JP6865005B2 - Method for manufacturing resist composition and resist pattern - Google Patents

Description

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

Patent Document 1 describes a resist composition containing a compound represented by the following formula.

Japanese Unexamined Patent Publication No. 2010-83870

In the conventional resist composition, the line edge roughness (LER) at the time of producing the resist pattern is not always satisfactory.

［式（Ｉ）中、
Ｌ^１は、２価の炭素数１〜１２の飽和炭化水素基を表す。
Ｘ^１及びＸ^２は、互いに独立に、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−、＊−Ｏ−ＣＯ−Ｏ−又は＊−Ｏ−を表し、＊はＬ^１との結合位を表す。
Ｒ^１及びＲ^２は、互いに独立に、炭素数１〜８のフッ化アルキル基を表す。］
［２］Ｘ^１及びＸ^２が、＊−Ｏ−ＣＯ−である［１］記載のレジスト組成物。
［３］Ｌ^１が、炭素数１〜６のアルカンジイル基である［１］又は［２］記載のレジスト組成物。
［４］Ｌ^１が、−ＣＨ_２−Ｃ（ＣＨ_３）_２−ＣＨ_２−である［１］〜［３］のいずれか記載のレジスト組成物。
［５］Ｒ^１及びＲ^２が、互いに独立に、炭素数１〜４のフッ化アルキル基である［１］〜［４］のいずれか記載のレジスト組成物。
［６］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［１］〜［５］のいずれか記載のレジスト組成物。
［７］（１）［１］〜［６］のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present application includes the following inventions.
[1] A resist composition containing a compound represented by the formula (I), a resin having an acid unstable group, and an acid generator.

[In formula (I),
L ¹ represents a saturated hydrocarbon group having 1 to 12 divalent carbon atoms.
X ¹ and X ² independently represent * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * represents the binding ^{site with L 1.} Represent.
R ¹ and R ² represent alkyl fluoride groups having 1 to 8 carbon atoms independently of each other. ]
[2] The resist composition according to [1], ^{wherein X 1} and X ^{2 are * -O-CO-.}
[3] The resist composition according to [1] or [2], wherein ^{L 1 is an alkanediyl group having 1 to 6 carbon atoms.}
[4] The resist composition according to any one of [1] to [3], wherein ^{L 1} is −CH _2- C (CH ₃ ) _2- CH _2-.
[5] The resist composition according to any one of [1] to [4], wherein ^{R 1} and R ^{2 are alkyl fluoride groups having 1 to 4 carbon atoms independently of each other.}
[6] The resist composition according to any one of [1] to [5], further containing a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[7] (1) A step of applying the resist composition according to any one of [1] to [6] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
A method for producing a resist pattern, which comprises a step of (4) heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

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

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, a group that can take a linear or branched form such as an "aliphatic hydrocarbon group" includes any of them and is a "aliphatic type". "Hydrocarbon group" means a group obtained by removing a number of hydrogen atoms corresponding to a valence from the ring of an alicyclic hydrocarbon. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
As used herein, the term "(meth) acrylic monomer" means at least one type of monomer having a structure of _{"CH 2} = CH-CO-" or "CH ₂ = C (CH _{3) -CO-".} To do. Similarly, "(meth) acrylate" and "(meth) acrylic acid" mean "at least one of acrylate and methacrylate" and "at least one of acrylic acid and methacrylic acid", respectively. In addition, any of the groups described in the present specification that can have both a linear structure and a branched structure may be used.
Further, in the present specification, the “solid content of the resist composition” means the total amount of the components excluding the solvent (E) from the total amount of the resist composition.

<Resist composition>
The resist composition of the present invention comprises a compound represented by the formula (I) (hereinafter, may be referred to as “compound (I)”) and a resin having an acid unstable group (hereinafter, “resin (A)”). ) And an acid generator (hereinafter, may be referred to as “acid generator (B)”).
The "acid-unstable group" here has a leaving group, and the leaving group is eliminated by contact with an acid to convert it into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means a group.
In the resist composition of the present invention, in addition to the compound (I), the resin (A) and the acid generator (B), a weak acid intramolecular salt (hereinafter, may be referred to as “weak acid intramolecular salt (D)”) and the like. Contains a quencher (hereinafter, may be referred to as "citric acid (C)") and / or a solvent (hereinafter, may be referred to as "solvent (E)") such as a salt that generates a weakly acidic acid. Is preferable.

［式（Ｉ）中、
Ｌ^１は、２価の炭素数１〜１２の飽和炭化水素基を表す。
Ｘ^１及びＸ^２は、互いに独立に、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−、＊−Ｏ−ＣＯ−Ｏ−又は＊−Ｏ−を表し、＊はＬ^１との結合位を表す。
Ｒ^１及びＲ^２は、互いに独立に、炭素数１〜８のフッ化アルキル基を表す。］ <Compound (I)>

[In formula (I),
L ¹ represents a saturated hydrocarbon group having 1 to 12 divalent carbon atoms.
X ¹ and X ² independently represent * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * represents the binding ^{site with L 1.} Represent.
R ¹ and R ² represent alkyl fluoride groups having 1 to 8 carbon atoms independently of each other. ]

Examples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, among these groups. It may be a combination of two or more types.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl Group, Octane-1,8-Diyl Group, Nonan-1,9-Diyl Group, Decane-1,10-Diyl Group, Undecane-1,11-Diyl Group, Dodecane-1,12-Diyl Group Linear alkanediyl groups such as;
A linear alkanediyl group with an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, etc.) Propyl-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2,2-dimethylpropane-1,3 -Diyl group, 2-methylpropane-1,2-diyl group, pentane-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-1,2-diyl group, 1-methylcyclohexane-1,2-diyl group, cyclohexane-1,4-diyl group, cyclo A monocyclic divalent alicyclic saturated hydrocarbon group which is a cycloalkanediyl group such as an octane-1,2-diyl group and a cyclooctane-1,5-diyl group;
Norbornane-2,3-diyl group, norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantan-1,5-diyl group, adamantan-2,6-diyl group, etc. Examples thereof include a divalent alicyclic saturated hydrocarbon group.

As X ¹ and X ² , * -O-CO-, * -CO-O- or * -O-CO-O- (* ^{represents the binding site with L 1} ) is preferable, and * -O- CO- or * -CO-O- is preferable, and * -O-CO- (* represents the binding site with ^{L 1) is more preferable.}

Examples of the alkyl fluoride group include 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, and 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -2,2,2-trifluoro Ethyl group, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-Hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2- Trifluoroethyl group, 2- (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, 1,1,2,2,3,3,4,5,5,6,6-dodecafluoro Fluoroalkyl groups such as a hexyl group, a perfluoropentylmethyl group and a perfluorohexyl group can be mentioned. Of these, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a 1- (trifluoromethyl) -2,2,2-trifluoroethyl group and the like are preferable.

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

The content of compound (I) is 0.001 to 10% by mass, preferably 0.005 to 8% by mass, and more preferably 0.01 to 5% by mass, based on the solid content of the resist composition. %. The solid content of the resist composition and the content of the compound and / or resin relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

［式中、Ｌ^１、Ｘ^１、Ｘ^２、Ｒ^１及びＲ^２は、上記と同義である。］ <Method for producing compound (I)>
The ^{compound (I1) in which X 1} and X ² are * -O-CO- is a compound represented by the formula (I1-a), a compound represented by the formula (I1-b), and a compound represented by the formula (I1-b) and the formula (I1-c). ) Can be obtained by reacting with a compound represented by) in a solvent such as acetonitrile in the presence of a catalyst.
Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
Examples of the catalyst include a base catalyst (for example, pyridine, dimethylaminopyridine) and the like.

[In the formula, L ¹ , X ¹ , X ² , R ¹ and R ² are synonymous with the above. ]

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

Examples of the compounds represented by the formulas (Ib) and (Ic) include the compounds represented by the following, which are easily available on the market.

<Resin (A)>
The resin (A) has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). The "acid-unstable group" means a group having a leaving group, which is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group).
The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit (s) and a structural unit (t), which will be described later, and other structural units derived from monomers known in the art.

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

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

[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.
na represents 0 or 1.
* Represents a bond. ]

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

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

Examples of the group in which the alkyl group and the alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group and an adamantylmethyl group. Examples include a group, an adamantyldimethyl group, a norbornylmethyl group and the like.
na is preferably 0.

^{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 is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

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

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

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

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

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

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

In the resin (A), the content of the structural unit (a1) is preferably 30 to 90 mol%, more preferably 35 to 85 mol%, and further, with respect to all the structural units of the resin (A). It is preferably 40 to 80 mol%.

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

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

[In equation (a1-0),
L ^a01 represents an oxygen atom or _{^{* -O- (CH 2) k01 -CO}} -O- the stands, k01 represents an integer of 1-7, * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03, and R ^a04 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. ]

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

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

^La01 is preferably an oxygen atom or ^* -O- (CH ₂ ) _k01- CO-O- (where k01 is preferably an integer of 1 to 4, more preferably 1), more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03 and R ^a04 , the alicyclic hydrocarbon group and the group combining these groups include the same groups as those mentioned in ^{R a1 to} R ^{a3 of the formula (1).}
The alkyl groups of R ^a02 , R ^a03 and R ^a04 are preferably alkyl groups having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 are preferably aliphatic hydrocarbon groups having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
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 with these alkyl groups and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like. Be done.
R ^a02 and R ^a03 are preferably alkyl groups having 1 to 6 carbon atoms, and more preferably methyl groups or ethyl groups.
^Ra04 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.

^La1 and ^La2 are preferably −O− or ^* −O− (CH ₂ ) _{k1 ′} −CO−O− (where k1 ′ is an integer of 1 to 4, preferably 1). Yes), more preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and the group formed by combining them include the same groups as those listed in ^{R a1 to} R ^{a3 of the formula (1).}
The alkyl groups of R ^a6 and R ^a7 are preferably alkyl groups having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a6 and R ^a7 are preferably alicyclic hydrocarbon groups having 3 to 8 carbon atoms, more preferably 3 to 6 or less alicyclic hydrocarbon groups.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1'is preferably 0 or 1.

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

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

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

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

When the resin (A) contains a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is the total structure of the resin (A). 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（ａ１−３）中、
Ｒ^a9は、ヒドロキシ基を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基、水素原子又は−ＣＯＯＲ^a13を表す。
Ｒ^a13は、炭素数１〜８の脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、又はこれらを組み合わせることにより形成される基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表すか、Ｒ^a10及びＲ^a11は互いに結合して、それらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。］ Further, as the structural unit (a1) having the group (1), a structural unit represented by the formula (a1-3) can also be mentioned. The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Further, the monomer for inducing the structural unit (a1-3) may be referred to as a monomer (a1-3).

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

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

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

Specifically, the monomer (a1-3) is 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 5-norbornene-2-carboxylic acid. Acid 1-methylcyclohexyl, 5-norbornen-2-carboxylic acid 2-methyl-2-adamantyl, 5-norbornen-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornen-2-carboxylic acid 1- (4) -Methylcyclohexyl) -1-methylethyl, 5-norbornen-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornen-2-carboxylic acid 1-methyl-1- (4-oxo) Cyclohexyl) ethyl and 5-norbornen-2-carboxylic acid 1- (1-adamantyl) -1-methylethyl and the like can be mentioned.

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

When the resin (A) contains structural units (a1-3), the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). 20-85 mol% is more preferred.

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

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

^Examples of the alkyl group of R a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -Perfluorohexyl group and the like can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon group R ^a34 and R ^a35, include the same groups as R ^{a1 'and} R ^a2' of formula (2).
The R ^a36, include alkyl groups having 1 to 18 carbon atoms, alicyclic hydrocarbon group having 3 to 18 carbon atoms, a group formed by combining these or aromatic hydrocarbon group having 6 to 18 carbon atoms Be done.

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

Examples of the monomer for deriving the structural unit (a1-4) include the monomers described in JP-A-2010-204646. Among them, the monomers represented by the formulas (a1-4-1) to (a1-4-8) are preferable, and the formulas (a1-4-1) to (a1-4-5 and a1-4) are preferable. The monomers represented by -8)) are more preferable.

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

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

In equation (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms, 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 from 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 methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group and trifluoromethyl. Group is mentioned.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
s1 is preferably 1.
s1'preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH _2- CO-O-. * Represents a bond with ^{L 51.}

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

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

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

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid-labile 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-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a lactone ring and no acid-labile group. If a resin having a unit (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

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

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

［式（ａ２−０）中、
Ｒ^a30は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一であっても異なってもよい。］ Examples of the structural unit (a2) having a phenolic hydroxy group include a structural unit represented by the formula (a2-0) (hereinafter, may be referred to as “structural unit (a2-0)”).

[In equation (a2-0),
^Ra30 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or the like. Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, the plurality of Ra ^31s may be the same or different from each other. ]

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an n-pentyl group, an n-hexyl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -Perfluorohexyl group and the like can be mentioned. R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkoxy group of Ra31 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
The ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

Examples of the monomer for inducing the structural unit (a2-0) include the monomers described in JP-A-2010-204634.
Among them, the structural unit (a2-0) is represented by the formula (a2-0-1), the formula (a2-0-2), the formula (a2-0-3) and the formula (a2-0-4), respectively. The one represented by the formula (a2-0-1) or the formula (a2-0-2) is more preferable.

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

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

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

[In equation (a2-1),
^La3 represents −O− or ^* −O− (CH ₂ ) _k2 −CO−O−.
k2 represents an integer of 1-7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents an integer from 0 to 10. ]

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

Examples of the monomer for inducing the structural unit (a2-1) include the monomers described in JP-A-2010-204646. The monomer represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable, and the monomer represented by any of the formulas (a2-1-1) to (a2-1-4) is represented. The monomer represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

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

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

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

[In equation (a3-1),
^La4 represents a group represented by −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer from 0 to 5. When p1 is 2 or more, a plurality of Ra ^21s are the same or different from each other.
In equation (a3-2),
^La5 represents a group represented by −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer from 0 to 3. When q1 is 2 or more, a plurality of ^Ra22s are the same or different from each other.
In formula (a3-3),
^La6 represents a group represented by −O− or ^* −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer from 0 to 3. When r1 is 2 or more, a plurality of ^Ra23s are the same or different from each other.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
L ^a7 is -O-, ^* -O-L ^a8- O-, ^* -O-L ^a8- CO-O-, ^* -O-L ^a8- CO-O-L ^a9- CO-O- or ^* Represents −O−L ^a8 −O−CO−L ^a9 −O−.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other.
w1 represents an integer from 0 to 8.
^Ra25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. ]

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

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

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

In formula (a3-4)
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably −O− or ^* −O−L ^a8 −CO—O−, and more preferably −O−, −O—CH ₂ −CO—O− or −O—C ₂ H. _4- CO-O-.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.

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 formulas (a3-1-1) to formula (a3-1-4), formulas (a3-2-1) to formulas (a3-2-4), and formulas (a3-3-3). 1) The structural unit represented by any of the formulas (a3-3-4) and the formulas (a3-4-1) to (a3-4-6) is preferable, and the formula (a3-1-1), It is represented by any of the formulas (a3-1-2), formulas (a3-2-3) to formulas (a3-2-4), and formulas (a3-4-1) to formulas (a3-4-12). The structural unit is more preferable, and the structural unit represented by any of the formulas (a3-4-1) to (a3-4-12) is more preferable, and the structural units represented by the formulas (a3-4-1) to (a3-4-1) are more preferable. The structural unit represented by any of 4-6) is even more preferable.

In the structural unit represented by the following formula (a3-4-1) ~ formula (a3-4-12), compound methyl group corresponding to R ^a24 is replaced by a hydrogen atom, the structural unit (a3-4 ) Can be given 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 to 60 mol%.
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 each relative to all the structural units of the resin (A). Therefore, 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

<Structural unit (t)>
The resin (A) may contain other structural units (t) as structural units other than the structural unit (a1) and the structural unit (s). The structural unit (t) is a structural unit other than the structural unit (a2) and the structural unit (a3) and may have a halogen atom (hereinafter, may be referred to as a “structural unit (a4)”. ) And a structural unit having a non-desorbed hydrocarbon group (hereinafter, may be referred to as “structural unit (a5)”) and the like.

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

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

Examples of the aliphatic saturated hydrocarbon group of L ⁵ include 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 perfluoro alkanediyl group L ^3, difluoromethylene group, a perfluoroalkyl ethylene group, perfluoroethyl fluoro methylene group, perfluoro-1,3-diyl group, perfluoro-1,2-diyl group, perfluoropropane-2,2 -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -Diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like can be mentioned.
The perfluorocycloalkanes diyl group L ^3, perfluoro-cyclohexane diyl group, perfluoro cyclopentanediyl group, perfluoro cycloheptane-diyl group, a perfluoroalkyl adamantane-diyl group and the like.

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

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

Among the compounds represented by the formulas (a4-0-1) to (a4-0-16), the compounds in which ^{the methyl group corresponding to R 5} is replaced with a hydrogen atom are also represented by the formula (a4-0). It can be mentioned as a specific example of the structural unit.

［式（ａ４−１）中、
Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^ａ４２は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ａ^ａ４１は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１）で表される基を表す。］

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

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-. Good.
^Aa41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). ]

[In the formula (ag1),
s represents 0 or 1.
A a ⁴² and A a ⁴⁴ represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent independently of each other.
A ^a43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 represent an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group independently of each other.
However, the total number of carbon atoms of ^{A a42} , A ^a43 , A ^a44 , X ^a41 and X ^{a42 is 7 or less.}
** and ** represent a bond, and ** is a bond with -O-CO-R ^a42 . ]

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

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 an alkyl group such as a group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. The cyclic aliphatic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* is a bond). A polycyclic group such as (representing a hand) can be mentioned.

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

［式（ａ−ｇ３）中、
Ｘ^ａ４３は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ａ４５は、少なくとも１つのハロゲン原子を有する炭素数１〜１７の脂肪族炭化水素基を表す。
＊は、結合手を表す。］ ^Examples of the substituent of R a42 include a halogen atom or a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (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 ^{Ra 42.}
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and is an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). Is more preferable.
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, 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 carbons. It is a perfluoroalkyl group of 1 to 6, and more 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 group 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 ^{number of carbon atoms of the aliphatic hydrocarbon group of A a46} is preferably 1 to 6, and more preferably 1 to 3.
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 cyclohexyl group or an adamantyl group.

The preferred structure represented by * -A ^a46- X ^a44- A ^a47 is the following structure.

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

^{The aliphatic hydrocarbon groups A a42 to} A ^a44 in the group (a-g1) may have a carbon-carbon unsaturated bond, but chain-type and cyclic aliphatic saturated hydrocarbon groups and these are used. Groups formed by combining are preferred. The aliphatic saturated hydrocarbon group includes a linear and branched alkyl group, an alicyclic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining an alkyl group and an alicyclic hydrocarbon group. Can be mentioned. 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 to} A a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

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

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

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

The ^{alkanediyl group of A f1} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexine-1,6-diyl group and other linear alkanediyl groups; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 Examples thereof include branched alkanediyl groups such as −diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type and a group formed by a combination thereof. 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 -Ethylhexyl group is mentioned.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group. 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 ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
As the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-Hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2- Trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3 , 4,4,5,5-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, 1,1,2,2,3,3,4,5,5,6,6-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.

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

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

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

^Examples of the alkanediyl group of A f11 include the same groups as the alkanediyl group of A ^f1 .
The aliphatic hydrocarbon group of A ^f13 includes a chain type and a cyclic type aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 include an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Be done.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group; a difluoromethylene group and a perfluoroethylene group. Examples thereof include a perfluoroalkandyl group such as a group, a perfluoropropanediyl group, a perfluorobutandyl group and a perfluoropentandyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantandiyl group, a norbornanediyl group, and a perfluoroadamantandiyl group.

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

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

Examples of the structural unit represented by the formula (a4-2) include the structural units represented by the formulas (a4-1-1) to (a4-1-22).

Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1'-1) to (a4-1'-22).

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

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

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

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 units.

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

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

The alicyclic hydrocarbon group of R ⁵² may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
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. Alkyl groups such as octyl group and 2-ethylhexyl group can be mentioned.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

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

［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、互いに独立に、単結合又は炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^ｘ５〜Ｌ^ｘ７の合計炭素数は、１５以下である。
式（Ｌ１−４）中、
Ｌ^ｘ８及びＬ^ｘ９は、互いに独立に、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^ｘ１は、炭素数３〜１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^ｘ８、Ｌ^ｘ９及びＷ^ｘ１の合計炭素数は、１５以下である。］ Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by 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 x1} and L ^{x2 is 16 or less.}
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total number of carbon atoms of ^{L x3} and L ^{x4 is 17 or less.}
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms independently of each other.
However, the total number of carbon atoms of ^{L x5 to} 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 independently of each other.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total number of carbon atoms 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 ^x5 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 ^x1 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 following divalent groups.

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

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

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

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

Examples of the structural unit (a5-1) include the following.

In the formulas (a5-1-1) to (a5-1-18), ^{the structural unit in which the methyl group corresponding to R 51} is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a5-1). it can.

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

The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is, a copolymer of a monomer (a1) and a monomer (s).
The structural unit (a1) is preferably at least one of a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably a structural unit (a1-). 1).
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). It is at least one of the structural units represented by.

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

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

<Resin 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 composed of only the structural unit (s) and a resin containing the structural unit (a4) (however, the resin does not include the structural unit (a1), and may be hereinafter referred to as "resin (X)". .) Etc. can be mentioned. Of these, the resin (X) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, based on the total of all the structural units of the resin (X). , 50 mol% or more is more preferable.
Examples of the structural unit that the resin (X) may further include include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers.
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).
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 2 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 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. The following is preferable.

<Acid generator (B)>
The acid generator is classified into a nonionic 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 nonionic acid generators 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. 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 Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, and Japanese Patent Application Laid-Open No. 63-163452. Kaisho 62-153853, Japanese Patent Application Laid-Open No. 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. Moreover, you may use the compound produced by the known method. As the acid generator (B), one type may be used alone, or two or more types may be used in combination.

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

[In equation (B1),
Q ¹ and ^{Q 2} independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. _{-CH 2-} contained in the hydrogen group may be replaced with -O-, -SO _{2- or -CO-.}
Z ⁺ represents an organic cation. ]

The perfluoroalkyl group of Q ¹ and Q ^2, a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, a perfluoro sec- butyl group, perfluoro-tert- butyl group, perfluoropentyl group, and a perfluoro Hexyl groups and the like can be mentioned.
Q ¹ and Q ² 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 of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl Group, Octane-1,8-Diyl Group, Nonan-1,9-Diyl Group, Decane-1,10-Diyl Group, Undecane-1,11-Diyl Group, Dodecane-1,12-Diyl Group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Ethan-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-} contained in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- are any of the formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with −Y.

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

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

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

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

[In equation (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In equation (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total 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 number of carbon atoms 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. You may. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total 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. You may. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

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

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, an oxocyclohexylcarbonyloxy group, a hydroxycyclohexylcarbonyloxy 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 monovalent alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11).
_{When -CH 2-} contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. There may be more than one. Examples of such a group include groups represented by the formulas (Y12) to (Y38).

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

Among them, the group represented by any one of the formulas (Y1) to (Y20), the formula (Y30), and the formula (Y31) is preferably mentioned, and the formula (Y11), the formula (Y15), and the formula (Y31) are more preferable. Examples include groups represented by Y16), formula (Y19), formula (Y20), formula (Y30) or formula (Y31), more preferably represented by formula (Y11), formula (Y15) or formula (Y30). The group to be used is mentioned.

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. 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 and a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. Alternatively, it represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Ja represents an integer of 0 to 4) and the like.
Examples of the substituent of the monovalent alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkyl group containing a hydroxy group having 1 to 12 carbon atoms, and 3 carbon atoms. ~ 16 monovalent alicyclic hydrocarbon group, 1 to 12 carbon number alkoxy group, 6 to 18 carbon number monovalent aromatic hydrocarbon group, 7 to 21 carbon number aralkyl group, 2 to 2 carbon number 4 acyl group, 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 and a monovalent fat having 3 to 16 carbon atoms. It represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Ja represents an integer of 0 to 4) and the like.

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
The monovalent aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group; a trill group, a xsilyl group, a cumenyl group and a mesityl. Examples thereof include an aryl group such as a group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl 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.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bonding position with Y. It is preferable that the -CH _{2- of the} group is replaced with -O- or -CO-. _{In this case, -CH 2-} contained in the methyl group of Y does not replace -O- or -CO-.

Y is preferably a monovalent 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. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented 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-46) [hereinafter, "anion (B1)" according to the formula number. -A-1) "etc. ] Are preferable, and formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), formulas (B1-A-24) to formulas (B1-A-24) to formulas. Anions represented by any of (B1-A-33) and formulas (B1-A-36) to (B1-A-40) are more preferable.

Here, R ^{i2 to} R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. It is a group formed by the above, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and ^{Q 2} are the same as above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

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

Among them, equations (B1a-1) to (B1a-3) and equations (B1a-7) to (B1a-16), equations (B1a-18), equations (B1a-19), and equations (B1a-22). ) Is preferred.
Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodine cation. These include, more preferably aryl sulfonium cations.
^{Z +} in the formula (B1) is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" or the like according to the formula number. In some cases. ].

［式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^ｂ４〜Ｒ^ｂ６は、互いに独立に、炭素数１〜３０の１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜３６の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の１価の脂肪族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の１価の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、互いに独立に、０〜５の整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上のとき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、炭素数１〜３６の１価の脂肪族炭化水素基又は炭素数３〜３６の１価の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−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１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数３〜１８の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素基に含まれる水素原子は、炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２のアルコキシ基又は炭素数１〜１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^ｂ１１とＲ^ｂ１２とは、一緒になってそれらが結合する−ＣＨ−ＣＯ−を含む環を形成していてもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ１３〜Ｒ^ｂ１８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の１価の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^ｂ３１は、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、互いに独立に、０〜５の整数を表す。
ｑ２及びｒ２は、互いに独立に、０〜４の整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 are independent of each other, a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group represents a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, and a monovalent alicyclic hydrocarbon having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom and has 1 to 18 carbon atoms. It may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom or a hydroxy. It may be substituted with a 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, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent integers 0 to 5 independently of each other.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring 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 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 contains a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the monovalent aromatic hydrocarbon group may be substituted. The contained hydrogen atom may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be combined to form a ring containing -CH-CO- to which they are bonded, and -CH _2- contained in the ring is -O-, -SO-. Alternatively, it may be replaced with −CO−.
R ^{b13 to} R ^b18 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 represent integers 0 to 5 independently of each other.
q2 and r2 represent integers 0 to 4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s may be the same or different, and 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１価の脂環式炭化水素基の炭素数は、好ましくは３〜１８であり、より好ましくは４〜１２である。 The monovalent aliphatic hydrocarbon group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 -Alkyl groups of ethylhexyl groups can be mentioned. Among them, the ^{monovalent aliphatic hydrocarbon groups of R b9 to} R ^b12 preferably have 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic monovalent alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclo. Cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

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

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

Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a tolyl group, a xsilyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a p-cyclohexylphenyl group and a p-. Examples thereof include aryl groups such as adamantylphenyl group, biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl group.
When the monovalent aromatic hydrocarbon group contains a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, the monovalent aliphatic hydrocarbon group or carbon having 1 to 18 carbon atoms A monovalent alicyclic hydrocarbon group having a number of 3 to 18 is preferable.
Examples of the monovalent aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the monovalent aliphatic hydrocarbon group in which the hydrogen atom is 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 methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, and the like. Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.

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

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

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

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

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

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

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

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

Examples of the acid generator (B1) preferably include those represented by the formulas (B1-1) to (B1-40), and preferably the formulas (B1-1) and the formula (B1-1) containing an arylsulfonium cation. B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1) -13), formula (B1-14), formula (B1-17), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-24), formula (B1-2) 25), formula (B1-26), formula (B1-29), formula (B1-31), formula (B1-32), formula (B1-33), formula (B1-34), formula (B1-35) ), Formula (B1-36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40), respectively.

The content of the acid generator (B1) is preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less, based on the total amount of the acid generator (B). Preferably, it is substantially only the acid generator (B1).
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). (Below). The resist composition of the present invention may contain one kind of acid generator (B) or a plurality of kinds.

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

Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. Esters; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butylolactone; 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 amine and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine. , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine , Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, Triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4) −Pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethane, 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.

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

<Salt that generates acid with 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. , And more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid intramolecular salt represented by the formula (D), and JP-A-2012-229206, JP-A-2012-229206. Examples thereof include the salts described in Japanese Patent Application Laid-Open No. 2012-6908, Japanese Patent Application Laid-Open No. 2012-721109, Japanese Patent Application Laid-Open No. 2011-39502, and Japanese Patent Application Laid-Open No. 2011-191745.

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

[In formula (D),
R ^D1 and R ^D2 independently have a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, and an acyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group, a nitro group or a halogen atom having 2 to 7 carbon atoms.
m'and n'independently represent integers from 0 to 4, and when m'is 2 or more, multiple ^RD1s are the same or different, and when n'is 2 or more, multiple ^RD2s are. Same or different. ]

^{The hydrocarbon groups of RD1} and ^RD2 in the compound represented by the formula (D) include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Examples thereof include groups formed by combining these.
Examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and nonyl group.
The monovalent alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and may be saturated or unsaturated. Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group, norbonyl group, adamantyl group and the like can be mentioned.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group and 4-. Propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, trill group, xsilyl group , Cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and other aryl groups.
Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, and an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 1-phenyl-1 group. -Propyl group, 1-Phenyl-2-propyl group, 2-Phenyl-2-propyl group, 3-Phenyl-1-propyl group, 4-Phenyl-1-butyl group, 5-Phenyl-1-pentyl group, 6 −Phenyl-1-hexyl group, etc.) and the like.

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

In the formula (D), ^RD1 and ^RD2 independently have an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. An acyl group of 4 and an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom are preferable.
For m'and n', an integer of 0 to 2 is preferable, and 0 is more preferable, respectively. When m'is 2 or more, the plurality of R ^D1s are the same or different, and when n'is 2 or more, the plurality of R ^D2s are the same or different.

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

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

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

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

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (X), the resin (A) and the acid generator (B) of the present invention, as well as a quencher (C), a solvent (E) and other components used as necessary. It can be prepared by mixing (F). 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 resin or the like and the solubility of the resin or the like in the solvent (E). The mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing 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 on 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 prebaking), or by using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure at the time of vacuum drying is preferably about 1~1.0 × 10 ⁵ Pa.

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

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

The heated composition layer is usually developed using a developing solution using a developing device. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The developing temperature is preferably 5 to 60 ° C., and the developing 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 developing solution include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples thereof include ether solvents; amide solvents such as N and N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, 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 even 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 developed resist pattern with a rinse 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 ArF. It is suitable as a resist composition for excimer laser immersion exposure and is useful for fine processing of semiconductors.

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicating the content or the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
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 analysis (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３．３６部、テトラヒドロフラン１６．８０部及びピリジン６．３８部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１−ｂ）で表される化合物２５．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル２２５部及び５％塩酸７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１）で表される化合物６．８９部を得た。
ＭＳ（質量分析）：３９６．０（分子イオンピーク） Synthesis Example 1 [Synthesis of compound represented by formula (I-1)]

3.36 parts of the compound represented by the formula (I-1-a), 16.80 parts of tetrahydrofuran and 6.38 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 25.00 parts of the compound represented by the formula (I-1-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 225 parts of ethyl acetate and 70 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) and represented by the formula (I-1). 6.89 parts of the compound was obtained.
MS (Mass Spectrometry): 396.0 (Molecular Ion Peak)

式（Ｉ−１１−ａ）で表される化合物３．８１部、テトラヒドロフラン１６．８０部及びピリジン６．３８部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１１−ｂ）で表される化合物２５．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル２２５部及び５％塩酸７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１１）で表される化合物５．８２部を得た。
ＭＳ（質量分析）：４１０．１（分子イオンピーク） Synthesis Example 2 [Synthesis of compound represented by formula (I-11)]

3.81 parts of the compound represented by the formula (I-11-a), 16.80 parts of tetrahydrofuran and 6.38 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 25.00 parts of the compound represented by the formula (I-11-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 225 parts of ethyl acetate and 70 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) and represented by the formula (I-11). To obtain 5.82 parts of the compound.
MS (Mass Spectrometry): 410.1 (Molecular Ion Peak)

式（ａ４−１−ｘ１−ａ）で表される化合物６７．５６部、テトラヒドロフラン１３５部、ピリジン１５．３９部及びジメチルアミノピリジン０．７９部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ１−ｂ）で表される化合物２０．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル３８０部及び５％塩酸１７１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液５４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮することにより、式（ａ４−１−ｘ１−ｃ）で表される化合物１５．２６部を得た。

式（ａ４−１−ｘ１−ｃ）で表される化合物１５．２５部、テトラヒドロフラン１０５部及びピリジン８．４１部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ１−ｄ）で表される化合物３２．９５部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル５３０部及び５％塩酸９３部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１０５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液４４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１６０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（ａ４−１−ｘ１）で表される化合物２２．５６部を得た。
ＭＳ（質量分析）：３１８．１（分子イオンピーク） Synthesis Example 3 [Synthesis of compound represented by formula (a4-1-x1)]

67.56 parts of the compound represented by the formula (a4-1-x1-a), 135 parts of tetrahydrofuran, 15.39 parts of pyridine and 0.79 parts of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 20.00 parts of the compound represented by the formula (a4-1-x1-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 380 parts of ethyl acetate and 171 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 77 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 54 parts of a 10% potassium carbonate aqueous solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 15.26 parts of the compound represented by the formula (a4-1-x1-c) was obtained.

15.25 parts of the compound represented by the formula (a4-1-x1-c), 105 parts of tetrahydrofuran and 8.41 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 32.95 parts of the compound represented by the formula (a4-1-x1-d) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 530 parts of ethyl acetate and 93 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 105 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 44 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 160 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) by the formula (a4-1-x1). 22.56 parts of the represented compound was obtained.
MS (Mass Spectrometry): 318.1 (Molecular Ion Peak)

式（ａ４−１−ｘ２−ａ）で表される化合物１０部、テトラヒドロフラン５０部、ピリジン４．０６部及びジメチルアミノピリジン０．５２部を添加した後、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ２−ｂ）で表される化合物１３．０４部を３０分かけて添加し、さらに、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル２５０部及び５％塩酸８９部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液３５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮することにより、式（ａ４−１−ｘ２−ｃ）で表される化合物１０．９４部を得た。

式（ａ４−１−ｘ２−ｃ）で表される化合物１０．９４部、テトラヒドロフラン６５部及びピリジン５．５７部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ２−ｄ）で表される化合物２１．８６部を３０分かけて添加した。その後、さらに、２３℃で６時間攪拌した。得られた反応物に、酢酸エチル３２０部及び５％塩酸６２部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水６５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液３０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した後、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（ａ４−１−ｘ２）で表される化合物１５．７３部を得た。
ＭＳ（質量分析）：３３２．１（分子イオンピーク） Synthesis Example 4 [Synthesis of compound represented by formula (a4-1-x2)]

After adding 10 parts of the compound represented by the formula (a4-1-x2-a), 50 parts of tetrahydrofuran, 4.06 parts of pyridine and 0.52 parts of dimethylaminopyridine, the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 13.04 parts of the compound represented by the formula (a4-1-x2-b) was added over 30 minutes, and the mixture was further stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 250 parts of ethyl acetate and 89 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 35 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 75 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 10.94 parts of the compound represented by the formula (a4-1-x2-c) was obtained.

10.94 parts of the compound represented by the formula (a4-1-x2-c), 65 parts of tetrahydrofuran and 5.57 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 21.86 parts of the compound represented by the formula (a4-1-x2-d) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 6 hours. The obtained reaction product was charged with 320 parts of ethyl acetate and 62 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 65 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 30 parts of a 10% potassium carbonate aqueous solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 100 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. After concentrating the recovered organic layer, the concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to formulate (Kanto Chemical Co., Ltd.) 15.73 parts of the compound represented by a4-1-x2) was obtained.
MS (Mass Spectrometry): 332.1 (Molecular Ion Peak)

式（Ｉ−１６−ａ）で表される化合物２．４５部、テトラヒドロフラン１２．２７部及びピリジン７．６５部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１−ｂ）で表される化合物２５．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル１６５部及び５％塩酸８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１６）で表される化合物６．４８部を得た。
ＭＳ（質量分析）：３６８．０（分子イオンピーク） Synthesis Example 5 [Synthesis of compound represented by formula (I-16)]

2.45 parts of the compound represented by the formula (I-16-a), 12.27 parts of tetrahydrofuran and 7.65 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 25.00 parts of the compound represented by the formula (I-1-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 165 parts of ethyl acetate and 85 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 85 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 5 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) and represented by the formula (I-16). 6.48 parts of the compound was obtained.
MS (Mass Spectrometry): 368.0 (Molecular Ion Peak)

式（Ｉ−１６−ａ）で表される化合物３０．６８部、テトラヒドロフラン１５５部及びピリジン９．５７部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１−ｂ）で表される化合物２５．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル６８５部及び５％塩酸１０６部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１４０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液１１２部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１４０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、回収された有機層を濃縮することにより、式（ａ４−１−ｘ３−ｃ）で表される化合物１０．４０部を得た。

式（ａ４−１−ｘ３−ｃ）で表される化合物１０．３９部、テトラヒドロフラン１２５部、ピリジン２．２４部及びジメチルアミノピリジン０．２９部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ３−ｄ）で表される化合物７．５７部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル４８０部及び５％塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液２１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１４０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（ａ４−１−ｘ３）で表される化合物１０．８２部を得た。
ＭＳ（質量分析）：２９０．１（分子イオンピーク） Synthesis Example 6 [Synthesis of compound represented by formula (a4-1-x3)]

30.68 parts of the compound represented by the formula (I-16-a), 155 parts of tetrahydrofuran and 9.57 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 25.00 parts of the compound represented by the formula (I-1-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 685 parts of ethyl acetate and 106 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 140 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 112 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 140 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The recovered organic layer is concentrated by separating the obtained concentrated mass into a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). To obtain 10.40 parts of the compound represented by the formula (a4-1-x3-c).

10.39 parts of the compound represented by the formula (a4-1-x3-c), 125 parts of tetrahydrofuran, 2.24 parts of pyridine and 0.29 parts of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 7.57 parts of the compound represented by the formula (a4-1-x3-d) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 480 parts of ethyl acetate and 50 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 100 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 21 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 140 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) by the formula (a4-1-x3). 10.82 parts of the represented compound was obtained.
MS (Mass Spectrometry): 290.1 (Molecular Ion Peak)

式（Ｉ−１６−ａ）で表される化合物４９．３６部、テトラヒドロフラン１３５部、ピリジン１５．３９部及びジメチルアミノピリジン０．７９部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４−１−ｘ３−ｄ）で表される化合物２０．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル３８０部及び５％塩酸１７１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液５４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、回収された有機層を濃縮することにより、式（ａ４−１−ｘ４−ｃ）で表される化合物３８．４８部を得た。

式（ａ４−１−ｘ４−ｃ）で表される化合物１２．７７部、テトラヒドロフラン１０５部及びピリジン８．４１部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１−ｂ）で表される化合物３２．９５部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル５３０部及び５％塩酸９３部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１０５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液４４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１６０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（ａ４−１−ｘ４）で表される化合物１６．４８部を得た。
ＭＳ（質量分析）：２９０．１（分子イオンピーク） Synthesis Example 7 [Synthesis of compound represented by formula (a4-1-x4)]

49.36 parts of the compound represented by the formula (I-16-a), 135 parts of tetrahydrofuran, 15.39 parts of pyridine and 0.79 parts of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 20.00 parts of the compound represented by the formula (a4-1-x3-d) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 380 parts of ethyl acetate and 171 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 77 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 54 parts of a 10% potassium carbonate aqueous solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The recovered organic layer is concentrated by separating the obtained concentrated mass into a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). Obtained 38.48 parts of the compound represented by the formula (a4-1-x4-c).

12.77 parts of the compound represented by the formula (a4-1-x4-c), 105 parts of tetrahydrofuran and 8.41 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 32.95 parts of the compound represented by the formula (I-1-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. The obtained reaction product was charged with 530 parts of ethyl acetate and 93 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 105 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 44 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 160 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) by the formula (a4-1-x4). 16.48 parts of the represented compound was obtained.
MS (Mass Spectrometry): 290.1 (Molecular Ion Peak)

特開２００８−２０９９１７号公報に記載された方法によって得られた式（Ｂ１−２１−ｂ）で表される化合物３０．００部、式（Ｂ１−２１−ａ）で表される塩３５．５０部、クロロホルム１００部及びイオン交換水５０部を仕込み、２３℃で１５時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水３０部を添加し、水洗した。この操作を５回繰り返した。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ−ブチルメチルエーテル１００部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１−２１−ｃ）で表される塩４８．５７部を得た。 Synthesis Example 8 [Synthesis of salt represented by formula (B1-21)]

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

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

20.00 parts of the salt represented by the formula (B1-21-c), 2.84 parts of the compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23 ° C. for 30 minutes. .. To the obtained mixed solution, 0.21 part of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 1 hour. The obtained reaction solution was concentrated, 200 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the liquid was separated and the organic layer was taken out. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and the obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. Then, 113.05 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 10.47 parts of a salt represented by the formula (B1-21).
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 339.1

式（Ｂ１−２２−ａ）で表される塩１１．２６部、式（Ｂ１−２２−ｂ）で表される化合物１０．００部、クロロホルム５０部及びイオン交換水２５部を仕込み、２３℃で１５時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水１５部を添加し、水洗した。この操作を５回繰り返した。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ−ブチルメチルエーテル５０部を加えて２３℃で３０分間攪拌した。その後、ろ過することにより、式（Ｂ１−２２−ｃ）で表される塩１１．７５部を得た。 Synthesis Example 9 [Synthesis of salt represented by formula (B1-22)]

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

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

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged and charged at 23 ° C. for 30 minutes. Stirred. To the obtained mixed solution, 0.12 parts of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 30 minutes. The obtained reaction solution was concentrated, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the liquid was separated and the organic layer was taken out. 12.50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to remove the organic layer. This washing operation was repeated 8 times. The obtained organic layer was concentrated, and 50 parts of tert-butyl methyl ether was added to the obtained residue and stirred.
Then, by filtration, 6.84 parts of a salt represented by the formula (B1-22) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

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

Synthesis Example 10 [Synthesis of resin A1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio [monomer (a1-1-1)] is used. -3): Monomer (a1-2-9): Monomer (a2-1-1): Monomer (a3-4-2)] are mixed so as to be 45: 14: 2.5: 38.5. A propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is dissolved again in propylene glycol monomethyl ether acetate, and the obtained solution is poured into a methanol / water mixed solvent to precipitate the resin, and the resin is filtered. the resin A1 having a molecular weight of 7.9 × 10 ³ was obtained in 70% yield. This resin A1 has the following structural units.

Synthesis Example 11 [Synthesis of resin X1]
A monomer (a4-1-7) was used as a monomer, and methyl isobutyl ketone 1.5% by mass of the total amount of the monomer was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to this solution in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total amount of monomers, and these were added at 75 ° C. It was heated for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, to obtain a resin X1 of weight average molecular weight 1.7 × 10 ⁴ in 81% yield. This resin X1 has the following structural units.

Synthesis Example 12 [Synthesis of resin X2]
As the monomer, a monomer (a4-1-x1) and a monomer (a4-1-7) are used, and the molar ratio thereof (monomer (a4-1-x1): monomer (a4-0-12)) is 50:50. Methyl isobutyl ketone was added in an amount of 0.6% by mass of the total amount of the monomers to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 4.5 mol% based on the total amount of monomers, and the mixture was heated at 75 ° C. for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, the weight-average molecular weight 9.2 × 10 ³ of the resin X2 (copolymer) 80% yield I got it in. This resin X2 has the following structural units.

Synthesis Example 13 [Synthesis of resin X3]
As the monomer, a monomer (a4-1-x2) and a monomer (a4-1-7) are used, and the molar ratio (monomer (a4-1-x2): monomer (a4-0-12)) is 80:20. Propylene glycol monomethyl ether acetate, which is 1.5 times by mass of the total amount of monomers, was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 4.5 mol% based on the total amount of monomers, and the mixture was heated at 75 ° C. for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, the weight-average molecular weight 8.8 × 10 ³ of the resin X3 (copolymer) to yield 78% I got it in. This resin X3 has the following structural units.

Synthesis Example 14 [Synthesis of resin X4]
As the monomer, a monomer (a4-1-x3) and a monomer (a4-1-7) are used, and the molar ratio (monomer (a4-1-x3): monomer (a4-0-12)) is 80:20. Propylene glycol monomethyl ether acetate, which is 1.5 times by mass of the total amount of monomers, was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 4.5 mol% based on the total amount of monomers, and the mixture was heated at 75 ° C. for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, the weight-average molecular weight 8.2 × 10 ³ of the resin X4 (copolymer) 75% yield I got it in. This resin X4 has the following structural units.

Synthesis Example 15 [Synthesis of resin X5]
As the monomer, a monomer (a4-1-x4) and a monomer (a4-1-7) are used, and the molar ratio thereof (monomer (a4-1-x4): monomer (a4-0-12)) is 80:20. Propylene glycol monomethyl ether acetate, which is 1.5 times by mass of the total amount of monomers, was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 4.5 mol% based on the total amount of monomers, and the mixture was heated at 75 ° C. for about 5 hours. The reaction mixture obtained, the resin was precipitated by pouring into a large amount of methanol / water mixed solvent, the resin was filtered, the weight-average molecular weight 8.6 × 10 ³ of the resin X5 (copolymer) 70% yield I got it in. This resin X5 has the following structural units.

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

＜クエンチャー（Ｃ）＞
Ｃ１：２，６−ジイソプロピルアニリン（東京化成工業（株）製）
Ｃ２：テトラブチルアンモニウムヒドロキシド（東京化成工業（株）製）
Ｄ１：（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２−ヘプタノン ２０部
γ−ブチロラクトン ３．５部 <Resin>
A1, X1 to X5: Resin A1, Resin X1 to Resin X5
<Acid generator>
B1-21: Salt represented by the formula (B1-21) B1-22: Salt represented by the formula (B1-22) <Compound (I)>
I-1: Compound represented by formula (I-1) I-11: Compound represented by formula (I-11) I-16: Compound represented by formula (I-16) <Compound (IX) ＞
IX: Compound represented by the formula (IX): Synthesized according to an example of JP-A-2010-83870.

<Quencher (C)>
C1: 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)
C2: Tetrabutylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene Glycol Monomethyl Ether Acetate 265 Parts Propylene Glycol Monomethyl Ether 20 Parts 2-Heptanone 20 Parts γ-Butyrolactone 3.5 Parts

<Manufacturing of resist pattern and its evaluation>
A composition for an organic antireflection film [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] is applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (prebaking) was 85 nm.
The obtained silicon wafer was prebaked (PB) on a direct hot plate at the temperature listed in the "PB" column of Table 1 for 60 seconds. On the wafer on which the resist composition film was formed in this way, the exposure amount was stepwise using an ArF excimer stepper for immersion exposure [XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Anal XY polarization]. The line and space pattern was immersed in the liquid exposure. Ultrapure water was used as the immersion medium.
After exposure, post-exposure baking (PEB) is performed on a hot plate at the temperature listed in the “PEB” column of Table 1 for 60 seconds, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed to obtain a resist pattern.

In each of the obtained resist pattern films, the exposure amount at which the line-and-space pattern of 50 nm was 1: 1 was defined as the effective sensitivity.

<Line edge roughness evaluation (LER)>
The wall surface of the resist pattern after the lithography process was observed with a scanning electron microscope, and the deflection width (nm) of the unevenness of the side wall of the resist pattern was determined. The results of this swing width are shown in Table 2.

上記の結果から、本発明のレジスト組成物によれば、ラインエッジラフネスが良好であることがわかる。

From the above results, it can be seen that the resist composition of the present invention has good line edge roughness.

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

Claims (8)

A resist composition containing a compound represented by the formula (I), a resin having an acid unstable group, and an acid generator.

[In formula (I),
L ¹ represents a saturated hydrocarbon group having 1 to 12 divalent carbon atoms.
X ¹ and ^{X 2,} * -O-CO - represents, * represents a binding position with the ^{L 1.}
R ¹ and R ² represent alkyl fluoride groups having 1 to 8 carbon atoms independently of each other. ] A resist composition containing a compound represented by the formula (I), a resin having an acid unstable group, and an acid generator.

[In formula (I),
L ¹ represents −CH ₂ −C (CH ₃ ) ₂ −CH ₂₋ .
X ¹ and X ² independently represent * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * represents the binding ^{site with L 1.} Represent.
R ¹ and R ² represent alkyl fluoride groups having 1 to 8 carbon atoms independently of each other. ] A resist composition containing a compound represented by the formula (I), a resin having an acid unstable group, and an acid generator.

[In formula (I),
L ¹ represents a saturated hydrocarbon group having 1 to 12 divalent carbon atoms.
X ¹ and X ² independently represent * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * represents the binding ^{site with L 1.} Represent.
R ¹ and R ² represent alkyl fluoride groups having 1 to 4 carbon atoms independently of each other. ] The resist composition according to claim 2 or 3 , wherein X ¹ and X ² are * -O-CO-. The resist composition according to any one of claims 1 and 3 and claim 4, wherein L ¹ is an alkanediyl group having 1 to 6 carbon atoms. The resist composition according to claim 4 , wherein L ¹ _{is −CH 2} −C (CH ₃ ) ₂ −CH ₂ −. The resist composition according to any one of claims 1 to 6 , 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 any one of claims 1 to 7 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 step of heating the composition layer after exposure, and (5) A step of developing the composition layer after heating,
A method for producing a resist pattern including.