JP2013079228A - Salt and resist composition - Google Patents

Abstract

［式中、Ｑ^１及びＱ^２は、同一又は相異なり、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^１は、炭素数１〜１７の２価の脂肪族飽和炭化水素基を表し、該２価の脂肪族飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。Ｚ^＋は、有機カチオンを表す。＊は、ヒドロキシ芳香族環との結合手を表す。］
【選択図】なしAn acid generator for forming a resist composition having a good line edge roughness (LER) at the time of producing a resist pattern is provided.
A hydroxyaromatic derivative having a group represented by formula (1).

[In formula, Q < ¹ > and Q < ² > are the same or different, and represent a fluorine atom or a C1-C6 perfluoroalkyl group. L ¹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. . Z ⁺ represents an organic cation. * Represents a bond with a hydroxy aromatic ring. ]
[Selection figure] None

Description

  The present invention relates to a salt useful as an acid generator for a resist composition, a resist composition containing the salt, and the like.

  Chemically amplified resist compositions used for semiconductor microfabrication usually contain an acid generator.

［式（Ｚ１）中、複数存在するＤは、それぞれ独立に、水素原子、式（Ｚ１−a）で表される基又は式（Ｚ１−ｂ）で表される基を表す。］ As such an acid generator for a resist composition, for example, Patent Document 1 describes a salt represented by the following formula (Z1).

[In Formula (Z1), a plurality of D's independently represent a hydrogen atom, a group represented by Formula (Z1-a), or a group represented by Formula (Z1-b). ]

JP 2008-191413 A

  Conventionally known resist compositions containing the above-mentioned acid generators are not always satisfactory in terms of line edge roughness (LER) during the production of resist patterns.

［式（１）中、
Ｑ^１及びＱ^２は、同一又は相異なり、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^１は、炭素数１〜１７の２価の脂肪族飽和炭化水素基を表し、該２価の脂肪族飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。
＊は、ヒドロキシ芳香族環との結合手を表す。］
〔２〕式（Ｉ）、式（ＩＩ）、式（ＩＩＩ）又は式（ＩＶ）で表される前記〔１〕記載のヒドロキシ芳香族誘導体。

［式（Ｉ）中、
Ｒ^Ｉａ１〜Ｒ^Ｉａ４は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜１２の飽和炭化水素基、炭素数６〜１２の芳香族炭化水素基、炭素数７〜１３のアラルキル基又は式（１）で表される基を表す。
Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^Ｉａ１〜Ｒ^Ｉａ４、Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５の少なくとも１つは、ヒドロキシ基である。］

［式（ＩＩ）中、
Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表し、Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９の少なくとも１つは、ヒドロキシ基である。
Ｐ^ＩＩ１〜Ｐ^ＩＩ５は、それぞれ独立に、水素原子、炭素数１〜４の飽和炭化水素基、炭素数２〜４の不飽和炭化水素基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数７〜１３のアラルキル基を示す。
Ｐ^ＩＩ１及びＰ^ＩＩ２並びにＰ^ＩＩ４及びＰ^ＩＩ５は、互いに結合して環を形成していてもよい。］

［式（ＩＩＩ）中、
Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}、Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}、Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}の少なくとも１つは、ヒドロキシ基である。
ｎ^uは、１〜５の整数を表す。］

［式（ＩＶ）中、
Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２、Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２、Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８の少なくとも１つは、ヒドロキシ基である。
Ｐ^ＩＶ6は、１価の炭素数６〜１２の芳香族炭化水素基、又は、２価の炭素数６〜１２の芳香族炭化水素基を表す。前記芳香族炭化水素基はヒドロキシ基及び炭素数１〜６のアルキル基よりなる群から選択される少なくとも１種で置換されていてもよい。
Ｐ^ＩＶ7は、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２の芳香族炭化水素基又は炭素数７〜１３のアラルキル基を示す。前記芳香族炭化水素基、アラルキル基はヒドロキシ基及び炭素数１〜６のアルキル基よりなる群から選択される少なくとも１種で置換されていてもよい。該アルキル基、アラルキル基に含まれる−ＣＨ₂−は−Ｏ−、−ＣＯ−又は−ＮＲ^d−で置き換わっていてもよい。
Ｒ^dは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｐ^ＩＶ6及びＰ^ＩＶ7は互いに結合して環を形成していてもよい。
ｎ^vは１又は２を表す。］
〔３〕式（１）のＬ^１が、＊−ＣＯ−Ｏ−、＊−ＣＯ−Ｏ−（ＣＨ_２）_ｕ１−Ｏ−（ｕ１は、１〜６の整数を表す。＊は、Ｑ^１及びＱ^２と結合した炭素原子との結合手を表す。
）又は式（Ｌ^１−Ａ）で表される基である前記〔１〕又は〔２〕記載のヒドロキシ芳香族誘導体。

［式（Ｌ^１−Ａ）中、
ｕ２は、０又は１を表す。
Ｘ^１は、メチレン基又は酸素原子を表す。
＊ は、Ｑ^１及びＱ^２と結合した炭素原子との結合手を表す。］
〔４〕式（１）のＺ^＋が、トリアリールスルホニウムカチオンである前記〔１〕〜〔３〕のいずれか記載のヒドロキシ芳香族誘導体。
〔５〕前記〔１〕〜〔４〕のいずれか記載のヒドロキシ芳香族誘導体と、アルカリ水溶液に不溶又は難溶であり、酸の作用によりアルカリ水溶液に溶解し得る樹脂とを含有するレジスト組成物。
〔６〕さらに、塩基性化合物を含有する前記〔５〕記載のレジスト組成物。
〔７〕（１）前記〔５〕又は〔６〕記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥して組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程、
を含むレジストパターンの製造方法。 Under such circumstances, the present inventors diligently studied, and as a result, reached the following present invention.
The present invention includes the following inventions.
[1] A hydroxyaromatic derivative having a group represented by the formula (1).

[In Formula (1),
Q ¹ and Q ² are the same or different and each represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ¹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
Z ⁺ represents an organic cation.
* Represents a bond with a hydroxy aromatic ring. ]
[2] The hydroxy aromatic derivative according to the above [1], which is represented by the formula (I), the formula (II), the formula (III) or the formula (IV).

[In the formula (I),
R ^Ia1 to R ^Ia4 are independently a hydrogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group, or the formula of 7-13 carbon atoms The group represented by (1) is represented.
R ^{Ib1 to} R ^Ib15 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
Provided ^that at least one of ^{R Ia1 ~R Ia4, R Ib1 ~R} Ib15 is a group represented by the formula (1), and ^at least one of R ^{Ib1 to R IB15} are hydroxy groups. ]

[In the formula (II),
R ^{IIc1 to} R ^IIc9 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms or a group represented by the formula (1), and at least one of R ^{IIc1 to} R ^IIc9 is represented by the formula: It is a group represented by (1), and at least one of R ^{IIc1 to} R ^IIc9 is a hydroxy group.
P ^{II1 to} P ^II5 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, an unsaturated hydrocarbon group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, An aromatic hydrocarbon group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms is shown.
P ^II1 and ^{P II2} and ^{P II4} and ^{P II5} may be bonded to each other to form a ring. ]

[In the formula (III),
R ^{IIId1 to} R ^IIId10 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
R ^{IIIe1 to} R ^IIIe4 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is a group represented by the formula (1), and at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is It is a hydroxy group.
n ^u represents an integer of 1 to 5. ]

[In the formula (IV),
R ^IVf1 and R ^IVf2 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
R ^{IVg1 to} R ^IVg8 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is a group represented by the formula (1), and at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is It is a hydroxy group.
^PIV6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms.
P ^IV7 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The aromatic hydrocarbon group and aralkyl group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. —CH ₂ — contained in the alkyl group or aralkyl group may be replaced by —O—, —CO— or —NR ^d —.
R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ^IV6 and P ^IV7 may be bonded to each other to form a ring.
n ^v represents 1 or 2. ]
[3] L ^{1 in the} formula (1) is * —CO—O—, * —CO—O— (CH ₂ ) _u1 —O— (u1 represents an integer of 1 to 6. * represents Q ^1. And a bond to a carbon atom bonded to Q ² .
) Or the hydroxyaromatic derivative according to the above [1] or [2], which is a group represented by the formula (L ¹ -A).

[In the formula (L ¹ -A),
u2 represents 0 or 1.
X ¹ represents a methylene group or an oxygen atom.
* Represents a bond with a carbon atom bonded to Q ¹ and Q ² . ]
[4] The hydroxy aromatic derivative according to any one of [1] to [3], wherein Z ^{+ in} formula (1) is a triarylsulfonium cation.
[5] A resist composition comprising the hydroxy aromatic derivative according to any one of [1] to [4] above and a resin that is insoluble or hardly soluble in an alkaline aqueous solution and can be dissolved in an alkaline aqueous solution by the action of an acid. .
[6] The resist composition according to [5], further containing a basic compound.
[7] (1) A step of applying the resist composition according to [5] or [6] on a substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

  The salt of the present invention is useful as an acid generator that is one of the components of a resist composition, and provides a resist composition having excellent line edge roughness (LER) during the production of a resist pattern.

The present invention relates to a hydroxy aromatic derivative having a group represented by the formula (1), a hydroxy aromatic derivative having a group represented by the formula (1), and an insoluble or hardly soluble acid solution in an alkaline aqueous solution. And a resist composition (hereinafter, sometimes referred to as “resin (A)”) that can be dissolved in an alkaline aqueous solution by the above action (hereinafter, sometimes referred to as “the present resist composition”).
)I will provide a.
First, the constituents of the resist composition are a hydroxy aromatic derivative having a group represented by the formula (1), a resin (A), and a basic compound contained in the resist composition as necessary (hereinafter, In some cases, referred to as “basic compound (C)” and solvent (hereinafter, sometimes referred to as solvent (D)) will be described in this order, and further, a method for preparing the resist composition and a resist pattern using the resist composition The manufacturing method will be described.

Before describing the components of the resist composition, common substituents and the like in this specification will be described. In the present specification, unless otherwise specified, the following examples of substituents are applied to any chemical structural formula having the same substituents while appropriately selecting the number of carbon atoms. Among the aliphatic hydrocarbon groups, those that can be linear or branched, such as an alkyl group, include any of them. When stereoisomers exist, all stereoisomers are included. In the following examples of substituents, the numerical value attached to “C” indicates the number of carbon atoms of each group.
Further, in the present specification, "(meth) acrylic monomer", "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " at least one monomer having the structure Means. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group includes both a chain type and a cyclic type, and includes a combination of a chain type and an alicyclic aliphatic hydrocarbon group unless otherwise defined. Further, these aliphatic hydrocarbon groups may contain a carbon-carbon double bond in a part thereof, but a saturated group (aliphatic saturated hydrocarbon group) is preferable.

Of the chain aliphatic hydrocarbon groups, the monovalent one typically includes an alkyl group. Specific examples of the alkyl group include a methyl group (C ₁ ), an ethyl group (C ₂ ), a propyl group (C ₃ ), a butyl group (C ₄ ), a pentyl group (C ₅ ), a hexyl group (C ₆ ), heptyl _(C 7), octyl _(C 8), decyl (C _10), dodecyl (C _12), hexadecyl (C _14), pentadecyl (C _15), hexyl decyl group (C _16), A heptadecyl group (C ₁₇ ) and an octadecyl group (C ₁₈ ).
Examples of the divalent group of chain aliphatic hydrocarbon groups include alkanediyl groups in which one hydrogen atom has been removed from an alkyl group. Specific examples of the alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 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-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1 , 3- Yl group, 2-methylpropane-1,2-diyl, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group and the like.

  The cyclic aliphatic hydrocarbon group (hereinafter sometimes referred to as “alicyclic hydrocarbon group” in some cases) is typically a cycloalkyl group, and any of the monocyclic and polycyclic groups shown below can be used. Is also included.

As a monovalent alicyclic hydrocarbon group, a monocyclic aliphatic hydrocarbon group represents 1 hydrogen atom of a cycloalkane represented by the following formulas (KA-1) to (KA-7). It is a group that has been removed.

The polycyclic aliphatic hydrocarbon group is a group in which one hydrogen atom of a cycloalkane represented by the following formulas (KA-8) to (KA-22) is removed.

  Examples of the divalent alicyclic hydrocarbon group include groups in which two hydrogen atoms have been removed from the alicyclic hydrocarbon of formula (KA-1) to formula (KA-22).

  The aliphatic hydrocarbon group may have a substituent. Examples of such a substituent include a halogen atom, a hydroxy group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aralkyl group, and an aryloxy group.

Examples of alkoxy groups include methoxy group (C ₁ ), ethoxy group (C ₂ ), propoxy group (C ₃ ), butoxy group (C ₄ ), pentyloxy group (C ₅ ), hexyloxy group (C ₆ ), heptyl Examples thereof include an oxy group (C ₇ ), an octyloxy group (C ₈ ), a decyloxy group (C ₁₀ ), and a dodecyloxy group (C ₁₂ ).
Examples of the acyl group include acetyl group (C ₂ ), propionyl group (C ₃ ), butyryl group (C ₄ ), valeryl group (C ₅ ), hexanoyl group (C ₆ ), heptanoyl group (C ₇ ), octanoyl group ( C ₈ ), decanoyl group (C ₁₀ ) and dodecanoyl group (C ₁₂ ) and other alkyl groups and carbonyl groups bonded, and benzoyl group (C ₇ ) and other aryl groups and carbonyl groups bonded Can be mentioned.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
Examples of the aralkyl group include benzyl group (C ₇ ), phenethyl group (C ₈ ), phenylpropyl group (C ₉ ), naphthylmethyl group (C ₁₁ ), and naphthylethyl group (C ₁₂ ).
Aryloxy groups include phenyloxy group (C ₆ ), naphthyloxy group (C ₁₀ ), anthryloxy group (C ₁₄ ), biphenyloxy group (C ₁₂ ), phenanthryloxy group (C ₁₄ ) and full A combination of an aryl group such as an oleenyloxy group (C ₁₃ ) and an oxygen atom is exemplified.

The monovalent aromatic hydrocarbon group typically includes an aryl group.
Examples of the aryl group include a phenyl group (C ₆ ), a naphthyl group (C ₁₀ ), an anthryl group (C ₁₄ ), a biphenyl group (C ₁₂ ), a phenanthryl group (C ₁₄ ), and a fluorenyl group (C ₁₃ ). . Examples of the divalent aromatic hydrocarbon group include an arylene group in which one hydrogen atom is further removed from the aryl group exemplified here.

  The aromatic hydrocarbon group may also have a substituent. Although such a substituent is defined each time, a halogen atom, an alkoxy group, an acyl group, an alkyl group, and an aryloxy group can be mentioned. Among these, the alkyl group is the same as those exemplified as the chain aliphatic hydrocarbon group, and among the substituents optionally present in the aromatic hydrocarbon group, those other than the alkyl group are aliphatic hydrocarbon groups. The same thing as what was illustrated as a substituent of is included.

［式（１）中、
Ｑ^１及びＱ^２は、同一又は相異なり、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^１は、炭素数１〜１７の２価の脂肪族飽和炭化水素基を表し、該２価の脂肪族飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。
＊は、ヒドロキシ芳香族環との結合手を表す。］
即ち、本発明のヒドロキシ芳香族誘導体とは、式（１）で表される基を有する芳香族環とヒドロキシ基を有する芳香族環とを含む塩をいう。ここで、式（１）で表される基とヒドロキシ基とは、同一の芳香族環上に有していても、異なる芳香族環上に有していてもよい。 <Hydroxy aromatic derivative having a group represented by the formula (1)>
The hydroxy aromatic derivative has a group represented by the formula (1).

[In Formula (1),
Q ¹ and Q ² are the same or different and each represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ¹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
Z ⁺ represents an organic cation.
* Represents a bond with a hydroxy aromatic ring. ]
That is, the hydroxy aromatic derivative of the present invention refers to a salt containing an aromatic ring having a group represented by the formula (1) and an aromatic ring having a hydroxy group. Here, the group represented by the formula (1) and the hydroxy group may be present on the same aromatic ring or different aromatic rings.

In this resist composition, the hydroxy aromatic derivative having a group represented by the formula (1) is a novel salt useful as an acid generator.
In the following description, those having a negative charge obtained by removing the organic cation (Z ⁺ ) from the group represented by the formula (1) are sometimes referred to as “sulfonate anions”.

First, the sulfonate anion constituting the group represented by the formula (1) will be described.
Q ¹ and Q ² are the same or different and each represents a fluorine atom or a C 1-6 perfluoroalkyl group. Examples of the perfluoroalkyl group include those in which all the hydrogen atoms contained in the alkyl group in the alkyl group having 1 to 6 carbon atoms already exemplified are replaced with fluorine atoms. Specifically, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group and the like can be mentioned. . Here, the perfluoroalkyl group has been described with specific examples thereof, but Q ¹ and Q ² are the same or different and are preferably a fluorine atom or a trifluoromethyl group, and both Q ¹ and Q ² are More preferably, it is a fluorine atom.

The divalent aliphatic saturated hydrocarbon group represented by L ¹ is an alkanediyl group exemplified above in the range of 1 to 17 carbon atoms, any of the above-mentioned formulas (KA-1) to (KA-22). Examples thereof include a divalent alicyclic hydrocarbon group obtained by removing two hydrogen atoms from a cyclic hydrocarbon. The alkanediyl group may be linear or branched. In addition, the divalent aliphatic saturated hydrocarbon group of L ^{1 is} a divalent group in which an alkanediyl group and a divalent alicyclic hydrocarbon group are arbitrarily combined as long as the carbon number is 17 or less. It's okay.

The methylene group constituting the divalent aliphatic saturated hydrocarbon group for L ¹ may be replaced with an oxygen atom or a carbonyl group. Thus, the group represented by the formula (1) having a group in which the methylene group constituting the aliphatic saturated hydrocarbon group is replaced by an oxygen atom or a carbonyl group as L ¹ is represented by the formula (1). Considering the ease of production of the group, it is preferable. In addition, the manufacturing method of the hydroxy aromatic derivative which has group represented by Formula (1) is mentioned later.

式（ｂ１−１）〜式（ｂ１−８）中、
Ｌ^b2は、炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b3及びＬ^b4は、互いに独立に、炭素数１〜１２の２価の脂肪族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及びＬ^b6は、互いに独立に、炭素数１〜１４の２価の脂肪族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及びＬ^b８は、互いに独立に、炭素数１〜１５の２価の脂肪族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価の脂肪族飽和炭化水素基を表す。
Ｌ^b10は、炭素数１〜１４の２価の脂肪族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^b13は、互いに独立に、炭素数１〜１１の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b12は、単結合又は炭素数１〜１０の２価の脂肪族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^b16は、それぞれ独立に、炭素数１〜１３の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b15は、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。但しＬ^b14、Ｌ^b15及びＬ^b16の合計炭素数の上限は１４である。
Ｌ^b17及びＬ^b18は、互いに独立に、炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。但しＬ^b17及びＬ^b18の合計炭素数の上限は１３である。 Specific examples of the group in which the methylene group constituting the divalent aliphatic saturated hydrocarbon group of L ¹ is replaced with an oxygen atom or a carbonyl group include, for example, the following formulas (b1-1) to (b1-8) ) Or a group represented by any of the above. L ¹ is preferably a group represented by any one of the formula (b1-1), the formula (b1-2), the formula (b1-5), or the formula (b1-8), and more preferably the formula (b1 -1), a group represented by formula (b1-5) or formula (b1-8). In addition, * which shows the bond in Formula (b1-1)-Formula (b1-8) is described according to the group represented by Formula (1) on the left and right, and the left bond is Q It is bound to ¹ and Q ² and bonded carbon atoms. The same applies to specific examples of formula (b1-1) to formula (b1-8) shown below.

In formula (b1-1) to formula (b1-8),
L ^b2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 and L ^b4 each independently represent a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 and L ^b6 each independently represent a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b5 and L ^b6 is 15.
L ^b7 and L ^b8 each independently represent a C 1-15 divalent aliphatic saturated hydrocarbon group. 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 aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b10 represents a divalent aliphatic 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 ^b13 each independently represent a ^C 1-11 divalent aliphatic saturated hydrocarbon group.
L ^b12 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 10 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 ^b16 each independently represent a C 1-13 divalent aliphatic saturated hydrocarbon group.
L ^b15 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 14.
L ^b17 and L ^b18 each independently represent a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b17 and L ^b18 is 13.

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

［式（Ｌ^１−Ａ）中、
ｕ２は、０又は１を表す。
Ｘ^１は、メチレン基又は酸素原子を表す。
＊ は、Ｑ^１及びＱ^２と結合した炭素原子との結合手を表す。］ Among them, L ¹ is a divalent group represented by the formula (b1-1), a divalent group represented by the formula (b1-5), or a divalent group represented by the formula (b1-8). A divalent group represented by the formula (b1-1) in which L ^b2 is a saturated hydrocarbon group having 1 to 6 carbon atoms, L ^b9 is a single bond, and L ^b10 is a carbon number. A divalent group represented by formula (b1-5) which is a saturated hydrocarbon group having 1 to 12 or L ^b17 is a saturated hydrocarbon group having 1 to 6 carbon atoms, and L ^b18 is 1 to 1 carbon atoms. more preferably a divalent group represented by the formula (b1-8) is a saturated hydrocarbon group having ^{12, * - CO-O- (} CR 2 R 3) v - (R 2 and ^{R 3,} Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, v represents an integer of 1 to 6. When v is 2 or more, R ² and R ³ may be the same or different. , ^{Q 1}及Groups represented by) represents a bond to bonded carbon atoms and ^{Q 2, * -.. CO} -O- (CH 2) w -O- (w is an integer from 1 to 6 * is, Q more preferably a group represented by represents a bond to ¹ and ^{Q 2} and bonded carbon atoms), a group represented by or the formula ^{(L 1 -A), * -} . CO-O-CH 2 _{-, * - CO-O- (} CH 2) 2 -O-, or a group represented by the formula ^(L 1 -A), even more preferred.

[In the formula (L ¹ -A),
u2 represents 0 or 1.
X ¹ represents a methylene group or an oxygen atom.
* Represents a bond with a carbon atom bonded to Q ¹ and Q ² . ]

Next, the organic cation (Z ⁺ ) constituting the group represented by the formula (1) will be described.
Examples of the organic cation represented by Z ⁺ include organic onium cations such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.

More preferably, Z ⁺ is an organic cation represented by any one of the following formulas (b2-1) to (b2-4) (hereinafter, depending on the number of each formula, in some cases, “cation (b2 -1) "," cation (b2-2) "," cation (b2-3) "and" cation (b2-4) "].

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 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 saturated cyclic hydrocarbon group May be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, a hydroxy group, or a carbon atom. It may be substituted with an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R ^b4 and R ^b5 may be combined to form a ring containing a sulfur atom.

The ring containing a sulfur atom which R ^b4 and R ^b5 may form together may be 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 13 carbon atoms is more preferable.

R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is an integer of 2 or more, the plurality of R ^b7 may be the same or different from each other. When n2 is an integer of 2 or more, the plurality of R ^b8 are the same or different from each other. May be.

R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^{b9 to} R ^b11 each independently represents an alkyl having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. As for carbon number of this alkyl group, 1-12 are preferable. As for carbon number of this alicyclic hydrocarbon group, 4-12 are preferable.
R ^b12 represents an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group The atom may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 1 to 12 carbon atoms. Good.
R ^b9 and R ^b10 and / or R ^b11 and R ^b12 are independently bonded to each other, and together with the atoms to which they are bonded, a 3- to 12-membered ring (preferably a 3- to 7-membered ring) Ring), and the methylene group contained in these rings may be replaced by an oxygen atom, a sulfur atom or a carbonyl group.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents an oxygen atom or a sulfur atom.
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 an integer of 2 or more, the plurality of R ^b13 may be the same or different from each other. When p2 is an integer of 2 or more, the plurality of R ^b14 are the same or different from each other. When s2 is an integer of 2 or more, the plurality of R ^b17 may be the same as or different from each other. When u2 is an integer of 2 or more, the plurality of R ^b18 are the same as each other. When q2 is an integer of 2 or more, the plurality of R ^b15 may be the same or different from each other. When r2 is an integer of 2 or more, the plurality of R ^b16 are They may be the same or different.

  Examples of the aliphatic hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and octyl group. Group, a C1-C30 alkyl group, such as 2-ethylhexyl group, etc. are mentioned.

  The saturated cyclic hydrocarbon group having 3 to 18 carbon atoms is formed by removing one hydrogen atom from the alicyclic hydrocarbon of any one of the above formulas (KA-1) to (KA-22). Groups.

  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 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.

  As the alkyl group having 1 to 18 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group), Examples include dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.

  The alicyclic hydrocarbon group having 3 to 18 carbon atoms is formed by removing one hydrogen atom from the alicyclic hydrocarbon of any one of the above formulas (KA-1) to (KA-22). Group.

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

Preferred examples of the alkyl group ^{represented by} R ^{b9 to} R ^b12 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and an octyl group. And 2-ethylhexyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group and an alkyl group include a 1- (adamantan-1-yl) 1-alkylalkane-1-yl group.
Preferable examples of the alicyclic hydrocarbon group represented by R ^{b9 to} R ^b11 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, and an isobornyl group.
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.
Preferred examples of the aromatic hydrocarbon group for R ^b12 include phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, And biphenylyl and naphthyl groups.
A group in which an aromatic hydrocarbon group of R ^b12 and an alkyl group are bonded is typically an aralkyl group.

Examples of the ring formed by combining the combination of R ^b9 and R ^b10 include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. Etc.
Examples of the ring formed by combining the combination of R ^b11 and R ^b12 include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Specific examples of the organic cation represented by each of the formulas (b2-1) to (b2-4) include cations described in JP2010-204646A. Among these, a cation (b2-1), a cation (b2-2), and a cation (b2-3) are preferable, and a cation (b2-1) is particularly preferable. Specific examples of cation (b2-2) and cation (b2-3) are given below. In addition, the specific example of a cation (b2-1) will mention later the more preferable specific example of a cation (b2-1-1).

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

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

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１〜１８の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。また、Ｒ^b19〜Ｒ^b21から選ばれる２つが一緒になってヘテロ原子を有してもよい環を形成してもよい。
この脂肪族炭化水素基の炭素数は１〜１２であると好ましく、炭素数１〜１２のアルキル基及び炭素数４〜１８の脂環式炭化水素基がより好ましく、さらには置換基として、ハロゲン原子、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数６〜１８の芳香族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基を有していてもよい。
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の全部又は一部は同じであってもよい。ｗ２が２以上のとき、複数のＲ^b20の全部又は一部は同じであってもよい。ｘ２が２以上のとき、複数のＲ^b21の全部又は一部は同じであってもよい。
なかでも、Ｒ^b19、Ｒ^b20及びＲ^b21は、それぞれ独立に、好ましくは、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、又は炭素数１〜１２のアルコキシ基である。 As described above, among the organic cations constituting the gas represented by the formula (1), the cation (b2-1) is preferable, and the organic cation represented by the following formula (b2-1-1) [below In some cases, it is referred to as “cation (b2-1-1)”. ], More preferably a triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0) or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = X2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups).

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 aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is also possible to form two of which may have a hetero atom together ring selected from R ^b19 to R ^b21.
The aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms and an alicyclic hydrocarbon group having 4 to 18 carbon atoms. You may have an atom, a hydroxy group, a C1-C12 alkoxy group, a C6-C18 aromatic hydrocarbon group, a C2-C4 acyl group, or a glycidyloxy group.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, all or some of the plurality of R ^b19 may be the same. When w2 is 2 or more, all or some of the plurality of R ^b20 may be the same. When x2 is 2 or more, all or some of the plurality of R ^b21 may be the same.
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 a group.

The alkyl group of R ^{b19 to} R ^b21 preferably has 1 to 12 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms. It may be substituted with a hydrocarbon group.
The alicyclic hydrocarbon group of R ^{b19 to} R ^b21 preferably has a carbon number of 4 to 18, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom or an acyl group of 2 to 4 carbon atoms. Alternatively, it may be substituted with a glycidyloxy group.
Among these, R ^{b19 to} 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.

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

Examples of the group represented by the formula (1) include groups represented by the following.

［式（Ｉ）中、
Ｒ^Ｉａ１〜Ｒ^Ｉａ４は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜１２の飽和炭化水素基、炭素数６〜１２の芳香族炭化水素基、炭素数７〜１３のアラルキル基又は式（１）で表される基を表す。
Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^Ｉａ１〜Ｒ^Ｉａ４、Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^Ｉｂ１〜Ｒ^Ｉｂ１５の少なくとも１つは、ヒドロキシ基である。］

［式（ＩＩ）中、
Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表し、Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^ＩＩｃ１〜Ｒ^ＩＩｃ９の少なくとも１つは、ヒドロキシ基である。
Ｐ^ＩＩ１〜Ｐ^ＩＩ５は、それぞれ独立に、水素原子、炭素数１〜４の飽和炭化水素基、炭素数２〜４の不飽和炭化水素基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１２の芳香族炭化水素基又は炭素数７〜１３のアラルキル基を示す。
Ｐ^ＩＩ１及びＰ^ＩＩ２並びにＰ^ＩＩ４及びＰ^ＩＩ５は、互いに結合して環を形成していてもよい。］

［式（ＩＩＩ）中、
Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}、Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^{ＩＩＩｄ１}〜Ｒ^{ＩＩＩｄ１０}、Ｒ^{ＩＩＩｅ１}〜Ｒ^{ＩＩＩｅ４}の少なくとも１つは、ヒドロキシ基である。
ｎ^uは、１〜５の整数を表す。］

［式（ＩＶ）中、
Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数１〜６のアルキル基又は式（１）で表される基を表す。
但し、Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２、Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８の少なくとも１つは、式（１）で表される基であり、かつ、Ｒ^ＩＶｆ１、Ｒ^ＩＶｆ２、Ｒ^ＩＶｇ１〜Ｒ^ＩＶｇ８の少なくとも１つは、ヒドロキシ基である。
Ｐ^ＩＶ6は、１価の炭素数６〜１２の芳香族炭化水素基、又は、２価の炭素数６〜１２の芳香族炭化水素基を表す。前記芳香族炭化水素基はヒドロキシ基及び炭素数１〜６のアルキル基よりなる群から選択される少なくとも１種で置換されていてもよい。
Ｐ^ＩＶ7は、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２の芳香族炭化水素基又は炭素数７〜１３のアラルキル基を示す。前記芳香族炭化水素基、アラルキル基はヒドロキシ基及び炭素数１〜６のアルキル基よりなる群から選択される少なくとも１種で置換されていてもよい。該アルキル基、アラルキル基に含まれる−ＣＨ₂−は−Ｏ−、−ＣＯ−又は−ＮＲ^d−で置き換わっていてもよい。
Ｒ^dは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｐ^ＩＶ6及びＰ^ＩＶ7は互いに結合して環を形成していてもよい。
ｎ^vは１又は２を表す。］ <Hydroxy aromatic derivative>
The hydroxy aromatic derivative is preferably a derivative represented by formula (I), formula (II), formula (III) or formula (IV), and more preferably a derivative represented by formula (I). preferable.

[In the formula (I),
R ^Ia1 to R ^Ia4 are independently a hydrogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group, or the formula of 7-13 carbon atoms The group represented by (1) is represented.
R ^{Ib1 to} R ^Ib15 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
Provided ^that at least one of ^{R Ia1 ~R Ia4, R Ib1 ~R} Ib15 is a group represented by the formula (1), and ^at least one of R ^{Ib1 to R IB15} are hydroxy groups. ]

[In the formula (II),
R ^{IIc1 to} R ^IIc9 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms or a group represented by the formula (1), and at least one of R ^{IIc1 to} R ^IIc9 is represented by the formula: It is a group represented by (1), and at least one of R ^{IIc1 to} R ^IIc9 is a hydroxy group.
P ^{II1 to} P ^II5 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, an unsaturated hydrocarbon group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, An aromatic hydrocarbon group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms is shown.
P ^II1 and ^{P II2} and ^{P II4} and ^{P II5} may be bonded to each other to form a ring. ]

[In the formula (III),
R ^{IIId1 to} R ^IIId10 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
R ^{IIIe1 to} R ^IIIe4 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is a group represented by the formula (1), and at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is It is a hydroxy group.
n ^u represents an integer of 1 to 5. ]

[In the formula (IV),
R ^IVf1 and R ^IVf2 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
R ^{IVg1 to} R ^IVg8 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is a group represented by the formula (1), and at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is It is a hydroxy group.
^PIV6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms.
P ^IV7 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The aromatic hydrocarbon group and aralkyl group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. —CH ₂ — contained in the alkyl group or aralkyl group may be replaced by —O—, —CO— or —NR ^d —.
R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ^IV6 and P ^IV7 may be bonded to each other to form a ring.
n ^v represents 1 or 2. ]

  Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include linear, branched and cyclic saturated hydrocarbon groups. For example, a linear saturated hydrocarbon group such as methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; isopropyl group , Sec-butyl group, tert-butyl group, 2-ethylhexyl group and other branched saturated hydrocarbon groups; cyclohexyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (1-adamantane-1 -Yl) cyclic saturated hydrocarbon groups such as alkane-1-yl group, isobornyl group and the like.

An aryl group is mentioned as a C6-C12 aromatic hydrocarbon group.
Examples of the aryl group include a phenyl group (C ₆ ), a naphthyl group (C ₁₀ ), and a biphenyl group (C ₁₂ ).
Examples of the aralkyl group having 7 to 13 carbon atoms include benzyl group (C ₇ ), phenethyl group (C ₈ ), phenylpropyl group (C ₉ ), naphthylmethyl group (C ₁₁ ), and naphthylethyl group (C ₁₂ ). Can be mentioned.
Examples of the alkyl having 1 to 6 carbon atoms include a methyl group (C ₁ ), an ethyl group (C ₂ ), a propyl group (C ₃ ), a butyl group (C ₄ ), a pentyl group (C ₅ ), and a hexyl group (C ₆ ) And the like.
Examples of the unsaturated hydrocarbon group having 2 to 4 carbon atoms include an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propenyl group, a butynyl group, and a 2-methylpropenyl group.
Examples of the alicyclic hydrocarbon having 3 to 18 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, and 1-adamantyl group. , 2-adamantyl group, isobornyl group, groups shown below and the like.

Examples of the hydroxy aromatic derivative represented by the formula (I) include the following compounds. A plurality of R ^s2 each independently represents a group represented by the formula (1-X) [X represents 1 to 10] or a hydroxy group, and the numerical value in parentheses is the formula (1-X). The group represented [X represents 1-10] and the introduction rate (mol%) of a hydroxy group.

Examples of the hydroxy aromatic derivative represented by the formula (II) include the following compounds.

Examples of the group hydroxyaromatic derivative represented by the formula (III) include the following compounds.

Examples of the hydroxy aromatic derivative represented by the formula (IV) include the following compounds.

  The hydroxy aromatic derivative is described in WO 2008/136372, JP 2008-133266, JP 2-84650, JP 3-185447, JP 6-250386, and WO 2005/101127. It can be manufactured with reference.

（式中、Ｑ^１、Ｑ^２及びＺは、それぞれ前記と同じ意味を表す。） Next, an example is given and demonstrated about the manufacturing method of the hydroxy aromatic derivative which has group represented by Formula (1). For example, the hydroxy aromatic derivative (I1) in which L ¹ in the formula (1) is * —CO—O— (* represents a bond with —C (Q ¹ ) (Q ² ) —) It can be produced by reacting a salt represented by the formula (Ia) with a compound represented by the formula (Ib) in a solvent. This reaction is shown in the form of a reaction formula as follows.

(In the formula, Q ¹ , Q ² and Z each have the same meaning as described above.)

この反応の溶媒としては、アセトニトリルなどが用いられる。式（Ｉ１−ｃ）で表される化合物は、例えば、特開２００８−１２７３６７号公報に記載された方法で合成することができる。 The compound represented by the formula (I1-a) can be obtained by reacting the compound represented by the formula (I1-c) with the compound represented by the formula (I1-d) in a solvent. it can. This reaction is shown in the form of a reaction formula as follows.

As a solvent for this reaction, acetonitrile or the like is used. The compound represented by the formula (I1-c) can be synthesized, for example, by the method described in JP 2008-127367 A.

Next, the resist composition will be described. The resist composition is insoluble or hardly soluble in an aqueous alkaline solution and can be dissolved in an aqueous alkaline solution by the action of an acid (hereinafter, sometimes referred to as “resin (A)”), and represented by the above formula (1). And a hydroxyaromatic derivative having the above group.
Moreover, you may contain acid generators other than the hydroxy aromatic derivative which has group represented by Formula (1).
The resist composition further contains a basic compound (hereinafter sometimes referred to as “basic compound (C)”) and a solvent (hereinafter sometimes referred to as “solvent (D)”). It is preferable.

<Acid generator other than hydroxy aromatic derivative having a group represented by formula (1)>
The present resist composition obtained by using a hydroxyaromatic derivative having a group represented by a single type or a plurality of types of formula (1) as an acid generator has excellent line edge roughness (LER). However, a known acid generator other than the hydroxy aromatic derivative having the group represented by the formula (1) can be further used in the resist composition. The acid generator other than the hydroxy aromatic derivative having the group represented by the formula (1) may be an ionic acid generator or a nonionic generator, but is preferably an ionic acid generator. Hereinafter, the acid generator other than the hydroxy aromatic derivative having the group represented by the formula (1), which can be contained in the resist composition, is sometimes referred to as “acid generator (B)”.

Examples of the acid generator (B) include those represented by formulas (B1-1) to (B1-20), respectively. Among them, those containing a triarylsulfonium cation are preferable. Formula (B1-1), Formula (B1-2), Formula (B1-3), Formula (B1-6), Formula (B1-7), Formula (B1- 11), the salt represented by Formula (B1-12), Formula (B1-13), and Formula (B1-14), respectively, is more preferable.

<Resin (A)>
As described above, the resin (A) is insoluble or hardly soluble in an alkaline aqueous solution and has a characteristic that it becomes soluble in an alkaline aqueous solution by the action of an acid (hereinafter, sometimes referred to as “acidic action characteristic”). Note that “can be dissolved in an alkaline aqueous solution by the action of an acid” means “insoluble or hardly soluble in an alkaline aqueous solution before contact with an acid, but soluble in an alkaline aqueous solution after contact with an acid”. Means.

The resin (A) having acid action characteristics has an acid labile group (hereinafter, sometimes referred to as “acid labile group”) in its molecule. Such a resin (A) is a monomer having an acid labile group (hereinafter, this monomer is sometimes referred to as “monomer (a1)”, and the structural unit derived from the monomer (a1) is referred to as “structural unit (a1)”. Can be produced by polymerization.
In producing the resin (A) having acid action characteristics, the monomer (a1) may be used alone, or two or more kinds may be used in combination.

［式（１）中、
Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜２０の脂環式炭化水素基を表すか、Ｒ^a1及びＲ^a2は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］ <Acid labile group>
The “acid labile group” means a group that has a leaving group, and the leaving group is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). Examples of the acid labile group include a group represented by the formula (1) (acid labile group (1)) and a group represented by the formula (2) (acid labile group (2)). .

[In Formula (1),
R ^{a1 to} R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 are bonded to each other to form 2 to 2 carbon atoms. 20 divalent hydrocarbon groups are formed. * Represents a bond. ]

［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いてもよい。＊は結合手を表す。］

[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 hydrocarbon group having 1 to 20 carbon atoms, or R ^{a3 ′ 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. ]

The alkyl groups and alicyclic hydrocarbon groups represented by R ^{a1 to} R ^a3 of the acid labile group (1) include those already exemplified in each carbon number range. However, carbon number of this alicyclic hydrocarbon group becomes like this. Preferably it is the range of 3-16.

When R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group, the group represented by —C (R ^a1 ) (R ^a2 ) (R ^a3 ) is any of the following groups: This is the case. The carbon number of the divalent hydrocarbon group is preferably in the range of 3-12.

Examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), groups in which R ^{a1 to} R ^a3 are alkyl groups, preferably tert-butyl groups), 2-alkyl An adamantane-2-yloxycarbonyl group (in formula (1), R ^a1 and R ^a2 combine to form an adamantyl ring, and R ^a3 is an alkyl group) and 1- (adamantan-1-yl ) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the R ^{a1 ′} and R ^{a2 ′} hydrocarbon groups of the acid labile group (2) include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these groups, the same groups are included in the range having 20 or less carbon atoms. However, at least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

Specific examples of the acid labile group (2) include the following groups.

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

  Among them, the monomer (a1) having an acid labile group (1) and / or an acid labile group (2) is preferable, and having an acid labile group (1) and / or an acid labile group (2) (meta ) Acrylic monomers are particularly preferred.

  Of the (meth) acrylic monomers having an acid labile group, the monomer (a1) having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is preferred. Since the resin (A) obtained using such a monomer (a1) has a bulky structure such as an alicyclic hydrocarbon group, the resist composition containing the resin (A) The resolution tends to be even better.

［式（ａ１−１）中、
Ｌ^a1は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−（ｋ１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。）で表される基を表す。
Ｒ^a4は、水素原子又はメチル基を表す。
Ｒ^a6は、炭素数１〜１０の脂肪族炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
式（ａ１−２）中、
Ｌ^a2は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−（ｋ１は前記と同義である。
）で表される基を表す。
Ｒ^a5は、水素原子又はメチル基を表す。
Ｒ^a7は、炭素数１〜１０の脂肪族炭化水素基を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］ <Preferred structural unit (a1)>
A suitable resin (A) obtained using the monomer (a1) having such an alicyclic hydrocarbon group will be described in further detail. Among the resins (A), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as “structural unit (a1-1)”) or a structural unit represented by the formula (a1-2) A resin (A) having (hereinafter referred to as “structural unit (a1-2)” in some cases) is preferable. Such resin (A) may have the structural unit (a1-1) as a single species, may have a plurality of types, or may have the structural unit (a1-2) as a single species. In addition, a plurality of types may be included, and the structural unit (a1-1) and the structural unit (a1-2) may be combined.

[In the formula (a1-1),
L ^a1 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k1 —CO—O— (k1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group). Represent.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
m1 represents the integer of 0-14.
In formula (a1-2),
L ^a2 is an oxygen atom or * —O— (CH ₂ ) _k1 —CO—O— (k1 is as defined above).
) Represents a group represented by
R ^a5 represents a hydrogen atom or a methyl group.
R ^a7 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

L ^a1 and L ^a2 are preferably an oxygen atom or a group represented by * —O— (CH ₂ ) _k1 —CO—O—, wherein k1 is an integer of 1 to 4, more preferably an oxygen atom. or * -O-CH ₂ -CO-O- and, still more preferably an oxygen atom.
R ^a4 and R ^a5 are preferably methyl groups.
Of the aliphatic hydrocarbon groups of R ^a6 and R ^a7 , preferably an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and within the range of the upper limit of the carbon number, Includes the same as those already exemplified. The aliphatic hydrocarbon groups for R ^a6 and R ^a7 are each independently preferably an alkyl group having 8 or less carbon atoms or an alicyclic hydrocarbon group having 8 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms. Or it is an alicyclic hydrocarbon group having 6 or less carbon atoms.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As the structural unit (a1-1), structural units represented by any of the following formulas (a1-1-1) to (a1-1-8) are preferable, and the structural units (a1-1-1) to (a1-1-1) The structural unit represented by any one of formulas (a1-1-4) is more preferable.

  Examples of the monomer (a1) from which these structural units (a1-1) can be derived include those described in JP-A No. 2010-204646.

On the other hand, the structural unit (a1-2) is preferably a structural unit represented by any of the following formulas (a1-2-1) to (a1-2-6). Among these, the structural unit represented by any one of formulas (a1-2-1) to (a1-2-4) and formulas (a1-2-9) to (a1-2-10) is more preferable. The structural unit represented by the formula (a1-2-3) or (a1-2-9) is more preferable.

  Examples of the monomer (a1) capable of deriving the structural unit (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethyl. Examples include cycloheptan-1-yl (meth) acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, and 1-isopropylcyclopentan-1-yl (meth) acrylate.

  When the resin (A) has the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is based on the total structural unit (100 mol%) of the resin (A). The range of 10-95 mol% is preferable, the range of 15-90 mol% is more preferable, the range of 20-85 mol% is further more preferable, and the range of 20-60 mol% is still more preferable. When the structural unit (a1) has a structural unit (a1) having an adamantyl group (particularly preferably, the structural unit (a1-1)), the total of the structural units (a1) in the resin (A) The structural unit (a1) having an adamantyl group is preferably 15 mol% or more with respect to (100 mol%). With such a content ratio, the resin (A) having the structural unit (a1) having an adamantyl group tends to have good dry etching resistance of a resist pattern produced from the resist composition containing the resin (A). There is. In addition, in order to make the total content rate of a structural unit (a1-1) and / or a structural unit (a1-2) into the above-mentioned range, when manufacturing resin (A), it is with respect to the usage-amount of all monomers. What is necessary is just to adjust the usage-amount of the monomer which induces | guides | derives a structural unit (a1-1) and / or a structural unit (a1-2).

  Among the structural units of the resin (A), the structural unit (a1-1) and the structural unit (a1-2) that are preferable for the resin (A) to have acid action characteristics are described in detail. It is particularly preferable that the resin (A) has the unit (a1-1).

  The resin (A) may have a structural unit (a1) other than the structural unit (a1-1) and the structural unit (a1-2) which are suitable structural units (a1). Hereinafter, the structural unit (a1) other than the structural unit (a1-1) and the structural unit (a1-2) will be described by showing a monomer (a1) that derives the structural unit (a1).

式（ａ１−３）中、
Ｒ^a9は、水素原子、置換基（例えばヒドロキシ基）を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基、又は−ＣＯＯＲ^a13で表される基を表し、Ｒ^a13は、炭素数１〜８の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子はヒドロキシ基などで置換されていてもよく、該脂肪族炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１〜１２の脂肪族炭化水素基を表すか、或いはＲ^a10及びＲ^a11は互いに結合して環を形成している。該脂肪族炭化水素基及に含まれる水素原子はヒドロキシ基などで置換されていてもよく、該脂肪族炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。 The resin (A) may have a structural unit (a1) derived from a monomer represented by the following formula (a1-3) (hereinafter sometimes referred to as “monomer (a1-3)”). . Since the resin (A) having the structural unit (a1) derived from the monomer (a1-3) contains a rigid norbornane ring in its main chain, the present resist containing such a resin (A) The composition tends to produce a resist pattern having excellent dry etching resistance.

In formula (a1-3),
R ^a9 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a substituent (for example, a hydroxy group), a carboxy group, a cyano group, or a group represented by —COOR ^a13. , R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group or the like, and constitutes the aliphatic hydrocarbon group The methylene group may be replaced by an oxygen atom or a carbonyl group. R ^a10 , R ^a11 and R ^a12 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or R ^a10 and R ^a11 are bonded to each other to form a ring. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group or the like, and the methylene group constituting the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

The aliphatic hydrocarbon group which may have a substituent of R ^a9 is typically an alkyl group which may have a substituent, and among these alkyl groups, an alkyl having no substituent The group includes those already exemplified in the range of 1 to 8 carbon atoms. Examples of the substituent, particularly the aliphatic hydrocarbon group (alkyl group) having a hydroxy group include a hydroxymethyl group and a 2-hydroxyethyl group. ^Examples of R ^a13 include a methyl group, an ethyl group, a propyl group, a 2-oxo-oxolan-3-yl group, and a 2-oxo-oxolan-4-yl group.

The aliphatic hydrocarbon groups of R ^{a10 to} R ^a12 are also typically alkyl groups, and specific examples thereof are the same as those of R ^a9 . The ring formed by combining R ^a10 and R ^a11 together with the carbon atom to which they are bonded includes a cyclohexane ring and an adamantane ring.

Specific examples of the monomer (a1-3) are described in JP-A No. 2010-204646. Among these, a monomer represented by any of the following formula (a1-3-1), formula (a1-3-2), formula (a1-3-3) and formula (a1-3-4) The monomer represented by formula (a1-3-2) or (a1-3-4) is more preferred, and the monomer represented by formula (a1-3-2) is more preferred.

  When the resin (A) has the structural unit (a1) derived from the monomer (a1-3), the content ratio is preferably in the range of 10 to 95 mol% with respect to all the structural units of the resin (A). The range of 15-90 mol% is more preferable, and the range of 20-85 mol% is more preferable.

式（ａ１−４）中、
Ｒ¹⁰は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
ｌ^ａは０〜４の整数を表す。
Ｒ¹¹は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイル基又はメタクリロイル基を表し、ｌ^ａが２以上である場合、複数のＲ¹¹は互いに同一であっても異なってもよい。
Ｒ¹²及びＲ¹³はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｘ^a2は、置換基を有していてもよい炭素数１〜１７の脂肪族炭化水素基又は単結合を表し、該脂肪族炭化水素基を構成するメチレン基は、酸素原子、硫黄原子、カルボニル基、スルホニル基又は−Ｎ（Ｒ^ｃ）−（ただし、Ｒ^ｃは、水素原子又は炭素数１〜６のアルキル基を表す）で表される基に置き換わっていてもよい。
Ｙ^a3は、置換基を有していてもよい炭素数１〜１８の炭化水素基を表す。 The resin (A) may have a structural unit (a1) derived from a monomer represented by the following formula (a1-4) (hereinafter sometimes referred to as “monomer (a1-4)”).

In formula (a1-4),
R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
l ^a represents an integer of 0 to 4;
R ¹¹ is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyl group, or methacryloyl. In the case where l ^a is 2 or more, a plurality of R ¹¹ may be the same as or different from each other.
R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
X ^a2 represents an ^optionally substituted aliphatic hydrocarbon group having 1 to 17 carbon atoms or a single bond, and the methylene group constituting the aliphatic hydrocarbon group includes an oxygen atom, a sulfur atom, a carbonyl A group, a sulfonyl group, or a group represented by —N (R ^c ) — (wherein R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) may be substituted.
Y ^a3 represents an ^optionally substituted hydrocarbon group having 1 to 18 carbon atoms.

Among “an alkyl group having 1 to 6 carbon atoms which may have a halogen atom”, the alkyl group includes those already exemplified in the range of 1 to 6 carbon atoms. The alkyl group having a halogen atom is preferably an alkyl group having a fluorine atom, and specific examples thereof are the same as those exemplified for Q ¹ and Q ² of the salt (I). Among these, as R < ¹⁰ >, a C1-C4 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is further more preferable.
The alkoxy group of R ¹¹ includes those already exemplified in the range of 1 to 6 carbon atoms. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is further included. preferable.
The acyl group and acyloxy group of R ¹¹ include those already exemplified in the range of 2 to 4 carbon atoms.
The hydrocarbon groups of R ¹² and R ¹³ are those having 1 to 12 carbon atoms, and the hydrocarbon group of Y ^a3 is the aliphatic hydrocarbon group exemplified above in the range of 1 to 18 carbon atoms. Contains any of the aromatic hydrocarbon groups.
The aliphatic hydrocarbon group of X ^a2 is a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined. And groups obtained by appropriately combining the groups already exemplified in the range of 1 to 17 carbon atoms.

As a monomer (a1-4), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, monomers represented by any of the following formulas (a1-4-1) to (a1-4-7) are preferable, and those represented by formulas (a1-4-1) to (a1-4-5) are preferable. A monomer represented by any one is more preferable.

  When the resin (A) has a structural unit (a1) derived from the monomer (a1-4), the content ratio is preferably in the range of 10 to 95 mol% with respect to all the structural units of the resin (A). The range of 15 to 90 mol% is more preferable, and the range of 20 to 85 mol% is particularly preferable.

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。
Ｌ^３〜Ｌ^５は、酸素原子、硫黄原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−で表される基を表す。ここで、ｋ４は１〜７の整数を表し、＊はカルボニル基（−ＣＯ−）との結合手である。
Ｚ^１’は、単結合又は炭素数１〜６のアルカンジイル基であり、該アルカンジイル基中に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ｓ１及びｓ１’は、それぞれ独立して、０〜４の整数を表す。 As the other monomer (a1), for example, a monomer represented by the formula (a1-5) (hereinafter sometimes referred to as “monomer (a1-5)”) may be used.

In 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.
L ^{3 to} L ⁵ represent an oxygen atom, a sulfur atom, or a group represented by * —O— (CH ₂ ) _k4 —CO—O—. Here, k4 represents an integer of 1 to 7, and * is a bond with a carbonyl group (—CO—).
Z ^{1 ′} is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
s1 and s1 ′ each independently represents an integer of 0 to 4.

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ⁵ is preferably an oxygen atom.
One of L ³ and L ⁴ 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 ^{1 ′} is preferably a single bond or * —CH ₂ —CO—O—.

Examples of the monomer (a1-5) include the following monomers.

  When the resin (A) has a structural unit derived from the monomer (a1-5), the content thereof is in the range of 1 to 95 mol% with respect to all the structural units (100 mol%) of the resin (A). Is preferable, the range of 3-90 mol% is more preferable, and the range of 5-85 mol% is further more preferable.

<Acid stable structural unit>
Resin (A) is a structural unit having no acid labile group in addition to the structural unit (a1) containing an acid labile group (hereinafter referred to as “acid stable structural unit” in some cases). The derivatizable monomer is preferably referred to as “acid-stable monomer”). In the resin (A), the acid stable structural unit may have only one type, or may have a plurality of types.

  When the resin (A) has an acid stable structural unit, the content ratio of the acid stable structural unit may be determined based on the content ratio of the structural unit (a1). The ratio of the content ratio of the structural unit (a1) and the content ratio of the acid-stable structural unit is represented by [structural unit (a1)] / [acid-stable structural unit], and preferably 10 to 80 mol% / 90 to It is 20 mol%, More preferably, it is 20-60 mol% / 80-40 mol%. If it does in this way, there exists a tendency for the dry etching tolerance of the resist pattern obtained from this resist composition containing resin (A) to become still better.

Next, a preferable thing is demonstrated among an acid stable structural unit.
The acid stable structural unit is preferably a structural unit having a hydroxy group or a lactone ring. An acid stable structural unit having a hydroxy group (hereinafter, sometimes referred to as “acid stable structural unit (a2)”.
) And / or an acid-stable structural unit having a lactone ring (hereinafter, sometimes referred to as “acid-stable structural unit (a3)”) is used as the resist composition containing the resin (A). When applied to a substrate, a coating film formed on the substrate or a composition layer obtained from the coating film is excellent in adhesion to the substrate, so that a resist pattern can be produced with good resolution. In addition, the manufacturing method of the resist pattern using this resist composition here is mentioned later. First, the acid stable structural unit (a2) and the acid stable structural unit (a3) suitable as the acid stable structural unit will be described with specific examples.

<Acid stable structural unit (a2)>
When the acid-stable structural unit (a2) is introduced into the resin (A), a suitable acid-stable structure is used depending on the type of exposure source when producing a resist pattern from the resist composition containing the resin (A). The unit (a2) can be selected. That is, when this resist composition is used for exposure using a KrF excimer laser (wavelength: 248 nm) as an exposure source, or exposure using a high energy beam such as an electron beam or EUV light as an exposure source, an acid stable structural unit ( As a2), it is preferable to introduce an acid stable structural unit (a2-0) having a phenolic hydroxy group into the resin (A). When using exposure using a short wavelength ArF excimer laser (wavelength: 193 nm) as an exposure source, an acid stable structural unit represented by the formula (a2-1) described later is used as a resin ( It is preferable to introduce into A). Thus, each of the acid stable structural units (a2) possessed by the resin (A) can be selected according to the exposure source used for producing the resist pattern, but the acid stable structural units possessed by the resin (A) ( a2) may have only one type of acid stable structural unit (a2) suitable for the type of exposure source, and two or more types of acid stable structural unit (a2) suitable for the type of exposure source. Or an acid stable structural unit (a2) suitable for the type of exposure source and a combination of other acid stable structural units (a2).

式（ａ２−１）中、
Ｌ^a3は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−（ｋ２は１〜７の整数を表し、＊はカルボニル基（−ＣＯ−）との結合手を表す。）で表される基を表す。
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。 One specific example of the acid stable structural unit (a2) is one represented by the following formula (a2-1) (hereinafter sometimes referred to as “acid stable structural unit (a2-1)”).

In formula (a2-1),
L ^a3 is an oxygen atom or * —O— (CH ₂ ) _k2 —CO—O— (k2 represents an integer of 1 to 7, and * represents a bond to a carbonyl group (—CO—)). Represents the group represented.
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.

L ^a3 is preferably an oxygen atom or a group represented by * —O— (CH ₂ ) _k2 —CO—O—, wherein k2 is an integer of 1 to 4, and more preferably an oxygen atom or * —O—CH ₂ —CO—O—, and more preferably an oxygen atom.
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 an acid stable structural unit (a2-1), the following are mentioned, for example.

  As described above, the exemplified acid stable structural unit (a2-1) is derived from, for example, an acid stable monomer described in JP 2010-204646 A. Among these, the acid stable structural unit represented by any one of formula (a2-1-1), formula (a2-1-2), formula (a2-1-3), or formula (a2-1-4) Are more preferable, and an acid stable structural unit represented by the formula (a2-1-1) or (a2-1-3) is more preferable.

  When the resin (A) has an acid stable structural unit (a2-1), the content ratio is preferably in the range of 3 to 45 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range of 5-40 mol% is more preferable, and the range of 5-35 mol% is more preferable.

式（ａ２−０）中、
Ｒ^a30は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は同一でも異なっていてもよい。 Next, the acid stable structural unit which has a phenolic hydroxy group among the acid stable structural units which have a hydroxy group is demonstrated. The acid stable structural unit is preferably one represented by the following formula (a2-0) (hereinafter sometimes referred to as “acid stable structural unit (a2-0)”).

In formula (a2-0),
R ^a30 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 may be the same or different.

Specific examples of the “alkyl group having 1 to 6 carbon atoms” in the “alkyl group having 1 to 6 carbon atoms which may have a halogen atom” for R ^a30 include those already exemplified in this range. . The “C 1-6 alkyl group having a halogen atom” is one in which at least a part of the hydrogen atoms contained in the C 1-6 alkyl group is substituted with a halogen atom. The specific example of the halogen atom is as already described. Among these, R ^a30 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and further preferably a methyl group.
Specific examples of the alkoxy group of R ^a31 include those already exemplified in the range of 1 to 6 carbon atoms. Among these, R ^a31 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and particularly preferably a methoxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

Among the acid stable structural units (a2-0), the following formula (a2-0-1), formula (a2-0-2), formula (a2-0-3) or formula (a2-0-4) Those represented are preferred. An acid stable monomer capable of deriving such a structural unit is described in, for example, JP 2010-204634 A.

  Acid-stable monomer capable of deriving acid-stable structural unit (a2-0) such as p-hydroxystyrene and p-hydroxy-α-methylstyrene [hereinafter referred to as “acid-stable monomer (a2)” in some cases. ] In the production of the resin (A), the acid stable structural unit (a2-0) represented by the formula (a2-0-1) or the formula (a2-0-2) is converted into the resin (A). After the phenolic hydroxy group in the acid stable monomer (a2) is protected with a protecting group such as an acetyl group to form a protected acid stable monomer (a2), the protected acid Resin (A) can also be manufactured using a stable monomer (a2). A resin (A) having an acid-stable structural unit (a2-0) can be produced by deprotecting a resin having a structural unit derived from the protected acid-stable monomer (a2) and removing the protecting group. . However, when carrying out the deprotection treatment, it is necessary to carry out the deprotection treatment without significantly damaging the other structural unit (a1).

  When the resin (A) has an acid stable structural unit (a2-0), the content ratio is preferably in the range of 5 to 90 mol% with respect to the total structural unit (100 mol%) of the resin (A). The range of 10-85 mol% is more preferable, and the range of 15-80 mol% is further more preferable.

<Acid stable structural unit (a3)>
The lactone ring included in the acid stable structural unit (a3) may be monocyclic such as β-propiolactone ring, γ-butyrolactone ring and δ-valerolactone ring, and the monocyclic lactone ring and other rings Or a condensed ring. Among these lactone rings, a γ-butyrolactone ring and a condensed ring of a γ-butyrolactone ring and another ring are preferable.

［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。
ｐ１は０〜５の整数を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表し、ｐ１が２以上の場合、複数のＲ^a21は同一でも異なっていてもよい。
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。
ｑ１は、０〜３の整数を表す。
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し、ｑ１が２以上の場合、複数のＲ^a22は同一でも異なっていてもよい。
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。
ｒ１は、０〜３の整数を表す。
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し、ｒ１が２以上の場合、複数のＲ^a23は同一でも異なっていてもよい。］ The acid stable structural unit (a3) is preferably one represented by the following formula (a3-1), formula (a3-2) or formula (a3-3). Resin (A) may have only 1 type among these, and may have 2 or more types. In the following description, what is represented by formula (a3-1) may be referred to as “acid-stable structural unit (a3-1)”, and what is represented by formula (a3-2) is “acid In some cases, it is referred to as “stable structural unit (a3-2)”, and what is represented by the formula (a3-3) may be referred to as “acid stable structural unit (a3-3)”.

[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.
p1 represents an integer of 0 to 5.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when p1 is 2 or more, a plurality of R ^a21 may be the same or different.
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.
q1 represents an integer of 0 to 3.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when q1 is 2 or more, a plurality of R ^a22 may be the same or different.
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.
r1 represents an integer of 0 to 3.
R ^a23 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. When r1 is 2 or more, a plurality of R ^a23 may be the same or different. ]

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 preferably integers of 0 to 2, more preferably 0 or 1. When p1 is 2, two R ^a21 may be the same as or different from each other. When q1 is 2, two R ^a22 may be the same as or different from each other, and r1 is 2. Two R ^a23 may be the same or different from each other.

  Hereinafter, preferred examples of the acid stable structural unit (a3-1), the acid stable structural unit (a3-2), and the acid stable structural unit (a3-3) will be shown.

Preferred examples of the acid stable structural unit (a3-1) include the following formula (a3-1-1), formula (a3-1-2), formula (a3-1-3) or formula (a3-1-4). ).

Preferred examples of the acid stable structural unit (a3-2) include the following formula (a3-2-1), formula (a3-2-2), formula (a3-2-3), or formula (a3-2-4). ).

Preferred examples of the acid stable structural unit (a3-3) include the following formula (a3-3-1), formula (a3-3-2), formula (a3-3-3) or formula (a3-3-4). ).

  The acid stable structural unit (a3-1), the acid stable structural unit (a3-2), and the acid stable structural unit (a3-3) can be derived from an acid stable monomer described in JP 2010-204646 A. Among the specific examples of the acid stable structural unit (a3), the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-3), or the formula (a3-2-4) Is more preferable, and the acid stable structural unit represented by Formula (a3-1-1) or Formula (a3-2-3) is more preferable.

When the resin (A) has an acid stable structural unit (a3), the total content is preferably in the range of 5 to 70 mol% with respect to all the structural units (100 mol%) of the resin (A). The range of 10 to 65 mol% is more preferable, and the range of 10 to 60 mol% is more preferable.
The content of each of the acid stable structural unit (a3-1), the acid stable structural unit (a3-2), and the acid stable structural unit (a3-3) is the total structural unit (100 mol%) of the resin (A). On the other hand, 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Other acid stable structural units>
The preferred acid stable structural unit (a2) and acid stable structural unit (a3) have been described as the acid stable structural unit possessed by the resin (A). However, the resin (A) contains the acid stable structural unit (a2) and the acid stable structural unit. It may have an acid stable structural unit other than the structural unit (a3). Here, the acid stable structural unit (a4) other than the acid stable structural unit (a2) and the acid stable structural unit (a3) is referred to. Hereinafter, the acid-stable structural unit (a4) will be described by showing an acid-stable monomer (hereinafter sometimes referred to as “acid-stable monomer (a4)”) from which the acid-stable structural unit (a4) can be derived.

［式（ａ４−１）中、
Ｒ^４１は、水素原子又はメチル基を表す。
Ａ^４１は、式（ａ４−ｇ１）で表される基を表す。

（式（ａ４−ｇ１）中、
ｓｓは０〜２の整数を表す。
Ａ^４０及びＡ^４１は、それぞれ独立に、炭素数１〜５の脂肪族炭化水素基を表す。
ｓｓが２のとき、複数存在するＡ^４０は、互いに同一であるか相異なる。
Ｘ^４０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。
ｓｓが２のとき、複数存在するＸ^４０は、互いに同一であるか相異なる。）
Ｒ^4２は、フッ素原子を有する炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。］
Ａ^４１の脂肪族炭化水素基は、典型的にはアルカンジイル基であり、当該アルカンジイル基は直鎖状であっても、分岐していてもよい。当該アルカンジイル基は炭素数１〜５の範囲ですでに例示したものを含むが、中でも、Ａ^４１としては、炭素数１〜４のアルカンジイル基がより好ましく、エチレン基がさらに好ましい。 A specific example of the acid stable monomer (a4) is, for example, a monomer represented by the following formula (a4-1) (hereinafter sometimes referred to as “monomer (a4-1)”).

[In the formula (a4-1),
R ⁴¹ represents a hydrogen atom or a methyl group.
A ⁴¹ represents a group represented by the formula (a4-g1).

(In the formula (a4-g1),
ss represents an integer of 0-2.
A ⁴⁰ and A ⁴¹ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
When ss is 2, a plurality of A ⁴⁰ are the same or different from each other.
X ⁴⁰ represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
When ss is 2, a plurality of X ⁴⁰ are the same or different from each other. )
R ⁴² represents a C 1-18 aliphatic hydrocarbon group having a fluorine atom, and the methylene group constituting the aliphatic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]
The aliphatic hydrocarbon group for A ⁴¹ is typically an alkanediyl group, and the alkanediyl group may be linear or branched. The alkanediyl group includes those already exemplified in the range of 1 to 5 carbon atoms. Among them, as A ⁴¹ , an alkanediyl group having 1 to 4 carbon atoms is more preferable, and an ethylene group is more preferable.

  Specific examples of the group represented by the formula (a4-g1) (hereinafter may be referred to as “group (a4-g1)”) are shown below. In each specific example, * represents a bond. In addition, when the said group (a4-g1) has both an oxygen atom and a carbonyl group, it is preferable to have in the form of a carbonyloxy group or an oxycarbonyl group.

などが挙げられる。 As the group having an oxygen atom (a4-g1),

Etc.

などが挙げられる。 As the group having a carbonyl group (a4-g1),

Etc.

などが挙げられる。 As the group having a carbonyloxy group (a4-g1),

Etc.

などが挙げられる。 As the group having an oxycarbonyl group (a4-g1),

Etc.

R ⁴² is a group in which at least one of the hydrogen atoms contained in the aliphatic hydrocarbon group is replaced with a fluorine atom. The aliphatic hydrocarbon group may partially have a carbon-carbon unsaturated bond, but an aliphatic saturated hydrocarbon group having no carbon-carbon unsaturated bond is preferable. Examples of the aliphatic saturated hydrocarbon group include alkyl groups (straight and branched) and alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups obtained by combining alkyl groups and alicyclic hydrocarbon groups.

Specific examples of the aliphatic hydrocarbon group having a fluorine atom of R ⁴² include 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- Perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5 -Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, perfluorocyclopentyl 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-dodecafluoro Examples include a hexyl group, a perfluorocyclohexyl group, a perfluoropentylmethyl group, and a perfluorohexyl group.

（式（ａ−ｇ２）中、
Ａ¹³は、フッ素原子を有していてもよい炭素数１〜１５の２価の脂肪族炭化水素基を表す。
Ｘ¹²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。
Ａ¹⁴は、フッ素原子を有していてもよい炭素数１〜１５の１価の脂肪族炭化水素基を表す。
但し、Ａ¹³又はＡ¹⁴の少なくともいずれかはフッ素原子を有するものであり、Ａ¹³及びＡ¹⁴の炭素数の合計は１７以下である。） Examples of the group in which the methylene group constituting the aliphatic hydrocarbon group of R ⁴² is replaced by an oxygen atom or a carbonyl group include a group represented by the formula (a-g2) (hereinafter, “group (a-g2 ) ”)).

(In the formula (a-g2),
A ¹³ represents a C 1-15 divalent aliphatic hydrocarbon group which may have a fluorine atom.
X ¹² represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ¹⁴ represents a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a fluorine atom.
Provided that at least one of A ¹³ or A ¹⁴ are those having a fluorine atom, the total number of carbon atoms of A ¹³ and A ¹⁴ is 17 or less. )

When A ¹³ is a divalent aliphatic hydrocarbon group having a fluorine atom, the aliphatic hydrocarbon group is typically an alkanediyl group having a fluorine atom and a divalent alicyclic carbon having a fluorine atom. Examples thereof include a hydrogen group (preferably a cycloalkanediyl group having a fluorine atom). The alkanediyl group having a fluorine atom is one in which part or all of the hydrogen atoms contained in the alkanediyl group are substituted with a fluorine atom, and the divalent alicyclic hydrocarbon group having a fluorine atom is 2 Some or all of the hydrogen atoms contained in the valent alicyclic hydrocarbon group are substituted with fluorine atoms.

Here, when the monomer (a4-1) is shown as a specific example in the case where R ⁴² is an aliphatic hydrocarbon group having a fluorine atom and A ⁴¹ is an ethylene group, the following formula (a4-1-1) To a compound represented by any one of formulas (a4-1-22).

The aliphatic hydrocarbon group having a fluorine atom of R ⁴² is a perfluoroalkyl group in which all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms (for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro group). A butyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, etc.) or a perfluorocycloalkyl group in which all of the hydrogen atoms contained in the cycloalkyl group are substituted with fluorine atoms is preferred.

The compound in which R ⁴² is a perfluoroalkyl group or a perfluorocycloalkyl group includes the above-described formula (a4-1-3), formula (a4-1-4), formula (a4-1-7), and formula (a4- 1-8), formula (a4-1-11), formula (a4-1-12), formula (a4-1-15), formula (a4-1-16), formula (a4-1-19), A compound represented by any one of formula (a4-1-20), formula (a4-1-21) and formula (a4-1-22) is applicable.

R ⁴² is more preferably a perfluoroalkyl group. More preferably, it is a C1-C6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group.

［式（ａ４−１’）中の符号はいずれも、前記と同義である。］ The monomer (a4-1) in which R ⁴² is a group represented by the formula (a-g2) is represented by the following formula (a4-1 ′) (hereinafter, “monomer (a4-1 ′” ) ").

[All the symbols in formula (a4-1 ′) have the same meanings as described above. ]

In the monomer (a4-1 ′), both A ¹³ and A ¹⁴ may have a fluorine atom, but A ¹³ is an aliphatic hydrocarbon group having a fluorine atom, or A ¹⁴ has a fluorine atom. What is an aliphatic hydrocarbon group is preferable. Further, it is preferable that A ¹³ is an aliphatic hydrocarbon group having a fluorine atom, among them, A ¹³ is more preferable alkanediyl group having a fluorine atom, and more preferred is a perfluoro alkanediyl group . The “perfluoroalkanediyl group” refers to an alkanediyl group in which all hydrogen atoms are substituted with fluorine atoms.

As the monomer (a4-1 ′) in which R ⁴² is a perfluoroalkanediyl group and A ⁴¹ is an ethylene group, any of the following formulas (a4-1′-1) to (a4-1′-46) A monomer represented by

The number of carbon atoms of A ¹³ and A ¹⁴ is their sum is arbitrarily selected in the range of 17 or less, the number of carbon atoms of A ¹³ are members preferably 1-6, 1-3 is more preferable. On the other hand, the number of carbon atoms of A ¹⁴ is preferably 4 to 15, 5 to 12 is more preferable. Further preferred A ¹⁴ is an alicyclic hydrocarbon group having 6 to 12 carbon atoms, and a cyclohexyl group and an adamantyl group are even more preferred.

The group (a-g2) is as follows when A ¹³ is an aliphatic hydrocarbon group having a fluorine atom and A ¹⁴ is a cyclohexyl group or an adamantyl group.

このような基（ａ−ｇ２）を有するモノマー（ａ４−１’）は、上述した具体例の中では、式（ａ４−１’−７）〜式（ａ４−１’−４２）で表されるものが該当する。

The monomer (a4-1 ′) having such a group (a-g2) is represented by the formula (a4-1′-7) to the formula (a4-1′-42) in the specific examples described above. Is applicable.

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

<Method for producing resin (A)>
The resin (A) is obtained by copolymerizing the monomer (a1) for deriving the structural unit (a1), more preferably the monomer (a1) and an acid stable monomer, and more preferably the structural unit. (A1-1) and / or monomer (a1) for deriving structural unit (a1-2) and acid-stable monomer for deriving acid-stable structural unit (a2) and / or acid-stable structural unit (a3) Polymerized. Moreover, a monomer (a4-1) can also be used as an acid stable monomer as needed. When the resist composition is used for, for example, EUV exposure, the monomer (a1) for deriving the structural unit (a1-1) and / or the structural unit (a1-2), and the acid stable structural unit (a2- And an acid-stable monomer derived from 0).
The resin (A) further preferably has a structural unit (a1-1) having an adamantyl group as the structural unit (a1). The resin (A) can be produced by subjecting the monomer as described above to a known polymerization method (for example, radical polymerization method) and polymerizing (copolymerizing) it.

  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). 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.

<Resin (X)>
Apart from the resin (A), a resin having a structural unit derived from the monomer (a4-1) and having no acid action property (hereinafter, sometimes referred to as “resin (X)”) is the above-mentioned resist composition. It can also be included in the product. In other words, the resin (A) having an acid labile group [structural unit (a1)] in the molecule and the structural unit derived from the monomer (a4-1) having no acid labile group in the molecule. It can be made to contain in this resist composition combining resin (X). More specifically, the resin (X) preferably has a structural unit derived from the monomer (a4-1 ′) among the structural units derived from the monomer (a4-1).

  Resin (X) may consist essentially of a structural unit derived from monomer (a4-1), or may have a structural unit other than the structural unit derived from monomer (a4-1). Also good. As the structural unit other than the structural unit derived from the monomer (a4-1), a structural unit known in the art can be used as long as it is composed of a structural unit having no acid labile group. Examples thereof include an acid stable structural unit (a2) and an acid stable structural unit (a3).

  The content ratio of the structural unit derived from the monomer (a4-1) in the resin (X) is preferably 80 mol% or more, and 85 mol% with respect to all the structural units (100 mol%) of the resin (X). The above is more preferable, and 90 mol% or more is more preferable.

  The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).

<Basic compound (C)>
This resist composition preferably further contains a basic compound (C). Such a basic compound (C) is called a quencher in the art. 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. The basic compound (C) is preferably a compound represented by the formula (C1) to a compound represented by the formula (C8), more preferably a compound represented by the formula (C1-1). It is done.

［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６〜１０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で置換されていてもよい。］

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

［式（Ｃ１−１）中、
Ｒ^c2及びＲ^c3は、前記と同義である。
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の全部又は一部は同じであってもよい。］

[In the formula (C1-1),
R ^c2 and R ^c3 are as defined 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, all or some of the plurality of R ^c4 may be the same. ]

［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と同義である。
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の全部又は一部は同じであってもよい。］

[In Formula (C2), Formula (C3) and Formula (C4),
R ^c5 , R ^c6 , R ^c7 and R ^c8 are each independently synonymous with 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, all or some of the plurality of R ^c9 may be the same. ]

［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と同義である。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同義である「。
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の全部又は一部は同じであってもよい。ｐ３が２以上であるとき、複数のＲ^c15の全部又は一部は同じであってもよい。
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 are each independently synonymous with R ^c1 .
R ^c14 , R ^c15 and R ^c17 are each independently synonymous with R ^c4 .
o3 and p3 each independently represent an integer of 0 to 3. When o3 is 2 or more, all or some of the plurality of R ^c14 may be the same. When p3 is 2 or more, all or some of the plurality of R ^c15 may be the same.
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と同義である。
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の全部又は一部は同じであってもよい。ｒ３が２以上であるとき、複数のＲ^c19の全部又は一部は同じであってもよい。ｓ３が２以上であるとき、複数のＲ^c20の全部又は一部は同じであってもよい。
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。］

[In Formula (C7) and Formula (C8),
R ^c18, R ^c19 and R ^c20 in each occurrence independently has 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, all or some of the plurality of R ^c18 may be the same. When r3 is 2 or more, all or some of the plurality of R ^c19 may be the same. When s3 is 2 or more, all or some of the plurality of R ^c20 may be the same.
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. ]

  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 thereof include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, and 4,4′-diamino-3,3′-diethyldiphenylmethane. Propyl aniline, and more preferably include 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 Examples include ammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

<Solvent (D)>
The resist composition may further contain a solvent (D). The solvent (D) is a resist composition formed on the substrate in the production of a resist pattern, which will be described later, according to the type and amount of the hydroxyaromatic derivative having the group represented by the formula (1) and the resin (A). An optimal one can be appropriately selected from the viewpoint that the applicability at the time of applying an object is improved.

  Examples of the solvent (D) 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 Examples thereof include esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone. A solvent (D) may be used individually by 1 type, and may use 2 or more types together.

<Other ingredients>
The resist composition comprises a hydroxy aromatic derivative having a group represented by the formula (1), a resin (A), an acid generator (B), a basic compound (C) and a solvent (D) used as necessary. Constituents other than) may be contained. This component may be referred to as “component (F)”. Examples of the component (F) include additives known in the art, for example, polymer compounds other than the resin (A), sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes.

<Preparation method of the present resist composition>
The resist composition can be usually prepared by mixing a hydroxy aromatic derivative having a group represented by the formula (1) and a resin (A) in the presence of a solvent (D). Furthermore, you may mix an acid generator (B), a basic compound (C), and / or a component (F) as needed as above-mentioned. It is preferable to mix the basic compound (C). 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 solvent (D), such as a kind (resin (A)), such as resin (A). 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.
By selecting the amount of each component used when preparing the resist composition of the present invention, the content of each component in the resist composition of the present invention can be adjusted.

  The content ratio of the acid generator in the resist composition is preferably 40% by mass or less, more preferably 35% by mass or less, and preferably 1% by mass or more, more preferably based on the solid content of the resist composition. Is 3% by mass or more. In addition, solid content here means the sum total of what remove | excluded the solvent (D) from this resist composition. The solid content can be determined by subjecting the resist composition to analysis such as liquid chromatography and gas chromatography. When the acid generator contained in the resist composition is substantially only a hydroxyaromatic derivative having a group represented by the formula (1), the “content ratio of acid generator” described here is “ It can be read as “content ratio of hydroxyaromatic derivative having a group represented by formula (1)”.

  On the other hand, as described above, in addition to the hydroxyaromatic derivative having the group represented by the formula (1), other acids other than the hydroxyaromatic derivative having the group represented by the formula (1) are added to the resist composition. When the generator (preferably an ionic acid generator, particularly preferably the acid generator (B)) is used, the above-mentioned “content ratio of acid generator” is expressed by the formula (1 The total content of hydroxyaromatic derivatives having a group represented by (II) and other acid generators "can be read. In this case, the hydroxyaromatic derivative having a group represented by the formula (1) is preferably 10 parts by mass or more and particularly preferably 30 parts by mass or more with respect to 100 parts by mass of the total amount of the acid generator. . In the resist composition, when the hydroxy aromatic derivative having a group represented by the formula (1) is used in combination with another ionic acid generator as the acid generator, the other ionicity is obtained. It has been found that the resolution is further improved as compared with a resist composition using only an acid generator as an acid generator.

  A preferable range of the content ratio of the resin (A) in the resist composition is determined based on the solid content of the resist composition. Specifically, the resin (A) is preferably 80% by mass or more based on the mass of the solid content. The resist composition is a resin other than the resin (A), that is, a resin not having the above-mentioned acid action characteristics (hereinafter sometimes referred to as “resin (X)”) as long as the effects of the present invention are not significantly impaired. Can also be included. The resin (X) preferably has a fluorine atom in its molecule, and more preferably has a structural unit derived from an acid-stable monomer having a fluorine atom. More specifically, when this resin (X) is exemplified, a resin (X) having a structural unit derived from the monomer (a4-1) can be exemplified. In the resin (X) in this case, the content ratio of the structural unit derived from the monomer (a4-1) is preferably in the range of 70 to 100 mol% with respect to all the structural units of the resin (X), and 80 to 100 The range of mol% is more preferable, and the range of 90 to 100 mol% is more preferable.

  When the resin composition (A) and the resin (X) are contained in the resist composition, the content ratio of the resin (X) in the resist composition is 0.1 to 30 based on the solid content of the resist composition. About mass% is preferable, about 0.5-20 mass% is more preferable, and about 1-15 mass% is further more preferable.

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

  When the solvent (D) is contained in the resist composition, the content is 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, based on the total mass of the resist composition. For example, it is 99.9 mass% or less, Preferably it is 99 mass% or less.

  When the resist composition contains the component (F), an appropriate content can be determined according to the type of the component (F).

  Thus, an acid generator and a resin (A) containing a hydroxy aromatic derivative having a group represented by the formula (1), an acid generator (B) used as necessary, a basic compound (C), After mixing each of the solvent (D) and the component (F) with a preferable content, 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>
Specifically showing a method for producing a resist pattern using the present resist composition,
(1) a step of applying the resist composition 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,
Examples of the method include (4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating. Hereinafter, each of the steps shown here is referred to as “step (1)” to “step (5)”.

  Application of the resist composition on the substrate in the step (1) can be performed by a coating apparatus widely used for applying a resist material for semiconductor microfabrication, such as a spin coater. Thus, a coating film made of a resist composition is formed on the substrate. The film thickness of the coating film can be adjusted by variously adjusting the conditions (coating conditions) of the coating apparatus. You can choose the conditions. Various substrates to be subjected to microfabrication can be selected as the substrate before applying the resist composition. The substrate may be washed or an antireflection film may be formed before applying the resist composition. For example, a commercially available composition for an organic antireflection film can be used for forming the antireflection film.

In the step (2), the present resist composition coated on the substrate, that is, the coated film is dried to remove the solvent (D). Drying is performed, for example, by evaporating the solvent from the coating film by heating means using a heating device such as a hot plate (so-called pre-baking), decompressing means using a decompressing device, or by combining these means. Is called. The drying conditions can be selected according to the type of the solvent (D) contained in the resist composition. For example, in the case of a hot plate, the surface temperature of the hot plate is preferably in the range of about 50 to 200 ° C. . In the decompression means, it is preferable to enclose the substrate on which the coating film is formed in an appropriate decompressor, and then set the internal pressure of the decompressor to about 1 to 1.0 × 10 ⁵ Pa. Thus, the composition layer is formed on the substrate by removing the solvent from the coating film.

Step (3) is a step of exposing the composition layer, and preferably a step of exposing the composition layer using an exposure machine. The exposure is performed through a mask (photomask) on which a desired pattern to be finely processed is formed. As an exposure light source of the exposure machine, an ultraviolet light source such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm), or a solid-state laser light source (YAG In addition, various lasers such as a laser beam from a laser beam from a semiconductor laser or the like to emit a harmonic laser beam in the far ultraviolet region or the vacuum ultraviolet region can be used. The exposure machine may be an immersion exposure machine. The exposure machine may irradiate an electron beam or extreme ultraviolet light (EUV). In this specification, irradiating these radiations may be collectively referred to as “exposure”.
By exposing through a mask, the composition layer has an exposed portion (exposed portion) and an unexposed portion (unexposed portion). In the composition layer of the exposed part, the hydroxy aromatic derivative having the group represented by the formula (1) and the acid generator (B) contained in the composition layer generate an acid upon receiving exposure energy, and further generated. Due to the action with an acid, the acid labile group in the resin (A) of the “resin that is insoluble or hardly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid” is converted into a hydrophilic group by a deprotection reaction. Therefore, the resin (A) in the composition layer of the exposed area becomes soluble in the aqueous alkali solution. On the other hand, since the exposure energy is not received in the unexposed area, the resin (A) remains insoluble or hardly soluble in the alkaline aqueous solution. Since the composition layer in the exposed portion and the composition layer in the unexposed portion are significantly different in solubility in an alkaline aqueous solution, a resist pattern can be formed by development with the alkaline aqueous solution.

  In step (4), the composition layer after exposure is subjected to heat treatment (so-called post-exposure baking). Such heat treatment is preferably the heating means using the hot plate shown in the step (2). In addition, when performing the heating means using a hot plate in the step (4), the surface temperature of the hot plate is preferably about 50 to 200 ° C, more preferably about 70 to 150 ° C. The deprotection reaction is promoted by the heat treatment.

Step (5) is a step of developing the heated composition layer, and preferably the heated composition layer is developed with a developing device. In the developing step, when the composition layer after heating is brought into contact with an alkaline aqueous solution, the exposed composition layer is dissolved and removed in the alkaline aqueous solution, and the unexposed composition layer remains on the substrate. A resist pattern is manufactured on the substrate.
As the alkaline aqueous solution, those known in this technical field called “alkaline developer” can be used. Examples of the alkaline aqueous solution include an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).

  After the development, it is preferable to perform a rinsing treatment with ultrapure water or the like. Furthermore, it is preferable to remove moisture remaining on the substrate and the resist pattern.

  According to the resist pattern manufacturing method including the steps (1) to (5) as described above, a fine resist pattern can be manufactured with excellent line edge roughness (LER) due to the effect of the present resist composition. .

<Application>
This resist composition is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) irradiation, or a resist composition for EUV exposure.

Hereinafter, the present invention will be described in detail by way of examples.
In Examples and Comparative Examples, “%” and “part” representing the content and the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography (HLC-8120GPC type manufactured by Tosoh Corporation, three columns are “TSKgel Multipore HXL-M”, and the solvent is tetrahydrofuran) using polystyrene as a standard product.
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

  The structure of the compound is NMR (GX-270 type or EX-270 type; both manufactured by JEOL Ltd.), mass spectrometry (LC; type 1100; Agilent, MASS; LC / MSD type or LC / MSD TOF Type; both were made by Agilent).

式（Ｉ−１−ａ）で表される塩５．００部及びクロロホルム３０部を、反応器に仕込み、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｂ）で表される化合物２．０３部を添加し、６０℃程度まで昇温した後、同温度で２時間攪拌し、式（Ｉ−１−ｃ）で表される化合物を含む溶液を得た。得られた式（Ｉ−１−ｃ）で表される化合物を含む溶液に、２３℃で、式（Ｉ−１−ｄ）で表される化合物６．８５部、クロロホルム５０部及びアセトニトリル３０部の混合溶液を仕込み、さらに、トリフルオロ酢酸２．６０部を仕込み、２３℃で３時間攪拌した。得られた反応マスに、イオン交換水３５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル６０部を加えて攪拌した後、ろ過することにより、式（Ｉ−１−１）がメイン成分であるヒドロキシ芳香族誘導体９．６９部を得た。 Example 1 [Synthesis of Hydroxy Aromatic Derivative Represented by Formula (I-1-1)]

5.00 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were charged into a reactor and stirred at 23 ° C. for 30 minutes. Thereafter, 2.03 parts of a compound represented by the formula (I-1-b) was added, the temperature was raised to about 60 ° C., and the mixture was stirred at the same temperature for 2 hours, and represented by the formula (I-1-c). A solution containing the compound to be obtained was obtained. In a solution containing the compound represented by the formula (I-1-c) thus obtained, at 23 ° C., 6.85 parts of the compound represented by the formula (I-1-d), 50 parts of chloroform and 30 parts of acetonitrile. Then, 2.60 parts of trifluoroacetic acid was added and stirred at 23 ° C. for 3 hours. To the resulting reaction mass, 35 parts of ion exchange water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was further repeated 5 times. The recovered organic layer is concentrated, 60 parts of tert-butyl methyl ether is added to the resulting concentrate, and the mixture is stirred and then filtered to obtain a hydroxy fragrance having formula (I-1-1) as the main component. 9.69 parts of a group derivative were obtained.

In the case of triphenylsulfonium proton 15H on the cation side of NMR analysis formula (I-1-1),
Anion side methyl proton 12.01H

式（Ｉ−２−ａ）で表される塩５．４８部及びクロロホルム４０部を、反応器に仕込み、２３℃で３０分間攪拌した。その後、式（Ｉ−２−ｂ）で表される化合物２．０３部を添加し、６０℃程度まで昇温した後、同温度で２時間攪拌し、式（Ｉ−２−ｃ）で表される化合物を含む溶液を得た。得られた式（Ｉ−２−ｃ）で表される化合物を含む溶液に、２３℃で、式（Ｉ−２−ｄ）で表される化合物６．８５部、クロロホルム５０部及びアセトニトリル３０部の混合溶液を仕込み、さらに、トリフルオロ酢酸２．６０部を仕込み、２３℃で３時間攪拌した。得られた反応マスに、イオン交換水３５部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗操作をさらに５回繰り返した。回収された有機層を濃縮し、得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル６０部を加えて攪拌した後、ろ過することにより、式（Ｉ−１−２）がメイン成分であるで表されるヒドロキシ芳香族誘導体９．８９部を得た。 Example 2 [Synthesis of Hydroxy Aromatic Derivative Represented by Formula (I-1-2)]

5.48 parts of the salt represented by the formula (I-2-a) and 40 parts of chloroform were charged into a reactor and stirred at 23 ° C. for 30 minutes. Thereafter, 2.03 parts of the compound represented by the formula (I-2-b) was added, the temperature was raised to about 60 ° C., and the mixture was stirred at the same temperature for 2 hours, and represented by the formula (I-2-c). A solution containing the compound to be obtained was obtained. In a solution containing the compound represented by the formula (I-2-c) thus obtained, at 23 ° C., 6.85 parts of the compound represented by the formula (I-2-d), 50 parts of chloroform and 30 parts of acetonitrile. Then, 2.60 parts of trifluoroacetic acid was added and stirred at 23 ° C. for 3 hours. To the resulting reaction mass, 35 parts of ion exchange water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was further repeated 5 times. The recovered organic layer was concentrated, 60 parts of tert-butyl methyl ether was added to the resulting concentrate, and the mixture was stirred and filtered to obtain the formula (I-1-2) as the main component. 9.89 parts of a hydroxy aromatic derivative were obtained.

When the aryl proton 12H on the cation side in NMR analysis formula (I-1-2) is 12H,
Anion side methyl proton 12.02H

以下、これらのモノマーをその式番号に応じて、「モノマー（ａ１−１−２）」などという。 Synthesis of Resin (A) Monomers used for the synthesis of resin (A) are shown below.

Hereinafter, these monomers are referred to as “monomer (a1-1-2)” or the like according to the formula number.

Synthesis Example 1: [Synthesis of Resin A1]
The monomer (a1-1-3), the monomer (a1-2-3), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (a3-2-3) are mixed in a molar ratio [ Monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] is 30:14 : 6: 20: 30 The mixture was further mixed, and 1.5 mass times of dioxane was further mixed with this monomer mixture with respect to the total mass of all monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. It added so that it might become. This was polymerized by heating at 73 ° C. for about 5 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. It is again dissolved in dioxane, poured into a mixed solvent of a large amount of methanol and water to precipitate the resin, and the precipitated resin is filtered and collected twice to perform reprecipitation purification, and the weight average molecular weight is 8 Resin A1 of .1 × 10 ³ was obtained with a yield of 65%. This resin A1 is a monomer (a1-1-3), a monomer (a1-2-3), a monomer (a2-1-1), a monomer (a3-1-1), and a monomer (a3-2-3). Each of these has the following structural units.

Synthesis Example 2: [Synthesis of Resin A2]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3) are mixed in a molar ratio [ Monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] is 30:14 : 6: 20: 30 The mixture was further mixed, and 1.5 mass times of dioxane was further mixed with this monomer mixture with respect to the total mass of all monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. It added so that it might become. This was polymerized by heating at 73 ° C. for about 5 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, it is dissolved in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and collected twice to perform reprecipitation purification, and the weight average molecular weight is 7 Resin A2 of .8 × 10 ³ was obtained with a yield of 68%. This resin A2 is a monomer (a1-1-2), a monomer (a1-2-3), a monomer (a2-1-1), a monomer (a3-1-1), and a monomer (a3-2-3). Each of these has the following structural units.

Synthesis Example 3: [Synthesis of Resin A3]
Monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) are mixed in a molar ratio [monomer (a1-1-2): monomer (a2-1-1): 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. Then, this was heated at 80 ° C. for about 8 hours to carry out polymerization. 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 obtained resin is dissolved in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered three times for reprecipitation purification. A resin A3 having a weight average molecular weight of about 9.2 × 10 ³ was obtained in a yield of 60%. This resin A3 has structural units derived from the following monomers derived from the monomer (a1-1-2), the monomer (a2-1-1) and the monomer (a3-1-1), respectively. .

Synthesis Example 4: [Synthesis of Resin A4]
1.18 parts of monomer (a1-1-2), 14.60 parts of p-acetoxystyrene, and 3.55 parts of monomer (a2-1-1) were added 28.82 parts of 1,4-dioxane to form a solution, The temperature was raised to 87 ° C. To the obtained solution, 2.96 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 291.41 parts of methanol and 124.89 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 2.93 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated under reflux for 15 hours. After cooling, the resulting reaction solution was neutralized with 2.16 parts of glacial acetic acid, and then poured into a large amount of water to cause precipitation. A polymer having a weight average molecular weight of about 3.4 × 10 ³ is purified by repeating the operation of separating the precipitated polymer by filtration, dissolving in acetone, and pouring into a large amount of water for precipitation three times. 71 parts were obtained. This copolymer has structural units derived from the following monomers derived from the monomer (a1-1-2), p-hydroxystyrene and the monomer (a2-1-1), respectively. It is set as Resin A4.

Synthesis Example 5: [Synthesis of Resin A5]
A monomer (a1-1-2) 10.54 parts, p-acetoxystyrene 14.60 parts, monomer (a2-1-1) 3.55 parts, 1,4-dioxane 47.09 parts was added to make a solution, The temperature was raised to 87 ° C. To the obtained solution, 2.96 parts of azobisisobutyronitrile as an initiator was added, and kept at 87 ° C. for 6 hours. After cooling, the reaction solution was poured into a mixed solution of 285.67 parts of methanol and 122.43 parts of ion-exchanged water, and the polymer was precipitated and filtered. The obtained filtrate and 2.93 parts of 4-dimethylaminopyridine were added to the same amount of methanol as the obtained filtrate and heated under reflux for 15 hours. After cooling, the resulting reaction solution was neutralized with 2.16 parts of glacial acetic acid, and then poured into a large amount of water to cause precipitation. A polymer having a weight average molecular weight of about 3.7 × 10 ³ is purified by repeating the operation of filtering the precipitated polymer, dissolving it in acetone, pouring it into a large amount of water and precipitating it three times. 15 parts were obtained. This copolymer has structural units derived from the following monomers derived from the monomer (a1-1-2), p-hydroxystyrene and the monomer (a2-1-1), respectively. This is Resin A5.

Synthesis Example 6 [Synthesis of Resin A6]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1) are mixed in a molar ratio ( Monomer (a1-1-2): Monomer (a1-2-3): Monomer (a2-1-1): Monomer (a3-2-3): Monomer (a3-1-1)) is 30:14 : 6: 20: 30 The mixture was mixed and 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.2. A × 10 ³ copolymer A6 was obtained with a yield of 78%. This resin A6 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A7]
Monomer (a1-1-2), monomer (a1-5-1), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1) are mixed in a molar ratio ( Monomer (a1-1-2): Monomer (a1-5-1): Monomer (a2-1-1): Monomer (a3-2-3): Monomer (a3-1-1)) is 30:14 : 6: 20: 30 The mixture was mixed and 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.2. Copolymer A7 of × 10 ³ was obtained with a yield of 78%. This resin A7 has the following structural units.

Synthesis Example 6 [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.

Examples 3-11, Comparative Example 1
<Preparation of resist composition>
As shown in Table 1, each component was mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

ヒドロキシ芳香族誘導体Ｚ１：特開２００８−１９１４１３号公報の実施例に従って合成

ヒドロキシ誘導体Ｚ１は、式（Ｚ１）で表される塩の混合物であり、数値（％）は、前記混合物における水素原子、式（Ｚ１−a）で表される基及び式（Ｚ１−ｂ）で表される基の導入率（mol％）を表す。 <Hydroxy aromatic derivative having a group represented by the formula (1)>
I-1-1: Hydroxy aromatic derivative represented by the formula (I-1-1) I-1-2: Hydroxy aromatic derivative represented by the formula (I-1-2) <Acid generator>
Acid generator B1-3: synthesized according to the examples of JP 2010-152341 A

Hydroxyaromatic derivative Z1: synthesized according to the examples of JP 2008-191413 A

The hydroxy derivative Z1 is a mixture of salts represented by the formula (Z1), and the numerical value (%) is a hydrogen atom in the mixture, a group represented by the formula (Z1-a), and a formula (Z1-b). It represents the introduction rate (mol%) of the group represented.

<Resin>
A1: Resin A1
A2: Resin A2
A3: Resin A3
A6: Resin A6
A7: Resin A7
X1: Resin X1
<Basic compound (C): quencher>
C1: 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene glycol monomethyl ether acetate 265.0 parts Propylene glycol monomethyl ether 20.0 parts 2-heptanone 20.0 parts γ-butyrolactone 3.5 parts

<Manufacture of resist pattern and its evaluation>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Co., Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 780 mm. An organic antireflection film was formed. Subsequently, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm.
After applying the resist composition, the obtained silicon wafer was pre-baked (PB) for 60 seconds at the temperature described in the “PB” column of Table 1 on a direct hot plate to form a composition layer. An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] was used for the wafer on which the composition layer (resist composition film) was thus formed. The line and space pattern was subjected to immersion exposure by changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post exposure bake (PEB) is performed on the hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed to obtain a resist pattern.

  In forming a resist pattern from each resist composition, the exposure amount at which the line width of a 50 nm line-and-space pattern was 1: 1 was defined as effective sensitivity.

  In manufacturing the resist pattern as described above, the following items were evaluated.

<Line edge roughness evaluation (LER)>
The wall surface of the resist pattern obtained with effective sensitivity is observed with a scanning electron microscope, and the unevenness fluctuation width (LER) of the side wall of the resist pattern is
If it is 3.5 nm or less, ◎,
O exceeding 3.5 nm and not more than 4.5 nm
What exceeded 4.5 nm was set as x.
The result of the line edge roughness evaluation (LER) obtained as described above was expressed by the above-mentioned level evaluation, and the LER (nm) was indicated by a numerical value in parentheses. The results are summarized in Table 2.

Examples 12 to 15 and Comparative Example 2
<Preparation of resist composition>
The components shown in Table 3 are mixed with the solvents shown below in parts by mass shown in Table 3 and dissolved, and the resulting mixture is filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition. did.

ヒドロキシ誘導体Ｚ１は、式（Ｚ１）で表される塩の混合物であり、数値（％）は、前記混合物における水素原子、式（Ｚ１−a）で表される基及び式（Ｚ１−ｂ）で表される基の導入率（mol％）を表す。
＜塩基性化合物：クエンチャー＞
Ｃ２：テトラブチルアンモニウムヒドロキシド（東京化成工業（株）製）
Ｃ３：下式で表される化合物（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １００部
γ−ブチロラクトン ５部 <Resin>
A4: Resin A4
A5: Resin A5
<Hydroxy aromatic derivative having a group represented by the formula (1)>
I-1-1: Hydroxyaromatic derivative represented by the formula (I-1-1) <acid generator>
Hydroxyaromatic derivative Z1: synthesized according to the examples of JP 2008-191413 A

The hydroxy derivative Z1 is a mixture of salts represented by the formula (Z1), and the numerical value (%) is a hydrogen atom in the mixture, a group represented by the formula (Z1-a), and a formula (Z1-b). It represents the introduction rate (mol%) of the group represented.
<Basic compound: Quencher>
C2: Tetrabutylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C3: Compound represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

(Production and evaluation of resist patterns by electron beam irradiation)
A silicon wafer is treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds, and the above resist composition is spin-coated so that the film thickness after drying (pre-baking) is 0.06 μm. did. Then, it prebaked for 60 seconds on the direct hot plate at the temperature shown in the "PB" column of Table 3, and formed the composition layer. Each wafer having the composition layer thus formed is exposed to a line-and-space pattern by using an electron beam drawing machine ["HL-800D 50 keV" manufactured by Hitachi, Ltd., and gradually changing the exposure amount. did.
After exposure, post-exposure baking is performed for 60 seconds on the hot plate at the temperature indicated in the “PEB” column of Table 3, and then paddle development is performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. Got a pattern.

Line edge roughness evaluation (LER): The wall surface of the resist pattern obtained with an exposure amount at which the line width of the 80 nm line and space pattern is 1: 1 is observed with a scanning electron microscope, and the unevenness of the side wall of the resist pattern is shaken. The width (LER) is
If it is 5 nm or less, ◎,
The thing exceeding 5 nm was set as x.
The result of the line edge roughness evaluation (LER) obtained as described above was expressed by the above-mentioned level evaluation, and the LER (nm) was indicated by a numerical value in parentheses. The results are summarized in Table 4.

(Production of resist pattern by EUV exposure and its evaluation)
A silicon wafer is treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds, and the resist composition shown in Table 3 is dried (prebaked) so that the film thickness becomes 0.05 μm. Spin coated.
Then, it prebaked for 60 seconds on the direct hot plate at the temperature shown in the "PB" column of Table 3, and formed the composition layer. The wafer on which the composition layer was thus formed was exposed to a line and space pattern using an EUV exposure machine while changing the exposure amount stepwise.
After exposure, post-exposure baking is performed for 60 seconds on the hot plate at the temperature indicated in the “PEB” column of Table 2, and then paddle development is performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. Got a pattern.

Line edge roughness evaluation (LER): The wall surface of the resist pattern obtained with an exposure amount at which the line width of a 50 nm line and space pattern is 1: 1 is observed with a scanning electron microscope, and the unevenness of the sidewall of the resist pattern is shaken. The width (LER) is
If it is 5 nm or less, ◎,
The thing exceeding 5 nm was set as x. The results are shown in Table 5.
The result of the line edge roughness evaluation (LER) obtained as described above was expressed by the above-mentioned level evaluation, and the LER (nm) was indicated by a numerical value in parentheses. The results are summarized in Table 5.

  The resist composition of the present invention containing a hydroxy aromatic derivative having a group represented by the formula (1) has a line edge roughness (LER) of “◯” or “「 ”, and the line edge roughness ( A resist pattern with a good (LER) could be produced. On the other hand, the resist composition of Comparative Example 1 which does not contain a hydroxy aromatic derivative having a group represented by the formula (1) has a poor line edge roughness (LER) (x).

  If a resist composition containing a hydroxy aromatic derivative having a group represented by the formula (1) of the present invention as an acid generator is used, a resist pattern having excellent line edge roughness (LER) can be produced.

Claims (7)

The hydroxy aromatic derivative which has group represented by Formula (1).

[In Formula (1),
Q ¹ and Q ² are the same or different and each represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ¹ represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. .
Z ⁺ represents an organic cation.
* Represents a bond with a hydroxy aromatic ring. ] The hydroxy aromatic derivative according to claim 1, which is represented by formula (I), formula (II), formula (III) or formula (IV).

[In the formula (I),
R ^Ia1 to R ^Ia4 are independently a hydrogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an aralkyl group, or the formula of 7-13 carbon atoms The group represented by (1) is represented.
R ^{Ib1 to} R ^Ib15 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
Provided ^that at least one of ^{R Ia1 ~R Ia4, R Ib1 ~R} Ib15 is a group represented by the formula (1), and ^at least one of R ^{Ib1 to R IB15} are hydroxy groups. ]

[In the formula (II),
R ^{IIc1 to} R ^IIc9 each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms or a group represented by the formula (1), and at least one of R ^{IIc1 to} R ^IIc9 is represented by the formula: It is a group represented by (1), and at least one of R ^{IIc1 to} R ^IIc9 is a hydroxy group.
P ^{II1 to} P ^II5 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, an unsaturated hydrocarbon group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, An aromatic hydrocarbon group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms is shown.
P ^II1 and ^{P II2} and ^{P II4} and ^{P II5} may be bonded to each other to form a ring. ]

[In the formula (III),
R ^{IIId1 to} R ^IIId10 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by Formula (1).
R ^{IIIe1 to} R ^IIIe4 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is a group represented by the formula (1), and at least one of R ^{IIId1 to} R ^IIId10 and R ^{IIIe1 to} R ^IIIe4 is It is a hydroxy group.
n ^u represents an integer of 1 to 5. ]

[In the formula (IV),
R ^IVf1 and R ^IVf2 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
R ^{IVg1 to} R ^IVg8 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the formula (1).
However, at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is a group represented by the formula (1), and at least one of R ^IVf1 , R ^IVf2 and R ^{IVg1 to} R ^IVg8 is It is a hydroxy group.
^PIV6 represents a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. The aromatic hydrocarbon group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms.
P ^IV7 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The aromatic hydrocarbon group and aralkyl group may be substituted with at least one selected from the group consisting of a hydroxy group and an alkyl group having 1 to 6 carbon atoms. —CH ₂ — contained in the alkyl group or aralkyl group may be replaced by —O—, —CO— or —NR ^d —.
R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ^IV6 and P ^IV7 may be bonded to each other to form a ring.
n ^v represents 1 or 2. ] L ^{1 in the} formula (1) is * —CO—O—, * —CO—O— (CH ₂ ) _u1 —O— (u1 represents an integer of 1 to 6. * represents Q ¹ and Q ^2. And a group represented by the formula (L ¹ -A). 3. The hydroxyaromatic derivative according to claim 1, which is a group represented by the formula (L ¹ -A).

[In the formula (L ¹ -A),
u2 represents 0 or 1.
X ¹ represents a methylene group or * ₁ —CH ₂ —O—. * ₁ represents a bond with -CO-.
* Represents a bond with a carbon atom bonded to Q ¹ and Q ² . ] Z ^{<+> of} Formula (1) is a triarylsulfonium cation, The hydroxy aromatic derivative in any one of Claims 1-3.   A resist composition comprising the hydroxyaromatic derivative according to any one of claims 1 to 4 and a resin that is insoluble or hardly soluble in an alkaline aqueous solution and can be dissolved in an alkaline aqueous solution by the action of an acid.   Furthermore, the resist composition of Claim 5 containing a basic compound. (1) The process of apply | coating the resist composition of Claim 5 or 6 on a board | substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: