JP7079591B2 - Method for manufacturing resin, resist composition and resist pattern - Google Patents

Description

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

特許文献２には、下記化合物に由来する構造単位と酸不安定基を有する構造単位を含む樹脂と、酸発生剤とを含有するレジスト組成物が記載されている。

Patent Document 1 describes a resist composition containing a structural unit derived from the following compound, a resin containing a structural unit having an acid unstable group, and an acid generator.

Patent Document 2 describes a resist composition containing a structural unit derived from the following compound, a resin containing a structural unit having an acid unstable group, and an acid generator.

Japanese Unexamined Patent Publication No. 2005-208366 Japanese Unexamined Patent Publication No. 2012-012577

In the resist composition using the above resin, the line edge roughness (LER) may not always be satisfactory.

［式（Ｉ）中、
Ｒ^１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。
Ａｒは、置換基を有していてもよい炭素数６～２４の２価の芳香族炭化水素基を表す。
Ｌ^１は、単結合又はーＣＯ－Ｏ－＊（＊はＡｒとの結合手を表す。）を表す。］
〔２〕Ａｒが、置換基を有していてもよいフェニレン基である〔１〕記載の樹脂。
〔３〕Ａｒが、ハロゲン原子、ヒドロキシ基、カルボキシル基及び炭素数１～６のアルキル基（該アルキル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。）からなる群より選ばれる置換基を少なくとも一つ有するフェニレン基である〔１〕又は〔２〕記載の樹脂。
〔４〕〔１〕～〔３〕のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物。
〔５〕酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する〔４〕に記載のレジスト組成物。
〔６〕（１）〔４〕又は〔５〕に記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin containing a structural unit derived from the compound represented by the formula (I) and a structural unit having an acid unstable group.

[In formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
Ar represents a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent.
L ¹ represents a single bond or -CO-O- * (* represents a bond with Ar). ]
[2] The resin according to [1], wherein Ar is a phenylene group which may have a substituent.
[3] Ar is a group consisting of a halogen atom, a hydroxy group, a carboxyl group and an alkyl group having 1 to 6 carbon atoms (the methylene group contained in the alkyl group may be replaced with an oxygen atom or a carbonyl group). The resin according to [1] or [2], which is a phenylene group having at least one substituent selected from the above.
[4] A resist composition containing the resin and acid generator according to any one of [1] to [3].
[5] The resist composition according to [4], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[6] (1) A step of applying the resist composition according to [4] or [5] onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using the resist composition using the resin of the present invention, a resist pattern having good line edge roughness (LER) can be produced.

As used herein, the term "(meth) acrylate" means "at least one of acrylate and methacrylate," respectively. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning.
Further, unless otherwise specified, a group capable of taking a linear, branched and / or ring such as "aliphatic hydrocarbon group" includes any of them. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

〔resin〕
The resin of the present invention contains a structural unit (hereinafter sometimes referred to as "structural unit (I)") derived from a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)") and an acid. A resin (hereinafter, may be referred to as “resin (A)”) including a structural unit (a1) having an unstable group (hereinafter, may be referred to as “structural unit (a1)”).

［式（Ｉ）中、
Ｒ^１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。
Ａｒは、置換基を有していてもよい炭素数６～２４の２価の芳香族炭化水素基を表す。
Ｌ^１は、単結合又はーＣＯ－Ｏ－＊（＊はＡｒとの結合手を表す。）を表す。］ <Compound (I)>

[In formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
Ar represents a divalent aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent.
L ¹ represents a single bond or -CO-O- * (* represents a bond with Ar). ]

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

Examples of the divalent aromatic hydrocarbon group represented by Ar include divalent aryl groups such as phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group and binaphthylene group, methylphenylene group, dimethylphenylene group and methyl. Examples thereof include an alkyl-aryl group of an ethylphenylene group, a cycloalkyl-aryl group such as cyclohexylphenylene, and a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. It is a divalent aromatic hydrocarbon group of.
Examples of the substituent that the divalent aromatic hydrocarbon group represented by Ar may have include a halogen atom, a hydroxy group, a carboxyl group, a nitro group, a cyano group and an alkoxy group having 1 to 12 carbon atoms. Be done.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group and an n-hexitoxy group, which are preferable. Is an alkoxy group having 1 to 4 carbon atoms.
The substituent of the aromatic hydrocarbon group of Ar is preferably a halogen atom, a hydroxy group or a carboxyl group, more preferably a halogen atom other than the iodine atom, a hydroxy group or a carboxyl group, and more preferably hydroxy. It is more preferably a group or a carboxyl group. Further, it is more preferable to have two or more hydroxy groups as the substituent.
Ar is preferably a phenylene group which may have a substituent. Substituents of the phenylene group include a hydroxy group, a nitro group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. , An aromatic hydrocarbon group or a carboxyl group having 6 to 10 carbon atoms can be mentioned. Of these, a hydroxy group, a nitro group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms is preferable, and a halogen atom, a hydroxy group and a carboxyl group are more preferable. It may have two or more substituents.
Examples of the alkyl group include the same groups as ^R1 .
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and specific examples thereof include the groups shown below and cycloalkyl groups. * Represents a bond with an aromatic hydrocarbon group.

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

Among the compounds represented by the formulas (I-1) to (I-28), a compound in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom can also be mentioned as a specific example of the compound (I).

［式中、Ｒ¹、Ｒ²及びＡｒは、上記と同義である。］
塩基触媒としては、ピリジン、ジメチルアミノピリジンなどが挙げられる。
溶媒としては、テトラヒドロフラン、メチルイソブチルケトン及びトルエンなどが挙げられる。
反応温度は通常１０℃～８０℃であり、反応時間は通常０．５時間～２４時間である。
式（Ｉ１－ａ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができる。

式（Ｉ１－ｂ１）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができる。

<Method for producing compound (I)>
The compound (I1) in which L ¹ is -CO-O- * (* represents a bond with Ar) is represented by the compound represented by the formula (I1-a) and the formula (I1-b1). Can be obtained by reacting the above compounds in a solvent under a base catalyst.

[In the formula, R ¹ , R ² and Ar are synonymous with the above. ]
Examples of the base catalyst include pyridine, dimethylaminopyridine and the like.
Examples of the solvent include tetrahydrofuran, methyl isobutyl ketone, toluene and the like.
The reaction temperature is usually 10 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.
Examples of the compound represented by the formula (I1-a) include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (I1-b1) include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (I2) in which L ¹ is a single bond include compounds represented by the following formula, which can be easily obtained from the market.

The resin (A) may contain two or more kinds of structural units (I).
The content of the structural unit (I) contained in the resin (A) is usually 1 to 50 mol%, preferably 2 to 30 mol%, and more preferably 3 with respect to all the structural units of the resin (A). It is ~ 20 mol%, more preferably 5 ~ 15 mol%.

The resin (A) of the present invention further has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”) in addition to the structural unit (I). The "acid-unstable group" is a structural unit having a leaving group, and the leaving group is removed by contact with an acid, and the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means the group to do.

［式（１）中、Ｒ^a1～Ｒ^a3は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３～２０の２価の脂環式炭化水素基を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合手を表す。］

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１～１２の炭化水素基を表し、Ｒ^a3’は、炭素数１～２０の炭化水素基を表すか、Ｒ^a2’及びＲ^a3’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３～２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる－ＣＨ₂－は、－Ｏ－又は－Ｓ－で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
ｎａ’は、０又は１を表す。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”).
The acid unstable group contained in the resin (A) is preferably a group represented by the formula (1) and / or a group represented by the formula (2).

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

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the hydrocarbon group and the divalent complex are formed. -CH _2- contained in the ring group may be replaced with -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na'represents 0 or 1.
* Represents a bond. ]

アルキル基と脂環式炭化水素基とを組み合わせた基としては、例えば、シクロヘキシルメチル基、アダマンチルメチル基、アダマンチルジメチル基、ノルボルニルエチル基等のシクロアルキル－アルキル基が挙げられる。
好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して２価の脂環式炭化水素基を形成する場合の－Ｃ（Ｒ^a1）（Ｒ^a2）（Ｒ^a3）としては、下記の基が挙げられる。２価の脂環式炭化水素基は、好ましくは炭素数３～１２である。＊は－Ｏ－との結合手を表す。

Examples of the alkyl group of R ^a1 to R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.
The alicyclic hydrocarbon groups of R ^a1 to R ^a3 may be monocyclic, polycyclic or spiro ring, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, methylcyclohexyl group, dimethylcyclohexyl group and methylnorbornyl group. Can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, an adamantylcyclohexyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^a1 to R ^a3 has preferably 3 to 16 carbon atoms.

Examples of the group in which the alkyl group and the alicyclic hydrocarbon group are combined include a cycloalkyl-alkyl group such as a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group and a norbornylethyl group.
Preferably, ma is 0 and na is 1.
Examples of -C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R a ² are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

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。
ｎａ’は、好ましくは０である。 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 groups.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group and phenanthryl group, trill group, xylyl group, cumenyl group, mesityl group, p-tert-butylphenyl group, 2,6. Examples thereof include an alkyl-aryl group such as a diethylphenyl group and a 2-methyl-6-ethylphenyl group; and a cycloalkyl-aryl group such as a p-adamantylphenyl group.
Examples of the group combining an alkyl group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group include a cycloalkyl-alkyl group (adamantylmethyl group, adamantylethyl group, cyclohexylmethyl group, cyclopentylmethyl group) and an aralkyl group (for example, an aralkyl group). Phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl Group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.) and the like.
When R ^a2'and R ^a3'bond to each other to form a divalent heterocyclic group with the carbon atom and X to which they bond, -C (R ^a1' ) (R ^a3' )-X-R ^a2' Examples include the following groups. * Represents a bond.

Of R ^a1'and R ^a2' , at least one is preferably a hydrogen atom.
na'is preferably 0.

As the group represented by the formula (1), a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^a1 to R ^a3 are alkyl groups, ma = 0, na = 1, preferably tert-butoxycarbonyl). Group), 2-alkyl adamantan-2-yloxycarbonyl group (in formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded are adamantyl groups, R ^a3 is an alkyl group, ma = 0, na = 1 ) And 1- (adamantan-1-yl) -1-alkylalkoxycarbonyl group (in formula (1), R ^a1 and R ^a2 are alkyl groups, R ^a3 is adamantyl group, ma = 0, na = 1), etc. Further, the following groups can be mentioned. * Represents a bond.

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

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

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

［式（ａ１－０）、式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、－Ｏ－又は^＊－Ｏ－（ＣＨ_２）_ｋ１－ＣＯ－Ｏ－を表し、ｋ１は１～７のいずれかの整数を表し、＊は－ＣＯ－との結合手を表す。
Ｒ^a01、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は０～１４のいずれかの整数を表す。
ｎ１は０～１０のいずれかの整数を表す。
ｎ１’は０～３のいずれかの整数を表す。］ 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 a structural unit (a1-0)). In some cases), a structural unit represented by the formula (a1-1) (hereinafter, may be referred to as a structural unit (a1-1)) or a structural unit represented by the formula (a1-2) (hereinafter, referred to as a structural unit). It may be referred to as a structural unit (a1-2)). These may be used alone or in combination of two or more.

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
^La01 , ^La1 and ^La2 independently represent -O- or ^* -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. -Represents a bond with CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
^La01 , La1 and ^La2 are preferably oxygen atoms or * -O- (CH ₂ ) _k01 -CO-O- (where ^k01 is preferably an integer of 1 to 4, more preferably. Is 1), more preferably an oxygen atom.
The alkyl groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 , the alicyclic hydrocarbon group and the group combining these are the same as the groups mentioned in R ^a1 to R ^a3 of the formula (1). The group is mentioned.
The alkyl groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 have preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1'is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any one of the formulas (a1-0-1) to (a1-0-12) and a methyl group corresponding to ^Ra01 are used as hydrogen atoms. Examples thereof include the replaced structural units, and structural units represented by any of the formulas (a1-0-1) to (a1-0-10) are preferable.

Examples of the monomer for deriving the structural unit (a1-1) include the monomers described in JP-A-2010-204646. Among them, the structural unit represented by any of the formulas (a1-1-1) to ( ^a1-1-4 ) and the structural unit in which the methyl group corresponding to Ra4 is replaced with a hydrogen atom are preferable, and the formula (a1) is preferable. The structural unit represented by any of 1-1) to (a1-1-4) is more preferable.

As the structural unit (a1-2), the structural unit represented by any of the formulas (a1-2-1) to ( ^a1-2-6 ) and the methyl group corresponding to Ra5 were replaced with hydrogen atoms. Structural units are mentioned, and the formula (a1-2-2), the formula (a1-2-5) and the formula (a1-2-6) are preferable.

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

式（ａ１－５）中、
Ｒ^a8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。
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。 The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2) is a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”). There is).

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

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

Examples of the monomer for deriving the structural unit (a1-5) include the monomers described in JP-A-2010-61117. Among them, the structural units represented by the formulas (a1-5-1) to (a1-5-4) are preferable, and they are represented by the formula (a1-5-1) or the formula (a1-5-2). Structural units are more preferred.

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

Moreover, the following structural unit is also mentioned as a structural unit (a1).

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

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

<Structural unit (s)>
The resin (A) is further described as a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”) and a structural unit having a halogen atom (hereinafter, structural unit (hereinafter, may be referred to as “structural unit”). It may contain a4) ”), a structural unit having a non-desorbed hydrocarbon group (a5), and a structural unit derived from other known monomers. Above all, it is preferable to include the structural unit (s). The structural unit (s) is derived from a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”). As the monomer (s), a monomer having no acid unstable group known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid unstable group is preferable. A structure having a hydroxy group and no acid unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or having a lactone ring and no acid unstable group. If a resin having a unit (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

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

［式（ａ２－Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～４のアシル基、炭素数２～４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は^＊－Ｘ^a51－（Ａ^a52－Ｘ^a52）_na－を表し、＊は－Ｒ^a50が結合する炭素原子との結合手を表す。
Ａ^a52は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎａは、０又は１を表す。
ｍｂは０～４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複数のＲ^a51は互いに同一であっても異なってもよい。］ Examples of the structural unit (a2) having a phenolic hydroxy group include structural units represented by the formula (a2-A) (hereinafter, may be referred to as “structural unit (a2-A)”).

[In formula (a2-A),
R ^a50 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
A ^a50 represents a single bond or ^* -X ^a51- (A ^a52- X ^a52 ) _na- , and * represents a bond with a carbon atom to which -R ^a50 is bonded.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 independently represent —O—, —CO—O— or —O—CO—, respectively.
na represents 0 or 1.
mb represents any integer from 0 to 4. When mb is any integer of 2 or more, the plurality of Ra ^51s may be the same as or different from each other. ]

Examples of the halogen atom in R ^a50 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in ^Ra50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, and 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, n-pentyl group, n- Examples include a hexyl group and an n-perfluorohexyl group.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group of R ^a51 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.
Examples of the alkoxy group of R ^a51 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the acyl group in ^Ra51 include an acetyl group, a propionyl group, a butyryl group and the like.
Examples of the acyloxy group in ^Ra51 include an acetyloxy group, a propionyloxy group and a butyryloxy group.
R ^a51 is preferably a methyl group.

^* -X ^a51- (A ^a52- X ^a52 ) _na -is ^* -O-, ^* -CO-O-, ^* -O-CO-, ^* -CO-O-A ^a52 -CO-O-, ^* -O-CO-A ^a52 -O-, ^* -O-A ^a52 -CO-O-, ^* -CO-O-A ^a52 -O-CO-, ^* -O-CO-A ^a52 -O-CO -, Can be mentioned. Of these, ^* -CO-O-, ^* -CO-O-A ^a52 -CO-O- or ^* -O-A ^a52 -CO-O- are preferable.

The alcandiyl group includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a 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 and 2 -Methylbutane-1,4-diyl group and the like can be mentioned.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably single bond, ^* -CO-O- or ^* -CO-O-A ^a52 -CO-O-, and is preferably single bond, ^* -CO-O- or ^* -CO-O-CH. ₂ -CO-O- is more preferred, and single bond or ^* -CO-O- is even more preferred.

The mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
The hydroxyl group is preferably bonded to the o-position or the p-position of the benzene ring, and more preferably to the p-position.

Examples of the structural unit (a2-A) include structural units represented by the formulas (a2-2-1) to (a2-2-8). The structural unit (a2-A) is represented by a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-1), and a formula (a2-2-5). It is preferable that the structural unit is a structural unit and a structural unit represented by the formula (a2-2-6).

Examples of the monomer for inducing the structural unit (a2-A) include the monomers described in JP-A-2010-204634 and JP-A-2012-12577.

When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 5 to 80 mol% with respect to all the structural units. It is 10 to 70 mol%, more preferably 15 to 65 mol%.

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 structural units represented by the formula (a2-1) (hereinafter, may be referred to as “structural unit (a2-1)”).

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

In the formula (a2-1), ^La3 is preferably -O-, -O- (CH ₂ ) _f1 -CO-O- (the f1 is an integer of 1 to 4). , More preferably -O-.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable.

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

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

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

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

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

Examples of the aliphatic hydrocarbon group of 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. Alkyl groups can be mentioned.
Examples of the halogen atom of ^Ra24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group of R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
Examples of the alkyl group having a halogen atom of ^Ra24 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. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The alcandiyl groups of ^La8 and ^La9 include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group and pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formulas (a3-1) to (a3-3), ^La4 to ^La6 are independent of each other, preferably −O— or k3 is an integer of any one 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 an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are independent of each other, preferably a carboxy group, a cyano group or a methyl group.
p1, q1, r1 and w1 are independent of each other, preferably an integer of 0 to 2, and more preferably 0 or 1.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In the formula (a3-4), ^Ra24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group. Is.
^Ra25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably -O- or ^* -OL ^a8 -CO-O-, and more preferably -O-, -O-CH ₂ -CO-O- or -O-C ₂ H _4- . It is CO-O-.
In particular, the formula (a3-4) is preferably the formula (a3-4)'.

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

Examples of the monomer for deriving the structural unit (a3) include the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Can be mentioned. The structural unit (a3) includes equations (a3-1-1) to (a3-1-4), equations (a3-2-1) to equations (a3-2-4), and equations (a3-3-3). 1) The structural unit represented by any of the formulas (a3-3-4) and the formulas (a3-4-1) to (a3-4-12) is preferable.

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

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

［式（ａ４－０）中、Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁴は、単結合又は炭素数１～４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0).

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

Examples of the aliphatic saturated hydrocarbon group of L ⁴ include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and an ethane-1,1-. Branched alkanediyl such as diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group The group is mentioned.

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

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

Examples of the structural unit ( ^a4-0 ) include the structural unit shown below and the structural unit in which the methyl group corresponding to R5 in the following structural unit is replaced with a hydrogen atom.

［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、単結合又は置換基を有していてもよい炭素数１～５の２価の脂肪族炭化水素基を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊は結合手であり、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合手を表す。］ The structural unit (a4) also includes a structural unit represented by the equation (a4-1).

[In the formula (a4-1), R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-. good.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). However, at least one of ^Aa41 and ^Ra42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (ag1), s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 independently represent -O-, -CO-, -CO-O- or -O-CO-, respectively.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is a bond, and * on the right side represents a bond with -O-CO-R ^a42 . ]

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

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基等のアリール基；２－メチルフェニル基等のアルキル－アリール基；４－シクロヘキシルフェニル基等のシクロアルキル－アリール基等が挙げられる。 Chain-type aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl. Examples thereof include a group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. The cyclic aliphatic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a methylcyclohexyl group, a dimethylcyclohexyl group and a methylnorbornyl group; decahydro. Examples thereof include a polycyclic alicyclic hydrocarbon group such as a naphthyl group, an adamantyl group, a norbornyl group, an adamantylcyclohexyl group and the following group (* indicates a bond).

Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group and a fluorenyl group; an alkyl-aryl group such as a 2-methylphenyl group; and a cyclo such as a 4-cyclohexylphenyl group. Examples thereof include an alkyl-aryl group.

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素基を表す。
＊は結合手を表す。］ As the hydrocarbon group of R ^a42 , a chain type or a ring type aliphatic hydrocarbon group and a group formed by a combination thereof are preferable, and a chain type may have a carbon-carbon unsaturated bond, but a chain type. And cyclic aliphatic saturated hydrocarbon groups and groups formed by combining them are more preferable.
Examples of R ^a42 include a halogen atom or a group represented by the formula (ag3) as a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.
* Represents a bond. ]

Examples of the aliphatic hydrocarbon group of A ^a45 include the same groups as those exemplified in R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). 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 further preferably having a carbon number of carbon. It is a perfluoroalkyl group of 1 to 6, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (ag3), the aliphatic hydrocarbon includes the number of carbon atoms contained in the group represented by the formula (ag3). The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［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 (ag3) is more preferably a group represented by the formula (ag2).

[In the formula (ag2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with a carbonyl group. ]

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

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

The alcandiyl group of A ^a41 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group. Linear alkandiyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, etc. Examples thereof include a branched alkandiyl group 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 further preferably an ethylene group.

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

Examples of the group represented by the formula (ag1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the following examples, * and ** represent the bond, respectively, and ** represents the bond with -O-CO-R ^a42 .

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

［式（ａ４－４）中、Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、－（ＣＨ₂）_j1－、－（ＣＨ₂）_j2－Ｏ－（ＣＨ₂）_j3－又は－（ＣＨ₂）_j4－ＣＯ－Ｏ－（ＣＨ₂）_j5－を表す。
ｊ１～ｊ５は、それぞれ独立に、１～６のいずれかの整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１～１０の炭化水素基を表す。］ The structural unit (a4) also includes a structural unit represented by the formula (a4-4).

[In formula (a4-4), R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents-(CH ₂ ) _j1 -,-(CH ₂ ) _j2 -O- (CH ₂ ) _{j3- or-} (CH ₂ ) _j4 -CO-O- (CH ₂ ) _j5- .
j1 to j5 each independently represent an integer of 1 to 6.
R ^f22 represents a hydrocarbon group having a fluorine atom and having 1 to 10 carbon atoms. ]

Hydrocarbon groups having a fluorine atom of R ^f22 include chain-type and cyclic-type aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and groups formed by combining them. As the aliphatic hydrocarbon group, an alkyl group (straight or branched) and an alicyclic hydrocarbon group are preferable.
Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2 -Examples include ethylhexyl groups.
The alicyclic hydrocarbon group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloheptyl group, a cyclodecyl group and the like. Cycloalkyl groups can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, and a norbornyl group. Examples thereof include a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of R ^f22 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
As the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-Hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2- Trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3 , 4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1 , 1,2,2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6-dodecafluoro Fluoroalkyl groups such as hexyl groups, perfluoropentylmethyl groups and perfluorohexyl groups can be mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorocycloalkyl group such as a perfluorocyclohexyl group and a perfluoroadamantyl group.
R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom. Preferably, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is more preferable.

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

Examples of the structural unit represented by the formula (a4-4) include the following structural unit and the structural unit in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom in the structural unit represented by the following formula. Be done.

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

［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、Ｌ^5５との結合位置にある炭素原子に結合する水素原子は、炭素数１～８の脂肪族炭化水素基で置換されない。
Ｌ^5５は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a group having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably contains a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group 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 bond position with L ⁵⁵ is not substituted with the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
^L55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group of R ⁵² may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms includes, for example, 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. Examples thereof include an alkyl group such as an octyl group and a 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 of ^L55 include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent aliphatic saturated hydrocarbon group is preferable. ..
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

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

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

L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^{x 5} is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
W ^x 1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantandiyl group.

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

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

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

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

L ⁵⁵ is preferably a single bond or a group represented by the formula (L1-1).

樹脂（Ａ）が、構造単位（ａ５）を有する場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１～３０モル％が好ましく、２～２０モル％がより好ましく、３～１５モル％がさらに好ましい。 Examples of the structural unit (a5-1) include the structural unit shown below and the structural unit in which the methyl group corresponding to R ⁵¹ in the following structural unit is replaced with a hydrogen atom.

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

<Structural unit (II)>
The resin (A) may further contain a structural unit (hereinafter, may be referred to as “structural unit (II)”) that decomposes by exposure to generate an acid. The structural unit (II) is specifically. Examples thereof include a structural unit containing a group represented by the formula (III-1) or the formula (III-2) described in JP-A-2016-79235, and the side chain includes a sulfonate group or a carboxylate group and an organic substance. It is preferably a structural unit having a cation or a structural unit having a sulfonio group and an organic anion on the side chain.

［式（ＩＩ－２－Ａ’）中、
Ｘ^ＩＩＩ３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－ＣＨ_２－は、－Ｏ－、－Ｓ－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、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１～６のアルキル基又はヒドロキシ基で置き換わっていてもよい。
Ａ^ｘ１は、炭素数１～８のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、フッ素原子又は炭素数１～６のペルフルオロアルキル基で置換されていてもよい。
ＲＡ^－は、スルホナート基又はカルボキシレート基を表す。
Ｒ^ＩＩＩ３は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｚ^ａ＋は、有機カチオンを表す。］ The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by the formula (II-2-A').

[In the formula (II-2-A'),
X ^III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atom contained in the saturated hydrocarbon group may be replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group.
A ^x1 represents an angandyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the angandyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ^- represents a sulfonate group or a carboxylate group.
R ^III3 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
Z ^{a +} represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3 includes an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 . The same can be mentioned.
Examples of the alcandiyl group having 1 to 8 carbon atoms represented by A ^x1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentan-2, 4-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. Can be mentioned.
Examples of the group in which the alkanediyl group and the alicyclic saturated hydrocarbon group are combined include a cycloalkyl-alkandyl group such as a cyclohexylmethylene group, an adamantylmethylene group and a norbornylethylene group.

Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. And may be a combination of these.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-Diyl group, Heptane-1,7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decan-1,10-Diyl group, Undecane-1,11-Diyl group , Dodecane-1,12-diyl group and other linear alkanediyl groups; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , Pentan-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-Diyl group, cyclooctanediyl group such as cyclooctane-1,5-diyl group; norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantan-1,5-diyl group, adamantan Examples thereof include a divalent polycyclic alicyclic saturated hydrocarbon group such as -2,6-diyl group.

When -CH _2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-, for example, a divalent group represented by the formulas (X1) to (X53) is used. Can be mentioned. However, the number of carbon atoms before that -CH _2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following equation, * represents a bond with A ^x1 .

X ³ represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
X ⁴ represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
X ⁵ represents a saturated hydrocarbon group having 1 to 13 divalent carbon atoms.
X ⁶ represents an alkyl group having 1 to 14 carbon atoms.
X ⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁸ represents a saturated hydrocarbon group having 1 to 13 divalent carbon atoms.

［式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^ｂ４～Ｒ^ｂ６は、それぞれ独立に、炭素数１～３０のアルキル基、炭素数３～３６の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８のアルキル基、炭素数２～４のアシル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に、０～５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上のとき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、それぞれ独立に、炭素数１～３６のアルキル基又は炭素数３～３６の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ１１は、水素原子、炭素数１～３６のアルキル基、炭素数３～３６の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表し、該アルキル基に含まれる水素原子は、炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^ｂ１１とＲ^ｂ１２とは、一緒になってそれらが結合する－ＣＨ－ＣＯ－を含む環を形成していてもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ１３～Ｒ^ｂ１８は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
Ｌ^ｂ３１は、－Ｓ－又は－Ｏ－を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０～５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０～４のいずれかの整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］ Examples of the organic cation represented by Z ^{a +} include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, an organic benzothiazolium cation, an organic phosphonium cation, and the like, and an organic sulfonium cation and an organic iodine cation cation. Is preferred, and aryl sulfonium cations are more preferred.
Z ^{a +} is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, may be referred to as "cation (b2-1)" depending on the formula number. ].

[In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 independently represent an alkyl 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 may be substituted with 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 may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the aromatic. The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b7 and R ^b8 independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent an alkyl group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b11 represents a hydrogen atom, an alkyl 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 alkyl 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 the hydrogen atom contained in the alkyl group is It may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy having 1 to 12 carbon atoms. It may be substituted with a group.
R ^b11 and R ^b12 may be used together to form a ring containing -CH-CO- to which they are bound, and -CH _2- contained in the ring is -O-, -SO-. Alternatively, it may be replaced with -CO-.
R ^b13 to R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents —S— or —O—.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represent an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s may be the same or different, when p2 is 2 or more, a plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , A plurality of R ^b15s may be the same or different, and when r2 is 2 or more, a plurality of R ^b16s may be the same or different, and when s2 is 2 or more, a plurality of R ^b17s may be present. It may be the same or different, and when t2 is 2 or more, a plurality of R ^b18s may be the same or different. ]

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

Above all, the number of carbon atoms of the alkyl group of R ^b9 to R ^b12 is preferably 3 to 18, and more preferably 4 to 12.

Examples of the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, an isobornyl group and the like. Can be mentioned. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with a certain group, the total number of carbon atoms of the alicyclic hydrocarbon group and the alkyl group is preferably 20 or less.
Examples of the aliphatic hydrocarbon groups of R ^b7 and R ^b8 , and R ^b13 to R ^b18 include the above-mentioned alkyl groups, alicyclic hydrocarbon groups, and groups similar to those combined thereof.

Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenylyl group, naphthyl group and phenanthryl group; trill group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group and p-tert-butylphenyl group. Alkyl-aryl groups such as 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl group; cycloalkyl-aryl groups such as p-cyclohexylphenyl group and p-adamantylphenyl group can be mentioned.
When the aromatic hydrocarbon group contains an alkyl group or an alicyclic hydrocarbon group, an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferable.
Examples of the aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the alkyl group in which the hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.

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

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

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

Among the cations (b2-1) to cations (b2-4), cations (b2-1) are preferable.

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

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

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

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

［式（ＩＩ－２－Ａ）中、Ｒ^ＩＩＩ３、Ｘ^ＩＩＩ３及びＺ^ａ＋は、上記と同じ意味を表す。
Ｚは、０～６のいずれかの整数を表す。
Ｒ^ＩＩＩ２及びＲ^ＩＩＩ４は、それぞれ独立して、水素原子、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し、ｚが２以上のとき、複数のＲ^ＩＩＩ２及びＲ^ＩＩＩ４は互いに同一であってもよいし、異なっていてもよい。
Ｑ^ａ及びＱ^ｂは、それぞれ独立して、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。］ The structural unit represented by the formula (II-2-A') is preferably the structural unit represented by the formula (II-2-A).

[In the formula (II-2-A), R ^III3 , X ^III3 and Za ⁺ have the same meanings as described above.
Z represents an integer of 0 to 6.
R ^III2 and R ^III4 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are identical to each other. It may or may not be different.
Q ^a and Q ^b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ]

Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R ^III2 , R ^III4 , ^Qa and ^Qb include the same perfluoroalkyl group having 1 to 6 carbon atoms represented by ^Q1 described later. ..

［式（ＩＩ－２－Ａ－１）中、
Ｒ^ＩＩＩ２、Ｒ^ＩＩＩ３、Ｒ^ＩＩＩ４、Ｑ^a、Ｑ^b、ｚ及びＺ^a＋は、上記と同じ意味を表す。
Ｒ^ＩＩＩ５は、炭素数１～１２の飽和炭化水素基を表す。
Ｘ²は、炭素数１～１１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－、－Ｓ－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、ハロゲン原子又はヒドロキシ基で置換されていてもよい。］ The structural unit represented by the formula (II-2-A) is preferably the structural unit represented by the formula (II-2-A-1).

[In the formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b , z and Z ^{a +} have the same meanings as described above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
X ² represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples thereof include a linear or branched alkyl group such as a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
Examples of the divalent saturated hydrocarbon group having 1 to 11 carbon atoms represented by X ² include those having up to 11 carbon atoms among the divalent saturated hydrocarbon groups represented by X ^III3 .

［式（ＩＩ－２－Ａ－２）中、Ｒ^ＩＩＩ３、Ｒ^ＩＩＩ５及びＺ^a＋は、上記と同じ意味を表す。
ｍ及びｎは、互いに独立に、１又は２を表す。］ As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable.

[In the formula (II-2-A-2), R ^III3 , R ^III5 and Z ^{a +} have the same meanings as described above.
m and n represent 1 or 2 independently of each other. ]

Examples of the structural unit represented by the formula (II-2-A-1) include the following structural units and the structural units described in WO2012 / 050015. Z ^{a +} represents an organic cation.

［式（ＩＩ－１－１）中、
Ａ^ＩＩ１は、単結合又は２価の連結基を表す。
Ｒ^IIは、炭素数６～１８の２価の芳香族炭化水素基を表す。
Ｒ^ＩＩ２及びＲ^ＩＩ３は、それぞれ独立して、炭素数１～３０のアルキル基、炭素数３～３６の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８のアルキル基、炭素数２～４のアシル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されていてもよい。また、Ｒ^ＩＩ２とＲ^ＩＩ３とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^II4は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ａ^－は、有機アニオンを表す。］ The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1).

[In formula (II-1-1),
A ^II1 represents a single bond or a divalent linking group.
R ^II represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 independently represent an alkyl 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. Even if the hydrogen atom contained in the group is substituted with 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. Often, the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the fragrance may be used. The hydrogen atom contained in the group hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms. Further, R ^II2 and R ^II3 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring is replaced with -O-, -SO- or -CO-. May be good.
R ^II4 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
A ^- represents an organic anion. ]

Examples of the divalent linking group represented by A ^II1 include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ − contained in the divalent saturated hydrocarbon group is It may be replaced by -O-, -S- or -CO-. Specifically, the same as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 can be mentioned.
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
Alkyl group represented by R ^II2 and R ^II3 , alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group which is a substituent of alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alicyclic The halogen atom, alkyl group, alkylcarbonyl group, halogen atom and alkoxy group which are substituents of the aromatic hydrocarbon group are R ^b4 to R ^b6 of the above-mentioned formula (b2-1). The same thing can be mentioned.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 includes an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 . The same can be mentioned.

Examples of the structural unit containing a cation in the formula (II-1-1) include structural units represented by the following.

Examples of the organic anion represented by A ⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, a carboxylic acid anion and the like. The organic anion represented by A ⁻ is preferably a sulfonic acid anion, and more preferably the above-mentioned anion.

Examples of the sulfonylimide anion represented by A ⁻ include the following.

Examples of the structural unit (II-1) include structural units represented by the following.

When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to all the structural units of the resin (A), and more. It is preferably 2 to 15 mol%, more preferably 3 to 10 mol%.

The resin (A) is preferably a resin composed of a structural unit (I), a structural unit (a1), and a structural unit (s), that is, a copolymer of the compound (I), the monomer (a1), and the monomer (s). It is a polymer.
The structural unit (a1) is preferably at least one selected from a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably a structural unit (a1). It is at least two kinds selected from a1-1) or a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably a structural unit represented by the formulas (a3-1-1) to (a3-1-4), and the formulas (a3-2-1) to (a3-2-4). And at least one selected from the structural units represented by the formulas (a3-4-1) to (a3-4-2).
In the resin (A), among the substituents of the aromatic hydrocarbon group in the structural unit derived from the compound represented by the formula (I), when the number of the substituents by iodine is 2 or more, the structural unit (a3). ) Is preferably included, and the structural unit (a3) may not be included when the number of substituents due to iodine is one.

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

[Resist composition]
The resist composition of the present invention contains a resin (A) and an acid generator.
The resist composition further contains a resin other than the resin (A), a quencher (hereinafter, may be referred to as “quencher (C)”), and a solvent (hereinafter, may be referred to as “solvent (E)”). Is preferable.

<Resin (X) other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin containing a structural unit (a4) (hereinafter, may be referred to as “resin (X)”).
Examples of the structural unit that the resin (X) may further include include a structural unit (a1), a structural unit (a2), a structural unit (a3), a structural unit (a5), and other known structural units.
The resin (X) is more preferably a resin composed of the structural unit (a4) and / or the structural unit (a5).
When the resin (X) contains the structural unit (a4), the content thereof is preferably 40 mol% or more, more preferably 45 mol% or more, and 50 mol% or more with respect to all the structural units of the resin (X). Is even more preferable.
When the resin (X) contains the structural unit (a5), the content thereof is preferably 10 to 60 mol%, more preferably 20 to 55 mol%, and 25 to 25 to all the structural units of the resin (X). 50 mol% is more preferred.

Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 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 of the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further, with respect to 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, and particularly preferably 2 to 30 parts by mass.

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

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

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

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、置換基を有していてもよい炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、水素原子又は置換基を有していてもよい炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter, may be referred to as “acid generator (B1)”).

[In formula (B1),
^Q1 and ^Q2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the divalent saturated hydrocarbon group is -O- or. It may be replaced with —CO—, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced with a fluorine atom or a hydroxy group.
Y represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a hydrogen atom or a substituent, and —CH ₂ − contained in the alicyclic hydrocarbon group is —O—, It may be replaced with -SO _2- or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups of ^Q1 and ^Q2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. A hexyl group and the like can be mentioned.
^Q1 and ^Q2 are preferably fluorine atoms or trifluoromethyl groups independently of each other, and more preferably both are fluorine atoms.

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

［式（ｂ１－１）中、
Ｌ^ｂ２は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ３は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ２とＬ^ｂ３との炭素数合計は、２２以下である。
式（ｂ１－２）中、
Ｌ^ｂ４は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ５は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ４とＬ^ｂ５との炭素数合計は、２２以下である。
式（ｂ１－３）中、
Ｌ^ｂ６は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
Ｌ^ｂ７は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ６とＬ^ｂ７との炭素数合計は、２３以下である。］ Examples of the group in which -CH _2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- are any of the formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with −Y.

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

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

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

The group in which _-CH2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- is a group represented by the formula (b1-1) or the formula (b1-3). Is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
When -CH _2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. .. Examples of such a group include groups represented by the formulas (Y12) to (Y35), the formula (Y39), and the formula (Y40).

That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each replaced with an oxygen atom, and the two oxygen atoms are combined with an arcandyl group having 1 to 8 carbon atoms to form a ketal ring. Alternatively, it may contain a structure in which an oxygen atom is bonded to different carbon atoms. However, in the case of forming a spiro ring of the formula (Y28) to the formula (Y33), the formula (Y39), the formula (Y40) and the like, the alkanediyl group between the two oxygens has one or more fluorine atoms. Is preferable. Further, among the alkanediyl groups contained in the ketal structure, those in which the fluorine atom is not substituted in the methylene group adjacent to the oxygen atom are preferable.

Among them, a group represented by any one of the formula (Y1) to the formula (Y20), the formula (Y30), the formula (Y31), the formula (Y39) or the formula (Y40) is preferably mentioned, and the formula (Y40) is more preferable. Examples include groups represented by Y11), formula (Y15), formula (Y16), formula (Y19), formula (Y20), formula (Y30), formula (Y31), formula (Y39) or formula (Y40). More preferably, the group represented by the formula (Y11), the formula (Y15), the formula (Y30), the formula (Y39) or the formula (Y40) can be mentioned.

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

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

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent, and constitutes these groups. The methylene group to be used may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group or a group represented by the following.

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-55) [hereinafter, "anion (B1)" according to the formula number. -A-1) "and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-55). Anions are more preferred.

Here, R ⁱ² to R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an 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 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.
^Q1 and ^Q2 are the same as above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

Examples of the sulfonic acid anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-34).

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). )-Anion represented by any of the formulas (B1a-34) is preferable.
Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodine cation. These include, more preferably aryl sulfonium cations.
Specifically, the same as those exemplified for the organic cation in the structural unit (II) can be mentioned.

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

Examples of the acid generator (B1) include those represented by the formulas (B1-1) to (B1-48), among which the formulas (B1-1) to the formula (B1-3) and the formula (B1) are used. -5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-17), formula (B1-20) to formula (B1-26), formula (B1-26) 29), those represented by the formulas (B1-31) to (B1-48) are preferable.

The acid generator (B) may contain an acid generator other than the acid generator (B1).
In the resist composition of the present invention, the acid generator (B1) may contain one kind alone or a plurality of kinds. Among them, the acid generator (B1) preferably contains two or more kinds of acid generators. The content of the acid generator (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on the total amount of the acid generator (B), and acid generation. It is particularly preferable that only the agent (B1) is used.
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass) with respect to 100 parts by mass of the resin (A). (Below).

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

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

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

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

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

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

<Salt that produces acid with weak acidity>
The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. It is more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid intramolecular salt described in JP-A-2015-147926, and JP-A-2012-229206. Examples thereof include the salts described in JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502 and JP-A-2011-191745.

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

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

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

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

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

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

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a depressurizing device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is preferably about ¹ to 1.0 × 105 Pa.

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

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

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

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

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

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

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

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

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

式（Ｉ－１－ａ）で表される化合物８０部、メチルイソブチルケトン３２０部、ピリジン３５．７部及びジメチルアミノピリジン１．３部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物２５．３部を添加し、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル９５０部及び５％塩酸１５０部を混合して２３℃で３０分間攪拌し、分液することにより有機層を回収した。得られた有機層に、イオン交換水３００部を混合して２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。得られた有機層を濃縮した後、回収された濃縮残渣をカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ－１）で表される化合物５０．８４部を得た。
ＭＳ（質量分析）：４５８．９ ［Ｍ＋Ｈ］^＋ Synthesis Example 1 [Synthesis of compound represented by formula (I-1)]

80 parts of the compound represented by the formula (I-1-a), 320 parts of methyl isobutyl ketone, 35.7 parts of pyridine and 1.3 parts of dimethylaminopyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 25.3 parts of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 23 ° C. for 18 hours. The obtained reaction product was mixed with 950 parts of ethyl acetate and 150 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. 300 parts of ion-exchanged water was mixed with the obtained organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed three times. After concentrating the obtained organic layer, the recovered concentrated residue was put on a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1. ) By fractionation, 50.84 parts of the compound represented by the formula (I-1) was obtained.
MS (Mass Spectrometry): 458.9 [M + H] ⁺

式（Ｉ－５－ａ）で表される化合物８０部、メチルイソブチルケトン３２０部、ピリジン５９部及びジメチルアミノピリジン２．１部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物４１．８部を添加し、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル１０００部及び５％塩酸２５０部を混合して２３℃で３０分間攪拌し、分液することにより有機層を回収した。得られた有機層に、イオン交換水５００部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。得られた有機層を濃縮した後、回収された濃縮残渣をカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ－５）で表される化合物６８．４９部を得た。
ＭＳ（質量分析）：３０５．０ ［Ｍ＋Ｈ］^＋ Synthesis Example 2 [Synthesis of compound represented by formula (I-5)]

80 parts of the compound represented by the formula (I-5a), 320 parts of methyl isobutyl ketone, 59 parts of pyridine and 2.1 parts of dimethylaminopyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 41.8 parts of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 23 ° C. for 18 hours. 1000 parts of ethyl acetate and 250 parts of 5% hydrochloric acid were mixed with the obtained reaction product, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. 500 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed three times. After concentrating the obtained organic layer, the recovered concentrated residue was put on a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1. ) By fractionation, 68.49 parts of the compound represented by the formula (I-5) was obtained.
MS (Mass Spectrometry): 305.0 [M + H] ⁺

式（Ｉ－２２－ａ）で表される化合物１．６５部、メチルイソブチルケトン２０部、ピリジン０．５９部及びジメチルアミノピリジン０．０２部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物０．４２部を添加し、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１０部を混合して２３℃で３０分間攪拌し、分液することにより有機層を回収した。得られた有機層に、イオン交換水２０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。得られた有機層を濃縮した後、回収された濃縮残渣をカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／４）分取することにより、式（Ｉ－２２）で表される化合物０．９４部を得た。
ＭＳ（質量分析）：５５６．８ ［Ｍ＋Ｈ］^＋ Synthesis Example 3 [Synthesis of compound represented by formula (I-22)]

1.65 parts of the compound represented by the formula (I-22-a), 20 parts of methyl isobutyl ketone, 0.59 parts of pyridine and 0.02 parts of dimethylaminopyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 0.42 part of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 23 ° C. for 18 hours. The obtained reaction product was mixed with 50 parts of ethyl acetate and 10 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed three times. After concentrating the obtained organic layer, the recovered concentrated residue was put on a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/4. ) By fractionation, 0.94 parts of the compound represented by the formula (I-22) was obtained.
MS (Mass Spectrometry): 556.8 [M + H] ⁺

式（Ｉ－２３－ａ）で表される化合物１．７０部、メチルイソブチルケトン２０部、ピリジン０．５９部及びジメチルアミノピリジン０．０２部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物０．４２部を添加し、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル５０部及び５％塩酸１０部を混合して２３℃で３０分間攪拌し、分液することにより有機層を回収した。得られた有機層に、イオン交換水２０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。得られた有機層を濃縮した後、回収された濃縮残渣をカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－２３）で表される化合物０．２２部を得た。
ＭＳ（質量分析）：５７２．８ ［Ｍ＋Ｈ］^＋ Synthesis Example 4 [Synthesis of compound represented by formula (I-23)]

1.70 parts of the compound represented by the formula (I-23-a), 20 parts of methyl isobutyl ketone, 0.59 part of pyridine and 0.02 part of dimethylaminopyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 0.42 part of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 23 ° C. for 18 hours. The obtained reaction product was mixed with 50 parts of ethyl acetate and 10 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed three times. After concentrating the obtained organic layer, the recovered concentrated residue was separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: ethyl acetate). 0.22 parts of the compound represented by (I-23) was obtained.
MS (Mass Spectrometry): 572.8 [M + H] ⁺

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

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

Example 1 [Synthesis of resin A1]
As the monomer, the monomer (a1-4-2), the monomer (I-1), the monomer (a1-1-3), the monomer (a1-2-6), the monomer (a3-1-1) and the monomer (II-). 2-A-1-1) is used, and its molar ratio [monomer (a1-4-2): monomer (I-1): monomer (a1-1-3): monomer (a1-2-6): monomer (A3-4-2): Monomer (II-2-A-1-1)] is mixed so as to have a ratio of 22:10:25:35: 5: 3, and further, this monomer mixture is added. A methylisobutylketone 1.5 times by mass was mixed with respect to the total mass of all the monomers. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% with respect to the total number of moles of all the monomers, and this was polymerized by heating at 85 ° C. for about 5 hours. Was done. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 6 hours and then separated. The recovered organic layer is poured into a large amount of n-heptane to precipitate a resin, and the resin is filtered and recovered to obtain a resin A1 (copolymer) having a weight ^average molecular weight of about 7.9 × 103 in a yield of 55. Obtained in%. This resin A1 has the following structural units.

Example 2 [Synthesis of resin A2]
As the monomer, a monomer (a1-4-2), a monomer (I-1), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and the molars thereof are used. The ratio [monomer (a1-4-2): monomer (I-1): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] is 25:10. Mixing so as to have a ratio of: 25: 35: ⁵ , a resin A2 (polymer) having a weight average molecular weight of about 7.7 × 103 is obtained in a yield of 64% by the same method as that of the resin A1. rice field. This resin A2 has the following structural units.

Example 3 [Synthesis of resin A3]
As the monomer, a monomer (a1-4-2), a monomer (I-1), a monomer (a1-1-3) and a monomer (a1-2-6) are used, and the molar ratio [monomer (a1-4-2-2)] is used. ): Monomer (I-1): Monomer (a1-1-3): Monomer (a1-2-6)] are mixed so as to have a ratio of 25:10:25:40, and is the same as the resin A1. By the method, a resin A3 (monomer) having a weight ^average molecular weight of about 7.4 × 103 was obtained in a yield of 60%. This resin A3 has the following structural units.

Example 4 [Synthesis of resin A4]
As the monomer, a monomer (a2-2-1), a monomer (I-1), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and their molars are used. The ratio [monomer (a1-4-2): monomer (I-1): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] is 25:10. The mixture was mixed so as to have a ratio of: 25: 35: 5, and further, 1.5 mass times of methyl isobutyl ketone was mixed with this monomer mixture with respect to the total mass of all the monomers. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% with respect to the total number of moles of all the monomers, and this was polymerized by heating at 75 ° C. for about 5 hours. Was done. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is added to a mixed solvent of methanol / water, repulped, and then filtered, which is performed twice to obtain a resin A4 (copolymer) having a weight ^average molecular weight of about 7.9 × 103. It was obtained with a yield of 58%. This resin A4 has the following structural units.

Example 5 [Synthesis of resin A5]
As the monomer, a monomer (a1-4-2), a monomer (I-5), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and their molars are used. The ratio [monomer (a1-4-2): monomer (I-5): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] is 25:10. Mixing so as to have a ratio of: 25: 35: ⁵ , a resin A5 (polymer) having a weight average molecular weight of about 8.2 × 103 is obtained in a yield of 60% by the same method as that of the resin A1. rice field. This resin A5 has the following structural units.

Example 6 [Synthesis of Resin A6]
As the monomer, a monomer (a1-4-2), a monomer (I-5), a monomer (a1-1-3) and a monomer (a1-2-6) are used, and the molar ratio [monomer (a1-4-2-2)] is used. ): Monomer (I-5): Monomer (a1-1-3): Monomer (a1-2-6)] are mixed so as to have a ratio of 25:10:25:40, and is the same as the resin A1. By the method, a resin A6 (polymer) having a weight ^average molecular weight of about 6.9 × 103 was obtained in a yield of 58%. This resin A6 has the following structural units.

Example 7 [Synthesis of Resin A7]
As the monomer, a monomer (a1-4-2), a monomer (I-22), a monomer (a1-1-3) and a monomer (a1-2-6) are used, and the molar ratio [monomer (a1-4-2-2)] is used. ): Monomer (I-22): Monomer (a1-1-3): Monomer (a1-2-6)] are mixed so as to have a ratio of 25:10:25:40, and is the same as the resin A1. By the method, a resin A7 (polymer) having a weight ^average molecular weight of about 7.1 × 103 was obtained in a yield of 50%. This resin A7 has the following structural units.

Example 8 [Synthesis of Resin A8]
As the monomer, a monomer (a1-4-2), a monomer (I-23), a monomer (a1-1-3) and a monomer (a1-2-6) are used, and the molar ratio [monomer (a1-4-2-2)] is used. ): Monomer (I-23): Monomer (a1-1-3): Monomer (a1-2-6)] are mixed so as to have a ratio of 25:10:25:40, and is the same as the resin A1. By the method, a resin A8 (polymer) having a weight ^average molecular weight of about 7.6 × 103 was obtained in a yield of 45%. This resin A8 has the following structural units.

Synthesis Example 5 [Synthesis of resin AX1]
As the monomer, a monomer (a1-4-2), a monomer (IX-1), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and their molars are used. The ratio [monomer (a1-4-2): monomer (IX-1): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] is 25:10. Mixing so as to have a ratio of: 25: 35: ⁵ , a resin AX1 (polymer) having a weight average molecular weight of about 7.8 × 103 is obtained in a yield of 66% by the same method as that of the resin A1. rice field. This resin AX1 has the following structural units.

Synthesis Example 6 [Synthesis of resin AX2]
As the monomer, a monomer (a1-4-2), a monomer (IX-5), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (a3-1-1) are used, and their molars are used. The ratio [monomer (a1-4-2): monomer (IX-5): monomer (a1-1-3): monomer (a1-2-6): monomer (a3-4-2)] is 25:10. Mixing so as to have a ratio of: 25: 35: 5, a resin AX2 (polymer) having a weight average molecular weight of about 8.8 × 10 ³ is obtained in a yield of 60% by the same method as that of the resin A1. rice field. This resin AX2 has the following structural units.

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

<Resin (A)>
A1 to A8, AX1, AX2: Resin A1 to Resin A8, Resin AX1, Resin AX2
<Acid generator (B)>
B1-25: Salt represented by the formula (B1-25); synthesized by the method described in JP-A-2011-126869

Ｄ１：（東京化成工業（株）製）

＜溶剤（Ｅ）＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １００部
γ－ブチロラクトン ５部 <Quencher (C)>
C1: Synthesized by the method described in JP-A-2011-390502.

D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent (E)>
Propylene Glycol Monomethyl Ether Acetate 400 Parts Propylene Glycol Monomethyl Ether 100 Parts γ-Butyrolactone 5 Parts

(Evaluation of electron beam exposure of resist composition)
A 6 inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, on a direct hot plate, a composition layer was formed by prebaking at the temperature shown in the “PB” column of Table 1 for 60 seconds. A line-and-space pattern was directly drawn on the composition layer formed on the wafer by using an electron beam lithography machine [“HL-800D 50keV” manufactured by Hitachi, Ltd.] by changing the exposure amount stepwise. ..
After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the “PEB” column of Table 1 for 60 seconds, and further paddle development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. , A resist pattern was obtained.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and the space width of the 60 nm line and space pattern were 1: 1 was defined as the effective sensitivity.

Line edge roughness evaluation (LER): The fluctuation width of the unevenness of the side wall surface of the resist pattern manufactured with effective sensitivity was measured with a scanning electron microscope, and the line edge roughness was determined. The results are shown in Table 2.

The resist composition of the present invention has good line edge roughness and is useful for microfabrication of semiconductors.

Claims (4)

A structural unit derived from the compound represented by the formula (I'), and a structural unit having an acid unstable group selected from at least one selected from the group composed of the formulas (a1-1) and (a1-2). Resin containing.

[In formula (I'),
R ¹ represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
Ar represents a phenylene group having a carboxyl group at the ortho position with respect to the bond position of L ^1' , and the phenylene group may have two or more iodine atoms.
L ^1'represents a single bond or -CO-O- * (* represents a bond with Ar).
In the formula (a1-1) and the formula (a1-2),
L ^a1 and ^{La 2} 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 them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ] A resist composition containing the resin and acid generator according to claim 1. The resist composition according to claim 2, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to claim 2 or 3 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) Step of heating the composition layer after exposure, and (5) Step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.