JP2008094835A - Intermediate of acid generator of chemical amplification type resist composition - Google Patents

Intermediate of acid generator of chemical amplification type resist composition Download PDF

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JP2008094835A
JP2008094835A JP2007235108A JP2007235108A JP2008094835A JP 2008094835 A JP2008094835 A JP 2008094835A JP 2007235108 A JP2007235108 A JP 2007235108A JP 2007235108 A JP2007235108 A JP 2007235108A JP 2008094835 A JP2008094835 A JP 2008094835A
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JP5226994B2 (en
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Kazuki Takemoto
一樹 武元
Isao Yoshida
勲 吉田
Akio Watabe
昭雄 渡部
Taisuke Sato
泰輔 佐藤
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Sumitomo Chemical Co Ltd
Tosoh F Tech Inc
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Tosoh F Tech Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which is an intermediate such as triphenyl sulfonium 1-adamantane methoxycarbonyl difluoromethane sulfonate (salt) useful as a salt for an acid generator, does not corrode the equipment in the production, and can be easily produced and to provide a method for producing the same. <P>SOLUTION: The salt is characterized in that it is shown by formula (I). In the formula, Q<SP>1</SP>and Q<SP>2</SP>each independently represents a fluorine atom or a 1-6C perfluoroalkyl group, R represents a 2-30C hydrocarbon group which may be substituted, and A<SP>+</SP>represents an ammonium ion. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、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に使用される、化学増幅型レジスト組成物に含有される酸発生剤の中間体に関する。   The present invention relates to an acid generator intermediate contained in a chemically amplified resist composition used in a chemically amplified resist composition used for fine processing of semiconductors.

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。
半導体の微細加工においては、高い解像度で良好なパターン形状のパターンを形成することが望ましく、化学増幅型レジスト組成物としては、良好なパターン形状を有するパターンを作製することができ、高い解像度を示すものが求められている。 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.
In microfabrication of semiconductors, it is desirable to form a pattern with a good pattern shape at a high resolution, and as a chemically amplified resist composition, a pattern having a good pattern shape can be produced and exhibits a high resolution. Things are sought.

高い解像度を示す化学増幅型レジスト組成物を与える酸発生剤用の塩として、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）等の式（Ｘ）で示される塩が提案されており（例えば、特許文献１参照。）、これらの塩をより簡便に製造する方法が求められていた。   Recently, salts represented by the formula (X) such as triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) have been proposed as a salt for an acid generator that gives a chemically amplified resist composition exhibiting high resolution. (For example, refer to Patent Document 1), and a method for producing these salts more simply has been demanded.

Figure 2008094835
（式（Ｘ）中、Ｑ1および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し、Ｒは炭素数２〜３０の置換されていてもよい炭化水素基を表し、Ｐ1〜Ｐ3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 2008094835
(In formula (X), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R represents a C 2-30 optionally substituted hydrocarbon group. , P 1 to P 3 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. You may do it.)

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

前記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）は、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ン酸ナトリウムを中間体とし、該中間体とトリフェニルスルホニウム クロリドを反応させる製造方法により従来製造されており、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ン酸ナトリウムはジフルオロ（フルオロスルホニル）酢酸メチルエステルを水酸化ナトリウムで加水分解し、塩酸でジフルオロスルホ酢酸 ナトリウム塩を得た後、高温下でアルコールと脱水エステル化する方法により製造されていた。このジフルオロスルホ酢酸 ナトリウム塩は、その製造時に副生するフッ化水素がその取り出し工程及び高温下でのエステル化反応で設備を腐食させるため、設備の材料にはハステロイなどの高価な材料が必要であるという問題があった。   Triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) is conventionally produced by a production method in which sodium 1-adamantanemethoxycarbonyldifluoromethanesulfonate is used as an intermediate and the intermediate is reacted with triphenylsulfonium chloride. 1-adamantane methoxycarbonyl difluoromethane sulfonate is obtained by hydrolyzing difluoro (fluorosulfonyl) acetic acid methyl ester with sodium hydroxide to obtain sodium difluorosulfoacetate with hydrochloric acid, and then dehydrating alcohol and alcohol at high temperature. It was manufactured by the method to convert. This difluorosulfoacetate sodium salt corrodes the equipment by the hydrogen fluoride produced as a by-product during its production and the esterification reaction under high temperature, and therefore expensive materials such as Hastelloy are required for the equipment. There was a problem that there was.

本発明の目的は、式（Ｘ）で示される塩の製造に用いることができる中間体であり、製造にあたり設備を腐食させることが少なく簡便に製造することができる中間体およびその製造方法を提供することにある。   An object of the present invention is an intermediate that can be used in the production of the salt represented by the formula (X), and provides an intermediate that can be easily produced with little corrosion of equipment during production, and a method for producing the same. There is to do.

そこで本発明者らは、上記課題を解決するために式（Ｘ）で示される塩の製造に用いることができる中間体およびその製造方法について鋭意検討した結果、設備を腐食させることが少ないマイルドな条件下で合成可能であり、式（Ｘ）で示される塩の製造に用いることができる中間体となる塩およびその製造方法を見出し、本発明を完成させるに至った。   Therefore, as a result of intensive studies on an intermediate that can be used in the production of the salt represented by the formula (X) and a method for producing the same in order to solve the above-described problems, the present inventors have obtained a mild reaction that hardly corrodes equipment. The present invention has been completed by finding an intermediate salt that can be synthesized under the conditions and can be used for the production of the salt represented by the formula (X) and a production method thereof.

すなわち本発明は、式（Ｉ）で示されることを特徴とする塩を提供する。

Figure 2008094835
（式（Ｉ）中、Ｑ1および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し、Ｒは炭素数２〜３０の置換されていてもよい炭化水素基を表し、Ａ+はアンモニウムイオンを表す。） That is, the present invention provides a salt represented by the formula (I).
Figure 2008094835
(In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R represents a C 2-30 optionally substituted hydrocarbon group. A + represents an ammonium ion.)

また本発明は、式（III）で示されるアルコールと、

Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（IV）で示される化合物を脱酸剤の存在下に反応させて式（ＸＸ）で示される化合物を得た後、式（ＸＸ）で示される化合物をアミン水で加水分解することを特徴とする式（Ｉ）で示される塩の製造方法を提供する。
Figure 2008094835
（式（IV）中、Ｑ1およびＱ2は前記と同じ意味を表す。）
Figure 2008094835
（式（ＸＸ）中、Ｑ1、Ｑ2およびＲは前記と同じ意味を表す。） The present invention also provides an alcohol represented by the formula (III),
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
The compound represented by formula (IV) is reacted in the presence of a deoxidizing agent to obtain a compound represented by formula (XX), and then the compound represented by formula (XX) is hydrolyzed with amine water. A method for producing a salt represented by the formula (I) is provided.
Figure 2008094835
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
Figure 2008094835
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)

また本発明は、式（ＸＸ）で示される化合物を提供する。

Figure 2008094835
（式（ＸＸ）中、Ｑ1、Ｑ2およびＲは前記と同じ意味を表す。） The present invention also provides a compound represented by formula (XX).
Figure 2008094835
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)

また本発明は、式（III）で示されるアルコールと、式（IV）で示される化合物を脱酸剤の存在下で反応させることを特徴とする式（ＸＸ）で示される化合物の製造方法を提供する。   The present invention also provides a process for producing a compound represented by formula (XX), which comprises reacting an alcohol represented by formula (III) with a compound represented by formula (IV) in the presence of a deoxidizing agent. provide.

また本発明は、式（III）で示されるアルコールと、

Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（Ｖ）で示される化合物を反応させた後、アミン水で加水分解することを特徴とする式（Ｉ）で示される塩の製造方法を提供する。
Figure 2008094835
（式（Ｖ）中、Ｑ1およびＱ2は前記と同じ意味を表す。） The present invention also provides an alcohol represented by the formula (III),
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
Provided is a method for producing a salt represented by the formula (I), wherein the compound represented by the formula (V) is reacted and then hydrolyzed with an amine water.
Figure 2008094835
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)

また本発明は、式（III）で示されるアルコールと、

Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（IV）で示される化合物を反応させた後、脱酸剤の存在下で反応させることを特徴とする式（ＸＸ）で示されるフルオロスルホニル化合物の製造方法を提供する。
Figure 2008094835

（式（ＸＸ）中、Ｒは前記と同じ意味を表す。） The present invention also provides an alcohol represented by the formula (III),
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
Provided is a method for producing a fluorosulfonyl compound represented by the formula (XX), which comprises reacting a compound represented by the formula (IV) and then reacting in the presence of a deoxidizing agent.
Figure 2008094835

(In formula (XX), R represents the same meaning as described above.)

本発明の塩は、製造にあたり設備を腐食させることが少なく簡便に製造することができ、本発明の塩は高い解像度を示す化学増幅型レジスト組成物を与える酸発生剤用の塩を製造するための中間体として用いることができるので、本発明は工業的に極めて有用である。   The salt of the present invention can be easily produced with little corrosion on equipment during production, and the salt of the present invention produces a salt for an acid generator that gives a chemically amplified resist composition exhibiting high resolution. Therefore, the present invention is extremely useful industrially.

本発明の塩は、式（I）で示されることを特徴とする。

Figure 2008094835
ここで、式（I）中、Ｑ1および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し、Ｒは炭素数２〜３０の置換されていてもよい炭化水素基（酸素原子、窒素原子、硫黄原子が含まれていてもよい。）を表し、Ａ+はアンモニウムイオンを表す。
Ｑ1および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く、ともにフッ素原子である場合がさらに好ましい。 The salt of the present invention is represented by the formula (I).
Figure 2008094835
Here, in formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R is a C 2-30 optionally substituted hydrocarbon group. (An oxygen atom, a nitrogen atom, and a sulfur atom may be contained), and A + represents an ammonium ion.
Q 1 and Q 2 are preferably each independently a fluorine atom or —CF 3 , more preferably a fluorine atom.

式（Ｉ）におけるアンモニウムイオンＡ+としては、下記式で示されるアンモニウムイオンが好ましい。

Figure 2008094835
（式（ＸＩ）中、Ｚ1、Ｚ2およびＺ3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１〜６のアルコキシアルキル基、炭素数３〜１２のシクロアルキル基、置換されていてもよいフェニル基、置換されていてもよい炭素数７〜１２のアラルキル基、置換されていてもよいナフチル基、置換されていてもよい炭素数５〜１０のへテロ芳香族基、またはＺ1とＺ2およびＺ3の少なくとも二つ以上でヘテロ原子を含んでも良い環を表す。） As the ammonium ion A + in the formula (I), an ammonium ion represented by the following formula is preferable.
Figure 2008094835
(In the formula (XI), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. , An optionally substituted phenyl group, an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted naphthyl group, an optionally substituted heteroaromatic group having 5 to 10 carbon atoms A group or a ring which may contain a hetero atom in at least two of Z 1 , Z 2 and Z 3. )

式（ＸI）で示されるアンモニウムイオンとしては、下記式で示されるアンモニウムイオンが挙げられる。

Figure 2008094835
Examples of ammonium ions represented by the formula (XI) include ammonium ions represented by the following formula.
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

式（ＸＩ）で示されるカチオンの中でもＺ1、Ｚ2およびＺ3が互いに同一であり、水素原子、炭素数１〜３のアルキル基およびフェニル基のいずれかである場合がより好ましく、式（ＸII）で示されるカチオンである場合が最も好ましい。

Figure 2008094835
Among the cations represented by the formula (XI), it is more preferable that Z 1 , Z 2 and Z 3 are the same as each other and are any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a phenyl group. Most preferred is the cation represented by XII).
Figure 2008094835

式（Ｉ）におけるＲとしては、環（環としては、単環でも多環でもよく、二重結合を含んでいても芳香環でもよい。）を含んでいてもよい炭素数２〜３０の炭化水素で、Ｒに含まれる炭素原子はその一部が酸素原子で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い炭化水素の１価の残基などが挙げられ、いずれも炭素数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、水酸基又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（Ｒの炭素数には置換基の炭素数、炭素原子と置換した酸素原子の数も含まれる。）。   R in formula (I) is a carbon atom having 2 to 30 carbon atoms which may contain a ring (the ring may be monocyclic or polycyclic and may contain a double bond or an aromatic ring). Hydrogen is a carbon atom contained in R, part of which may be substituted with an oxygen atom, and examples thereof include a monovalent residue of a hydrocarbon which may form a carbonyl group, all of which have a carbon number One or more of a 1-6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group, or a cyano group is included as a substituent. (The number of carbon atoms in R includes the number of carbon atoms in the substituent and the number of oxygen atoms substituted with carbon atoms.)

式（Ｉ）で示される塩のアニオン部の具体例としては、下記式で示されるアニオンが挙げられる。

Figure 2008094835
Specific examples of the anion moiety of the salt represented by the formula (I) include anions represented by the following formula.
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

Figure 2008094835
Figure 2008094835

式（Ｉ）で示される塩としては、Ｒが式（VI）で示される基である場合が、式（Ｉ）で示される塩が優れた解像度及びパターン形状を示す化学増幅型レジスト組成物を与える酸発生剤の中間体となることから好ましい。

Figure 2008094835
環Ｘは環Ｘの一部を形成するように記載された二つの炭素原子とともに形成する炭素数３〜３０の、＝Ｏと結合している単環式または多環式炭化水素基を表す。 The salt represented by the formula (I) is a chemically amplified resist composition in which the salt represented by the formula (I) exhibits excellent resolution and pattern shape when R is a group represented by the formula (VI). Since it becomes the intermediate body of the acid generator to give, it is preferable.
Figure 2008094835
Ring X represents a monocyclic or polycyclic hydrocarbon group bonded to ═O having 3 to 30 carbon atoms formed with two carbon atoms described so as to form part of ring X.

中でも、本発明の式（Ｉ）で示される塩としては、Ｒが

Figure 2008094835
で示される基の場合である式（II）で示される塩が、優れた解像度及びパターン形状を示す化学増幅型レジスト組成物を与える酸発生剤の中間体となることからさらに好ましい。
Figure 2008094835
（式（II）中、Ｑ1、Ｑ2およびＡ+は前記と同じ意味を表す。） Among them, as the salt represented by the formula (I) of the present invention, R is
Figure 2008094835
The salt represented by the formula (II), which is a group represented by the formula (II), is more preferable because it is an intermediate of an acid generator that provides a chemically amplified resist composition exhibiting excellent resolution and pattern shape.
Figure 2008094835
(In formula (II), Q 1 , Q 2 and A + represent the same meaning as described above.)

式（Ｉ）で示される塩は、式（III）で示されるアルコールと、

Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（IＶ）で示される化合物とを、
Figure 2008094835
（式（IＶ）中、Ｑ1およびＱ2は前記と同じ意味を表す。）
例えば、クロロホルム等の不活性溶媒中にて、脱酸剤の存在下に０℃〜８０℃程度の温度範囲、好ましくは０℃〜４０℃の温度範囲にて攪拌して反応させ、式（ＸＸ）で示される化合物を得た後、
Figure 2008094835
（式（ＸＸ）中、Ｑ1、Ｑ2およびＲは前記と同じ意味を表す。）
例えば、クロロホルム等の不活性溶媒中、アミン水と、０℃〜８０℃程度の温度範囲、好ましくは０℃〜４０℃の温度範囲にて攪拌して加水分解させて製造することができる。脱酸剤としては、ジエチルアニリン、トリエチルアミン、ピリジンのような有機塩基あるいは、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、炭酸水素ナトリウムのような無機塩基あるいは、それらの混合物が挙げられる。好ましくは、トリエチルアミンのような有機塩基が挙げられる。脱酸剤は水溶液として用いることも可能である。脱酸剤の使用量としては、式（ＩＶ）で示されるジフルオロ化合物１モルに対して、０．５モル〜５モル程度で、好ましくは、１モル〜２モル程度である。アミン水に用いるアミンとしては、アンモニア、メチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、シクロヘキシルメチルアミン、アダマンチルアミン、アニリン、ジエチルアニリン、ピリジン、ピペリジン、モルホリンなどの有機アミンが挙げられるが、好ましくは低級トリアルキルアミンが挙げられ、より好ましくはトリエチルアミンが挙げられる。アミンの使用量としては、式（ＩＶ）で示されるジフルオロ化合物１モルに対して、０．０１モル〜３モル程度で、好ましくは、０．１モル〜１モル程度である。 The salt of formula (I) is an alcohol of formula (III)
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
A compound of formula (IV)
Figure 2008094835
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
For example, in an inert solvent such as chloroform, the reaction is carried out with stirring in the temperature range of about 0 ° C. to 80 ° C., preferably in the temperature range of 0 ° C. to 40 ° C. in the presence of a deoxidizing agent, and the formula (XX After obtaining the compound represented by
Figure 2008094835
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
For example, it can be produced by stirring and hydrolyzing in an inert solvent such as chloroform with amine water in a temperature range of about 0 ° C. to 80 ° C., preferably in a temperature range of 0 ° C. to 40 ° C. Examples of the deoxidizer include organic bases such as diethylaniline, triethylamine, and pyridine, inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium hydrogen carbonate, or mixtures thereof. Preferably, an organic base such as triethylamine is used. The deoxidizer can also be used as an aqueous solution. The amount of the deoxidizing agent used is about 0.5 mol to 5 mol, preferably about 1 mol to 2 mol, with respect to 1 mol of the difluoro compound represented by the formula (IV). Examples of amines used in the amine water include organic amines such as ammonia, methylamine, diethylamine, trimethylamine, triethylamine, cyclohexylmethylamine, adamantylamine, aniline, diethylaniline, pyridine, piperidine, morpholine, but preferably lower trialkyl. An amine is mentioned, More preferably, a triethylamine is mentioned. The amount of the amine used is about 0.01 mol to 3 mol, preferably about 0.1 mol to 1 mol, with respect to 1 mol of the difluoro compound represented by the formula (IV).

式（IＶ）の化合物の使用量としては、通常、式（III）で示されるアルコール１モルに対して、０．５〜２モル程度である。該塩（Ｉ）は再結晶で取り出してもよいし、水洗して精製してもよい。   The amount of the compound of the formula (IV) used is usually about 0.5 to 2 mol with respect to 1 mol of the alcohol represented by the formula (III). The salt (I) may be taken out by recrystallization or may be purified by washing with water.

また、式（Ｉ）で示される塩の製造方法の別法として、式（III）で示されるアルコールと、

Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（Ｖ）で示される化合物とを、
Figure 2008094835
（式（Ｖ）中、Ｑ1およびＱ2は前記と同じ意味を表す。）
例えば、クロロホルム等の不活性溶媒中にて、脱酸剤の存在下に０℃〜８０℃程度の温度範囲、好ましくは０℃〜４０℃の温度範囲にて攪拌して反応させた後、例えば、クロロホルム等の不活性溶媒中、アミン水と、０℃〜８０℃程度の温度範囲、好ましくは０℃〜４０℃の温度範囲にて攪拌して反応させて式（Ｉ）で示される塩を得る方法も本発明者らは見出した。 As another method for producing the salt represented by formula (I), an alcohol represented by formula (III);
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
A compound represented by the formula (V):
Figure 2008094835
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)
For example, after reacting in an inert solvent such as chloroform with stirring in the temperature range of about 0 ° C. to 80 ° C., preferably in the temperature range of 0 ° C. to 40 ° C. in the presence of a deoxidizer, A salt represented by the formula (I) by stirring and reacting with amine water in an inert solvent such as chloroform, in a temperature range of about 0 ° C to 80 ° C, preferably in a temperature range of 0 ° C to 40 ° C. The inventors have also found a method to obtain.

式（Ｖ）の化合物の使用量としては、通常、式（III）で示されるアルコール１モルに対して、０．５〜２モル程度である。該塩（Ｉ）は再結晶で取り出してもよいし、水洗して精製してもよい。   The amount of the compound of the formula (V) used is usually about 0.5 to 2 mol with respect to 1 mol of the alcohol represented by the formula (III). The salt (I) may be taken out by recrystallization or may be purified by washing with water.

なお、Ｑ1および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く、ともにフッ素原子である場合がさらに好ましい。 Q 1 and Q 2 are preferably each independently a fluorine atom or —CF 3 , more preferably a fluorine atom.

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ＪＮＭ−ＦＸ９０Ｑ型またはＶａｒｉａｎ製Ｇｅｍｉｎｉ−２００型）、質量分析（日本電子製ＪＭＳ−７００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 parts representing the content or amount used are based on weight unless otherwise specified. The structure of the compound was confirmed by NMR (JNM JFX-FX90Q type or Varian Gemini 200 type) and mass spectrometry (JEOL JMS-700 type).

（１）テトラフルオロβ−サルトンの合成

Figure 2008094835

１ＬのＳＵＳ３０４製耐圧オートクレイブにＳＯ3３４７ｇ（４．３３ｍｏｌ）を入れ、空間部をＮ2置換した後にテトラフルオロエチレンを圧入した。発熱反応が開始したのを確認後、内温を４０〜５０℃、圧力０．２〜０．４ＭＰａに調節しながらテトラフルオロエチレンの吸収がなくなるまで圧入を継続した。テトラフルオロエチレンを４４８ｇ（４．４８ｍｏｌ）圧入停止後、室温まで冷却し生成物として７７９ｇの無色液体を得た。得られた液体は、19Ｆ−ＮＭＲ測定によりテトラフルオロβ−サルトンであることを確認した。 (1) Synthesis of tetrafluoro β-sultone

Figure 2008094835

In a 1 L SUS304 pressure-resistant autoclave, 347 g (4.33 mol) of SO 3 was put, and after the space portion was substituted with N 2, tetrafluoroethylene was press-fitted. After confirming that the exothermic reaction had started, the press-fitting was continued until the absorption of tetrafluoroethylene disappeared while adjusting the internal temperature to 40 to 50 ° C. and the pressure to 0.2 to 0.4 MPa. After stopping the press-fitting of 448 g (4.48 mol) of tetrafluoroethylene, the mixture was cooled to room temperature to obtain 779 g of a colorless liquid as a product. The obtained liquid was confirmed to be tetrafluoro β-sultone by 19 F-NMR measurement.

19Ｆ−ＮＭＲ（ＣＤＣｌ3、内部標準物質ＣＦＣｌ3）：δ（ｐｐｍ）−９９．７（ｔ，ＣＦ2ＳＯ2）；−８９．８（ｔ，ＣＦ2Ｏ） 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -99.7 (t, CF 2 SO 2 ); -89.8 (t, CF 2 O)

（２）２−（フルオロスルホニル）ジフルオロアセチルフルオリドの合成

Figure 2008094835

撹拌機、滴下漏斗、温度計を備えた１００ｍＬ四つ口フラスコに、トリエチルアミン６．００ｇ（０．０６ｍｏｌ）を投入し０℃に冷却した。滴下漏斗よりテトラフルオロβ−サルトン１２１．７９ｇ（０．６８ｍｏｌ）を０〜５℃に維持しながら滴下し、投入後反応液を室温に戻した後１時間撹拌を継続した。得られた液体を常圧下３０℃で蒸留精製しテトラフルオロβ−サルトンの異性体である２−（フルオロスルホニル）ジフルオロアセチルフルオリド１０９．６１ｇ（０．６１ｍｏｌ）を得た。 (2) Synthesis of 2- (fluorosulfonyl) difluoroacetyl fluoride

Figure 2008094835

To a 100 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 6.00 g (0.06 mol) of triethylamine was added and cooled to 0 ° C. From the dropping funnel, 121.79 g (0.68 mol) of tetrafluoro β-sultone was added dropwise while maintaining the temperature at 0 to 5 ° C. After the addition, the reaction solution was returned to room temperature and stirred for 1 hour. The obtained liquid was purified by distillation at 30 ° C. under normal pressure to obtain 109.61 g (0.61 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride which is an isomer of tetrafluoro β-sultone.

19Ｆ−ＮＭＲ（ＣＤＣｌ3、内部標準物質ＣＦＣｌ3）：δ（ｐｐｍ）−１０４．４（ｄｄ，ＣＦ2）、２４．８（ｔｄ，ＣＯＦ）、４３．０（ｔｄ，ＳＯ2Ｆ） 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -104.4 (dd, CF 2 ), 24.8 (td, COF), 43.0 (td, SO 2 F)

（３）４−オキソアダマンタン−１−イル−オキシカルボニル（ジフルオロ）メタンスルホニルフルオリドの合成

Figure 2008094835

撹拌機、滴下漏斗、温度計を備えた２００ｍＬ四つ口フラスコに、５−ヒドロキシ−２−アダマンタノン５．００ｇ（０．０３ｍｏｌ）、トリエチルアミン３．６５ｇ（０．０４ｍｏｌ）、クロロホルム５８．４４ｇを投入した。滴下漏斗より上記２−（フルオロスルホニル）ジフルオロアセチルフルオライド５．９６ｇ（０．０３ｍｏｌ）を２０〜３５℃に維持しながら滴下し、投入後反応液を室温付近において１時間撹拌を継続した。この反応液に水３７ｇを加えて有機層を分離した。この水洗操作を更に2回実施した後、有機層を濃縮して反応混合物１０．７２ｇを得た。この反応混合物は、展開液にヘキサン：酢酸エチル＝５：１（体積比）を用いた５．０５ｇのシリカゲルカラムで精製した。溶媒を減圧下で除去後、６．６６ｇ（０．０２ｍｏｌ）の目的とするエステルが収率６８．１％で得られた。得られた液体は、19Ｆ−ＮＭＲ測定することにより、目的とするエステルであることを確認した。 (3) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonyl fluoride

Figure 2008094835

In a 200 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.65 g (0.04 mol) of triethylamine, and 58.44 g of chloroform were added. I put it in. From the dropping funnel, 5.96 g (0.03 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride was added dropwise while maintaining at 20 to 35 ° C. After the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. To this reaction solution, 37 g of water was added to separate the organic layer. This washing operation was further performed twice, and then the organic layer was concentrated to obtain 10.72 g of a reaction mixture. This reaction mixture was purified by a 5.05 g silica gel column using hexane: ethyl acetate = 5: 1 (volume ratio) as a developing solution. After removal of the solvent under reduced pressure, 6.66 g (0.02 mol) of the desired ester was obtained in 68.1% yield. The obtained liquid was confirmed to be the target ester by 19 F-NMR measurement.

19Ｆ−ＮＭＲ（ＣＤＣｌ3、内部標準物質ＣＦＣｌ3）：δ（ｐｐｍ）−１０３．６（ｄ，ＣＦ2）、４０．７（ｔ，ＳＯ2Ｆ） 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -103.6 (d, CF 2 ), 40.7 (t, SO 2 F)

同様にして、目的物を精製単離しないで次工程につなぐ合成を行った。
撹拌機、滴下漏斗、温度計を備えた２００ｍＬ四つ口フラスコに、５−ヒドロキシ−２−アダマンタノン５．００ｇ（０．０３ｍｏｌ）、トリエチルアミン３．６５ｇ（０．０４ｍｏｌ）、クロロホルム５８．４４ｇを投入した。滴下漏斗より上記２−（フルオロスルホニル）ジフルオロアセチルフルオリド５．９６ｇ（０．０３ｍｏｌ）を２０〜３５℃に維持しながら滴下し、投入後反応液を室温付近において１時間撹拌を継続した。得られた液体を19Ｆ−ＮＭＲ測定することにより、目的とするエステルが生成したことを確認した。 Similarly, the synthesis | combination which connected the following process was performed, without purifying and isolating the target object.
In a 200 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.65 g (0.04 mol) of triethylamine, and 58.44 g of chloroform were added. I put it in. 5.96 g (0.03 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride was dropped from the dropping funnel while maintaining at 20 to 35 ° C., and after the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. The obtained liquid was measured by 19 F-NMR to confirm that the target ester was produced.

19Ｆ−ＮＭＲ（ＣＤＣｌ3、内部標準物質ＣＦＣｌ3）：δ（ｐｐｍ）−１０３．６（ｄ，ＣＦ2）、４０．７（ｔ，ＳＯ2Ｆ） 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -103.6 (d, CF 2 ), 40.7 (t, SO 2 F)

（４）４−オキソアダマンタン−１−イル−オキシカルボニル（ジフルオロ）メタンスルホン酸 トリエチルアミン塩の合成

Figure 2008094835

撹拌機、温度計を備えた３００ｍＬ四つ口フラスコに上記で得られた液体を全量投入し、さらに水７．６１ｇ、トリエチルアミン１０．６６ｇ（０．１１ｍｏｌ）を液温２０〜３５℃に維持しながら投入した。投入後反応液を室温付近において１時間撹拌を継続した。19Ｆ−ＮＭＲ測定により原料消失を確認後、反応液を水４２ｇで２回洗浄し得られた有機層を濃縮することで目的のアンモニウム塩を１１．５２ｇ（収率は、９０％）得た。 (4) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonic acid triethylamine salt

Figure 2008094835

A 300 mL four-necked flask equipped with a stirrer and a thermometer was charged with the whole amount of the liquid obtained above, and further 7.61 g of water and 10.66 g (0.11 mol) of triethylamine were maintained at a liquid temperature of 20 to 35 ° C. While throwing. After the addition, stirring was continued for 1 hour at around room temperature. After confirming disappearance of the raw material by 19 F-NMR measurement, the reaction solution was washed twice with 42 g of water, and the organic layer obtained was concentrated to obtain 11.52 g (yield: 90%) of the target ammonium salt. .

1Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ6、内部標準物質ＤＭＳＯ）：δ（ｐｐｍ）１．７９−２．０１（ｃ，４Ｈ）、２．２１−２．５３（ｃ，９Ｈ）
19Ｆ−ＮＭＲ（ＣＤＣｌ3、内部標準物質ＣＦＣｌ3）：δ（ｐｐｍ）−１１０．８（ｓ，ＣＦ2） 1 H-NMR (DMSO-d 6 , internal standard substance DMSO): δ (ppm) 1.79-2.01 (c, 4H), 2.21-2.53 (c, 9H)
19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -110.8 (s, CF 2 )

（５）４−オキソアダマンタン−１−イル−オキシカルボニル（ジフルオロ）メタンスルホニルフルオリドの合成

Figure 2008094835

撹拌機、滴下漏斗、温度計を備えた１００ｍＬ四つ口フラスコに、５−ヒドロキシ−２−アダマンタノン５．００ｇ（０．０３ｍｏｌ）、トリエチルアミン３．３７ｇ（０．０３ｍｏｌ）、クロロホルム５６．５８ｇを投入した。滴下漏斗より上記（１）で得られたテトラフルオロβ−サルトン５．４２ｇ（０．０３ｍｏｌ）を２０〜３５℃に維持しながら滴下し、投入後反応液を室温付近において1時間撹拌を継続した。得られた液体を19Ｆ−ＮＭＲ測定することにより、目的化合物であるエステル体が生成した事を確認した。 (5) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonyl fluoride

Figure 2008094835

In a 100 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.37 g (0.03 mol) of triethylamine, and 56.58 g of chloroform were added. I put it in. From the dropping funnel, 5.42 g (0.03 mol) of tetrafluoro β-sultone obtained in (1) above was added dropwise while maintaining the temperature at 20 to 35 ° C. After the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. . By measuring 19 F-NMR of the obtained liquid, it was confirmed that the ester compound as the target compound was produced.

（６）４−オキソアダマンタン−１−イル−オキシカルボニル（ジフルオロ）メタンスルホン酸 トリエチルアミン塩の合成

Figure 2008094835

撹拌機、温度計を備えた１００ｍＬ四つ口フラスコに上記で得られた液体１５．０１ｇを投入し、さらに水１．００ｇ、トリエチルアミン１．００ｇ（０．０１ｍｏｌ）を液温２０〜３５℃に維持しながら投入した。投入後反応液を室温付近において２時間撹拌を継続した。19Ｆ−ＮＭＲ測定により原料消失を確認後、反応液を分層し得られた有機層を濃縮することでアンモニウム塩２．４６ｇ（収率は、９０％）を得た。 (6) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonic acid triethylamine salt

Figure 2008094835

A 100 mL four-necked flask equipped with a stirrer and a thermometer was charged with 15.01 g of the liquid obtained above, and further 1.00 g of water and 1.00 g (0.01 mol) of triethylamine were brought to a liquid temperature of 20 to 35 ° C. It was thrown in while maintaining. After the addition, the reaction solution was continuously stirred at around room temperature for 2 hours. After confirming disappearance of the raw material by 19 F-NMR measurement, the organic layer obtained by separating the reaction solution was concentrated to obtain 2.46 g (yield: 90%) of the ammonium salt.

本発明の塩は、優れた解像度及びパターン形状を与える化学増幅型ポジ型レジスト組成物用の酸発生剤の中間体として好適に用いられ、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高い解像度を示す化学増幅型ポジ型レジスト組成物用の酸発生剤の中間体として用いることができる。   The salt of the present invention is suitably used as an intermediate of an acid generator for a chemically amplified positive resist composition that gives excellent resolution and pattern shape. Among them, excimer laser lithography such as ArF and KrF, and ArF immersion It can be used as an intermediate of an acid generator for a chemically amplified positive resist composition showing high resolution suitable for exposure lithography.

Claims (9)

式（Ｉ）で示されることを特徴とする塩。
Figure 2008094835
（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し、Ｒは炭素数２〜３０の置換されていてもよい炭化水素基を表し、Ａ+はアンモニウムイオンを表す。） A salt represented by the formula (I):
Figure 2008094835
(In the formula (I), Q 1, Q 2 represents independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, R represents a hydrocarbon group which may be substituted having 2 to 30 carbon atoms A + represents an ammonium ion.) Ｑ1、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に記載の塩。 The salt according to claim 1 , wherein Q 1 and Q 2 are each independently a fluorine atom or -CF 3 . Ｒが環を含んでいてもよい炭素数２〜３０の炭化水素で、Ｒに含まれる炭素原子はその一部が酸素原子で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い炭化水素の１価の残基（いずれも炭素数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、水酸基又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。）である請求項１又は２に記載の塩。   R is a hydrocarbon having 2 to 30 carbon atoms which may contain a ring, and the carbon atoms contained in R may be partially substituted with oxygen atoms, and may form a carbonyl group A monovalent residue of hydrogen (all of which are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, perfluoroalkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups having 1 to 6 carbon atoms, hydroxyl groups or The salt according to claim 1 or 2, wherein one or more cyano groups may be contained as a substituent. 式（Ｉ）で示される塩が、式（II）で示される塩であることを特徴とする請求項１〜３のいずれかに記載の塩。
Figure 2008094835
（式（II）中、Ｑ1、Ｑ2およびＡ+は前記と同じ意味を表す。） The salt according to any one of claims 1 to 3, wherein the salt represented by the formula (I) is a salt represented by the formula (II).
Figure 2008094835
(In formula (II), Q 1 , Q 2 and A + represent the same meaning as described above.) Ａ+が一般式（ＸＩ）で示されるアンモニウムイオンである請求項１〜４のいずれかに記載の塩。
Figure 2008094835
（式（ＸＩ）中、Ｚ1、Ｚ2およびＺ3は、互いに独立に水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシアルキル基、炭素数３〜１２のシクロアルキル基、置換されていてもよいフェニル基、置換されていてもよい炭素数７〜１２のアラルキル基、置換されていてもよいナフチル基、置換されていてもよい炭素数５〜１０のへテロ芳香族基、またはＺ1、Ｚ2およびＺ3の少なくとも二つ以上でヘテロ原子を含んでもよい環を表す。） The salt according to any one of claims 1 to 4, wherein A + is an ammonium ion represented by the general formula (XI).
Figure 2008094835
(In the formula (XI), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Group, an optionally substituted phenyl group, an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted naphthyl group, an optionally substituted heteroaromatic group having 5 to 10 carbon atoms Represents a group or a ring which may contain a hetero atom in at least two of Z 1 , Z 2 and Z 3. ) 式（III）で示されるアルコールと、
Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（IV）
Figure 2008094835
（式（IV）中、Ｑ1およびＱ2は前記と同じ意味を表す。）
で示される化合物を脱酸剤の存在下で反応させて式（ＸＸ）で示される化合物を得た後、
Figure 2008094835
（式（ＸＸ）中、Ｑ1、Ｑ2およびＲは前記と同じ意味を表す。）
式（ＸＸ）で示される化合物をアミン水で加水分解することを特徴とする請求項１記載の式（Ｉ）で示される塩の製造方法。 An alcohol represented by the formula (III);
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
Formula (IV)
Figure 2008094835
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
After reacting the compound represented by formula (XX) in the presence of a deoxidizing agent,
Figure 2008094835
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
The method for producing a salt represented by the formula (I) according to claim 1, wherein the compound represented by the formula (XX) is hydrolyzed with amine water. 式（ＸＸ）で示されることを特徴とする化合物。
Figure 2008094835
（式（ＸＸ）中、Ｑ1、Ｑ2およびＲは前記と同じ意味を表す。） A compound represented by the formula (XX)
Figure 2008094835
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.) 請求項６記載の式（III）で示されるアルコールと、請求項６記載の式（IV）で示される化合物を脱酸剤の存在下で反応させることを特徴とする請求項７記載の式（ＸＸ）で示される化合物の製造方法。   The alcohol represented by the formula (III) according to claim 6 and the compound represented by the formula (IV) according to claim 6 are reacted in the presence of a deoxidizing agent. XX) A method for producing a compound represented by 式（III）で示されるアルコールと、
Figure 2008094835
（式（III）中、Ｒは前記と同じ意味を表す。）
式（Ｖ）で示される化合物を反応させた後、アミン水で加水分解することを特徴とする請求項１記載の式（Ｉ）で示される塩の製造方法。
Figure 2008094835
（式（Ｖ）中、Ｑ1およびＱ2は前記と同じ意味を表す。） An alcohol represented by the formula (III);
Figure 2008094835
(In formula (III), R represents the same meaning as described above.)
The method for producing a salt represented by the formula (I) according to claim 1, wherein the compound represented by the formula (V) is reacted and then hydrolyzed with amine water.
Figure 2008094835
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008069146A (en) * 2006-08-18 2008-03-27 Sumitomo Chemical Co Ltd Salt for acid-generating agent of chemically amplified resist composition
JP2008074843A (en) * 2006-08-22 2008-04-03 Sumitomo Chemical Co Ltd Salt for acid generator of chemically amplified type resist composition
JP2009149588A (en) * 2007-12-21 2009-07-09 Tokyo Ohka Kogyo Co Ltd New compound and its production method
WO2010050392A1 (en) * 2008-10-29 2010-05-06 セントラル硝子株式会社 Method for producing alkoxycarbonylfluoroalkanesulfonic acid salt
KR20110011575A (en) * 2009-07-27 2011-02-08 스미또모 가가꾸 가부시끼가이샤 Chemically amplified resist composition and salt employed therein
JP2011074061A (en) * 2009-10-01 2011-04-14 Korea Kumho Petrochemical Co Ltd Method for producing sulfonium salt and sulfonium salt produced thereby
JP2011246444A (en) * 2010-04-28 2011-12-08 Sumitomo Chemical Co Ltd Salt and resist composition
US8431324B2 (en) 2009-05-07 2013-04-30 Jsr Corporation Radiation-sensitive resin composition
KR20130076766A (en) 2011-12-28 2013-07-08 제이에스알 가부시끼가이샤 Photoresist composition, process for forming resist pattern and acid generator
US8592540B2 (en) 2008-12-25 2013-11-26 Central Glass Company, Limited Fluorine-containing compound, fluorine-containing polymer compound, resist composition and patterning method using same
US9034556B2 (en) 2007-12-21 2015-05-19 Tokyo Ohka Kogyo Co., Ltd. Compound and method of producing the same, acid generator, resist composition and method of forming resist pattern
US9104110B2 (en) 2012-06-04 2015-08-11 Shin-Etsu Chemical Co., Ltd. Polymer, resist composition and patterning process
KR101556096B1 (en) 2006-08-22 2015-09-30 스미또모 가가꾸 가부시키가이샤 A salt suitable for an acid generator and a chemically amplified positive resist composition containing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852554A (en) * 1956-07-12 1958-09-16 Du Pont Alpha-sulfopolyfluoromonocarboxylic acids and derivatives hydrolyzable thereto
JPS5297909A (en) * 1976-02-12 1977-08-17 Teijin Ltd Preparation of perfluoroacrylic acid derivatives
JP2007507580A (en) * 2003-05-22 2007-03-29 スリーエム イノベイティブ プロパティズ カンパニー Photoacid generator having perfluorinated polyfunctional anions
JP2008299069A (en) * 2007-05-31 2008-12-11 Shin Etsu Chem Co Ltd Resist material containing novel photoacid generator and method for forming pattern
JP2008297255A (en) * 2007-05-31 2008-12-11 Central Glass Co Ltd New sulfonate, onium sulfonate, sulfonic acid derivative and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852554A (en) * 1956-07-12 1958-09-16 Du Pont Alpha-sulfopolyfluoromonocarboxylic acids and derivatives hydrolyzable thereto
JPS5297909A (en) * 1976-02-12 1977-08-17 Teijin Ltd Preparation of perfluoroacrylic acid derivatives
JP2007507580A (en) * 2003-05-22 2007-03-29 スリーエム イノベイティブ プロパティズ カンパニー Photoacid generator having perfluorinated polyfunctional anions
JP2008299069A (en) * 2007-05-31 2008-12-11 Shin Etsu Chem Co Ltd Resist material containing novel photoacid generator and method for forming pattern
JP2008297255A (en) * 2007-05-31 2008-12-11 Central Glass Co Ltd New sulfonate, onium sulfonate, sulfonic acid derivative and method for producing the same

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
JPN6012059057; Ｊｏｕｒｎａｌ　ｏｆ　Ｆｌｕｏｒｉｎｅ　Ｃｈｅｍｉｓｔｒｙ ６９, 1994, ８９-９５ *
JPN6012059061; Ｊｏｕｒｎａｌ　ｏｆ　Ｆｌｕｏｒｉｎｅ　Ｃｈｅｍｉｓｔｒｙ １２５, 2004, ４５９-４６９ *
JPN6012059062; Ｊｏｕｒｎａｌ　ｏｆ　Ｆｌｕｏｒｉｎｅ　Ｃｈｅｍｉｓｔｒｙ １２１, 2003, １４７-１５２ *
JPN6012059069; 化学大辞典１ , 1960, ｐ．５３４ *
JPN7012004616; Ｊｏｕｒｎａｌ　ｆｕｅｒ　Ｐｒａｋｔｉｓｃｈｅ　Ｃｈｅｍｉｅ ３３３，３, 1991, ｐ．５０９-５１２ *
JPN7012004618; Ｉｚｖｅｓｔｉｙａ　Ａｋａｄｅｍｉｉ　Ｎａｕｋ　ＳＳＳＲ，　Ｓｅｒｉｙａ　Ｋｈｉｍｉｃｈｅｓｋａｙａ ７, 1968, ｐ．１５６５-１５７０ *
JPN7012004620; Ｊ．　ＣＨＥＭ．　ＳＯＣ．　ＰＥＲＫＩＮ　ＴＲＡＮＳ．　１ ６, 1994, ｐ．７２５-７３０ *
JPN7012004621; Ｈｕａｘｕｅ　Ｘｕｅｂａｏ ４２（６）, 1984, ５４１-５４８ *
JPN7012004622; Ｉｚｖｅｓｔｉｙａ　Ａｋａｄｅｍｉｉ　Ｎａｕｋ　ＳＳＳＲ．　Ｓｅｒｉｙａ　Ｋｈｉｍｉｃｈｅｓｋａｙａ ８, 1967, ｐ．１７５４-８ *
JPN7012004624; Ｉｚｖｅｓｔｉｙａ　Ａｋａｄｅｍｉｉ　Ｎａｕｋ　ＳＳＳＲ，　Ｓｅｒｉｙａ　Ｋｈｉｍｉｃｈｅｓｋａｙａ ６, 1967, ｐ．１２８９-９４ *

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JP2008074843A (en) * 2006-08-22 2008-04-03 Sumitomo Chemical Co Ltd Salt for acid generator of chemically amplified type resist composition
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US9034556B2 (en) 2007-12-21 2015-05-19 Tokyo Ohka Kogyo Co., Ltd. Compound and method of producing the same, acid generator, resist composition and method of forming resist pattern
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US9040220B2 (en) 2007-12-21 2015-05-26 Tokyo Ohka Kogyo Co., Ltd. Compound and method of producing the same, acid generator, resist composition and method of forming resist pattern
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