtrate was concentrated. 20 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.82 parts of the salt represented by the formula (I-19-d).

0.62 part of the salt represented by the formula (I-19-d), 0.26 part of the compound represented by the formula (I-2-e) and 15 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. . To the obtained mixture, 0.12 part of triethylamine was added and stirred at 75 ° C. for 3 hours. The obtained mixture was cooled to 23 ° C., 30 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was left still and separated to obtain an organic layer. This washing operation was further repeated 5 times. To the collected organic layer, 0.5 part of activated carbon was added, stirred and filtered. The obtained filtrate was concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred. The resulting supernatant was removed, and the residue after removing the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 0.44 parts of the salt represented by the formula (I-19).
MASS (ESI (+) Spectrum): M ⁺ 507.3
MASS (ESI (−) Spectrum): M ^- 337.1

<Synthesis of Resin (A) and Resin (X)>
The compounds (monomers) used for synthesizing the resin (A1) and the resin (A2) as the resin (A) and the resin (X1) and the resin (X2) as the resin (X) are shown below. Hereinafter, these compounds are referred to as “monomer (a1-1-3)” or the like according to the formula number.

[Synthesis Example 1] Synthesis of Resin (A1) As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-1) and monomer (a3-4-2) were used. The molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-4-2)] used is 35: 15: 2.5. : 47.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was added to a methanol / water mixed solvent, repulped, and then subjected to a refining operation of filtering twice to obtain a resin (A1) having a weight average molecular weight of 8.0 × 10 ^{3 in} a yield of 69%. It was. This resin (A1) has the following structural units.

[Synthesis Example 2] Synthesis of Resin (A2) As monomers, monomer (a1-1-3), monomer (a1-2-11), monomer (a2-1-1) and monomer (a3-4-2) were used. The molar ratio [monomer (a1-1-3): monomer (a1-2-11): monomer (a2-1-1): monomer (a3-4-2)] used is 35: 15: 2.5. : 47.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was added to a methanol / water mixed solvent, repulped and then filtered twice, and the resin (A2) having a weight average molecular weight of 7.9 × 10 ³ was obtained with a yield of 65%. It was. This resin (A2) has the following structural units.

[Synthesis Example 3] Synthesis of Resin (X1) Monomer (a4-1-7) was used as a monomer, and 1.5 mass times of methyl isobutyl ketone as a total monomer amount was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of 0.7 mol% and 2.1 mol%, respectively, with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X1 having a weight average molecular weight of 1.8 × 10 ^{4 in} a yield of 77%. This resin X1 has the following structural units.

[Synthesis Example 4] Synthesis of Resin (X2) Monomer (a5-1-1) and monomer (a4-0-12) were used as monomers, and the molar ratio [monomer (a5-1-1): monomer (a4) −0-12)] is 50:50, and methyl isobutyl ketone 1.2 times as much as the total amount of monomers is added to obtain a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X2 (copolymer) having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 91%. Got in. This resin X2 has the following structural units.

<Preparation of resist composition>
Each component and solvent shown in Table 15 were mixed, and the resulting mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare each resist composition.

ＩＸ−１：（特開２０１０−４４３４７号公報の実施例に従って合成）

ＩＸ−２：（特開２０１３−４７２０９号公報の実施例に従って合成）

ＩＸ−３：（特開２０１３−４７２０９号公報の実施例に従って合成）

＜クエンチャー（Ｃ）＞
Ｄ１：（東京化成工業（株）製）

<Resin>
A1, A2, X1, X2: Resin (A1), Resin (A2), Resin (X1), Resin (X2)
<Acid generator (B)>
B1-21: a salt represented by the formula (B1-21) (synthesized according to Examples in JP 2012-224611 A)
B1-22: a salt represented by the formula (B1-22) (synthesized according to Examples in JP 2012-224611 A)

IX-1: (Synthesis according to the examples of JP 2010-44347 A)

IX-2: (Synthesis according to the example of JP2013-47209A)

IX-3: (Synthesis according to the example of JP2013-47209A)

<Quencher (C)>
D1: (Tokyo Chemical Industry Co., Ltd.)

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

[Examples 5 to 13 and Comparative Examples 1 to 3] Production of resist pattern and evaluation thereof A silicon wafer was coated with an organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) at 205 ° C. The organic antireflection film having a film thickness of 78 nm was formed on the wafer by baking under the condition of 60 seconds. Next, on the organic antireflection film, the above resist composition was applied (spin coated) so that the film thickness after drying was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate for 60 seconds at the temperature of PB described in the “PB / PEB” column of Table 15 to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which the composition layer is formed, and a contact hole pattern (hole pitch 90 nm) Using a mask for forming a hole diameter of 55 nm), the exposure amount was changed stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature of PEB described in the “PB / PEB” column of Table 15. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

<Evaluation of CD uniformity (CDU)>
In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was determined using a population of measurements of the average hole diameter of 400 patterns formed with a mask having a hole diameter of 55 nm in the same wafer.
A case where the standard deviation was 1.80 nm or less was evaluated as A with CDU being good.
A case where the standard deviation was larger than 1.80 nm was evaluated as B because CDU was not good.
The results are shown in Table 16. Numerical values in parentheses indicate standard deviation (nm).

<Evaluation of mask error factor (MEF)>
In terms of effective sensitivity, a resist pattern was formed using masks having mask hole diameters (hole diameters of light transmitting portions of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (all hole pitches were 90 nm). The slope of the regression line when the mask hole diameter was plotted on the horizontal axis and the hole diameter of the resist pattern formed (transferred) on the substrate by exposure was plotted on the vertical axis was calculated as the MEF value.
Those having a MEF value of 4.8 or less were evaluated as A because the MEF was good.
The MEF value exceeding 4.8 was evaluated as B because the MEF was not good.
The results are shown in Table 16. Numerical values in parentheses indicate MEF values.

  The salt of the present invention and the resist composition containing the salt are suitable for semiconductor microfabrication because they can provide a resist pattern having good CD uniformity (CDU), and are extremely useful industrially.

Claims (10)

A salt represented by the formula (I).

[In the formula (I),
R ¹ and R ² each independently represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
R ³ represents an acid labile group.
X ¹ represents a C1-C12 divalent aliphatic saturated hydrocarbon group, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
A ⁻ represents an organic anion. ] X ^{1 in the} formula (I) represents —X ¹² —O—X ²² — * (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the divalent aliphatic hydrocarbon group. X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, provided that the total carbon of X ¹² and X ²² may be substituted with an oxygen atom or a carbonyl group. The number is 11. * represents a bond to R ³ ). The salt according to claim 1 or 2, wherein R ¹ and R ^{2 in} the formula (I) are each independently a phenyl group which may have a substituent. The salt according to any one of claims 1 to 3, wherein R ^{3 in the} formula (I) is a group that forms a hydroxy group or a carboxy group when the leaving group is eliminated by contact with an acid. The salt according to any one of claims 1 to 4, wherein R ³ in the formula (I) is a group represented by the formula (1).

[In Formula (1), R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, and 3 to 20 carbon atoms which may have a substituent. R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represents 0 or 1, and at least one of ma and na is 1.
* Represents a bond. ]   The salt according to claim 5, wherein ma in the formula (1) is 0 and na is 1.   The acid generator containing the salt of any one of Claims 1-6.   A resist composition containing an acid generator and a resin containing a structural unit having an acid labile group, and containing the salt according to any one of claims 1 to 6 as the acid generator.   Furthermore, the resist composition of Claim 8 containing the salt which generate | occur | produces the acid whose acidity is lower than the acid generated from the said acid generator. (1) The process of apply | coating the resist composition of Claim 8 or 9 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: