JP2008127367A - Sulfonium compound for producing acid generator of chemical amplification type resist composition - Google Patents

Sulfonium compound for producing acid generator of chemical amplification type resist composition Download PDF

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JP2008127367A
JP2008127367A JP2006316703A JP2006316703A JP2008127367A JP 2008127367 A JP2008127367 A JP 2008127367A JP 2006316703 A JP2006316703 A JP 2006316703A JP 2006316703 A JP2006316703 A JP 2006316703A JP 2008127367 A JP2008127367 A JP 2008127367A
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JP5103878B2 (en
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Hiroshi Sakamoto
宏 坂本
Yukako Harada
由香子 原田
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Sumitomo Chemical Co Ltd
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Priority to CN2007101400779A priority patent/CN101125824B/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel sulfonium compound which comes to a synthetic intermediate simply producing an acid generator having a molecular structure of the carbonyldifluoromethane sulfonate type which is an acid generator to give a chemical amplification type resist composition showing high image resolution and a broad exposure margin. <P>SOLUTION: The sulfonium compound is represented by formula (I) (wherein Q<SP>1</SP>and Q<SP>2</SP>are each independently fluorine or a 1-6C perfluoroalkyl group, and A<SP>+</SP>is an organic counter ion). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、化学増幅型レジスト組成物の酸発生剤の合成中間体として用いられる、新規なスルホニウム化合物に関する。   The present invention relates to a novel sulfonium compound used as a synthetic intermediate for an acid generator of a chemically amplified resist composition.

リソグラフィ技術を用いた半導体の微細加工に用いられる化学増幅型レジスト組成物は、露光により酸を発生する化合物からなる酸発生剤を含有してなる。   A chemically amplified resist composition used for fine processing of a semiconductor using a lithography technique contains an acid generator composed of a compound that generates an acid upon exposure.

最近、トリフェニルスルホニウム 1−アダマンタンメトキシカルボニルジフルオロメタンスルホナート(塩)及びp−トリルジフェニルスルホニウム パーフルオロオクタンスルホネート(塩)を酸発生剤として含有してなる化学増幅型レジスト組成物が提案されているが、さらに高い解像度及び広い露光マージンを示す化学増幅型レジスト組成物を与える酸発生剤が求められており(例えば、特許文献1参照)、それらのカルボニルジフルオロメタンスルホナート型の分子構造をもつ酸発生剤を簡便に合成しうる中間体化合物が求められている。   Recently, a chemically amplified resist composition comprising triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) and p-tolyldiphenylsulfonium perfluorooctanesulfonate (salt) as an acid generator has been proposed. However, there is a need for acid generators that provide chemically amplified resist compositions that exhibit higher resolution and wider exposure margin (see, for example, Patent Document 1), and those acids having a molecular structure of carbonyldifluoromethanesulfonate type. There is a need for an intermediate compound that can synthesize a generator easily.

特開2004−4561号公報Japanese Patent Laid-Open No. 2004-4561

本発明の目的は、カルボニルジフルオロメタンスルホナート型の分子構造をもつ酸発生剤を簡便に製造できる合成中間体となる新規なスルホニウム化合物を提供することにある。   An object of the present invention is to provide a novel sulfonium compound serving as a synthetic intermediate that can easily produce an acid generator having a molecular structure of carbonyldifluoromethanesulfonate type.

そこで本発明者らは、上記課題を解決するために、カルボニルジフルオロメタンスルホナート型の分子構造をもつ酸発生剤の合成中間体として用いられる化合物について鋭意検討した結果、カルボキシル基を含む特定のスルホニウム化合物が該酸発生剤の合成中間体として好適であり、また該化合物より酸発生剤を簡便な方法で製造できることを見出し、本発明を完成させるに至った。   Therefore, in order to solve the above-mentioned problems, the present inventors have intensively studied a compound used as a synthesis intermediate of an acid generator having a carbonyldifluoromethanesulfonate type molecular structure, and as a result, have found that a specific sulfonium containing a carboxyl group. The present inventors have found that a compound is suitable as a synthetic intermediate for the acid generator, and that an acid generator can be produced from the compound by a simple method, thereby completing the present invention.

すなわち本発明は、式(I)で示されるスルホニウム化合物を提供する。

Figure 2008127367
(式(I)中、Q1、Q2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表す。A+は有機対イオンを表す。) That is, the present invention provides a sulfonium compound represented by the formula (I).
Figure 2008127367
(In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. A + represents an organic counter ion.)

また本発明は、式(V)で示される塩と式(VI)で示される化合物とを反応させることを特徴とする式(I)で示されるスルホニウム化合物の製造方法を提供する。

Figure 2008127367
(式(V)中、Q1、Q2は前記と同じ意味を表し、Mは、Li、Na、K又はAgを表す。)
Figure 2008127367
(式(VI)中、A+は、前記と同じ意味を表し、LはF、Cl、Br、I、BF4、AsF6、SbF6、PF6又はClO4を表す。) The present invention also provides a process for producing a sulfonium compound represented by the formula (I), which comprises reacting a salt represented by the formula (V) with a compound represented by the formula (VI).
Figure 2008127367
(In formula (V), Q 1 and Q 2 represent the same meaning as described above, and M represents Li, Na, K, or Ag.)
Figure 2008127367
(In formula (VI), A + represents the same meaning as described above, and L represents F, Cl, Br, I, BF 4 , AsF 6 , SbF 6 , PF 6, or ClO 4. )

また本発明は、式(I)で示されるスルホニウム化合物と式(VII)で示される化合物とを反応させることを特徴とする、式(VIII)で示される酸発生剤の製造方法を提供する。

Figure 2008127367
(式(VII)中、Xは炭素数1〜30の置換されていてもよい炭化水素基を表す。)
Figure 2008127367
(式(VIII)中、A+、Q1、Q2およびXは、前記と同じ意味を表す。) The present invention also provides a method for producing an acid generator represented by formula (VIII), comprising reacting a sulfonium compound represented by formula (I) with a compound represented by formula (VII).
Figure 2008127367
(In the formula (VII), X represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms.)
Figure 2008127367
(In the formula (VIII), A + , Q 1 , Q 2 and X have the same meaning as described above.)

本発明のスルホニウム化合物を酸発生剤の中間体として用いることにより、カルボニルジフルオロメタンスルホナート型の分子構造をもつ酸発生剤を簡便に製造することができ、得られた酸発生剤は、高い解像度及び広い露光マージンを示す化学増幅型レジスト組成物を与えるので、本発明は工業的に極めて有用である。   By using the sulfonium compound of the present invention as an intermediate of an acid generator, an acid generator having a carbonyldifluoromethanesulfonate type molecular structure can be easily produced, and the resulting acid generator has a high resolution. In addition, since the present invention provides a chemically amplified resist composition exhibiting a wide exposure margin, the present invention is extremely useful industrially.

本発明のスルホニウム化合物は、式(I)で示されることを特徴とする。

Figure 2008127367
(式(I)中、Q1、Q2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表す。A+は有機対イオンを表す。)
1、Q2としてはそれぞれ独立にフッ素原子または−CF3である場合が好ましい。 The sulfonium compound of the present invention is represented by the formula (I).
Figure 2008127367
(In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. A + represents an organic counter ion.)
Q 1 and Q 2 are preferably each independently a fluorine atom or —CF 3 .

式(I)で示されるスルホニウム化合物において、A+は、有機対イオンを表し、具体的には、式(IIa)、式(IIb)、式(IIc)又は式(IId)のいずれかで示されるカチオンからなる群から選ばれる少なくとも1種のカチオンが挙げられる。 In the sulfonium compound represented by the formula (I), A + represents an organic counter ion, specifically, represented by any one of the formula (IIa), the formula (IIb), the formula (IIc), or the formula (IId). And at least one cation selected from the group consisting of cations.

ここで、式(IIa)は、下記式である。

Figure 2008127367
式(IIa)中、P1〜P3は、互いに独立に、直鎖状又は分岐状の炭素数1〜30のアルキル基又は炭素数3〜30の環式炭化水素基を表す。P1〜P3がアルキル基である場合には水酸基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基の一つ以上を置換基として含んでいてもよく、P1〜P3が環式炭化水素基である場合には水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基の一つ以上を置換基として含んでいてもよい。 Here, the formula (IIa) is the following formula.
Figure 2008127367
In formula (IIa), P 1 to P 3 each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms or a cyclic hydrocarbon group having 3 to 30 carbon atoms. When P 1 to P 3 is an alkyl group hydroxyl, may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P When 1 to P 3 is a cyclic hydrocarbon group, it may contain one or more of a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms as a substituent.

該アルキル基の具体例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、2−エチルヘキシル基などが挙げられ、アルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヘキシルオキシ基、オクチルオキシ基、2−エチルヘキシルオキシ基などが挙げられる。
該環式炭化水素基の具体例としては、シクロペンチル基、シクロヘキシル基、アダマンチル基、フェニル基、ナフチル基、フルオレニル基などが挙げられる。
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.
Specific examples of the cyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a naphthyl group, and a fluorenyl group.

式(IIb)は、下記式である。

Figure 2008127367
式(IIb)中、P4、P5は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。該アルキル基及び該アルコキシ基は、式(IIa)のアルキル基及びアルコキシ基と同じ意味を表す。 Formula (IIb) is the following formula.
Figure 2008127367
In formula (IIb), P 4 and P 5 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group are They may be linear or branched. The alkyl group and the alkoxy group have the same meaning as the alkyl group and alkoxy group of the formula (IIa).

式(IIc)は、下記式である。

Figure 2008127367
式(IIc)中、P6、P7は、互いに独立に、炭素数1〜12のアルキル基又は炭素数3〜12のシクロアルキル基を表し、該アルキル基は、直鎖でも分岐していてもよい。該アルキル基の具体例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、2−エチルヘキシル基などが挙げられる。該シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基などが挙げられる。また、P6とP7とが結合してアルキレン基などの炭素数3〜12の2価の炭化水素基を表していてもよい。P8が水素原子を表し、P9が炭素数1〜12のアルキル基、炭素数3〜12のシクロアルキル基もしくは置換されていてもよい芳香環基を表すか、またはP8とP9が結合して炭素数3〜12の2価の炭化水素基を表す。P9がアルキル基の場合、該アルキル基は、直鎖でも分岐していてもよい。該アルキル基の具体例としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、2−エチルヘキシル基などが挙げられる。P9がシクロアルキル基の場合、該シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基などが挙げられる。ここで、2価の炭化水素基に含まれる炭素原子は、任意に、カルボニル基、酸素原子、硫黄原子に置換されていてもよい。 Formula (IIc) is the following formula.
Figure 2008127367
In formula (IIc), P 6 and P 7 each independently represent an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and the alkyl group is branched even in a straight chain. Also good. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Groups and the like. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. P 6 and P 7 may be bonded to each other to represent a C 3-12 divalent hydrocarbon group such as an alkylene group. P 8 represents a hydrogen atom, P 9 represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group, or P 8 and P 9 are It represents a divalent hydrocarbon group having 3 to 12 carbon atoms by bonding. When P 9 is an alkyl group, the alkyl group may be linear or branched. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl. Groups and the like. When P 9 is a cycloalkyl group, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group. Here, the carbon atom contained in the divalent hydrocarbon group may be optionally substituted with a carbonyl group, an oxygen atom, or a sulfur atom.

式(IId)は、下記式である。

Figure 2008127367
式(IId)中、P10〜P21は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。Bは、硫黄原子又は酸素原子を表す。kは、0又は1を表す。 Formula (IId) is a following formula.
Figure 2008127367
In formula (IId), P 10 to P 21 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group are They may be linear or branched. B represents a sulfur atom or an oxygen atom. k represents 0 or 1.

式(IIa)で示されるカチオンA+の具体例としては、下記式で示されるカチオンが挙げられる。

Figure 2008127367
Specific examples of the cation A + represented by the formula (IIa) include cations represented by the following formula.
Figure 2008127367


Figure 2008127367

Figure 2008127367

Figure 2008127367
Figure 2008127367

式(IIb)で示されるカチオンA+の具体例としては、下記式で示されるカチオンが挙げられる。

Figure 2008127367
Specific examples of the cation A + represented by the formula (IIb) include cations represented by the following formula.
Figure 2008127367

式(IIc)で示されるカチオンA+の具体例としては、下記式で示されるカチオンが挙げられる。

Figure 2008127367
Specific examples of the cation A + represented by the formula (IIc) include cations represented by the following formula.
Figure 2008127367

Figure 2008127367
Figure 2008127367

Figure 2008127367
Figure 2008127367

式(IId)で示されるカチオンA+の具体例としては、下記式で示されるカチオンが挙げられる。

Figure 2008127367
Specific examples of the cation A + represented by the formula (IId) include cations represented by the following formula.
Figure 2008127367

Figure 2008127367
Figure 2008127367

Figure 2008127367
Figure 2008127367

+としては、式(IIIa)、式(IIIb)または式(IIIc)で示されるカチオンである場合が好ましい。

Figure 2008127367
式(IIIa)〜(IIIc)中、P22〜P24は互いに独立に、直鎖状又は分岐状の炭素数1〜20のアルキル基、又はフェニル基以外の炭素数3〜30の環式炭化水素基を表す。P22〜P24がアルキル基である場合には水酸基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基の一つ以上を置換基として含んでいてもよく、P22〜P24が環式炭化水素基である場合には水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基の一つ以上を置換基として含んでいてもよい。式中のP25〜P30は、水酸基、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基を表し、l、m、n、o、p、qは、互いに独立に0〜5の整数を表す。 A + is preferably a cation represented by the formula (IIIa), the formula (IIIb) or the formula (IIIc).
Figure 2008127367
In formulas (IIIa) to (IIIc), P 22 to P 24 are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, or cyclic carbonization having 3 to 30 carbon atoms other than a phenyl group. Represents a hydrogen group. If P 22 to P 24 is an alkyl group hydroxyl, it may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P If 22 to P 24 is a cyclic hydrocarbon group hydroxyl, it may be included as one or more of the substituents for the alkyl group or alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. P 25 to P 30 in the formula represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cyclic hydrocarbon group having 3 to 12 carbon atoms, and l, m, n, o, p and q each independently represent an integer of 0 to 5.

式(I)で示されるスルホニウム化合物としては、中でも式(IV)で示されるスルホニウム化合物が優れた中間体となることから好ましい。

Figure 2008127367

式(IV)中のP25〜P27は、互いに独立に、水酸基、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基を表し、l、mおよびnは、互いに独立に0〜5の整数を表す。 As the sulfonium compound represented by the formula (I), the sulfonium compound represented by the formula (IV) is preferable because it is an excellent intermediate.
Figure 2008127367

P 25 to P 27 in the formula (IV) each independently represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cyclic hydrocarbon group having 3 to 12 carbon atoms. , L, m and n each independently represent an integer of 0 to 5.

式(I)で示されるスルホニウム化合物の製造方法としては、例えば、式(V)で示される塩と式(VI)で示される化合物とを反応させることにより製造することができる。

Figure 2008127367
(式(V)中、Q1、Q2は前記と同じ意味を表し、Mは、Li、Na、K又はAgを表す。)
Figure 2008127367
(式(VI)中、A+は、前記と同じ意味を表し、LはF、Cl、Br、I、BF4、AsF6、SbF6、PF6又はClO4を表す。) As a method for producing the sulfonium compound represented by the formula (I), for example, it can be produced by reacting a salt represented by the formula (V) with a compound represented by the formula (VI).

Figure 2008127367
(In formula (V), Q 1 and Q 2 represent the same meaning as described above, and M represents Li, Na, K, or Ag.)
Figure 2008127367
(In formula (VI), A + represents the same meaning as described above, and L represents F, Cl, Br, I, BF 4 , AsF 6 , SbF 6 , PF 6, or ClO 4. )

反応においては、例えば、水、アセトニトリル、クロロホルム、塩化メチレン等の不活性溶媒中、0℃〜100℃程度の温度範囲、好ましくは0℃〜60℃程度の温度範囲にて攪拌して式(V)で示される塩と式(VI)で示される化合物とを反応させる方法などが挙げられる。   In the reaction, for example, in an inert solvent such as water, acetonitrile, chloroform, methylene chloride, stirring is performed in a temperature range of about 0 ° C. to 100 ° C., preferably about 0 ° C. to 60 ° C. ) And a compound represented by the formula (VI).

式(VI)で示される化合物の使用量としては、通常、式(V)で示される塩1モルに対して、0.5〜2モル程度である。式(I)で示されるスルホニウム化合物は、結晶で取り出してもよいし、溶媒に溶解させたままでもよい。   The amount of the compound represented by the formula (VI) is usually about 0.5 to 2 mol with respect to 1 mol of the salt represented by the formula (V). The sulfonium compound represented by the formula (I) may be taken out as a crystal or may be dissolved in a solvent.

このようにして得られた式(I)で示されるスルホニウム化合物と、式(VII)で示される化合物とを反応させることにより、

Figure 2008127367
(式(VII)中、Xは炭素数1〜30の置換されていてもよい炭化水素基を表す。)
式(VIII)で示される酸発生剤を製造することができる。
Figure 2008127367
(式(VIII)中、A+、Q1、Q2およびXは、前記と同じ意味を表す。) By reacting the sulfonium compound represented by the formula (I) thus obtained with the compound represented by the formula (VII),
Figure 2008127367
(In the formula (VII), X represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms.)
An acid generator represented by the formula (VIII) can be produced.
Figure 2008127367
(In the formula (VIII), A + , Q 1 , Q 2 and X have the same meaning as described above.)

前記エステル化反応は、例えば、クロロホルム、塩化メチレン、ジクロロエタン、トルエン、キシレン、エチルベンゼン、モノクロロベンゼン、アセトニトリル、N,N−ジメチルホルムアミド等の非プロトン性溶媒中にて、20℃〜200℃程度の温度範囲、好ましくは、50℃〜150℃程度の温度範囲で攪拌して行えばよい。エステル化反応においては、酸触媒としてp−トルエンスルホン酸などの有機酸及び/又は硫酸等の無機酸を添加して行ってもよいし、あるいは脱水剤として1,1’−カルボニルジイミダゾール、N,N’−ジシクロヘキシルカルボジイミド等を添加して行ってもよい。   The esterification reaction is performed at a temperature of about 20 ° C. to 200 ° C. in an aprotic solvent such as chloroform, methylene chloride, dichloroethane, toluene, xylene, ethylbenzene, monochlorobenzene, acetonitrile, and N, N-dimethylformamide. The stirring may be performed in the range, preferably in the temperature range of about 50 ° C to 150 ° C. In the esterification reaction, an organic acid such as p-toluenesulfonic acid and / or an inorganic acid such as sulfuric acid may be added as an acid catalyst, or 1,1′-carbonyldiimidazole or N as a dehydrating agent. , N′-dicyclohexylcarbodiimide or the like may be added.

酸触媒を用いたエステル化反応は、ディーンスターク装置を用いるなどして、水を分離しながら実施すると、反応時間が短縮化される傾向があることから好ましく、さらに脱水剤としてモレキュラーシーブス、塩化カルシウム等を使用してもよい。   The esterification reaction using an acid catalyst is preferably carried out while separating water by using a Dean Stark apparatus or the like, since the reaction time tends to be shortened. Further, molecular sieves and calcium chloride are used as dehydrating agents. Etc. may be used.

エステル化反応における式(I)で示されるスルホニウム化合物(同時にカルボン酸でもある。)の使用量としては、式(VII)で示されるアルコール1モルに対して、0.2〜3モル程度、好ましくは0.5〜2モル程度である。エステル化反応における酸触媒は式(VII)で示されるアルコール1モルに対して、触媒量でも溶媒に相当する量でもよく、通常、0.001モル程度〜5モル程度である。エステル化反応における脱水剤は式(VII)で示されるアルコール1モルに対して、0.2〜5モル程度、好ましくは0.5〜3モル程度である。   The amount of the sulfonium compound represented by the formula (I) in the esterification reaction (which is also a carboxylic acid at the same time) is about 0.2 to 3 mol, preferably 1 mol per mol of the alcohol represented by the formula (VII). Is about 0.5 to 2 moles. The acid catalyst in the esterification reaction may be a catalytic amount or an amount corresponding to a solvent with respect to 1 mol of the alcohol represented by the formula (VII), and is usually about 0.001 mol to 5 mol. The dehydrating agent in the esterification reaction is about 0.2 to 5 mol, preferably about 0.5 to 3 mol, per 1 mol of the alcohol represented by the formula (VII).

前記反応における式(VII)で示されるアルコールの使用量としては、式(VI)で示される化合物1モルに対して、0.2〜3モル程度、好ましくは0.5〜2モル程度である。   The amount of the alcohol represented by the formula (VII) used in the reaction is about 0.2 to 3 mol, preferably about 0.5 to 2 mol, per 1 mol of the compound represented by the formula (VI). .

Xが含む炭素数が1〜30の炭化水素は、直鎖または分岐のアルキル基、単環または多環式炭化水素でもよく、二重結合を含んでいても芳香環でもよい。Xが含む炭素数が1〜30の環式炭化水素としては、シクロペンタン骨格、シクロヘキサン骨格、アダマンタン骨格、ノルボルナン骨格、ベンゼン骨格、ナフタレン骨格、アントラセン骨格、フェナントレン骨格、フルオレン骨格を含むものが挙げられる。
Xに含まれる炭素原子は酸素原子により置換されていてもよく、カルボニル基を形成していてもよく、炭素数1〜12のアルキル基、炭素数1〜6のアルコキシ基、炭素数1〜4のペルフルオロアルキル基、炭素数1〜6のヒドロキシアルキル基、水酸基またはシアノ基の一つ以上を置換基として含んでいてもよい。
The hydrocarbon having 1 to 30 carbon atoms contained in X may be a linear or branched alkyl group, a monocyclic or polycyclic hydrocarbon, and may include a double bond or an aromatic ring. Examples of the cyclic hydrocarbon having 1 to 30 carbon atoms contained in X include those containing a cyclopentane skeleton, a cyclohexane skeleton, an adamantane skeleton, a norbornane skeleton, a benzene skeleton, a naphthalene skeleton, an anthracene skeleton, a phenanthrene skeleton, and a fluorene skeleton. .
The carbon atom contained in X may be substituted with an oxygen atom and may form a carbonyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Or a perfluoroalkyl group, a hydroxyalkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a cyano group as a substituent.

Xの具体例としては、下記式で示される基が挙げられる。

Figure 2008127367
Specific examples of X include groups represented by the following formula.
Figure 2008127367

Figure 2008127367
Figure 2008127367

次に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。
実施例および比較例中、含有量ないし使用量を表す%及び部は、特記ないかぎり重量基準である。また、化合物の構造はNMR(日本電子製EX−270型)、質量分析(LCはAgilent製1100型、MASSはAgilent製LC/MSD型またはLC/MSD TOF型)で確認した。
EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on weight unless otherwise specified. Moreover, the structure of the compound was confirmed by NMR (JEOL EX-270 type) and mass spectrometry (LC is Agilent 1100 type, and MASS is Agilent LC / MSD type or LC / MSD TOF type).

合成例1:トリフェニルスルホニウム ヒドロキシカルボニルジフルオロメタンスルホナート(B1)の合成
14.2%トリフェニルスルホニウム クロライド水溶液573.7部に18.0%ジフルオロスルホ酢酸 ナトリウム塩水溶液300.0部を加えて25℃で約20時間攪拌した。析出した白色固体をろ別、イオン交換水100部で洗浄した後、乾燥してトリフェニルスルホニウム ヒドロキシカルボニルジフルオロメタンスルホナート(B1)を88.4部得た。

Figure 2008127367
Synthesis Example 1: Synthesis of triphenylsulfonium hydroxycarbonyldifluoromethanesulfonate (B1) 250.0 parts of 14.2% triphenylsulfonium chloride aqueous solution was added with 300.0 parts of 18.0% difluorosulfoacetic acid sodium salt aqueous solution and 25 Stir at about 20 ° C. for about 20 hours. The precipitated white solid was filtered off, washed with 100 parts of ion-exchanged water, and then dried to obtain 88.4 parts of triphenylsulfonium hydroxycarbonyldifluoromethanesulfonate (B1).
Figure 2008127367

1H−NMR(ジメチルスルホキシド−d6、内部標準物質テトラメチルシラン):δ(ppm)7.77−7.88(m,15H);13.90(br,1H)
MS(ESI(+)Spectrum):M+ 263.2(C1815+=263.09)
MS(ESI(−)Spectrum):M− 175.0(C2HF25-=174.95)
1 H-NMR (dimethyl sulfoxide-d 6 , internal standard substance tetramethylsilane): δ (ppm) 7.77-7.88 (m, 15H); 13.90 (br, 1H)
MS (ESI (+) Spectrum): M + 263.2 (C 18 H 15 S + = 263.09)
MS (ESI (-) Spectrum) : M- 175.0 (C 2 HF 2 O 5 S - = 174.95)

酸発生剤合成例1:トリフェニルスルホニウム メトキシカルボニルジフルオロメタンスルホナート(酸発生剤B2)の合成
還流液の脱水が可能なように、還流ラインにモレキュラーシーブス3Aの充填塔を備えた反応容器にトリフェニルスルホニウム ヒドロキシカルボニルジフルオロメタンスルホナート250.0部をメタノール750.0部に溶解した。硫酸5.56部を加えて還流するまで昇温し、還流下で12時間反応した。溶媒のメタノールを留去した後、クロロホルム854.4部およびイオン交換水213.6部を加えて攪拌後分液した。さらにクロロホルム層をイオン交換水213.6部で中性となるまで水洗を繰り返した。得られたクロロホルム層をろ過、濃縮し、さらにアセトニトリル160.8部を加えて濃縮した後、tert−ブチルメチルエーテル655.6部を加えて攪拌した。析出した白色固体をろ別、乾燥してトリフェニルスルホニウム メトキシカルボニルジフルオロメタンスルホナート(B2)を225.0部得た。

Figure 2008127367
Synthesis Example of Acid Generator 1: Synthesis of Triphenylsulfonium Methoxycarbonyldifluoromethanesulfonate (Acid Generator B2) Trial was placed in a reaction vessel equipped with a packed column of molecular sieves 3A in the reflux line so that the reflux liquid could be dehydrated. 250.0 parts of phenylsulfonium hydroxycarbonyldifluoromethanesulfonate were dissolved in 750.0 parts of methanol. 5.56 parts of sulfuric acid was added, the temperature was raised to reflux, and the reaction was carried out for 12 hours under reflux. After distilling off methanol as a solvent, 854.4 parts of chloroform and 213.6 parts of ion-exchanged water were added, followed by liquid separation after stirring. Further, the chloroform layer was washed repeatedly with 213.6 parts of ion-exchanged water until neutral. The resulting chloroform layer was filtered and concentrated, further concentrated by adding 160.8 parts of acetonitrile, and then added with 655.6 parts of tert-butyl methyl ether and stirred. The precipitated white solid was separated by filtration and dried to obtain 225.0 parts of triphenylsulfonium methoxycarbonyldifluoromethanesulfonate (B2).
Figure 2008127367

1H−NMR(ジメチルスルホキシド−d6、内部標準物質テトラメチルシラン):δ(ppm)3.76(s,3H);7.75−7.90(m,15H) 1 H-NMR (dimethyl sulfoxide-d 6 , internal standard substance tetramethylsilane): δ (ppm) 3.76 (s, 3H); 7.75-7.90 (m, 15H)

酸発生剤合成例2:トリフェニルスルホニウム 4−オキソ−1−アダマンチルオキシカルボニルジフルオロメタンスルホナート(酸発生剤B3)の合成
還流液の脱水が可能なように、還流ラインにモレキュラーシーブス3Aの充填塔を備えた反応容器にトリフェニルスルホニウム ヒドロキシカルボニルジフルオロメタンスルホナート18.3部、5−ヒドロキシ−2−アダマンタノン6.9部およびモノクロルベンゼン120.0部を仕込み攪拌した。そこへ硫酸0.8部を加えて還流するまで昇温し、還流下で15時間反応した。冷却後クロロホルム100.0部およびイオン交換水50部を加えて攪拌後分液した。クロロホルム層をイオン交換水50部で水洗を繰り返した。得られたクロロホルム層を濃縮し、さらにアセトニトリル60部を加えて濃縮した後、酢酸エチル170部を加えて攪拌した。析出した白色固体をろ別、酢酸エチル20部で洗浄後、乾燥してトリフェニルスルホニウム 4−オキソ−1−アダマンチルオキシカルボニルジフルオロメタンスルホナート(B3)を17.8部得た。

Figure 2008127367
Acid generator synthesis example 2: Synthesis of triphenylsulfonium 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate (acid generator B3) A packed column of molecular sieves 3A in the reflux line so that the reflux liquid can be dehydrated Was charged with 18.3 parts of triphenylsulfonium hydroxycarbonyldifluoromethanesulfonate, 6.9 parts of 5-hydroxy-2-adamantanone, and 120.0 parts of monochlorobenzene. Thereto was added 0.8 part of sulfuric acid, the temperature was raised to reflux, and the mixture was reacted for 15 hours under reflux. After cooling, 100.0 parts of chloroform and 50 parts of ion-exchanged water were added, followed by liquid separation after stirring. The chloroform layer was repeatedly washed with 50 parts of ion exchange water. The obtained chloroform layer was concentrated, 60 parts of acetonitrile was further added and concentrated, and 170 parts of ethyl acetate was added and stirred. The precipitated white solid was separated by filtration, washed with 20 parts of ethyl acetate, and then dried to obtain 17.8 parts of triphenylsulfonium 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate (B3).
Figure 2008127367

1H−NMR(ジメチルスルホキシド−d6、内部標準物質テトラメチルシラン):δ(ppm)1.83(d,2H,J=12.7Hz);2.00(d,2H,J=12.0Hz);2.29−2.32(m,7H);2.53(s,2H);7.75−7.91(m,15H)
MS(ESI(+)Spectrum):M+ 263.2(C1815+=263.09)
MS(ESI(−)Spectrum):M− 323.0(C121326-=323.04)
1 H-NMR (dimethyl sulfoxide-d 6 , internal standard substance tetramethylsilane): δ (ppm) 1.83 (d, 2H, J = 12.7 Hz); 2.00 (d, 2H, J = 12. 0Hz); 2.29-2.32 (m, 7H); 2.53 (s, 2H); 7.75-7.91 (m, 15H)
MS (ESI (+) Spectrum): M + 263.2 (C 18 H 15 S + = 263.09)
MS (ESI (−) Spectrum): M− 323.0 (C 12 H 13 F 2 O 6 S = 323.04)

本発明のスルホニウム化合物は、化学増幅型ポジ型レジスト組成物用の酸発生剤の合成中間体として好適に用いられ、本発明のスルホニウム化合物を中間体として製造された酸発生剤は、中でも、ArFやKrFなどのエキシマレーザーリソグラフィならびにArF液浸露光リソグラフィに好適な化学増幅型ポジ型レジスト組成物用の酸発生剤となる。   The sulfonium compound of the present invention is preferably used as a synthesis intermediate of an acid generator for a chemically amplified positive resist composition. Among the acid generators produced using the sulfonium compound of the present invention as an intermediate, ArF And an acid generator for a chemically amplified positive resist composition suitable for excimer laser lithography such as KrF and ArF immersion exposure lithography.

Claims (7)

式(I)で示されることを特徴とするスルホニウム化合物。
Figure 2008127367
(式(I)中、Q1、Q2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表す。A+は有機対イオンを表す。)
A sulfonium compound represented by the formula (I):
Figure 2008127367
(In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. A + represents an organic counter ion.)
1、Q2がそれぞれ独立にフッ素原子または−CF3である請求項1に記載のスルホニウム化合物。 The sulfonium compound according to claim 1 , wherein Q 1 and Q 2 are each independently a fluorine atom or -CF 3 . +が、式(IIa)、式(IIb)、式(IIc)又は式(IId)のいずれかで示されるカチオンからなる群から選ばれる少なくとも1種のカチオンである請求項1又は2に記載のスルホニウム化合物。
Figure 2008127367
(式(IIa)中、P1〜P3は、互いに独立に、直鎖状又は分岐状の炭素数1〜30のアルキル基又は炭素数3〜30の環式炭化水素基を表す。P1〜P3がアルキル基である場合には水酸基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基の一つ以上を置換基として含んでいてもよく、P1〜P3が環式炭化水素基である場合には水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基の一つ以上を置換基として含んでいてもよい。該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。)
Figure 2008127367
(式(IIb)中、P4、P5は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。)
Figure 2008127367
(式(IIc)中、P6、P7は、互いに独立に、炭素数1〜12のアルキル基又は炭素数3〜12のシクロアルキル基を表し、該アルキル基は、直鎖でも分岐していてもよい。又はP6とP7とが結合して炭素数3〜12の2価の炭化水素基を表す。P8は水素原子を表し、P9は炭素数1〜12のアルキル基、炭素数3〜12のシクロアルキル基もしくは置換されていてもよい芳香環基を表すか、又はP8とP9が結合して炭素数3〜12の2価の炭化水素基を表す。ここで、2価の炭化水素基に含まれる炭素原子は、任意に、カルボニル基、酸素原子又は硫黄原子に置換されていてもよい。)
Figure 2008127367
(式(IId)中、P10〜P21は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。Bは、硫黄原子又は酸素原子を表す。kは、0又は1を表す。)
The A + is at least one cation selected from the group consisting of cations represented by any one of formula (IIa), formula (IIb), formula (IIc) or formula (IId). Sulfonium compounds.
Figure 2008127367
(In Formula (IIa), P 1 to P 3 each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms or a cyclic hydrocarbon group having 3 to 30 carbon atoms. P 1 If to P 3 is an alkyl group hydroxyl, it may comprise as one or more substituents of the cyclic hydrocarbon group having 3 to 12 alkoxy group or a carbon number of 1 to 12 carbon atoms, P 1 ~ When P 3 is a cyclic hydrocarbon group, it may contain one or more of a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms as a substituent. The alkoxy group may be linear or branched.)
Figure 2008127367
(In Formula (IIb), P 4 and P 5 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group May be linear or branched.)
Figure 2008127367
(In formula (IIc), P 6 and P 7 each independently represent a C 1-12 alkyl group or a C 3-12 cycloalkyl group, and the alkyl group is branched even in a straight chain. Or P 6 and P 7 may be combined to represent a divalent hydrocarbon group having 3 to 12 carbon atoms, P 8 represents a hydrogen atom, P 9 represents an alkyl group having 1 to 12 carbon atoms, It represents a cycloalkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic ring group, or P 8 and P 9 are bonded to each other to represent a divalent hydrocarbon group having 3 to 12 carbon atoms. (The carbon atom contained in the divalent hydrocarbon group may be optionally substituted with a carbonyl group, an oxygen atom or a sulfur atom.)
Figure 2008127367
(In the formula (IId), P 10 ~P 21, independently of one another, a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, the alkyl group and the alkoxy group May be linear or branched, B represents a sulfur atom or an oxygen atom, and k represents 0 or 1.)
+が、式(IIIa)、式(IIIb)または式(IIIc)のいずれかで示されるカチオンである請求項1〜3のいずれかに記載の塩。
Figure 2008127367
(式(IIIa)〜(IIIc)中、P22〜P24は互いに独立に、直鎖状又は分岐状の炭素数1〜20のアルキル基、又はフェニル基以外の炭素数3〜30の環式炭化水素基を表す。P22〜P24がアルキル基である場合には水酸基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基の一つ以上を置換基として含んでいてもよく、P22〜P24が環式炭化水素基である場合には水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基の一つ以上を置換基として含んでいてもよい。式中のP25〜P30は、水酸基、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基を表し、l、m、n、o、p、qは、互いに独立に0〜5の整数を表す。)
The salt according to any one of claims 1 to 3, wherein A + is a cation represented by any one of formula (IIIa), formula (IIIb) or formula (IIIc).
Figure 2008127367
(In the formulas (IIIa) to (IIIc), P 22 to P 24 are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic group having 3 to 30 carbon atoms other than a phenyl group. Represents a hydrocarbon group, and when P 22 to P 24 is an alkyl group, it contains one or more of a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms or a cyclic hydrocarbon group having 3 to 12 carbon atoms as a substituent. In the case where P 22 to P 24 is a cyclic hydrocarbon group, it contains one or more of a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms as a substituent. P 25 to P 30 in the formula represents a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cyclic hydrocarbon group having 3 to 12 carbon atoms, l, m, n, o, p and q each independently represents an integer of 0 to 5.)
式(I)で示されるスルホニウム化合物が式(IV)で示される塩である請求項1〜4のいずれかに記載の塩。
Figure 2008127367
(式(IV)中のP25〜P27は、互いに独立に、水酸基、炭素数1〜12のアルキル基、炭素数1〜12のアルコキシ基又は炭素数3〜12の環式炭化水素基を表し、l、m、nは、互いに独立に0〜5の整数を表す。)
The salt according to any one of claims 1 to 4, wherein the sulfonium compound represented by the formula (I) is a salt represented by the formula (IV).
Figure 2008127367
(P 25 to P 27 in the formula (IV) are each independently a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a cyclic hydrocarbon group having 3 to 12 carbon atoms. And l, m and n each independently represent an integer of 0 to 5.)
式(V)で示される塩と式(VI)で示される化合物とを反応させることを特徴とする式(I)で示されるスルホニウム化合物の製造方法。
Figure 2008127367
(式(V)中、Q1、Q2は前記と同じ意味を表し、Mは、Li、Na、K又はAgを表す。)
Figure 2008127367
(式(VI)中、A+は、前記と同じ意味を表し、LはF、Cl、Br、I、BF4、AsF6、SbF6、PF6又はClO4を表す。)
A process for producing a sulfonium compound represented by formula (I), comprising reacting a salt represented by formula (V) with a compound represented by formula (VI).
Figure 2008127367
(In formula (V), Q 1 and Q 2 represent the same meaning as described above, and M represents Li, Na, K, or Ag.)
Figure 2008127367
(In the formula (VI), A + represents the same meaning as described above, and L represents F, Cl, Br, I, BF 4 , AsF 6 , SbF 6 , PF 6 or ClO 4. )
式(I)で示されるスルホニウム化合物と式(VII)で示される化合物とを反応させることを特徴とする式(VIII)で示される酸発生剤の製造方法。
Figure 2008127367
(式(VII)中、Xは炭素数1〜30の置換されていてもよい炭化水素基を表す。)
Figure 2008127367
(式(VIII)中、A+、Q1、Q2およびXは前記と同じ意味を表す。)
A process for producing an acid generator represented by formula (VIII), comprising reacting a sulfonium compound represented by formula (I) with a compound represented by formula (VII).
Figure 2008127367
(In the formula (VII), X represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms.)
Figure 2008127367
(In the formula (VIII), A + , Q 1 , Q 2 and X have the same meaning as described above.)
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TW096129162A TWI399365B (en) 2006-08-18 2007-08-08 A sulfonium compound
US11/889,352 US7612217B2 (en) 2006-08-18 2007-08-10 Sulfonium compound
CN2007101400779A CN101125824B (en) 2006-08-18 2007-08-14 Sulfonium compound
BE2007/0393A BE1017885A5 (en) 2006-08-18 2007-08-16 SULFONIUM COMPOUND.
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