JP2021193178A - Resin, resist composition and method for producing resist pattern - Google Patents

Abstract

To provide a resin which enables production of a resist pattern with good CD uniformity (CDU), and a resist composition containing the resin.SOLUTION: There are provided a resin having a structural unit including a group represented by a formula (aa1) and a structural unit represented by a formula (a1-0-X), a resist composition and a method for producing a resist pattern. In the formula (aa1), Xa and Xb each independently represent an oxygen atom or the like; and W1 and W2 each independently represent an alicyclic hydrocarbon group having 3 to 36 carbon atoms or the like.SELECTED DRAWING: None

Description

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

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

Japanese Unexamined Patent Publication No. 2006-146143

The resist pattern formed from the resist composition containing the above resin may not always be satisfactory in CD uniformity (CDU).

［式（ａａ１）中、
Ｘ^a及びＸ^bは、それぞれ独立に、酸素原子又は硫黄原子を表す。
Ｗ^１及びＷ^２は、それぞれ独立に、炭素数３〜３６の脂環式炭化水素基を含む炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−に置き換わっていてもよく、該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２〜１３のアシル基、炭素数２〜１３のアシルオキシ基、シアノ基、カルボキシル基又はこれらを組み合わせた基で置換されていてもよい。
＊は、結合手を表す。］

［式（ａ１−０−Ｘ）中、
Ｌ^a01’は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k00−ＣＯ−Ｏ−を表し、ｋ００は１〜７のいずれかの整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01’は、水素原子又はメチル基を表す。
Ｒ^a02’、Ｒ^a03’及びＲ^a04’は、それぞれ独立に、炭素数１〜６の直鎖又は分岐のアルキル基を表す。］
［２］式（ａａ１）で表される基を含む構造単位が、ビニル基、イソプロペニル基、アクリロイル基及びメタアクリロイル基からなる群から選ばれる少なくとも１つの基と、式（ａａ１）で表される基とを有するモノマーに由来する構造単位である［１］記載の樹脂。
［３］ビニル基、イソプロペニル基、アクリロイル基及びメタアクリロイル基からなる群から選ばれる少なくとも１つの基と、式（ａａ１）で表される基とを有するモノマーが、式（Ｉ）で表される化合物である［２］に記載の樹脂。

［式（Ｉ）中、
Ｗ^１、Ｗ^２、Ｘ^ａ及びＸ^ｂは、それぞれ、上記と同じ意味を表す。
Ｒ²は、水素原子又はメチル基を表す。
Ｘ^１は、式（Ｘ^１−１）〜式（Ｘ^１−４）のいずれかで表される基を表す。

（式（Ｘ^１−１）〜式（Ｘ^１−４）中、＊はＡ^１との結合手を表す。）
Ａ¹は、単結合又は炭素数１〜２４の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］
［４］さらに、式（ａ１−０−Ｘ）で表される構造単位とは異なる酸不安定基を有する構造単位を含む［１］〜［３］のいずれかに記載の樹脂。
［５］式（ａ１−０−Ｘ）で表される構造単位とは異なる酸不安定基を有する構造単位が、式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）で表される構造単位からなる群から選ばれる少なくとも一種である［４］記載の樹脂。

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01、Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a01、Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。但し、Ｒ^a02、Ｒ^a03及びＲ^a04の少なくとも一つは、炭素数３〜１８の脂環式炭化水素基を含む基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］
［６］［１］〜［５］のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物。
［７］酸発生剤が、式（Ｂ１）で表される塩である［６］記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８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−ＣＨ₂−は、−Ｏ−、−ＳＯ₂−又は−ＣＯ−に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］
［８］酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する［６］又は［７］記載のレジスト組成物。
［９］さらに、フッ素原子を有する構造単位を含む樹脂を含有する［６］〜［８］のいずれか記載のレジスト組成物。
［１０］（１）［６］〜［９］のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程、
を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin having a structural unit containing a group represented by the formula (aa1) and a structural unit represented by the formula (a1-0-X).

[In the formula (aa1),
X ^a and X ^b independently represent an oxygen atom or a sulfur atom, respectively.
W ¹ and W ² independently represent a hydrocarbon group containing an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and −CH ₂ − contained in the hydrocarbon group is −O−, −S. -, - CO- or -SO ₂ - may be replaced to a hydrogen atom contained in the hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, carbon It may be substituted with an acyloxy group, a cyano group, a carboxyl group, or a group combining these groups of numbers 2 to 13.
* Represents a bond. ]

[In the formula (a1-0-X),
L ^{a01 'represents} an oxygen atom or _{* -O- (CH 2) k00 -CO} -O- the stands, k00 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' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. ]
[2] The structural unit containing the group represented by the formula (aa1) is represented by the formula (aa1) and at least one group selected from the group consisting of a vinyl group, an isopropenyl group, an acryloyl group and a metaacryloyl group. The resin according to [1], which is a structural unit derived from a monomer having a group and a group.
[3] A monomer having at least one group selected from the group consisting of a vinyl group, an isopropenyl group, an acryloyl group and a metaacryloyl group and a group represented by the formula (aa1) is represented by the formula (I). The resin according to [2], which is a compound.

[In formula (I),
W ¹ , W ² , X ^a and X ^b have the same meanings as described above, respectively.
R ² represents a hydrogen atom or a methyl group.
X ¹ represents a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -4).

(Formula ^(X 1 -1) ~ Formula ^(X 1 -4) in which * represents a bond to ^{A 1.)}
A ¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]
[4] The resin according to any one of [1] to [3], further comprising a structural unit having an acid unstable group different from the structural unit represented by the formula (a1-0-X).
[5] The structural units having an acid unstable group different from the structural units represented by the formula (a1-0-X) are the formula (a1-0), the formula (a1-1) and the formula (a1-2). The resin according to [4], which is at least one selected from the group consisting of structural units represented by.

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^a01 , L ^a1 and L ^a2 independently represent −O− or * −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. Represents a bond with −CO−.
R ^a01 , R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups. However, ^{at least one of R a02} , R ^a03 and R ^{a04 represents} a group containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]
[6] A resist composition containing the resin and acid generator according to any one of [1] to [5].
[7] The resist composition according to [6], wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and −CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ − may be replaced with −O −, −SO _{2− or −CO−.}
Z ⁺ represents an organic cation. ]
[8] The resist composition according to [6] or [7], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[9] The resist composition according to any one of [6] to [8], further containing a resin containing a structural unit having a fluorine atom.
[10] (1) A step of applying the resist composition according to any one of [6] to [9] 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 manufacturing a resist pattern including.

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

As used herein, the term "(meth) acrylate" means "at least one of acrylate and methacrylate," respectively. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

〔resin〕
The resin of the present invention has a structural unit (hereinafter, may be referred to as "structural unit (aa1)") containing a group represented by the formula (aa1) and a structural unit represented by the formula (a1-0-X). Hereinafter, it is a resin (hereinafter, may be referred to as “resin (A)”) containing a “structural unit (a1-0-X)”).

［式（ａａ１）中、Ｘ^a及びＸ^bは、それぞれ独立に、酸素原子又は硫黄原子を表す。
Ｗ^１及びＷ^２は、それぞれ独立に、置換基を有していてもよい炭素数３〜３６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−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−に置き換わっていてもよい。
＊は、結合手を表す。］ [Structural unit (aa1)]

[In the formula (aa1), X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
W ¹ and W ² each independently represent an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a substituent, and −CH ₂ − contained in the alicyclic hydrocarbon group is , -O-, -S-, -CO- or -SO _2- may be replaced.
* Represents a bond. ]

X ^a and X ^b are preferably the same atom, and more preferably both oxygen atoms.
It is preferable that the carbon atom to which X ^a and W ¹ are bonded and the carbon atom to which X ^b and W ^{1 are bonded are different carbon atoms.}

The ^{alicyclic hydrocarbon group represented by W 1} and W ² may be a monocyclic ring or a polycyclic ring. Further, _-CH 2 contained in the alicyclic hydrocarbon group represented by ^{W 1} and ^{W 2} - is, -O -, - S -, - CO- or -SO ₂ - may be replaced in, - It is preferable to replace it with O- or -CO-.
The ^{alicyclic hydrocarbon group represented by W 1} and W ² may have a substituent, and examples of the substituent include the groups described in Group A.
Group A: hydroxy group, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, acyl group with 2 to 13 carbon atoms, acyloxy group with 2 to 13 carbon atoms, alkoxycarbonyl with 2 to 13 carbon atoms. Group, cyano group, carboxyl group or a group combining these

Alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Nonyl groups and the like can be mentioned.
The alkoxy group having 1 to 12 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and an undecyloxy group. Groups, dodecyloxy groups and the like can be mentioned.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group and a pentylcarbonyl. Examples thereof include an oxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.
Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, and a 2-ethylhexyloxycarbonyl group. Examples thereof include a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecyloxycarbonyl group, and a dodecyloxycarbonyl group.
Examples of the group combining these include an alkoxyalkoxyalkyl group, an alkoxyacyloxy group, and a hydroxyalkyl group.
The substituent is preferably a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms.

［式（ｗ１−１）〜式（ｗ１−１３）中、環に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−に置き換わっていてもよく、環に含まれる水素原子は、群Ａから選ばれる置換基で置換されていてもよい。］ Examples of the alicyclic hydrocarbon group represented by W ¹ and W ² include a group derived from a ring represented by the formulas (w1-1) to (w1-13).
The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and among them, the ring represented by the formula (w1-1) and the alicyclic hydrocarbon group represented by the formula (w1-2). A ring, a ring represented by the formula (w1-3), a ring represented by the formula (w1-6), or a ring represented by the formula (w1-12) is preferable.

Wherein (W1-1) ~ formula (w1-13), -CH ₂ contained in the ring - is, -O -, - S -, - CO- or -SO ₂ - may be replaced, the ring The hydrogen atom contained in may be substituted with a substituent selected from the group A. ]

Examples of the group represented by the formula (aa1) include the groups represented by the following.

［式（Ｉ）中、Ｗ^１、Ｗ^２、Ｘ^ａ及びＸ^ｂは、それぞれ、上記と同じ意味を表す。
Ｒ²は、水素原子又はメチル基を表す。
Ｘ^１は、式（Ｘ^１−１）〜式（Ｘ^１−４）のいずれかで表される基を表す。

（式（Ｘ^１−１）〜式（Ｘ^１−４）中、＊はＡ^１との結合手を表す。）
Ａ¹は、単結合又は炭素数１〜２４の２価の脂肪族炭化水素基を表し、該脂肪族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。］ The structural unit (aa1) is a structural unit derived from a monomer having at least one group selected from the group consisting of a vinyl group, an isopropenyl group, an acryloyl group and a metaacryloyl group, and a group represented by the formula (aa1). Is preferable,
It is more preferable that the structural unit is derived from the compound represented by the formula (I).

[In the formula (I), W ¹ , W ² , X ^a and X ^b have the same meanings as described above, respectively.
R ² represents a hydrogen atom or a methyl group.
X ¹ represents a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -4).

(Formula ^(X 1 -1) ~ Formula ^(X 1 -4) in which * represents a bond to ^{A 1.)}
A ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the aliphatic hydrocarbon group is replaced with -O- or -CO-. May be good. ]

Examples of the divalent aliphatic hydrocarbon group represented by A ¹ include an alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and two or more of these groups. It may be a combination of.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decane-1,10-Diyl group, Undecan-1,11-Diyl group, Dodecan-1,12-Diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic hydrocarbon group;
Polycyclic divalent alicyclic hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. And so on.

（式（ａ−ｇ１）中、ｓは０〜２のいずれかの整数を表す。
Ａ^１０は、炭素数１〜５の２価の脂肪族炭化水素基を表す。
Ａ^１１は、単結合又は炭素数１〜５の２価の脂肪族炭化水素基を表す。
ｓが２のとき、複数存在するＡ^１０は、互いに同一であるか相異なる。
Ｘ^１０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。
ｓが２のとき、複数存在するＸ^１０は、互いに同一であるか相異なる。） The ^{group in which the methylene group contained in the divalent aliphatic hydrocarbon group represented by A 1} is replaced with -O- or -CO- is a group represented by the formula (a-g1) (hereinafter, "group"). (A-g1) "may be mentioned.) And the like.

(In the equation (a-g1), s represents an integer of 0 to 2.
A ¹⁰ represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ¹¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When s is 2, A ¹⁰ there are a plurality, different or identical to each other.
X ¹⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
When s is 2, a plurality of X ^10s are the same as or different from each other. )

The divalent aliphatic hydrocarbon group represented by ^{A 10} and A ^{11 is preferably an alkanediyl group.} The alkanediyl group may be linear or branched, and may be, for example, a methylene group, an ethylene group, a 1,2-propanediyl group, a 1,3-propanediyl group, or a 1,4-butanediyl group. , 1,5-Pentandyl group, 1,3-Pentandyl group and the like, preferably a methylene group and an ethylene group.

Specific examples of the group (ag1) are shown below. In each specific example, * represents a bond.

A ¹ is preferably a single bond or a group (ag1), more preferably a single bond.

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

Among the above compounds, a compound in which ^{a methyl group corresponding to R 2} is replaced with a hydrogen atom can also be mentioned as a specific example of the compound represented by the formula (I).

The content of the structural unit (aa1) contained in the resin (A) is usually 1 to 60 mol%, preferably 3 to 40 mol%, more preferably, with respect to all the structural units of the resin (A). Is 5 to 25 mol%.
The resin (A) may contain two or more kinds of structural units (aa1).

［式（ａ１−０−Ｘ）中、Ｌ^a01’は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k00−ＣＯ−Ｏ−を表し、ｋ００は１〜７のいずれかの整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01’は、水素原子又はメチル基を表す。
Ｒ^a02’、Ｒ^a03’及びＲ^a04’は、それぞれ独立に、炭素数１〜６の直鎖又は分岐のアルキル基を表す。］ [Structural unit (a1-0-X)]

Wherein ^{(a1-0-X), L a01} ' represents an oxygen atom or _{* -O- (CH 2) k00 -CO} -O- the stands, k00 represents an integer of 1-7, * Represents a bond with a carbonyl group.
R ^{a01'represents} a hydrogen atom or a methyl group.
R ^a02' , R ^a03'and R ^a04' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. ]

The alkyl groups of R ^a02' , R ^a03' and R ^a04' include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group and the like. Can be mentioned.

As the structural unit (a1-0-X), for example, a structural unit represented by any of the formulas (a1-0-1) to (a1-0-4) is 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-X).

The content of the structural unit (a1-0-X) is usually 5 to 90 mol%, preferably 10 to 85 mol%, and more preferably 15 to 15 to 90 mol% with respect to all the structural units of the resin (A). It is 80 mol%.

The resin (A) may contain two or more kinds of structural units (a1-0-X).
The resin (A) may further contain a structural unit having an acid unstable group different from the structural unit represented by the formula (a1-0-X) (hereinafter, may be referred to as "structural unit (a1)"). good.

The "acid-unstable group" is a structural unit having a leaving group, and the leaving group is removed by contact with an acid, and the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means the group to do.

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。
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)”). The acid unstable group contained in the structural unit (a1) is a group represented by the following formula (1) (hereinafter, may be referred to as “group (1)”) and / or the following formula (2). The represented group (hereinafter, may be referred to as "group (2)") is 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, 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. _{-CH 2} − contained in the ring group may be replaced with −O − or −S−.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

アルキル基と脂環式炭化水素基とを組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 group of R ^{a1 to} R ^a3 may be either a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 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 hydrocarbon group R ^{a1 '~R a3',} for example, an alkyl group, an alicyclic hydrocarbon group, and a group formed by combining an aromatic hydrocarbon group and thereof.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group, mesityl group and biphenyl. Examples thereof include an aryl group such as a group, a phenanthryl group, a 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl.
^{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.

Examples of the group (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) and a 2-alkyladamantan-. 2-Iloxycarbonyl 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- (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) and the like.
Of R ^{a1 'and} R ^a2', it is preferable that at least one is a hydrogen atom.

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

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

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

As the structural unit derived from the (meth) acrylic monomer having the group (1), the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1) or the formula (a1-1) is preferable. Examples thereof include structural units represented by 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 for inducing structural unit (a1-1) and structural unit (a1-) The monomer that induces 2) may be referred to as a monomer (a1-0), a monomer (a1-1), and a monomer (a1-2), respectively.

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01、Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a01、Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。但し、Ｒ^a02、Ｒ^a03及びＲ^a04の少なくとも一つは、炭素数３〜１８の脂環式炭化水素基を含む基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^a01 , L ^a1 and L ^a2 independently represent −O− or * −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. Represents a bond with −CO−.
R ^a01 , R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups. However, ^{at least one of R a02} , R ^a03 and R ^{a04 represents} a group containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]

^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 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 group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 are preferably alicyclic hydrocarbon groups having 3 to 15 carbon atoms, more preferably 5 to 12 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are preferably −O− or * −O− (CH ₂ ) _{k1 ′} −CO−O− (where k1 ′ is an integer of any of 1 to 4, and is preferable. Is 1), 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 mentioned 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 group of R ^a6 and R ^a7 is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 or less.
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 (a1-0-5) to (a1-0-12) is preferable, and the structural units (a1-0-5) 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 1-methylcyclopentane-1-yl (meth) acrylate, 1-ethylcyclopentane-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, and the like. 1-Ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptane-1-yl (meth) acrylate, 1-ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentane-1-yl Examples thereof include (meth) acrylate and 1-isopropylcyclohexane-1-yl (meth) acrylate. Monomers represented by any of the formulas (a1-2-1) to (a1-2-12) are preferable, and formulas (a1-2-3), formulas (a1-2-4), and formulas (a1-) are preferable. The monomer represented by 2-9) or the formula (a1-2-10) is more preferable, and the monomer represented by the formula (a1-2-3) or the formula (a1-2-9) is further preferable.

When the resin (A) contains at least one selected from the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2), the total content of these is the total content 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 all structural units.

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

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

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

Further, as the structural unit (a1), the hydrogen atom bonded to the main chain of the following structural unit and the structural unit represented by the formulas (a1-4-4) to (a1-4-8) becomes a methyl group. Examples include replaced structural units.

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

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

The resin (A) may further contain a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”) and / or other structural unit (t) described later.

<Structural unit (s)>
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid unstable group is preferable. A structure having a hydroxy group and no acid unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or having a lactone ring and no acid unstable group. If a resin having a unit (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.

［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のいずれかの整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一であっても異なってもよい。］ Examples of the structural unit (a2) having a phenolic hydroxy group include structural units represented by the formula (a2-0) (hereinafter, may be referred to as “structural unit (a2-0)”).

[In the formula (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 Represents a methacryloyloxy group.
ma represents an integer of 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 1,1,1. 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 -Pelfluorohexyl 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 having 1 to 6 carbon atoms 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 having 2 to 4 carbon atoms include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
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) having a phenolic hydroxy group, the content thereof is preferably 5 to 95 mol%, preferably 10 to 80 mol% with respect to all the structural units of the resin (A). % Is more preferred, and 15-80 mol% is even more preferred.

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

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

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

Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable, and any of the formulas (a2-1-1) to (a2-1-4) is used. The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is further 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%.

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 , The structural unit (a2) having a phenolic hydroxy group is preferable. 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 may be a structural unit (a2-1). More preferred.
The resin (A) may contain two or more kinds of structural units (a2).

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

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。］

[In equation (a3-1),
L ^a4 represents −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 is an integer of any of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In formula (a3-2),
L ^a5 represents −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 is an integer of any of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents any 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 −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 is an integer of any of 1 to 7.
) Represents a group. * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents any 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, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents any integer from 0 to 3. When w1 is 2 or more, a plurality of ^Ra25s are the same or different from each other.

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. ]

Examples of the aliphatic hydrocarbon group of R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Alkyl groups can be mentioned.
Examples of the halogen atom of 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 a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formula (a3-1) ~ formula (a3-3), L ^a4 ~L ^a6 are each independently preferably, -O- or is either an integer k3 is 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 an integer of 0 to 2, and more preferably 0 or 1.

（式中、Ｒ^a2４、Ｌ^a７は、上記と同じ意味を表す。） In formula (a3-4)
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
L ^a7 is preferably -O- or * -O-L ^a8- CO-O-, and more preferably -O-, -O-CH ₂ -CO-O- or -O-C ₂ H. _4- CO-O-.
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4)'.

(In the formula, R ^a24 and ^{La 7} have the same meanings as above.)

Examples of the monomer for deriving the structural unit (a3) include the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and the monomer described in JP-A-2012-41274. Can be mentioned. The structural unit (a3) includes equations (a3-1-1) to (a3-1-4), equations (a3-2-1) to (a3-2-4), and equations (a3-3-3). 1) The structural unit represented by any one of the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12) 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 units are more preferable, and the structural units represented by any of the formulas (a3-4-1) to (a3-4-12) are more preferable, and 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 units represented by the following formulas (a3-4-1) to (a3-4-12), ^{the compound in which the methyl group corresponding to R a24} is replaced with a hydrogen atom is also a structural unit (a3-4). ) Can be mentioned as a specific example.

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

<Other structural units (t)>
The resin (A) may contain other structural units (t) as structural units other than the structural unit (a1) and the structural unit (s). As the structural unit (t), a structural unit having a halogen atom in addition to the structural unit (a2) and the structural unit (a3) (hereinafter, sometimes referred to as “structural unit (a4)”) and a non-desorbed hydrocarbon group are used. Examples thereof include structural units (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５〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
As the halogen atom in the structural unit (a4), a fluorine atom is preferable. Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0).

Wherein (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 5 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the aliphatic saturated hydrocarbon group of L ^5, include alkanediyl group having 1 to 4 carbon atoms, e.g., methylene group, ethylene group, propane-1,3-diyl, butane-1,4-diyl group Such as linear alkanediyl group, linear alkanediyl group having an alkyl group (among others, methyl group, ethyl group, etc.) side chain, ethane-1,1-diyl group, propane-1,2 Examples thereof include branched alkanediyl groups such as −diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

The perfluoroalkanediyl group of L ³ includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane-2,2. -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -Diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like can be mentioned.
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 represents preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ³ is preferably a perfluoro alkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoro alkanediyl group having 1 to 3 carbon atoms.

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

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

［式（ａ４−１）中、Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ａ^a41は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１１）で表される基を表す。

〔式（ａ−ｇ１１）中、ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の脂肪族炭化水素基を表す。
Ａ^a43は、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又は単結合を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は６以下である。〕
ただし、Ａ^a41及びＲ^a42のうち少なくとも一方は、置換基としてハロゲン原子を有する基である。
＊及び＊＊は結合手を表し、＊が−Ｏ−ＣＯ−Ｒ^ａ４２との結合手を表す。］
ｓは０が好ましい。 Examples of the structural unit (a4) include a structural unit represented by the formula (a4-1).

[In the formula (a4-1), R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and −CH ₂ − contained in the hydrocarbon group may be replaced with −O− or −CO−. good.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (a-g11).

[In the formula (a-g11), s represents 0 or 1.
A a ⁴² and A a ⁴⁴ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents an aliphatic hydrocarbon group or a single bond having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 independently represent -O-, -CO-, -CO-O- or -O-CO-, respectively.
However, the total number of carbon atoms of ^{A a42} , A ^a43 , A ^a44 , X ^a41 and X ^{a42 is 6 or less.} ]
However, ^{at least one of A a41} and R ^a42 is a group having a halogen atom as a substituent.
* And ** represent a bond, and * represents a bond with -O-CO-R ^a42 . ]
s is preferably 0.

芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基等が挙げられる。 ^Examples of the hydrocarbon group of R a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups. Chain-type aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, hexadecyl group, pentadecyl group and hexyldecyl group. , Heptadecyl group, octadecyl group and other alkyl groups. Cyclic alicyclic fatty group hydrocarbon groups include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (*). Represents a bond.) Examples thereof include a polycyclic alicyclic hydrocarbon group.

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

^As the hydrocarbon group of R a42, a chain type or a cyclic type aliphatic hydrocarbon group and a group formed by combining these are preferable. These groups may have a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups and groups formed by combining them are more preferable.

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

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

Examples of the aliphatic hydrocarbon group of A ^{a45 include} the same groups as those exemplified in ^{R a42.}
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). ..

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 particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.

When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (ag3), the aliphatic hydrocarbon includes the number of carbon atoms contained in the group represented by the formula (ag3). The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［式（ａ−ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
Ｘ^a44は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^a47は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合手を表す。］ The aliphatic hydrocarbon having a group represented by the formula (ag3) is more preferably a group represented by the formula (ag2).

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

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

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

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

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

^Examples of the group (a-g11) in which X a42 is an oxygen atom 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 the formula (a4-2), R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

The ^{alkanediyl group of A f1} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexine-1,6-diyl group and other linear alkanediyl groups; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 Examples thereof include branched alkanediyl groups such as a-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 and an alicyclic hydrocarbon group are preferable.
Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2 -Examples include ethylhexyl groups.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a methylcyclohexyl group. , Cycloalkyl groups such as dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, and a norbornyl group. Examples thereof include a methylnorbornyl group and an isobornyl group.

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.
Specifically, examples of the alkyl group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, and a 2,2,2-trifluoroethyl group. Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-Tetrafluoroethyl group, Perfluoropropyl group, 1,1,2,2-Tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3 , 4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl Fluoroalkyl groups such as 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.

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

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

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

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

The aliphatic hydrocarbon group of A ^f13 includes either a chain type or a cyclic type, and a divalent aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The ^{aliphatic hydrocarbon group which may have a fluorine atom of A f13} is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include 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 perfluoropentanediyl 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 either a chain type or a cyclic type, and an aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The ^{aliphatic hydrocarbon group which may have a fluorine atom of A f14} is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Chain-type aliphatic hydrocarbon groups that may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, and 1,1. , 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, Examples thereof include a heptyl group, a perfluoroheptyl group, an octyl group and a perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In the formula (a4-3), examples of ^{A f11,} ethylene group is preferable.
The aliphatic hydrocarbon group of A ^f13 preferably has 1 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^f14 preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, 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 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、それぞれ独立に、１〜６のいずれかの整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ The structural unit (a4) may be a structural unit represented by the formula (a4-4).

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

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

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

Examples of the structural unit represented by the formula (a4-4) include the following structural units.

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

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但し、Ｌ⁵⁵との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ⁵⁵は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-desorbing hydrocarbon group contained in the structural unit (a5) include a linear, branched or cyclic hydrocarbon group, and preferably an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

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

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

Examples of the divalent saturated hydrocarbon group of L ⁵⁵ include a divalent chain-type saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain-type saturated hydrocarbon group is preferable. ..
Examples of the divalent chain 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^x1及びＬ^x2の合計炭素数は、１７以下である。
式（Ｌ１−３）中、
Ｌ^x5は、炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x７は、それぞれ独立に、単結合又は炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x5、Ｌ^x6及びＬ^x7の合計炭素数は、１５以下である。
式（Ｌ１−４）中、
Ｌ^x8及びＬ^x9は、互いに独立に、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^x1は、炭素数３〜１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^x8、Ｌ^x9及びＷ^x1の合計炭素数は、１５以下である。 Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by the formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

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

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

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

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

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

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

L ⁵⁵ is preferably a single bond, a methylene group, an ethylene group or a group represented by the formula (L1-1), and more preferably a single bond or a group represented by the formula (L1-1). ..

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

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

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

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

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

<Resist composition>
The resist composition of the present invention contains the above-mentioned resin and an acid generator.
The resist composition preferably contains a quencher (hereinafter, may be referred to as “quencher (C)”), and preferably contains a solvent (hereinafter, may be referred to as “solvent (E)”).

<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 containing a structural unit (t).

As the resin other than the resin (A), a resin containing the structural unit (a4) (however, the resin does not include the structural unit (a1); hereinafter may be referred to as “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, still more preferably 50 mol% or more, based on all the structural units of the resin (X). ..
Examples of the structural unit that the resin (X) may further include include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers.
The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further, with respect to 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, and particularly preferably 2 to 30 parts by mass.

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

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

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

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、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の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter, may be referred to as “acid generator (B1)”).

[In formula (B1),
Q ¹ and ^{Q 2} 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 an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ - is, -O -, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]

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

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

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

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

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

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

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

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

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

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

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

In formulas (b1-10) and (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 alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
_{When -CH 2-} contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. .. Examples of such a group include groups represented by the formulas (Y12) to (Y35).

That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each replaced with an oxygen atom, and the two oxygen atoms are combined with an arcandyl group having 1 to 8 carbon atoms to form a ketal ring. Alternatively, it may contain a structure in which an oxygen atom is bonded to different carbon atoms. However, 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, it is preferably a group represented by any one of the formulas (Y1) to (Y20), formula (Y30) and formula (Y31), and more preferably the formula (Y11), formula (Y15) and formula (Y11). Y16), a group represented by the formula (Y20), the formula (Y30) or the formula (Y31), and more preferably a group represented by the formula (Y11), the formula (Y15) or the formula (Y30).

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

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

Examples of Y include the following.

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

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

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-46) [hereinafter, "anion (B1)" according to the formula number. -A-1) "and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. 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 formed, for example, by an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. Group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ⁴ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and ^{Q 2} are the same as above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

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

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). ) 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の鎖式炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の脂肪族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、互いに独立に０〜５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上のとき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、炭素数１〜３６の鎖式炭化水素基又は炭素数３〜３６の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ１１は、水素原子、炭素数１〜３６の鎖式炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１〜１２の鎖式炭化水素基、炭素数３〜１８の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表し、該鎖式炭化水素に含まれる水素原子は、炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２のアルコキシ基又は炭素数１〜１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^ｂ１１とＲ^ｂ１２とは、一緒になってそれらが結合する−ＣＨ−ＣＯ−を含む環を形成していてもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ１３〜Ｒ^ｂ１８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^ｂ３１は、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、互いに独立に、０〜５のいずれかの整数を表す。
ｑ２及びｒ２は、互いに独立に、０〜４のいずれかの整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b7 and R ^b8 independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent an integer of 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 chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the chain hydrocarbon group. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
The R ^b11 and ^{R b12,} together may form a ring containing a -CH-CO- which they are bond, _-CH 2 contained in the ring - is, -O -, - SO- Alternatively, it may be replaced with −CO−.
R ^{b13 to} R ^b18 independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 independently represent an integer of 0 to 5.
q2 and r2 represent an integer of 0 to 4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13s may be the same or different, when p2 is 2 or more, the plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , The plurality of R ^b15s may be the same or different, and when r2 is 2 or more, the plurality of R ^b16s may be the same or different, and when s2 is 2 or more, the plurality of R ^b17s are. It may be the same or different, and when t2 is 2 or more, the plurality of R ^b18s may be the same or different. ]

Chain hydrocarbon groups include 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-ethylhexyl group. Alkyl group of. In particular, ^{the chain hydrocarbon groups of R b9 to} R ^b12 preferably have 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclo. Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

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

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

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

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

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

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

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

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

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

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

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

Examples of the acid generator (B1) are preferably those represented by the formulas (B1-1) to (B1-40), among which the formula (B1-1) and the formula (B1) containing an aryl sulfonium cation are used. -2), Equation (B1-3), Equation (B1-5), Equation (B1-6), Equation (B1-7), Equation (B1-11), Equation (B1-12), Equation (B1-1). 13), formula (B1-14), formula (B1-13), formula (B1-20), formula (B1-21), formula (B1-22), formula (B1-23), formula (B1-24). ), Equation (B1-25), Equation (B1-26), Equation (B1-29), Equation (B1-31), Equation (B1-32), Equation (B1-33), Equation (B1-34). , Formula (B1-35), Formula (B1-36), Formula (B1-37), Formula (B1-38), Formula (B1-39) or Formula (B1-40), respectively. preferable.

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

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

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

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

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

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

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

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

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１〜１２の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４のいずれかの整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。］

[In formula (D),
R ^D1 and R ^D2 independently have a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, and a carbon number of carbon atoms. Represents 2-7 alkoxycarbonyl groups, nitro groups or halogen atoms.
m'and n'independently represent an integer of 0 to 4, and when m'is 2 or more, a plurality of R ^D1s may be the same or different, and n'is 2 or more. In the case of, a plurality of R ^D2s may be the same or different. ]

Examples of the hydrocarbon group of R ^D1 and R ^D2 include a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining them.
Examples of the chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and a nonyl group.
The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and may be saturated or unsaturated. Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbonyl group, adamantyl group and the like can be mentioned.
Examples of the aromatic hydrocarbon group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group and 4-propylphenyl group. , 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group , Mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl and the like.
Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, and an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 1-phenyl-1 group. -Propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6 -Phenyl-1-hexyl group, etc.) and the like.

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

R ^D1 and R ^D2 independently have an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, and a carbon number of carbon atoms. A acyloxy group of 2 to 4, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom is preferable.
It is preferable that m'and n'are independently an integer of 0 to 2, and more preferably 0. When m'is 2 or more, the plurality of R ^D1s may be the same or different, and when n'is 2 or more, the plurality of R ^D2s may be the same or different.

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 in the solid content of the resist composition. It is mass%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

式（Ｉ−５−ａ）で表される化合物８．００部、式（Ｉ−５−ｂ）で表される化合物１６．１６部、クロロホルム４０部及び硫酸０．７９９部を添加し、モレキュラーシーブ２０ｍｌ存在下、８時間還流攪拌した。得られた混合物を２３℃まで冷却し、１０％炭酸カリウム水溶液４０部を加え、２３℃で３０分間攪拌した。得られた混合物を、静置し、分液した。この洗浄の操作を２回行った。回収された有機層に、イオン交換水４０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。回収された有機層を濃縮し、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＝２／１）分取することにより、式（Ｉ−５−ｃ）で表される化合物１０．８８部を得た。 Synthesis Example 1: Synthesis of a compound represented by the formula (I-5)

8.00 parts of the compound represented by the formula (I-5a), 16.16 parts of the compound represented by the formula (I-5b), 40 parts of chloroform and 0.799 parts of sulfuric acid were added, and the molecular was added. The mixture was refluxed and stirred for 8 hours in the presence of 20 ml of sheave. The obtained mixture was cooled to 23 ° C., 40 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was allowed to stand and separated. This washing operation was performed twice. 40 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The recovered organic layer is concentrated, and the concentrated mass is separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 2/1) to formulate (I). 10.88 parts of the compound represented by −5-c) were obtained.

式（Ｉ−５−ｃ）で表される化合物９．５１部、テトラヒドロフラン７０．０５部、ピリジン４．２５部及びジメチルアミノピリジン０．２７部を混合した。得られた混合物を、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−５−ｄ）で表される化合物７．６０部を添加し、３０分間攪拌した後、さらに２３℃で３時間攪拌した。得られた反応物に酢酸エチル３００部及びシュウ酸２水和物１．７０部を加え、３０分間攪拌した。得られた反応物に、イオン交換水６０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、１０％炭酸カリウム水溶液２０．４４部を加え、２３℃で３０分間攪拌し、静置、分液した。この洗浄の操作を２回行った。回収された有機層に、イオン交換水９０部を加え、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（Ｉ−５）で表される化合物１２．１２部を得た。
ＭＡＳＳ：２８０．２（分子イオンピーク）

9.51 parts of the compound represented by the formula (I-5-c), 70.05 parts of tetrahydrofuran, 4.25 parts of pyridine and 0.27 parts of dimethylaminopyridine were mixed. The resulting mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixture, 7.60 parts of the compound represented by the formula (I-5d) was added at 5 ° C., the mixture was stirred for 30 minutes, and then further stirred at 23 ° C. for 3 hours. To the obtained reaction product, 300 parts of ethyl acetate and 1.70 parts of oxalic acid dihydrate were added, and the mixture was stirred for 30 minutes. To the obtained reaction product, 60 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 20.44 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. This washing operation was performed twice. 90 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. By concentrating the recovered organic layer, 12.12 parts of the compound represented by the formula (I-5) was obtained.
MASS: 280.2 (molecular ion peak)

式（Ｉ−１１−ａ）で表される化合物３０部、式（Ｉ−１１−ｂ）で表される化合物２０．４７部、クロロホルム１２０部及び硫酸１．６７１部を、モレキュラーシーブ３０部存在下、３時間還流攪拌した。得られた混合物を２３℃まで冷却し、１０％炭酸カリウム水溶液１４０部を加え、２３℃で３０分間攪拌した。得られた混合物を、静置し、分液した。回収された有機層に、イオン交換水３６部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。回収された有機層を濃縮した後、濃縮残に、ｎ−ヘプタン１５０部を加え、２３℃で３０分間攪拌し、ろ過することにより、式（Ｉ−１１−ｃ）で表される化合物１９．２３部を得た。 Synthesis Example 2: Synthesis of a compound represented by the formula (I-11)

There are 30 parts of the compound represented by the formula (I-11-a), 20.47 parts of the compound represented by the formula (I-11-b), 120 parts of chloroform and 1.671 parts of sulfuric acid, and 30 parts of the molecular sieve. Below, the mixture was refluxed and stirred for 3 hours. The resulting mixture was cooled to 23 ° C., 140 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was allowed to stand and separated. 36 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was performed three times. After concentrating the recovered organic layer, 150 parts of n-heptane was added to the concentrated residue, stirred at 23 ° C. for 30 minutes, and filtered to obtain the compound represented by the formula (I-11-c) 19. I got 23 copies.

式（Ｉ−１１−ｃ）で表される化合物１９．２３部、テトラヒドロフラン１００部、ピリジン５．９２部及びジメチルアミノピリジン０．３８部を混合した。得られた混合物を２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−１１−ｄ）で表される化合物１０．５８部を添加し、３０分間攪拌した後、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４２０部及び５％塩酸６６部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水８５部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、１０％炭酸カリウム水溶液３０部を加え、２３℃で３０分間攪拌した。この洗浄操作を２回繰り返した。回収された有機層に、イオン交換水１２５部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗操作を４回繰り返した。回収された有機層を濃縮した後、濃縮残に、ｎ−ヘプタン５５部を加え、２３℃で３０分間攪拌し、ろ過することにより、式（Ｉ−１１）で表される化合物１４．９１部を得た。
ＭＡＳＳ：３７６．２（分子イオンピーク）

19.23 parts of the compound represented by the formula (I-11-c), 100 parts of tetrahydrofuran, 5.92 parts of pyridine and 0.38 parts of dimethylaminopyridine were mixed. The resulting mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixture, 10.58 parts of the compound represented by the formula (I-11-d) was added at 5 ° C., the mixture was stirred for 30 minutes, and then further stirred at 23 ° C. for 6 hours. To the obtained reaction product, 420 parts of ethyl acetate and 66 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 85 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 30 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. This cleaning operation was repeated twice. 125 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was repeated 4 times. After concentrating the recovered organic layer, 55 parts of n-heptane was added to the concentrated residue, stirred at 23 ° C. for 30 minutes, and filtered to obtain 14.91 parts of the compound represented by the formula (I-11). Got
MASS: 376.2 (molecular ion peak)

式（Ｉ−３１−ａ）で表される化合物１０部、式（Ｉ−３１−ｂ）で表される化合物２４．０１部、メタノール３２部及び塩酸１．２部を添加し、２３℃で８時間攪拌した。得られた反応物に、酢酸エチル３９０部及び１０％炭酸カリウム水溶液５０部を加え、２３℃で３０分間攪拌した。得られた混合物を、静置し、分液した。回収された有機層に、イオン交換水１２０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を３回行った。回収された有機層を濃縮することにより、式（Ｉ−３１−ｃ）で表される化合物６．０９部を得た。 Synthesis Example 3: Synthesis of the compound represented by the formula (I-31)

10 parts of the compound represented by the formula (I-31-a), 24.01 parts of the compound represented by the formula (I-31-b), 32 parts of methanol and 1.2 parts of hydrochloric acid were added, and the temperature was 23 ° C. The mixture was stirred for 8 hours. To the obtained reaction product, 390 parts of ethyl acetate and 50 parts of a 10% aqueous potassium carbonate solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was allowed to stand and separated. 120 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed three times. By concentrating the recovered organic layer, 6.09 parts of the compound represented by the formula (I-31-c) was obtained.

式（Ｉ−３１−ｃ）で表される化合物６．０９部、テトラヒドロフラン７２．１５部、ピリジン２．３９部及びジメチルアミノピリジン０．１５部を混合した。得られた混合物を２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−２７−ｄ）で表される化合物４．２６部を添加し、３０分間攪拌した後、さらに２３℃で３時間攪拌した。得られた反応物に酢酸エチル４００部及び５％シュウ酸水溶液２０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水６０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、１０％炭酸カリウム水溶液１２部を加え、２３℃で３０分間攪拌した。この洗浄操作を２回繰り返した。回収された有機層に、イオン交換水９０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗操作を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（Ｉ−３１）で表される化合物６．８１部を得た。
ＭＡＳＳ：３１２．２（分子イオンピーク）

6.09 parts of the compound represented by the formula (I-31-c), 72.15 parts of tetrahydrofuran, 2.39 parts of pyridine and 0.15 parts of dimethylaminopyridine were mixed. The resulting mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixture, 4.26 parts of the compound represented by the formula (I-27-d) was added at 5 ° C., the mixture was stirred for 30 minutes, and then further stirred at 23 ° C. for 3 hours. To the obtained reaction product, 400 parts of ethyl acetate and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 12 parts of a 10% potassium carbonate aqueous solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. This cleaning operation was repeated twice. 90 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was repeated 4 times. By concentrating the recovered organic layer, 6.81 parts of the compound represented by the formula (I-31) was obtained.
MASS: 312.2 (molecular ion peak)

式（Ｉ−１−ａ）で表される化合物１２．２４部、式（Ｉ−５−ｂ）で表される化合物１６．１６部、クロロホルム４０部及び硫酸０．７９９部を添加し、モレキュラーシーブ２０ｍｌ存在下、８時間還流攪拌した。得られた混合物を２３℃まで冷却し、１０％炭酸カリウム水溶液４０部を加え、２３℃で３０分間攪拌した。得られた混合物を、静置し、分液した。この洗浄の操作を２回行った。回収された有機層に、イオン交換水４０部を仕込み２３℃で３０分間攪拌し、分液することにより有機層を回収した。この水洗の操作を４回行った。回収された有機層を濃縮し、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＝２／１）分取することにより、式（Ｉ−１−ｃ）で表される化合物１２．２５部を得た。 Synthesis Example 4: Synthesis of the compound represented by the formula (I-1)

12.24 parts of the compound represented by the formula (I-1-a), 16.16 parts of the compound represented by the formula (I-5-b), 40 parts of chloroform and 0.799 parts of sulfuric acid are added and molecular. The mixture was refluxed and stirred for 8 hours in the presence of 20 ml of sheave. The obtained mixture was cooled to 23 ° C., 40 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixture was allowed to stand and separated. This washing operation was performed twice. 40 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The recovered organic layer is concentrated, and the concentrated mass is separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 2/1) to formulate (I). 12.25 parts of the compound represented by -1-c) was obtained.

式（Ｉ−１−ｃ）で表される化合物１１．８４部、テトラヒドロフラン７０部、ピリジン４．２５部及びジメチルアミノピリジン０．２７部を混合した。得られた混合物を、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−５−ｄ）で表される化合物７．６０部を添加し、３０分間攪拌した後、さらに２３℃で３時間攪拌した。得られた反応物に酢酸エチル３００部及びシュウ酸２水和物１．７０部を加え、３０分間攪拌した。得られた反応物に、イオン交換水６０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、１０％炭酸カリウム水溶液２０部を加え、２３℃で３０分間攪拌し、静置、分液した。この洗浄の操作を２回行った。回収された有機層に、イオン交換水９０部を加え、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（Ｉ−１）で表される化合物１２．６９部を得た。
ＭＡＳＳ：３３２．２（分子イオンピーク）

11.84 parts of the compound represented by the formula (I-1-c), 70 parts of tetrahydrofuran, 4.25 parts of pyridine and 0.27 parts of dimethylaminopyridine were mixed. The resulting mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixture, 7.60 parts of the compound represented by the formula (I-5d) was added at 5 ° C., the mixture was stirred for 30 minutes, and then further stirred at 23 ° C. for 3 hours. To the obtained reaction product, 300 parts of ethyl acetate and 1.70 parts of oxalic acid dihydrate were added, and the mixture was stirred for 30 minutes. To the obtained reaction product, 60 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the recovered organic layer, 20 parts of a 10% potassium carbonate aqueous solution was added, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. This washing operation was performed twice. 90 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 4 times. By concentrating the recovered organic layer, 12.69 parts of the compound represented by the formula (I-1) was obtained.
MASS: 332.2 (molecular ion peak)

式（Ｉ−６０−ａ）で表される化合物３３．４８部、ジシクロヘキシルカルボジイミド２３．９３部及び塩化メチレン４０部を仕込み混合した。得られた混合物を０℃まで冷却した後、式（Ｉ−６０−ｂ）で表される化合物１８．８３部を加え、０℃のまま、１時間攪拌した。２３℃まで昇温し、さらに３０分間攪拌した。不溶物をろ過して除去し、得られたろ液を濃縮して、式（Ｉ−６０−ｃ）で表される化合物４４．２８部を得た。 Synthesis Example 5: Synthesis of the compound represented by the formula (I-60)

33.48 parts of the compound represented by the formula (I-60-a), 23.93 parts of dicyclohexylcarbodiimide and 40 parts of methylene chloride were charged and mixed. After cooling the obtained mixture to 0 ° C., 18.83 parts of the compound represented by the formula (I-60-b) was added, and the mixture was stirred at 0 ° C. for 1 hour. The temperature was raised to 23 ° C., and the mixture was further stirred for 30 minutes. The insoluble material was filtered off and the obtained filtrate was concentrated to obtain 44.28 parts of the compound represented by the formula (I-60-c).

式（Ｉ−６０−ｃ）で表される化合物１．９４部、式（Ｉ−１−ｃ）で表される化合物２．６４部及びアセトニトリル３０部を仕込み、５０℃で３時間攪拌した。得られた混合物を濃縮し、クロロホルム４０部及びイオン交換水２０部を加えた後、分液操作により、有機層を回収した。回収された有機層をイオン交換水２０部で水洗し、有機層を濃縮した。濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：酢酸エチル）することにより、式（Ｉ−６０）で表される化合物２．２２部を得た。
ＭＡＳＳ：３９０．２（分子イオンピーク）

1.94 parts of the compound represented by the formula (I-60-c), 2.64 parts of the compound represented by the formula (I-1-c) and 30 parts of acetonitrile were charged and stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and then the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 20 parts of ion-exchanged water to concentrate the organic layer. The concentrate was subjected to column preparative (column preparative conditions, stationary phase: Merck silica gel 60-200 mesh developing solvent: ethyl acetate) to obtain 2.22 parts of the compound represented by the formula (I-60). rice field.
MASS: 390.2 (molecular ion peak)

式（Ｉ−６０−ｃ）で表される化合物１．９４部、式（Ｉ−５−ｃ）で表される化合物２．１２部及びアセトニトリル３０部を仕込み、５０℃で３時間攪拌した。得られた混合物を濃縮し、クロロホルム４０部及びイオン交換水２０部を加えた後、分液操作により、有機層を回収した。回収された有機層をイオン交換水２０部で水洗し、有機層を濃縮した。濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：酢酸エチル）することにより、式（Ｉ−６１）で表される化合物１．９２部を得た。
ＭＡＳＳ：３３８．２（分子イオンピーク） Synthesis Example 6: Synthesis of a compound represented by the formula (I-61)

1.94 parts of the compound represented by the formula (I-60-c), 2.12 parts of the compound represented by the formula (I-5-c) and 30 parts of acetonitrile were charged and stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and then the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 20 parts of ion-exchanged water to concentrate the organic layer. The concentrate was subjected to column preparative (column preparative conditions, stationary phase: Merck silica gel 60-200 mesh developing solvent: ethyl acetate) to obtain 1.92 parts of the compound represented by the formula (I-61). rice field.
MASS: 338.2 (molecular ion peak)

式（Ｉ−６０−ｃ）で表される化合物１．９４部、式（Ｉ−１１−ｃ）で表される化合物３．０８部及びアセトニトリル３０部を仕込み、５０℃で３時間攪拌した。得られた混合物を濃縮し、クロロホルム４０部及びイオン交換水２０部を加えた後、分液操作により、有機層を回収した。回収された有機層をイオン交換水２０部で水洗し、有機層を濃縮した。濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：酢酸エチル）することにより、式（Ｉ−６２）で表される化合物２．９６部を得た。
ＭＡＳＳ：４３４．２（分子イオンピーク） Synthesis Example 7: Synthesis of the compound represented by the formula (I-62)

1.94 parts of the compound represented by the formula (I-60-c), 3.08 parts of the compound represented by the formula (I-11-c) and 30 parts of acetonitrile were charged and stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and then the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 20 parts of ion-exchanged water to concentrate the organic layer. The concentrate was subjected to column preparative (column preparative conditions, stationary phase: Merck silica gel 60-200 mesh developing solvent: ethyl acetate) to obtain 2.96 parts of the compound represented by the formula (I-62). rice field.
MASS: 434.2 (molecular ion peak)

式（Ｉ−６０−ｃ）で表される化合物１．９４部、式（Ｉ−３１−ｃ）で表される化合物２．４４部及びアセトニトリル３０部を仕込み、５０℃で３時間攪拌した。得られた混合物を濃縮し、クロロホルム４０部及びイオン交換水２０部を加えた後、分液操作により、有機層を回収した。回収された有機層をイオン交換水２０部で水洗し、有機層を濃縮した。濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：酢酸エチル）することにより、式（Ｉ−６３）で表される化合物２．１８部を得た。
ＭＡＳＳ：３７０．２（分子イオンピーク） Synthesis Example 8: Synthesis of the compound represented by the formula (I-63)

1.94 parts of the compound represented by the formula (I-60-c), 2.44 parts of the compound represented by the formula (I-31-c) and 30 parts of acetonitrile were charged and stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 40 parts of chloroform and 20 parts of ion-exchanged water were added, and then the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 20 parts of ion-exchanged water to concentrate the organic layer. The concentrate was subjected to column preparative (column preparative conditions, stationary phase: Merck silica gel 60-200 mesh developing solvent: ethyl acetate) to obtain 2.18 parts of the compound represented by the formula (I-63). rice field.
MASS: 370.2 (molecular ion peak)

Synthesis of Resin The compounds (monomers) used for the synthesis of the resin (A) are shown below. Hereinafter, these compounds are referred to as "monomers (a1-1-3)" and the like according to their formula numbers.

Example 1: Synthesis of resin A1 As the monomers, a monomer (a1-1-3), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) −5) was used, and the molar ratio [monomer (a1-1-3): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I−). 5)] was mixed so as to be 24:35:2.5:28.5:10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A1 having ^{a weight average molecular weight of 8.2 × 10 3 in a yield of 65%.} This resin A1 has the following structural units.

Example 2: Synthesis of Resin A2 As the monomers, a monomer (a1-1-3), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -11) was used, and its molar ratio [monomer (a1-1-3): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 11)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A2 having a weight-average molecular weight 8.8 × 10 ³ in 61% yield. This resin A2 has the following structural units.

Example 3: Synthesis of Resin A3 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) −5) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I−). 5)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a resin A3 having a weight-average molecular weight 8.9 × 10 ³ in 88% yield. This resin A3 has the following structural units.

Example 4: Synthesis of resin A4 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -11) was used, and its molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 11)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A4 having ^{a weight average molecular weight of 9.4 × 10 3 in a yield of 81%.} This resin A4 has the following structural units.

Example 5: Synthesis of resin A5 As the monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3) -4-2) and the monomer (I-5) are used, and their molar ratios are [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer (a2-). 1-3): Monomer (a3-4-2): Monomer (I-5)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is 1. 5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A5 of weight average molecular weight 8.3 × 10 ³ in 70% yield. This resin A5 has the following structural units.

Example 6: Synthesis of resin A6 As the monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3) -4-2) and the monomer (I-11) are used, and their molar ratios are [monomer (a1-1-3): monomer (a1-2-11): monomer (a1-0-1): monomer (a2-). 1-3): Monomer (a3-4-2): Monomer (I-11)] is mixed so as to be 10:14:35:2.5:28.5:10, and the total amount of monomer is 1. 5% by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a resin A6 of weight average molecular weight 8.9 × 10 ³ in 70% yield. This resin A6 has the following structural units.

Example 7: Synthesis of resin A7 As the monomer, a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-5) are used, and the molar ratio thereof is used. [Monomer (a1-0-1): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-5)] is 59: 2.5: 28.5: 10. Was mixed with propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a resin A7 of weight average molecular weight 9.4 × 10 ³ in 89% yield. This resin A7 has the following structural units.

Example 8: Synthesis of resin A8 As the monomer, a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-11) are used, and the molar ratio thereof is used. [Monomer (a1-0-1): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-11)] is 59: 2.5: 28.5: 10. Was mixed with propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a resin A8 a weight average molecular weight 9.4 × 10 ³ in 87% yield. This resin A8 has the following structural units.

Example 9: Synthesis of resin A9 As the monomer, a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-1-1) and a monomer (I-11) are used, and the molar ratio thereof is used. [Monomer (a1-0-1): Monomer (a2-1-3): Monomer (a3-1-1): Monomer (I-11)] were mixed so as to be 40:30:10:20. 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 0.8 mol% and 2.4 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A9 of weight average molecular weight 1.3 × 10 ⁴ in 94% yield. This resin A9 has the following structural units.

Example 10: Synthesis of resin A10 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) −31) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 31)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A10 of the weight average molecular weight 8.6 × 10 ³ in 79% yield. This resin A10 has the following structural units.

Example 11: Synthesis of resin A11 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -1) is used, and its molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 1)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A11 of the weight average molecular weight 8.4 × 10 ³ in 83% yield. This resin A11 has the following structural units.

Example 12: Synthesis of resin A12 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) −60) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I−). 60)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A12 of the weight average molecular weight 8.2 × 10 ³ in 85% yield. This resin A12 has the following structural units.

Example 13: Synthesis of resin A13 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -61) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 61)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin A13 having ^{a weight average molecular weight of 8.5 × 10 3 in a yield of 80%.} This resin A13 has the following structural units.

Example 14: Synthesis of resin A14 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -62) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 62)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation that filtered to give the resin A14 of the weight average molecular weight 8.6 × 10 ³ in 78% yield. This resin A14 has the following structural units.

Example 15: Synthesis of resin A15 As the monomers, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I) -63) was used, and the molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2): monomer (I-). 63)] was mixed so as to be 24:35: 2.5: 28.5: 10, and 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a weight average molecular weight 8.3 × 10 ³ of the resin A15 in 80% yield. This resin A15 has the following structural units.

Synthesis Example 9: Synthesis of resin AX1 As a monomer, a monomer (a1-2-7), a monomer (a2-1-3), a monomer (a3-1-1) and a monomer (I-11) are used, and the molar ratio thereof is used. [Monomer (a1-2-7): Monomer (a2-1-3): Monomer (a3-1-1): Monomer (I-11)] were mixed so as to be 40:30:10:20. 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 0.8 mol% and 2.4 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The resulting resin was added to a methanol / water mixed solvent, after repulping, performed twice a purification operation of filtration, to obtain a resin AX1 of the weight average molecular weight 1.3 × 10 ⁴ in 88% yield. This resin AX1 has the following structural units.

Synthesis Example 10: Synthesis of resin AX2 As the monomer, a monomer (a1-2-11), a monomer (a1-0-1), a monomer (a2-1-3) and a monomer (a3-4-2) are used, and the monomer is used. The molar ratio [monomer (a1-2-11): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-4-2)] is 24: 35: 2.5: 38. The mixture was mixed so as to have a value of 5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the 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 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a mixed solvent of methanol / water, repulped, and then filtered, which was performed twice to obtain a resin AX2 having ^{a weight average molecular weight of 8.5 × 10 3 in a yield of 82%.} This resin AX2 has the following structural units.

Synthesis Example 11: Synthesis of resin X1 A monomer (a5-1-1) and a monomer (a4-0-12) are used as the monomer, and the molar ratio thereof [monomer (a5-1-1): monomer (a4-0-). 12)] was mixed so that the ratio was 50:50, and methyl isobutyl ketone 1.2% by mass of the total amount of the monomers was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 3 mol% based on the total amount of monomers, and the mixture was heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed methanol / water solvent to precipitate a resin, and the resin was filtered to ^{obtain a resin X1 having a weight average molecular weight of 1.0 × 10 4 in} a yield of 91%. This resin X1 has the following structural units.

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

<Resin>
A1 to A15, AX1, AX2, X1: Resin A1 to Resin A15, Resin AX1, Resin AX2, Resin X1
<Acid generator>
B1-21: Salt represented by the formula (B1-21) (synthesized according to an example of JP2012-224611A)
B1-22: Salt represented by the formula (B1-22) (synthesized according to an example of JP2012-224611A)

<Compound (D)>
D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

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

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

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of the pattern formed by the mask having a hole diameter of 55 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained by measuring the average hole diameter of a pattern formed by a mask with a hole diameter of 55 nm in the same wafer at 400 points as a population.
"○" when the standard deviation is 1.80 nm or less,
When the standard deviation was larger than 1.80 nm, it was judged as "x".
The results are shown in Table 2. The numbers in parentheses indicate the standard deviation (nm).

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

Claims (9)

A structural unit derived from a compound represented by the formula (I), a structural unit represented by the formula (a1-0-X), a structural unit represented by the formula (a3-1), and a structural unit represented by the formula (a3-2). ), At least one selected from the group consisting of the structural unit represented by the formula (a3-3), the structural unit represented by the formula (a3-4), and the formula (a2-0). Have or have at least one selected from the group consisting of the structural unit represented and the structural unit represented by the formula (a2-1).
A structural unit derived from a compound represented by the formula (I), a structural unit represented by the formula (a1-0-X), a structural unit represented by the formula (a3-1), and a structural unit represented by the formula (a3-2). ), At least one selected from the group consisting of the structural unit represented by the formula (a3-3), the structural unit represented by the formula (a3-4), and the formula (a2-0). At least one selected from the group consisting of the structural unit represented by the formula (a2-1) and the structural unit represented by the formula (a2-1), and the structural unit represented by the formula (a1-0), represented by the formula (a1-1). A resin having at least one selected from the group consisting of structural units and structural units represented by the formula (a1-2).
For the total of all structural units of resin
The content of the structural unit derived from the compound represented by the formula (I) is 3 to 40 mol%.
The content of the structural unit represented by the formula (a1-0-X) is 5 to 90 mol%.
The structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), the structural unit represented by the formula (a3-3), and the structure represented by the formula (a3-4). The total content of the units is 5 to 70 mol%,
When the structural unit represented by the formula (a2-0) is included, the content of the structural unit represented by the formula (a2-0) is 10 to 80 mol%.
When the structural unit represented by the formula (a2-1) is included, the content of the structural unit represented by the formula (a2-1) is 1 to 40 mol%.
When at least one selected from the group consisting of 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) is included. The total content of 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) is 20 to 85 mol%. resin.

[In formula (I),
X ^a and X ^b independently represent an oxygen atom or a sulfur atom, respectively.
W ¹ represents a monocyclic alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a substituent, and when the alicyclic hydrocarbon group has 4 or more carbon atoms, the said is, -O - - -CH ₂ contained in the alicyclic hydrocarbon group, - S- or -SO ₂ - may be replaced with.
W ² represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a substituent, and −CH ₂ − contained in the alicyclic hydrocarbon group is −O−, −S. -, - CO- or -SO ₂ - may be replaced to.
The ^{carbon atom to which X a} and W ¹ are bonded and the carbon atom to which X ^b and W ¹ are bonded are different carbon atoms.
R ² represents a hydrogen atom or a methyl group.
X ¹ represents a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -4).

(Formula ^(X 1 -1) ~ Formula ^(X 1 -4) in which * represents a bond to ^{A 1.)}
A ¹ represents a single bond or a group represented by the formula (ag1).

(In the equation (a-g1), s represents an integer of 0 to 2.
A ¹⁰ represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ¹¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When s is 2, A ¹⁰ there are a plurality, different or identical to each other.
X ¹⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
When s is 2, a plurality of X ^10s are the same as or different from each other. )]

[In the formula (a1-0-X),
L ^{a01 'represents} an oxygen atom or _{* -O- (CH 2) k00 -CO} -O- the stands, k00 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' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. ]

[In equation (a3-1),
L ^a4 represents a group represented by −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of any of 1 to 7). * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In formula (a3-2),
L ^a5 represents a group represented by −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of any of 1 to 7). * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents any integer 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),
L ^a6 represents a group represented by −O− or * −O− (CH ₂ ) _k3 −CO−O− (k3 represents an integer of any of 1 to 7). * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents any integer 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, which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents any integer from 0 to 3. When w1 is 2 or more, a plurality of ^Ra25s are the same or different from each other.
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. ]

[In the formula (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 Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, a plurality of Ra ^31s may be the same or different from each other. ]

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

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^a01 , L ^a1 and L ^a2 independently represent −O− or * −O− (CH ₂ ) _k1 −CO−O−, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. Represents a bond with −CO−.
R ^a01 , R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups. However, ^{at least one of R a02} , R ^a03 and R ^a04 has (i) an alicyclic hydrocarbon group having 3 to 18 carbon atoms or (ii) an alicyclic hydrocarbon group having 3 to 18 carbon atoms and carbon. Represents a group in combination with an alkyl group of numbers 1-8.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ] The resin according to claim 1, which comprises at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2). The resin according to claim 1 or 2, which comprises a structural unit represented by the formula (a2-1). A claim including at least one selected from the group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). The resin according to any one of 1 to 3. A resist composition containing the resin and acid generator according to any one of claims 1 to 4. The resist composition according to claim 5, wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and −CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ − may be replaced with −O −, −SO _{2− or −CO−.}
Z ⁺ represents an organic cation. ] The resist composition according to claim 5 or 6, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. The resist composition according to any one of claims 5 to 7, further comprising a resin containing a structural unit having a fluorine atom. (1) A step of applying the resist composition according to any one of claims 5 to 8 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.