JP6213016B2 - Resist composition and method for producing resist pattern - Google Patents

Description

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

また、レジスト組成物から、フォトリソグラフィによりレジストパターンを形成する際、アルカリ現像液で現像するとポジ型レジストパターンが得られ、有機溶剤で現像するとネガ型レジストパターンが得られることが知られている（非特許文献１）。 In Patent Document 1, as a resin, a structural unit represented by formula (a1-1-2), a structural unit represented by formula (a2-1-1), and a formula (a3-1-1) are represented. A resist composition containing a resin comprising a structural unit is described.

Further, it is known that when a resist pattern is formed from a resist composition by photolithography, a positive resist pattern is obtained when developed with an alkaline developer, and a negative resist pattern is obtained when developed with an organic solvent ( Non-patent document 1).

JP 2007-161707 A

Published by Techno Times Inc. Monthly Display '11 June p. 31

  In a negative resist pattern formed by a conventional resist composition, the line edge roughness (LER) may not always be satisfied.

［式（ｘｘ）中、Ｘ^１は、置換基を有していてもよい炭素数２〜１８の３価の炭化水素基を表す。
Ｒ^１は、水素原子又は炭素数１〜１２の炭化水素基を表す。］

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

［式（ａ１−２）中、
Ｌ^a2は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a5は、水素原子又はメチル基を表す。
Ｒ^a7は、炭素数１〜８のアルキル基、炭素数３〜１０の脂環式炭化水素基又はこれらを組み合わせた基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］ The present invention includes the following inventions.
[1] Selected from the group consisting of a structural unit having a group represented by formula (xx), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2) A resist composition containing a resin containing at least one kind and an acid generator.

[In formula (xx), X ¹ represents a trivalent hydrocarbon group having 2 to 18 carbon atoms which may have a substituent.
R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ]

[In the formula (a1-1),
L ^a1 represents —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

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

［式（ｘｘＡ）中、Ｒ^２は、水素原子又はメチル基を表す。
Ｌ¹は、−Ｏ−、＊−Ｏ−Ｒ^ｗ２−ＣＯ−Ｏ−又は＊−Ｏ−Ｒ^ｗ３−Ｏ−ＣＯ−Ｏ−を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ｗ２及びＲ^ｗ３は、炭素数１〜７のアルカンジイル基又は炭素数３〜１８の２価の脂環式炭化水素基を表す。
Ｒ¹及びＸ¹は、上記と同じ意味を表す。］
〔３〕 式（ｘｘ）で表される基を有する構造単位が、式（ｘｘＡ−１）で表される構造単位である〔１〕に記載のレジスト組成物。

［式（ｘｘＡ−１）中、Ｒ^２’は、水素原子又はメチル基を表す。
Ｌ^1’は、下記式（ｘｘ−１）を表す。＊は−ＣＯ−との結合手を表す。

Ｘ^２は、置換基を有していてもよい炭素数１〜１８の３価の炭化水素基を表す。
Ｒ^1’は、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｘ^1’は、置換基を有していてもよい炭素数２〜１８の３価の炭化水素基を表す。］ [2] The resist composition according to [1], wherein the structural unit having a group represented by the formula (xx) is a structural unit represented by the formula (xxA).

[In the formula (xxA), R ² represents a hydrogen atom or a methyl group.
L ¹ represents —O—, * —O—R ^{w 2} —CO—O— or * —O—R ^{w 3} —O—CO—O—, and * represents a bond to —CO—.
R ^w2 and ^{R w3} represents a divalent alicyclic hydrocarbon radical of an alkane diyl group or a C 3-18 having 1 to 7 carbon atoms.
R ¹ and X ¹ represent the same meaning as described above. ]
[3] The resist composition according to [1], wherein the structural unit having a group represented by the formula (xx) is a structural unit represented by the formula (xxA-1).

[In the formula (xxA-1), R ^{2 ′} represents a hydrogen atom or a methyl group.
L ^{1 ′} represents the following formula (xx-1). * Represents a bond with -CO-.

X ² represents a trivalent hydrocarbon group having from 1 to 18 carbon atoms which may have a substituent.
R ^{1 ′} represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^{1 ′} represents a C 2-18 trivalent hydrocarbon group which may have a substituent. ]

[4] (1) A step of applying the resist composition according to [1] or [2] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  According to the resist composition of the present invention, a negative resist pattern with good line edge roughness (LER) can be produced.

  In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.

<Resist composition>
The resist composition of the present invention comprises:
At least one selected from the group consisting of a structural unit having a group represented by formula (xx), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2) A resin (hereinafter sometimes referred to as “resin (A)”), and an acid generator (hereinafter also referred to as “acid generator (B)”).
The resist composition of the present invention preferably further contains a solvent (E).
The resist composition of the present invention preferably further contains a basic compound (C).

［式（ｘｘ）中、Ｘ^１は、炭素数２〜１８の３価の炭化水素基を表す。
Ｒ^１は、水素原子又は炭素数１〜１２の炭化水素基を表す。］ <Resin (A)>
The resin (A) includes a structural unit having a group represented by the formula (xx) (hereinafter sometimes referred to as “structural unit (xx)”).

[In Formula (xx), X ¹ represents a trivalent hydrocarbon group having 2 to 18 carbon atoms.
R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ]

Examples of the trivalent hydrocarbon group for X ¹ include a trivalent aliphatic hydrocarbon group, a trivalent alicyclic hydrocarbon group, a trivalent aromatic hydrocarbon group, and a group obtained by combining these. It is done.
Examples of the trivalent aliphatic hydrocarbon group include an alkanetriyl group. Specific examples of the alkanetriyl group include methine group, ethane-1,1,2-triyl group, propane-1,2,3-triyl group, butane-1,2,4-triyl group, pentane-1,2 , 5-triyl group, pentane-1,3,5-triyl group, hexane-1,2,6-triyl group, hexane-1,3,6-triyl group, heptane-1,2,7-triyl group, Heptane-1,3,7-triyl group, octane-1,2,8-triyl group, octane-1,3,8-triyl group, octane-1,4,8-triyl group, nonane-1,2, 9-triyl group, nonane-1,3,9-triyl group, nonane-1,4,9-triyl group, decane-1,2,10-triyl group, decane-1,3,10-triyl group, decane -1,4,10-triyl group, decane-1,5,10-to Yl group, undecane-1,2,11-triyl group, undecane-1,3,11-triyl group, undecane-1,4,11-triyl group, undecane-1,5,11-triyl group, dodecane-1 , 2,12-triyl group, dodecane-1,3,12-triyl group, dodecane-1,4,12-triyl group, dodecane-1,5,12-triyl group, dodecane-1,6,12-triyl Group, tridecane-1,2,13-triyl group, tridecane-1,3,13-triyl group, tridecane-1,4,13-triyl group, tridecane-1,5,13-triyl group, tridecane-1, 6,13-triyl group, tetradecane-1,2,14-triyl group, tetradecane-1,3,14-triyl group, tetradecane-1,4,14-triyl group, tetradecane- , 5,14-triyl group, tetradecane-1,6,14-triyl group, tetradecane-1,7,14-triyl group, pentadecane-1,2,15-triyl group, pentadecane-1,3,15-triyl Group, pentadecane-1,4,15-triyl group, pentadecane-1,5,15-triyl group, pentadecane-1,6,15-triyl group, pentadecane-1,7,15-triyl group, hexadecane-1, 2,16-triyl group, hexadecane-1,3,16-triyl group, hexadecane-1,4,16-triyl group, hexadecane-1,5,16-triyl group, hexadecane-1,6,16-triyl group Hexadecane-1,7,16-triyl group, hexadecane-1,8,16-triyl group, heptadecane-1,2,17-triyl group, Ptadecane-1,3,17-triyl group, heptadecane-1,4,17-triyl group, heptadecane-1,5,17-triyl group, heptadecane-1,6,17-triyl group, heptadecane-1,7, Examples include alkanetriyl groups such as 17-triyl group and heptadecane-1,8,17-triyl group.

The trivalent alicyclic hydrocarbon group includes both monocyclic and polycyclic groups, and the trivalent monocyclic alicyclic hydrocarbon group includes, for example, the formula (KA-1) to the formula This is a group in which three hydrogen atoms have been removed from a cycloalkane represented by (KA-7).

The polycyclic alicyclic hydrocarbon group is, for example, a group obtained by removing three hydrogen atoms from the alicyclic hydrocarbon represented by the formula (KA-8) to the formula (KA-22).

  Examples of the substituent that the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may have include a halogen atom, a hydroxy group, an alkoxy group, an acyl group, an acyloxy group, and an aryloxy group.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Acyl groups include those in which an alkyl group such as an acetyl group, propionyl group, butyryl group, valeryl group, hexanoyl group, heptanoyl group, octanoyl group, decanoyl group and dodecanoyl group is bonded to a carbonyl group, and aryl such as benzoyl group And a group bonded to a carbonyl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
Examples of the aryloxy group include those in which an aryl group such as a phenyloxy group, a naphthyloxy group, an anthryloxy group, a biphenyloxy group, a phenanthryloxy group, and a fluorenyloxy group is bonded to an oxygen atom.

  Examples of the trivalent aromatic hydrocarbon group include groups in which three hydrogen atoms have been removed from the aromatic hydrocarbon. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, naphthalene, anthracene, biphenyl, phenanthrene and fluorene.

  Examples of the substituent that the trivalent aromatic hydrocarbon group may have include, for example, a halogen atom, a hydroxy group, an alkoxy group having 1 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 8 acyloxy groups.

Examples of the hydrocarbon group for R ¹ include a linear or branched alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these groups, 2 It may be a combination of more than one species.
Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the branched alkyl group include an isopropyl group, a sec-butyl group, and a tert-butyl group.
Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the polycyclic alicyclic hydrocarbon group include a norbornyl group and an adamantyl group.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, 2,6-diethylphenyl group, 2-methyl-6- An aryl group such as an ethylphenyl group is exemplified.
Among them, R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferably a hydrogen atom, a methyl group, or a phenyl group, and further preferably a hydrogen atom.

［式（ｘｘｉ）及び式（ｘｘｉｉ）中、Ｒ^１は上記と同じ意味を表す。
ｙ１及びｙ２は、それぞれ独立に、０〜２の整数を表す。
環Ｒ^ｗ１は、脂環式炭化水素の環又は芳香族炭化水素の環を表す。］
脂環式炭化水素の環としては、例えば、前記式（ＫＡ−１）〜式（ＫＡ−２２）で表される脂環式炭化水素の環が挙げられる。
芳香族炭化水素の環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、ビフェニル環、フェナントレン環及びフルオレン環等が挙げられ、好ましくはベンゼン環である。
ｙ１及びｙ２において、ｙ１＋ｙ２が１以上であることが好ましい。また、ｙ１及びｙ２は、好ましくは、それぞれ独立に、０又は１である。 The group represented by the formula (xx) is preferably a group represented by the formula (xxi) or the formula (xxii).

[In formula (xxi) and formula (xxii), R ¹ represents the same meaning as described above.
y1 and y2 each independently represents an integer of 0 to 2.
The ring R ^w1 represents an alicyclic hydrocarbon ring or an aromatic hydrocarbon ring. ]
Examples of the alicyclic hydrocarbon ring include alicyclic hydrocarbon rings represented by the above formulas (KA-1) to (KA-22).
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, a phenanthrene ring, and a fluorene ring, and a benzene ring is preferable.
In y1 and y2, y1 + y2 is preferably 1 or more. Y1 and y2 are preferably each independently 0 or 1.

As group represented by a formula (xx), the group represented by a following formula is mentioned, for example, Especially, group represented by either of a formula (xx-1)-a formula (xx-6) is shown. A group represented by any one of formulas (xx-1) to (xx-4) is more preferred, and a group represented by formula (xx-1) or formula (xx-2) is more preferred.

［式（ｘｘＡ）中、Ｒ^２は、水素原子又はメチル基を表す。
Ｌ¹は、−Ｏ−、＊−Ｏ−Ｒ^ｗ２−ＣＯ−Ｏ−又は＊−Ｏ−Ｒ^ｗ３−Ｏ−ＣＯ−Ｏ−を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ｗ２及びＲ^ｗ３は、炭素数１〜７のアルカンジイル基又は炭素数３〜１８の２価の脂環式炭化水素基を表す。
Ｒ¹及びＸ¹は、上記と同じ意味を表す。］
アルカンジイル基としては、メチレン基、エチレン基、プロパン−１，３−ジイル基、ブタン−１，４−ジイル基、ペンタン−１，５−ジイル基、ヘキサン−１，６−ジイル基、ヘプタン−１，７−ジイル基等の直鎖状アルカンジイル基；プロパン−１，２−ジイル基、ブタン−１，３−ジイル基、２−メチルプロパン−１，３−ジイル基、２−メチルプロパン−１，２−ジイル基、１−メチルブタン−１，４−ジイル基、２−メチルブタン−１，４−ジイル基等の分岐状アルカンジイル基が挙げられ、好ましくは、直鎖状アルカンジイル基である。
２価の脂環式炭化水素基としては、前記式（ＫＡ−１）〜式（ＫＡ−２２）で表される脂環式炭化水素から水素原子を２個取り去った基等が挙げられ、好ましくは、アダマンタンジイル基、シクロヘキサンジイル基である。 The structural unit (xx) is preferably a structural unit represented by the formula (xxA) and a structural unit represented by the formula (xxA-1).

[In the formula (xxA), R ² represents a hydrogen atom or a methyl group.
L ¹ represents —O—, * —O—R ^{w 2} —CO—O— or * —O—R ^{w 3} —O—CO—O—, and * represents a bond to —CO—.
R ^w2 and ^{R w3} represents a divalent alicyclic hydrocarbon radical of an alkane diyl group or a C 3-18 having 1 to 7 carbon atoms.
R ¹ and X ¹ represent the same meaning as described above. ]
Examples of the alkanediyl group include 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- Linear alkanediyl group such as 1,7-diyl group; propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane- Examples include branched alkanediyl groups such as 1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, and preferably a linear alkanediyl group. .
Examples of the divalent alicyclic hydrocarbon group include groups in which two hydrogen atoms have been removed from the alicyclic hydrocarbon represented by the formula (KA-1) to the formula (KA-22), and the like. Is an adamantanediyl group or a cyclohexanediyl group.

［式（ｘｘＡ−１）中、Ｒ^２’は、水素原子又はメチル基を表す。
Ｌ^1’は、下記式（ｘｘ−１）を表す。＊は−ＣＯ−との結合手を表す。

Ｘ^２は、置換基を有していてもよい炭素数１〜１８の３価の炭化水素基を表す。
Ｒ^1’は、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｘ^1’は、置換基を有していてもよい炭素数２〜１８の３価の炭化水素基を表す。］

[In the formula (xxA-1), R ^{2 ′} represents a hydrogen atom or a methyl group.
L ^{1 ′} represents the following formula (xx-1). * Represents a bond with -CO-.

X ² represents a trivalent hydrocarbon group having from 1 to 18 carbon atoms which may have a substituent.
R ^{1 ′} represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^{1 ′} represents a C 2-18 trivalent hydrocarbon group which may have a substituent. ]

［式（ｘｘＢ）、式（ｘｘＣ）及び式（ｘｘＤ）中、
Ｌ^２及びＬ^３は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k−ＣＯ−Ｏ−を表し、ｋは１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^１、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又はメチル基を表す。］ The structural unit (xx) is more preferably a structural unit represented by the formula (xxB), the formula (xxC), or the formula (xxD).

[In Formula (xxB), Formula (xxC), and Formula (xxD),
L ² and L ³ each independently represent —O— or * —O— (CH ₂ ) _k —CO—O—, k represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ¹ , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a methyl group. ]

Examples of the structural unit (xxA) include the structural units represented below.

The content of the structural unit (xx) is preferably 1 to 40 mol%, more preferably 2 to 35 mol%, still more preferably 3 to 30 mol%, particularly preferably based on all structural units of the resin (A). Is 3 to 25 mol%.

［式（ｘｘＡ’）中、Ｒ^１、Ｒ^２、Ｌ^１、Ｘ^１及びｎは、上記と同じ意味を表す。］ The structural unit represented by the formula (xxA) is derived from the compound represented by the formula (xxA ′).

[In Formula (xxA ′), R ¹ , R ² , L ¹ , X ¹ and n represent the same meaning as described above. ]

［式（ｘｘＡ−１’）中、Ｒ^１’、Ｒ^２’、Ｌ^１’及びＸ^１’は、上記と同じ意味を表す。］
中でも、式（ｘｘＢ）で表される構造単位は、式（ｘｘＢ’）で表される化合物から誘導される。

［式（ｘｘＢ’）中、Ｒ^３及びＬ^２は、上記と同じ意味を表す。］ The structural unit represented by the formula (xxA-1) is derived from the compound represented by the formula (xxA-1 ′).

[In formula (xxA-1 ′), R ^{1 ′} , R ^{2 ′} , L ^{1 ′} and X ^{1 ′} represent the same meaning as described above. ]
Among these, the structural unit represented by the formula (xxB) is derived from the compound represented by the formula (xxB ′).

[In Formula (xxB ′), R ³ and L ² represent the same meaning as described above. ]

［式中、Ｒ^３は、上記と同じ意味を表す。］ For example, the compound (xxB1 ′) in which L ² is an oxygen atom can be produced, for example, by the following reaction.

[Wherein R ³ represents the same meaning as described above. ]

  It is preferable to react the compound represented by the formula (xxB1'-a) and the compound represented by the formula (xxB1'-b) in a solvent in the presence of a base catalyst. Tetrahydrofuran or the like is used as the solvent. As the base catalyst, triethylamine, dimethylaminopyridine and the like are used.

The compound represented by the formula (xxB1′-b) is preferably a compound (commercially available) that can be easily obtained from the market. Such commercially available products include the compounds represented below.

［式（ｘｘＣ’）中、Ｒ^４及びＬ^３は、上記と同じ意味を表す。］ The structural unit (xxC) is derived from a compound represented by the formula (xxC ′).

[In formula (xxC ′), R ⁴ and L ³ represent the same meaning as described above. ]

［式中、Ｒ^４は、上記と同じ意味を表す。］ For example, the compound (xxC1 ′) in which L ³ is an oxygen atom can be produced, for example, by the following reaction.

[Wherein R ⁴ represents the same meaning as described above. ]

  The compound represented by the formula (xxC1'-a) and the compound represented by the formula (xxC1'-b) are preferably reacted in a solvent in the presence of a base catalyst. Tetrahydrofuran or the like is used as the solvent. As the base catalyst, triethylamine, dimethylaminopyridine and the like are used.

The compound represented by the formula (xxC1′-b) is preferably one that can be easily obtained from the market (commercial product). Such commercially available products include the compounds represented below.

［式（ｘｘＤ’）中、Ｒ^１、Ｒ^５は、上記と同じ意味を表す。］ The structural unit (xxD) is derived from a compound represented by the formula (xxD ′).

[In formula (xxD ′), R ¹ and R ⁵ represent the same meaning as described above. ]

［式中、Ｒ^１、Ｒ^５は、上記と同じ意味を表す。］ Compound (xxD ′) can be produced, for example, by the following reaction.

[Wherein R ¹ and R ⁵ represent the same meaning as described above. ]

  It is preferable to react the compound represented by the formula (xxD′-a) and the compound represented by the formula (xxD′-b) in a solvent in the presence of a base catalyst. Tetrahydrofuran or the like is used as the solvent. As the base catalyst, triethylamine, dimethylaminopyridine and the like are used.

式（ｘｘＤ’−ｂ）で表される化合物は、市場から容易に入手できるもの（市販品）が好ましい。このような市販品は、以下で表される化合物等がある。

The compound represented by the formula (xxD′-a) is preferably one that can be easily obtained from the market (commercial product). Such commercially available products include the compounds represented below.

The compound represented by the formula (xxD′-b) is preferably a compound (commercially available) that can be easily obtained from the market. Such commercially available products include the compounds represented below.

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

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１０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。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］ The resin (A) contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). In this specification, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are represented by the structural unit (a1-1) and the structural unit (a1-2), respectively. The monomer that derives the structural unit (a1-1) and the monomer that derives the structural unit (a1-2) may be referred to as a monomer (a1-1) and a monomer (a1-2), respectively.

[In the formula (a1-1),
L ^a1 represents —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14. ]

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

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, more preferably —O—. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
^Examples of the alkyl group for R ^a6 and R ^a7 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, and the like, and preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, more preferably 6 or less.
Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
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 a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptan-1-yl (meth). Acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (meth) acrylate, 1-isopropylcyclohexane-1- And yl (meth) acrylate. A monomer represented by any one of formula (a1-2-1) to formula (a1-2-12) is preferred, and formula (a1-2-3) to formula (a1-2-4) or formula (a1- The monomer represented by any one of 2-9) to formula (a1-2-10) is more preferred, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferred. .

  In the resin (A), the total content of the structural unit (a1-1) and the structural unit (a1-2) is usually 10 to 95 mol% with respect to all the structural units of the resin (A), preferably It is 15-90 mol%, More preferably, it is 20-85 mol%.

  The resin (A) may further have a structural unit other than the structural unit (xx), the structural unit (a1-1), and the structural unit (a1-2). Examples of such a structural unit include a structural unit having an acid labile group and a structural unit having no acid labile group.

［式（１）中、Ｒ^a1、Ｒ^ａ２及び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は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１〜１２の１価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’は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。該１価の炭化水素基及び該２価の炭化水素基を構成するメチレン基は、酸素原子又は硫黄原子に置き換わってもよい。＊は結合手を表す。］ <Structural unit having acid labile group>
Resin (A) is a structural unit having an acid labile group (however, different from structural unit (xx), structural unit (a1-1) and structural unit (a1-2)) (hereinafter referred to as “structural unit (a) May be included.).
In the present specification, the “acid labile group” is a group having a leaving group, and the leaving group is eliminated upon contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). means. Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

[In formula (1), R ^a1 , R ^a2 and R ^a3 each 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. R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a carbon atom having 1 to 20 carbon atoms. Represents a hydrogen group, or R ^{a2 ′} and R ^{a3 ′} combine with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. The monovalent hydrocarbon group and the methylene group constituting the divalent hydrocarbon group may be replaced with 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等が挙げられる。 ^Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group for R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. In each formula, R ^a3 has the same meaning as described above, and * represents a bond to —O—.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (in the 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- ( And adamantane-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include groups in which one hydrogen atom has been removed from the hydrocarbon groups of R ^{a1 ′ to} R ^{a3 ′} .
Of R ^{a1 ′} and R ^{a2 ′} , at least one is preferably a hydrogen atom.

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

  The monomer for deriving the structural unit (a) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer having an acid labile group.

［式（ａ１−５）中、
Ｒ^３１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］_k1−ＣＯ−Ｌ^ａ４−基を表す。ここで、ｋ１は１〜４の整数を表す。＊は、Ｌ^ａ１との結合手を表す。
Ｌ^ａ１、Ｌ^ａ２、Ｌ^ａ３及びＬ^ａ４は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。］ Examples of the structural unit (a) include a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”).

[In the formula (a1-5),
R ³¹ represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or a * — [CH ₂ ] _k1 —CO—L ^a4 — group. Here, k1 represents an integer of 1 to 4. * Represents a bond with L ^a1 .
L ^a1 , L ^a2 , L ^a3 and L ^a4 each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3. ]

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ^a1 is preferably an oxygen atom.
One of L ^a2 and L ^a3 is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

Examples of the monomer that leads to the structural unit (a1-5) include the following monomers.

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

  In the resin (A), the total content of the structural unit (xx), the structural unit (a1-1), the structural unit (a1-2), and the structural unit (a) is based on the total structural unit of the resin (A). , Preferably it is 30-98 mol%, More preferably, it is 35-90 mol%, More preferably, it is 40-80 mol%.

<Structural unit without acid labile group>
The monomer for deriving a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”) is not particularly limited as long as it does not have an acid labile group, and is well known in the resist field. Can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structural unit having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group ( If a resin having a “structural unit (a3)” hereinafter) is used for the resist composition, the resolution of the resist pattern and the adhesion to the substrate can be improved.

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

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

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

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

As a monomer which introduce | transduces structural unit (a2-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A monomer represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, and represented by any one of formula (a2-1-1) to formula (a2-1-4). The monomer represented by Formula (a2-1-1) or Formula (a2-1-3) is more preferable.

  When resin (A) contains structural unit (a2-1), the content rate is 3 to 45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1 to 40 mol%. More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

  When the resist composition is used for high energy ray exposure such as KrF excimer laser exposure (248 nm), electron beam or EUV (extreme ultraviolet light), the structural unit (a2) is preferably a structural unit having a phenolic hydroxy group ( It is preferable to use a2). When used for ArF excimer laser exposure (193 nm) or the like, the structural unit (a2) is preferably a structural unit (a2) having an alcoholic hydroxy group, more preferably a structural unit (a2-1). I like it. One type of structural unit (a2) may be contained alone, or two or more types may be contained.

<Structural unit (a3)>
The lactone ring contained in the structural unit (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a bridged ring including these monocyclic lactone ring structures. But you can. Among these lactone rings, a γ-butyrolactone ring or a bridged ring containing a γ-butyrolactone ring structure is preferable.

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), or the formula (a3-3). These 1 type may be contained independently and 2 or more types may be contained.

［式（ａ３−１）中、
Ｌ^a4は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異なる。
式（ａ３−２）中、
Ｌ^a5は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１は、０〜３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相異なる。
式（ａ３−３）中、
Ｌ^a6は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｒ１は、０〜３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相異なる。］

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

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are the same as those described for L ^a3 in formula (a2-1).
L ^{a4 to} L ^a6 are each independently an oxygen atom or a group represented by * —O— (CH ₂ ) _k3 —CO—O— in which k3 is an integer of 1 to 4, preferably an oxygen atom and * —O—CH ₂ —CO—O— is more preferable, and an oxygen atom is more preferable.
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 each independently preferably an integer of 0 to 2, more preferably 0 or 1.

  Examples of the monomer that leads to the structural unit (a3) include monomers described in JP 2010-204646 A. Formula (a3-1-1) to Formula (a3-1-4), Formula (a3-2-1) to Formula (a3-2-4), and Formula (a3-3-1) to Formula (a3-3) -4) is preferred, and the monomers represented by formula (a3-1-1) to formula (a3-1-2) and formula (a3-2-3) to formula (a3-2-4) are preferred. The monomer represented by either is more preferable, and the monomer represented by the formula (a3-1-1) or the formula (a3-2-3) is more preferable.

  When the resin (A) includes the structural unit (a3), the content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.

<Other structural units (s)>
Examples of the structural unit (s) include 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)”).

［式（ａ４−１）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ａ^a41は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１）

〔式（ａ−ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の脂肪族炭化水素基を表す。
Ａ^a43は、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。〕
で表される基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
ただし、Ａ^a41及びＲ^a４２のうち少なくとも一方は、ハロゲン原子を有する基である。］ As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
A ^a41 is an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a formula (a-g1).

[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an ^optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent or a single bond.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 6 or less. ]
Represents a group represented by
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
However, at least one of A ^a41 and R ^a42 is a group having a halogen atom. ]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.
The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably an aliphatic saturated hydrocarbon group. Examples of the aliphatic saturated hydrocarbon group include an alkyl group (the alkyl group may be linear or branched), an alicyclic hydrocarbon group, and an aliphatic combination of an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon group and the like.

芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基等が挙げられる。 ^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups in which these are combined. Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, pentadecyl, and hexyl. A decyl group, a heptadecyl group, an octadecyl group, etc. are mentioned. Examples of the cyclic aliphatic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* Represents a bond, and the like.) A polycyclic alicyclic hydrocarbon group such as 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.

［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３〜１７の脂肪族炭化水素基を表す。］
Ｒ^a4２が、式（ａ−ｇ３）で表される基を有する脂肪族炭化水素基である場合、式（ａ−ｇ３）で表される基に含まれる炭素数を含めて、脂肪族炭化水素基の総炭素数は、１５以下が好ましく、１２以下がより好ましい。式（ａ−ｇ３）で表される基を置換基として有する場合、その数は１個が好ましい。 The hydrocarbon group for R ^a42 is preferably a chain or cyclic aliphatic hydrocarbon group or a group in which these are combined, and may have a carbon-carbon unsaturated bond. Of these, aliphatic saturated hydrocarbon groups and combinations thereof are more preferred. Specifically, the same group as R ^a41 is ^exemplified .
R ^a42 is preferably an aliphatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group having a halogen atom and / or a group represented by the formula (a-g3).

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^3-17 aliphatic hydrocarbon group having at least one halogen atom. ]
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

［式（ａ−ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数３〜１７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３〜１７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。］ The aliphatic hydrocarbon having a group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2).

[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 3 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 3 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. ]

Preferred R ^a42 , an aliphatic hydrocarbon group having a substituent selected from the group consisting of a halogen atom and a group represented by formula (a-g3) (a group represented by formula (a-g2)) Detailed description.

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

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

Among the combinations of A ^a46 and A ^a47, the more preferable, * - is represented by the partial structure represented by A ^a46 -X ^a44 -A ^a47 (* represents a bond to a carbonyl group), the following structure Is mentioned.

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

In the group represented by the formula (a-g1) of A ^a41 (hereinafter sometimes referred to as “group (a-g1)”), A ^a44 is ^bonded to —O—CO—R ^a42 .
As the aliphatic hydrocarbon group for A ^a42 , A ^a43 and A ^{a44 in} the group (a-g1), a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane- Examples include 1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like. Examples of these substituents include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

^Examples of the group (a-g1) in which X ^a42 is an oxygen atom include the following groups. In the following examples, among the two bonds represented by *, * on the right side is a bond with —O—CO—R ^a42 .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the monomer for deriving the structural unit represented by formula (a4-2) include monomers represented by formula (a4-1-1) to formula (a4-1-22), respectively.

Examples of the monomer for deriving the structural unit represented by formula (a4-3) include monomers represented by formula (a4-1′-1) to formula (a4-1′-22), respectively.

［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。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4).

[In the 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 represents an integer of 1 to 6.
R ^f22 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

^Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same hydrocarbon groups as R ^f2 in formula (a4-2). R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In 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 monomer for deriving the structural unit represented by the formula (a4-4) include the following monomers.

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

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

The resin (A) is preferably a resin composed of the structural unit (xx), the structural unit (a1-1) and / or the structural unit (a1-2), and the structural unit (s), more preferably A resin comprising a structural unit (xxA), a structural unit (a1-1) and / or a structural unit (a1-2), and a structural unit (s). That is, the latter is a copolymer of the compound represented by the formula (xxA ′), the monomer (a1-1) and / or the monomer (a1-2), and the monomer (s).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-1). The structural unit (a3) is preferably at least one of the structural unit (a3-1) and the structural unit (a3-2).
Moreover, it is preferable that resin (A) has a characteristic which decomposes | disassembles by the effect | action of an acid and the solubility to butyl acetate or 2-heptanone reduces.
As a method for confirming that the resin is soluble in butyl acetate or 2-heptanone, for example, 1 part by mass of the resin is mixed with 10 parts by mass of butyl acetate or 2-heptanone and stirred at 23 ° C. for 3 minutes. Thereafter, there is a method of visually observing the mixture. In this case, if no insoluble matter is observed, it can be determined that the resin is soluble in butyl acetate or 2-heptanone.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Such a resin may be any resin that does not contain the structural unit (xx) or does not contain both the structural unit (a1-1) and the structural unit (a1-2). For example, only the structural unit (s) The resin which consists of is mentioned.
Especially, as resin other than resin (A), resin (henceforth "resin (X)") which has structural unit (a4) is preferable. In the resin (X), the content of the structural unit (a4) is preferably 80 mol% or more, more preferably 85 mol% or more, and still more preferably 90 mol% or more with respect to all the structural units of the resin (X). .
Examples of the structural unit that the resin (X) may further include a structural unit derived from the structural unit (a2), the structural unit (a3), and other known monomers.

<Production method of resin>
Resin (A) is obtained by using a known polymerization method (for example, a radical), a monomer for deriving structural unit (xx), monomer (a1-1) and / or monomer (a1-2), and monomer (s) used as necessary. (Polymerization method). The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for copolymerization.
On the other hand, the resin (X) is preferably obtained by polymerizing the monomer (a4-1) [monomer (a4-1 ′)] by a known polymerization method, and this polymerization [production of resin (X)] In addition to the monomer (a4-1) [monomer (a4-1 ′)], another monomer (s) [for example, a monomer that derives the structural unit (a2) or the structural unit (a3)] is used. These may be copolymerized.

The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less).
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).
In addition, the weight average molecular weight here is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis. Detailed analysis conditions for this analysis are described in the Examples of the present application.

  When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Preferably it is 3-40 mass parts, Most preferably, it is 5-30 mass parts.

  The resin content in the resist composition is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition. The solid content of the resist composition and the resin content relative to the solid content can be measured, for example, by known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of the acid generators (B) of the resist composition of the present invention may be used. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate 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, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712. A compound capable of generating an acid by radiation described in No. etc. can be used. Moreover, you may use the compound manufactured by the well-known method.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜１７の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキ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、該アルキル基及び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。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—, and the saturated The hydrogen atom contained in the hydrocarbon group may be replaced with a fluorine atom or a hydroxy group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Can be mentioned.
In formula (B1), Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and among these groups, Two or more types may be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1, Linear alkanediyl groups such as 1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

式（ｂ１−１）〜式（ｂ１−７）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の２価の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の合計炭素数の上限は１３である。
Ｌ^b５は、単結合又は炭素数１〜１４の２価の飽和炭化水素基を表す。
Ｌ^b６は、炭素数１〜１５の２価の飽和炭化水素基を表す。但しＬ^b5及びＬ^b6の合計炭素数の上限は１５である。
Ｌ^b７は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b８は、炭素数１〜１６の２価の飽和炭化水素基を表す。但しＬ^b７及びＬ^b８の合計炭素数の上限は１６である。
Ｌ^b9は、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^b10は、炭素数１〜１４の２価の飽和炭化水素基を表す。但しＬ^b9及びＬ^b10の合計炭素数の上限は１４である。
Ｌ^b11及びＬ^b12は、それぞれ独立に、単結合又は炭素数１〜１１の２価の飽和炭化水素基を表す。
Ｌ^b13は、炭素数１〜１２の２価の飽和炭化水素基を表す。但しＬ^b11、Ｌ^b12及びＬ^b13の合計炭素数の上限は１２である。
Ｌ^b14及びＬ^b15は、それぞれ独立に、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^b16は、炭素数１〜１４の２価の飽和炭化水素基を表す。但しＬ^b14、Ｌ^b15及びＬ^b16の合計炭素数の上限は１４である。 Specific examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include, for example, any one of formulas (b1-1) to (b1-7) The group represented by these is mentioned. L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably represented by formula (b1-1) or formula (b1-3). It is a group. In addition, Formula (b1-1)-Formula (b1-7) have described the right and left according to Formula (B1), and among two bonds represented by *, C (Q ¹ ) Combined with (Q ² ) and combined with Y on the right side. The same applies to specific examples of formula (b1-1) to formula (b1-7) shown below.

In formula (b1-1) to formula (b1-7),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b6 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b5 and L ^b6 is 15.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. However, the upper limit of the total carbon number of L ^b7 and L ^b8 is 16.
L ^b9 represents a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b10 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 14.
L ^b11 and L ^b12 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b11 , L ^b12 and L ^b13 is 12.
L ^b14 and L ^b15 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 14.

Examples of the divalent group represented by the formula (b1-1) include the following.

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

Examples of the divalent group represented by the formula (b1-3) include the following.

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

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

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

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

Examples of the group in which the hydrogen atom contained in the saturated hydrocarbon group of L ^b1 is substituted with a fluorine atom or a hydroxy group include the following divalent groups.

Ｙの脂環式炭化水素基としては、例えば、式（Ｙ１）〜式（Ｙ１１）で表される基が挙げられる。また、該脂環式炭化水素基に含まれる−ＣＨ_２−が、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わった基としては、例えば、式（Ｙ１２）〜式（Ｙ２６）で表される基が挙げられる。 Examples of the alkyl group for Y 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, and the like, and preferably an alkyl group having 1 to 6 carbon atoms. .

Examples of the alicyclic hydrocarbon group for Y include groups represented by formulas (Y1) to (Y11). Examples of the group in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced by —O—, —SO ₂ — or —CO— are represented by formulas (Y12) to (Y26). Group to be used.

  The alicyclic hydrocarbon group of Y is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably formula (Y11), formula (Y14), formula (Y15) or It is group represented by a formula (Y19), More preferably, it is group represented by a formula (Y11) or a formula (Y14).

Examples of the substituent for the alkyl group of Y include, for example, 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) j2 -O-CO-R} b1 group (wherein, R ^b1 represents an alkyl group having 1 to 16 carbon atoms, an aromatic alicyclic hydrocarbon group or a C6-18 3 to 16 carbon atoms carbide Represents a hydrogen group, j2 represents an integer of 0 to 4, and the like.
Examples of the substituent for the alicyclic hydrocarbon group of Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and an aliphatic group having 3 to 16 carbon atoms. A cyclic hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or- (CH ₂ ) _{j 2} —O—CO—R ^b1 group (wherein 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 group hydrocarbon group, j2 represents an integer of 0 to 4, and the like.

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

Examples of Y include the following.

In addition, when Y is an alkyl group and L ^b1 is a linear or branched alkanediyl group having 1 to 17 carbon atoms, —CH ₂ — of the alkanediyl group at the bonding position with Y is It is preferably replaced by —O— or —CO—. In this case, —CH ₂ — contained in the alkyl group of Y is not replaced with —O— or —CO—. The same applies when a hydrogen atom contained in the alkyl group of Y and / or the divalent linear or branched alkanediyl group of L ^b1 is substituted with a substituent.

Y is preferably a C 3-18 alicyclic hydrocarbon group which may have a substituent, and —CH ₂ — contained in the alicyclic hydrocarbon group is —CO—. More preferably, it is an adamantyl group which may have a substituent (for example, a hydroxy group, etc.), and —CH ₂ — contained in the adamantyl group is replaced with —CO—. More preferred is an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

The sulfonate anion in the salt represented by the formula (B1) is preferably an anion represented by the formula (b1-1-1) to the formula (b1-1-9) [hereinafter, depending on the formula number, It may be referred to as “anion (b1-1-1)” or the like. ]. In the following formulas, the definitions of the symbols have the same meaning as described above, and R ^b2 and R ^b3 each independently represent an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Examples of the organic cation of Z ⁺ include an organic onium cation such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, and preferably an organic sulfonium cation or an organic iodonium cation. More preferably an arylsulfonium cation.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formula (b2-1) to formula (b2-4) [hereinafter referred to as “cation (b2-1)” or the like depending on the formula number, etc. There is a case. ].

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon The hydrogen atom contained in the group may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group The atom may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.

R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the aliphatic hydrocarbon group includes The hydrogen atom contained may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more, the plurality of R ^b15 is When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 may be the same or different, and t2 is 2 or more. Sometimes, the plurality of R ^b18 may be the same or different.

特に、Ｒ^b4〜Ｒ^b6の脂環式炭化水素基は、好ましくは炭素数３〜１８である。Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 Examples of the aliphatic hydrocarbon group 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. And the like. In particular, the aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group includes the carbon number of the alkyl group, and is preferably 20 or less. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^{b4 to} R ^b6 preferably has 3 to 18 carbon atoms. The alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Can be mentioned.

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantyl group. Examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. The aromatic hydrocarbon group also includes an aryl group in which an aromatic hydrocarbon group or an alicyclic hydrocarbon group is bonded to an aromatic ring. In this case, the number of carbon atoms is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The number of carbons in the group can also be counted. The aromatic hydrocarbon group of R ^{b4 to} R ^b6 preferably has 6 to 224 carbon atoms.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

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

The ring containing a sulfur atom which may be formed by combining R ^b4 and R ^b5 is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. If it contains one or more sulfur atoms, it may further contain one or more sulfur atoms and / or one or more oxygen atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 18 carbon atoms is more preferable.

Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

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.

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable, more preferably a cation represented by the formula (b2-1-1) (hereinafter referred to as “cation ( more preferably triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cation (formula In (b2-1-1), v2 = w2 = 0, x2 = 1, and R ^b21 is a methyl group.) Or a tolylsulfonium cation (in the formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups.).

式（ｂ２−１−１）中、
Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）、ヒドロキシ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基又は炭素数３〜１８の脂環式炭化水素基を表す。また、Ｒ^b19〜Ｒ^b21から選ばれる２つが一緒になって硫黄原子を含む環を形成してもよい。
ｖ２、ｗ２及びｘ２は、それぞれ独立に０〜５の整数（好ましくは０又は１）を表す。
ｖ２が２以上のとき、複数のＲ^b19は同一又は相異なり、ｗ２が２以上のとき、複数のＲ^b20は同一又は相異なり、ｘ２が２以上のとき、複数のＲ^b21は同一又は相異なる。

In formula (b2-1-1),
R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 3 to 18 carbon atoms. Represents an alicyclic hydrocarbon group. It is also possible that two selected from R ^b19 to R ^b21 together form a ring containing a sulfur atom.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, the plurality of R ^b19 are the same or different, when w2 is 2 or more, the plurality of R ^b20 are the same or different, and when x2 is 2 or more, the plurality of R ^b21 are the same or different. .

Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is.

  Specific examples of the cation represented by the formula (b2-1-1) include cations described in JP 2010-204646 A.

  The salt represented by the formula (B1) is a combination of the above-described sulfonate anion and the above-described organic cation. These can be arbitrarily combined, and preferably a combination of any one of anion (b1-1-1) to anion (b1-1-9) and a cation (b2-1-1), and an anion (b1-1) -3) to an anion (b1-1-5) and a combination of a cation (b2-3).

  Preferred examples of the salt represented by the formula (B1) include those represented by the formula (B1-1) to the formula (B1-20). Among them, those containing a triphenylsulfonium cation or a tolylsulfonium cation are preferable, and are represented by formula (B1-1), formula (B1-2), formula (B1-3, formula (B1-6), formula (B1-7), The salts represented by formula (B1-11), formula (B1-12), formula (B1-13) and formula (B1-14) are more preferred.

The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).
In the resist composition of the present invention, the acid generator (B) may contain one kind alone or plural kinds.

<Solvent (E)>
The content of the solvent (E) is, for example, 90% by mass or more in the resist composition, preferably 92% by mass or more, more preferably 94% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. It is. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and pyruvic acid Examples thereof include esters such as ethyl; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may contain 1 type independently, and may contain 2 or more types.

<Basic compound (C)>
The basic compound means a compound having a property of capturing an acid, particularly a compound having a property of capturing an acid generated from an acid generator, and is called a quencher in the technical field.
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines. Preferred examples of the basic compound (C) include compounds represented by the formulas (C1) to (C8) and the formula (C1-1), and more preferred are compounds represented by the formula (C1-1). Is mentioned.

［式（Ｃ１）中、Ｒ^c1、Ｒ^c2及びＲ^c3は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数５〜１０の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基、アミノ基又は炭素数１〜６のアルコ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、炭素数１〜６のアルコキシ基で置換されていてもよい。］

[In formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 18 represents an aromatic hydrocarbon group, the hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 6 carbon atoms. ]

［式（Ｃ１−１）中、Ｒ^c2及びＲ^c3は、上記と同じ意味を表す。
Ｒ^c4は、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５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基を表す。
ｍ３は０〜３の整数を表し、ｍ３が２以上のとき、複数のＲ^c4は同一又は相異なる。］ The compound represented by the formula (C1) is preferably a compound represented by the formula (C1-1).

[In Formula (C1-1), R ^c2 and R ^c3 represent the same meaning as described above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, the plurality of R ^c4 are the same or different. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアルカノイル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は同一又は相異なる。］

[In Formula (C2), Formula (C3) and Formula (C4), R ^c5 , R ^c6 , R ^c7 and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different. ]

［式（Ｃ５）及び式（Ｃ６）中、Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に０〜３の整数を表し、ｏ３が２以上であるとき、複数のＲ^c1４は同一又は相異なり、ｐ３が２以上であるとき、複数のＲ^c15は、同一又は相異なる。
Ｌ^c1は、炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C5) and Formula (C6), R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 each independently represent the same meaning as R ^c1 .
R ^c14 , R ^c15 and R ^c17 each independently represent the same meaning as R ^c4 .
o3 and p3 each independently represent an integer of 0 to 3, when o3 is 2 or more, the plurality of R ^c14 are the same or different, and when p3 is 2 or more, the plurality of R ^c15 are the same or Different.
L ^c1 represents an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

［式（Ｃ７）及び式（Ｃ８）中、Ｒ^c18、Ｒ^c19及びＲ^c20は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｑ３、ｒ３及びｓ３は、それぞれ独立に０〜３の整数を表し、ｑ３が２以上であるとき、複数のＲ^c18は同一又は相異なり、ｒ３が２以上であるとき、複数のＲ^c1９は同一又は相異なり、及びｓ３が２以上であるとき、複数のＲ^c20は同一又は相異なる。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represents an integer of 0 to 3, and when q3 is 2 or more, the plurality of R ^c18 are the same or different, and when r3 is 2 or more, the plurality of R ^c19 are the same. Or when different and when s3 is 2 or more, the plurality of R ^c20 are the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group are the same as those described above. Is mentioned.
Examples of the alkanoyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and preferably diisopropyl. Piruanirin. Particularly preferred include 2,6-diisopropylaniline.

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1, 2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipiconylamine, bipyridine and the like.

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

  The content of the basic compound (C) in the solid content of the resist composition is preferably about 0.01 to 5% by mass, more preferably about 0.01 to 3% by mass, and particularly preferably 0.8. It is about 01 to 1% by mass.

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

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

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

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

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., for example, and the heating time is preferably 10 to 180 seconds, for example. The pressure during drying under reduced pressure is preferably about 1 to 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. At this time, exposure is usually performed through a mask corresponding to a required pattern. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various types of laser light such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do.

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

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example.

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

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

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

<Application>
The resist composition of the present invention is 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 a liquid. It is suitable as a resist composition for immersion exposure and useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The structure of the compound was confirmed by MASS (LC: Agilent 1100 type, MASS: Agilent LC / MSD type or LC / MSD TOF type).
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

式（ＩＢ´−１−１）で表される化合物及び式（ＩＣ´−１−１）で表される化合物の混合物（混合モル比１：１）３０．００部、テトラヒドロフラン１２０部、トリエチルアミン２７．３５部及びジメチルアミノピリジン１．７６部を仕込み、２３℃で３０分間攪拌した後、０℃に冷却した。０℃に保った状態で、式（Ｉ´−１−２）で表される化合物５７．７５部を添加し、２３℃に昇温後、２３℃で２時間攪拌した。得られた反応混合物に、ｎ−ヘプタン７２０部及び１０％炭酸カリウム水溶液１２０部を加えた後、分液操作により、有機層を回収した。回収された有機層に、イオン交換水２２０部を加えた後、分液操作により、有機層を回収した。この水洗の操作をさらに４回行った。回収された有機層を濃縮して、式（ＩＢ´−１）で表される化合物及び式（ＩＣ´−１）で表される化合物の混合物（混合モル比１：１）であるモノマー（Ｉ´−１）３０．２６部を得た。
ＭＳ（質量分析）：１７２．１（分子イオンピーク） Synthesis Example 1 (Synthesis of monomer (I′-1))

Mixture of compound represented by formula (IB′-1-1) and compound represented by formula (IC′-1-1) (mixing molar ratio 1: 1) 30.00 parts, tetrahydrofuran 120 parts, triethylamine 27 .35 parts and 1.76 parts of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the temperature at 0 ° C., 57.75 parts of the compound represented by the formula (I′-1-2) was added, and the temperature was raised to 23 ° C., followed by stirring at 23 ° C. for 2 hours. After adding 720 parts of n-heptane and 120 parts of 10% aqueous potassium carbonate solution to the obtained reaction mixture, the organic layer was recovered by a liquid separation operation. After adding 220 parts of ion-exchanged water to the recovered organic layer, the organic layer was recovered by a liquid separation operation. This washing operation was further performed 4 times. The recovered organic layer is concentrated, and the monomer (I) which is a mixture of the compound represented by the formula (IB′-1) and the compound represented by the formula (IC′-1) (mixing molar ratio 1: 1). '-1) 30.26 parts were obtained.
MS (mass spectrometry): 172.1 (molecular ion peak)

式（ＩＢ´−１−１）で表される化合物３．００部、テトラヒドロフラン１２部、トリエチルアミン２．７４部及びジメチルアミノピリジン０．１８部を仕込み、２３℃で３０分間攪拌した後、０℃に冷却した。０℃に保った状態で、式（Ｉ´−１−２）で表される化合物５．７６部を添加し、２３℃に昇温後、２３℃で２時間攪拌した。得られた反応混合物に、ｎ−ヘプタン８０部及び１０％炭酸カリウム水溶液１５部を加えた後、分液操作により、有機層を回収した。回収された有機層に、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。この水洗の操作をさらに４回行った。回収された有機層を濃縮して、式（ＩＢ´−１）で表される化合物２．８９部を得た。
ＭＳ（質量分析）：１７２．１（分子イオンピーク） Synthesis Example 2 (Synthesis of monomer (IB'-1))

A compound represented by the formula (IB′-1-1) (3.00 parts), tetrahydrofuran (12 parts), triethylamine (2.74 parts) and dimethylaminopyridine (0.18 part) were charged and stirred at 23 ° C. for 30 minutes. Cooled to. While maintaining at 0 ° C., 5.76 parts of the compound represented by the formula (I′-1-2) was added, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 2 hours. After adding 80 parts of n-heptane and 15 parts of 10% aqueous potassium carbonate solution to the obtained reaction mixture, the organic layer was recovered by a liquid separation operation. After adding 20 parts of ion-exchanged water to the recovered organic layer, the organic layer was recovered by a liquid separation operation. This washing operation was further performed 4 times. The recovered organic layer was concentrated to obtain 2.89 parts of a compound represented by the formula (IB′-1).
MS (mass spectrometry): 172.1 (molecular ion peak)

式（ＩＤ´−１−１）で表される化合物１．００部、テトラヒドロフラン１０部、トリエチルアミン０．３９部及びジメチルアミノピリジン０．０３部を仕込み、２３℃で３０分間攪拌した後、０℃に冷却した。０℃に保った状態で、式（Ｉ´−１−２）で表される化合物０．８１部を添加し、２３℃に昇温後、２３℃で２時間攪拌した。得られた反応混合物に、ｎ−ヘプタン１０部及び１０％炭酸カリウム水溶液５部を加えた後、分液操作により、有機層を回収した。回収された有機層に、イオン交換水１０部を加えた後、分液操作により、有機層を回収した。この水洗の操作をさらに４回行った。回収された有機層を濃縮して、式（ＩＤ´−１）で表される化合物１．２４部を得た。
ＭＳ（質量分析）：４８４．２（分子イオンピーク） Synthesis Example 3 (Synthesis of monomer (ID′-1))

1.00 part of a compound represented by the formula (ID′-1-1), 10 parts of tetrahydrofuran, 0.39 part of triethylamine and 0.03 part of dimethylaminopyridine were charged, stirred at 23 ° C. for 30 minutes, and then 0 ° C. Cooled to. While maintaining the temperature at 0 ° C., 0.81 part of the compound represented by the formula (I′-1-2) was added, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 2 hours. After adding 10 parts of n-heptane and 5 parts of 10% aqueous potassium carbonate solution to the resulting reaction mixture, the organic layer was recovered by a liquid separation operation. After adding 10 parts of ion-exchanged water to the recovered organic layer, the organic layer was recovered by a liquid separation operation. This washing operation was further performed 4 times. The collected organic layer was concentrated to obtain 1.24 parts of a compound represented by the formula (ID′-1).
MS (mass spectrometry): 484.2 (molecular ion peak)

Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below. Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Synthesis Example 4 [Synthesis of Resin A1]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (I′-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3) -1-1), and its molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I′-1): monomer (a2-1-3): monomer (a3 -2-3): monomer (a3-1-1)] is mixed so as to be 45: 9: 5: 2.5: 22: 16.5, and propylene glycol of 1.5 mass times the total monomer amount Monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and this resin is filtered to obtain a resin A1 having a weight average molecular weight of 8.2 × 10 ^3. Obtained at a rate of 62%. This resin A1 has the following structural units and was soluble in butyl acetate.

Synthesis Example 5 [Synthesis of Resin A2]
As the monomer, monomer (a1-1-2), monomer (I′-1), monomer (a2-1-1) and monomer (a3-1-1) were used, and their molar ratio [monomer (a1-1-1- 2): Monomer (I′-1): Monomer (a2-1-1): Monomer (a3-1-1)] are mixed at 45: 5: 25: 25. 5 mass times 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 0.95 mol% and 2.85 mol%, respectively, based on the total amount of monomers, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and the resin is filtered to collect a resin A1 having a weight average molecular weight of 8.3 × 10 ^3. Obtained at a rate of 62%. This resin A2 had the following structural units and was soluble in butyl acetate.

Synthesis Example 6 [Synthesis of Resin A3]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (IB′-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3) -1-1), and its molar ratio [monomer (a1-1-3): monomer (a3-1-1): monomer (IB'-1): monomer (a2-1-3): monomer (a3 -2-3): monomer (a3-1-1)] is mixed so as to be 45: 9: 5: 2.5: 22: 16.5, and propylene glycol of 1.5 mass times the total monomer amount Monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and the resin is filtered to collect a resin A3 having a weight average molecular weight of 7.9 × 10 ^3. Obtained at a rate of 58%. This resin A3 had the following structural units and was soluble in butyl acetate.

Synthesis Example 7 [Synthesis of Resin A4]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (ID′-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3) -1-1), and its molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (ID'-1): monomer (a2-1-3): monomer (a3 -2-3): monomer (a3-1-1)] is mixed so as to be 45: 9: 5: 2.5: 22: 16.5, and propylene glycol of 1.5 mass times the total monomer amount Monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and this resin is filtered to obtain a resin A4 having a weight average molecular weight of 7.7 × 10 ^3. Obtained at a rate of 56%. This resin A4 had the following structural units and was soluble in butyl acetate.

Synthesis Example 8 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-3), monomer (a1-5-1), monomer (ID′-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3) -1-1), and its molar ratio [monomer (a1-1-3): monomer (a1-5-1): monomer (ID'-1): monomer (a2-1-3): monomer (a3 -2-3): monomer (a3-1-1)] is mixed so as to be 45: 9: 5: 2.5: 22: 16.5, and propylene glycol of 1.5 mass times the total monomer amount Monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and this resin is filtered to collect a resin A5 having a weight average molecular weight of 7.6 × 10 ^3. Obtained at a rate of 53%. This resin A5 had the following structural units and was soluble in butyl acetate.

Synthesis Example 9 [Synthesis of Resin AX1]
The monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) are mixed in a molar ratio [monomer (a1-1-2): monomer (2-1-1): Monomer (a3-1-1)] was mixed so as to be 50:25:25, and 1.5 mass times dioxane was further mixed with respect to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in proportions of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. did. This was polymerized by heating at 80 ° C. for about 8 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin was filtered and collected. Again, the resin is dissolved in dioxane, poured into a mixed solvent of a large amount of methanol and water, the resin is precipitated, and the precipitated resin is filtered and recovered three times for reprecipitation purification, and the weight average Resin AX1 having a molecular weight of about 9.2 × 10 ³ was obtained in a yield of 60%. This resin AX1 has the following structural units and was soluble in butyl acetate.

Synthesis Example 10 [Synthesis of Resin X1]
Monomer (a4-1-7) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of 0.7 mol% and 2.1 mol%, respectively, with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered.
The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice to perform the reprecipitation operation twice. 8 × 10 ⁴ resin X1 was obtained with a yield of 77%. This resin X1 has the following structural units.

式（Ｂ１−５−ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応器に仕込み、２３℃で３０分間攪拌した後、式（Ｂ１−５−ｂ）で表される化合物１６．２７部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１−５−ｃ）で表される塩を含む溶液を得た。得られた式（Ｂ１−５−ｃ）で表される塩を含む溶液に、式（Ｂ１−５−ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加し、２３℃で１２時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水８４．１５部を添加し、水洗した。この操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部を添加攪拌した後、ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１２５．８７部を添加攪拌後、濃縮した。得られた残渣に、アセトニトリル２０．６２部及びｔｅｒｔ−ブチルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌した後、上澄み液を除去した後、濃縮した。得られた残渣に、ｎ−ヘプタン２００部を添加、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｂ１−５）で表される塩６１．５４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ３７５．２
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３３９．１ Synthesis Example 11: Synthesis of salt represented by formula (B1-5)

50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform are charged into a reactor, stirred at 23 ° C. for 30 minutes, and then represented by the formula (B1-5-b). 16.27 parts of the compound was added dropwise and stirred at 23 ° C. for 1 hour to obtain a solution containing a salt represented by the formula (B1-5-c). To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water are added, The mixture was stirred at 23 ° C. for 12 hours. Since the resulting reaction solution was separated into two layers, the chloroform layer was separated and removed, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. To the obtained chloroform layer, 3.88 parts of activated carbon was added and stirred, followed by filtration. The collected filtrate was concentrated, 125.87 parts of acetonitrile was added to the resulting residue, and the mixture was stirred and concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added and stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated. To the obtained residue, 200 parts of n-heptane was added, stirred at 23 ° C. for 30 minutes, and then filtered to obtain 61.54 parts of a salt represented by the formula (B1-5).
MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (−) Spectrum): M ^- 339.1

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

Ｂ１−Ｘ：特開２００７−１６１７０７号公報の実施例に従って合成

<Resin>
A1 to A5, AX1, X1: Resin A1 to Resin A5, Resin AX1, Resin X1
<Acid generator>
B1-5: salt represented by formula (B1-5)

B1-X: synthesized according to the example of JP-A No. 2007-161707

<Basic compound: Quencher>
C1: 2,6-diisopropylaniline (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

Examples 1 to 6 and Comparative Example 1
<Manufacture of negative resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm was obtained. An antireflection film was formed.
Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, the composition layer was formed on the silicon wafer by pre-baking on a direct hot plate for 60 seconds at the temperature described in the “PB” column of Table 1. An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annual σ _out = 0.85 σ _in = 0.65 XY− pol. Illumination], using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the obtained resist pattern, the exposure amount at which the width of the trench pattern was 40 nm was defined as effective sensitivity.

<Line edge roughness evaluation (LER)>
The side wall of the obtained resist pattern was observed with a scanning electron microscope, and the unevenness fluctuation width (nm) of the side wall was measured. The results are shown in Table 2.

Examples 7-12 and Comparative Example 2
Except for changing the developer to 2-heptanone (manufactured by Kyowa Hakko Co., Ltd.), the same operation as above was performed to produce a negative resist pattern, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

  From the above results, it can be seen that the resist composition of the present invention can produce a negative resist pattern having excellent line edge roughness.

  The resist composition of the present invention can produce a negative resist pattern with good line edge roughness (LER) and can be used for fine processing of semiconductors.

Claims (2)

At least one selected from the group consisting of a structural unit represented by the formula (xxA-1), a structural unit represented by the formula (a1-1), and a structural unit represented by the formula (a1-2) The resist composition containing resin to contain and an acid generator.

[In the formula (xxA-1), R ^{2 ′} represents a hydrogen atom or a methyl group.
L ^{1 ′} represents the following formula (xx-1). * Represents a bond with -CO-.

X ² represents a trivalent hydrocarbon group having from 1 to 18 carbon atoms which may have a substituent.
R ^{1 ′} represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^{1 ′} represents a C 2-18 trivalent hydrocarbon group which may have a substituent. ]

[In the formula (a1-1),
L ^a1 represents —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a combination thereof.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ] (1) applying the resist composition of claim 1 Symbol placement is coated on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.