JP3975346B2 - Novel sulfonic acid ester compounds - Google Patents

Description

［式中、Ｒ ² は、下記一般式（２）〜（４）で示される基から選ばれる酸不安定基、又は炭素数１〜４の直鎖状もしくは分岐状のオキソアルキル基である。
【化１４】

（式中、Ｒ ⁷ は炭素数４〜２０の三級アルキル基、又は炭素数４〜２０のオキソアルキル基を示し、ｂは０〜６の整数である。Ｒ ⁸ 及びＲ ⁹ は水素原子又は炭素数１〜１８の直鎖状、分岐状又は環状のアルキル基を示し、Ｒ ¹⁰ は炭素数１〜１８のヘテロ原子を有してもよい１価の炭化水素基を示す。Ｒ ⁸ とＲ ⁹ 、Ｒ ⁸ とＲ ¹⁰ 、Ｒ ⁹ とＲ ¹⁰ とは互いに結合して環を形成してもよく、環を形成する場合にはＲ ⁸ 、Ｒ ⁹ 、Ｒ ¹⁰ は炭素数１〜１８の直鎖状又は分岐状のアルキレン基を示す。Ｒ ¹¹ 、Ｒ ¹² 、Ｒ ¹³ は炭素数１〜２０のヘテロ原子を含んでもよい１価炭化水素基であり、Ｒ ¹¹ とＲ ¹² 、Ｒ ¹¹ とＲ ¹³ 、Ｒ ¹² とＲ ¹³ とは互いに結合してこれらが結合する炭素原子と共に環を形成してもよい。）］
【００１０】
以下、本発明について更に詳しく説明する。
本発明者の検討によれば、１５７ｎｍ付近の透過率を向上させる方法としては、カルボニル基や炭素−炭素間二重結合の数の低減化も一つの方法と考えられるが、モノマーユニット中へのフッ素原子の導入も透過率向上に大きく寄与することがわかってきた。特に本発明者は下記一般式（１ａ）〜（１ｃ）の構造で表されるようなスルホン酸エステルから得られるポリマーが１５７ｎｍ付近の高透明性を維持しつつ、従来のフッ素含有材料が抱えていた基板密着性の低下や現像液のはじきを抑えられることを見出したものである。
【００１１】
【化３】

（式中、Ｒ¹〜Ｒ⁵は上記と同様である。）
【００１２】
この場合、炭素数１〜４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が例示できる。
【００１３】
フッ素化されたアルキル基は、上記アルキル基の水素原子の一部又は全部がフッ素原子で置換されたものであり、トリフルオロメチル基、２，２，２−トリフルオロエチル基、３，３，３−トリフルオロプロピル基、１，１，１，３，３，３−ヘキサフルオロイソプロピル基、１，１，２，２，３，３，３−ヘプタフルオロプロピル基等が挙げられる。
【００１４】
炭素数１〜４のオキソアルキル基としては、アセチル基、エチルカルボニル基、ｎ−プロピルカルボニル基、イソプロピルカルボニル基などが用いられる。
【００１５】
次に、Ｒ²で表される酸不安定基について説明する。酸不安定基としては種々選定されるが、特に下記一般式（２）〜（４）で示される基である。
【００１６】
【化４】

【００１７】
式（２）において、Ｒ⁷は炭素数４〜２０、好ましくは４〜１５の三級アルキル基、又は炭素数４〜２０のオキソアルキル基を示し、三級アルキル基として具体的には、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、１，１−ジエチルプロピル基、１−エチルシクロペンチル基、１−ブチルシクロペンチル基、１−エチルシクロヘキシル基、１−ブチルシクロヘキシル基、１−エチル−２−シクロペンテニル基、１−エチル−２−シクロヘキセニル基、２−メチル−２−アダマンチル基等が挙げられ、オキソアルキル基として具体的には、３−オキソシクロヘキシル基、４−メチル−２−オキソオキサン−４−イル基、５−メチル−５−オキソオキソラン−４−イル基等が挙げられる。ｂは０〜６の整数である。
【００１８】
上記式（２）の酸不安定基としては、具体的にはｔｅｒｔ−ブトキシカルボニル基、ｔｅｒｔ−ブトキシカルボニルメチル基、ｔｅｒｔ−アミロキシカルボニル基、ｔｅｒｔ−アミロキシカルボニルメチル基、１，１−ジエチルプロピルオキシカルボニル基、１，１−ジエチルプロピルオキシカルボニルメチル基、１−エチルシクロペンチルオキシカルボニル基、１−エチルシクロペンチルオキシカルボニルメチル基、１−エチル−２−シクロペンテニルオキシカルボニル基、１−エチル−２−シクロペンテニルオキシカルボニルメチル基、１−エトキシエトキシカルボニルメチル基、２−テトラヒドロピラニルオキシカルボニルメチル基、２−テトラヒドロフラニルオキシカルボニルメチル基等が例示できる。
【００１９】
式（３）において、Ｒ⁸及びＲ⁹は水素原子又は炭素数１〜１８、好ましくは１〜１０の直鎖状、分岐状又は環状のアルキル基を示し、具体的にはメチル基、エチル基、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、シクロペンチル基、シクロヘキシル基、２−エチルヘキシル基、ｎ−オクチル基等を例示できる。Ｒ¹⁰は炭素数１〜１８、好ましくは１〜１０の酸素原子等のヘテロ原子を有してもよい１価の炭化水素基を示し、直鎖状、分岐状、環状のアルキル基、これらの水素原子の一部が水酸基、アルコキシ基、オキソ基、アミノ基、アルキルアミノ基等に置換されたものを挙げることができ、具体的には下記の置換アルキル基等が例示できる。
【００２０】
【化５】

【００２１】
Ｒ⁸とＲ⁹、Ｒ⁸とＲ¹⁰、Ｒ⁹とＲ¹⁰とは互いに結合して環を形成してもよく、環を形成する場合にはＲ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ炭素数１〜１８、好ましくは１〜１０の直鎖状又は分岐状のアルキレン基を示す。
【００２２】
上記式（３）で示される酸不安定基のうち直鎖状又は分岐状のものとしては、具体的には下記の基が例示できる。
【００２３】
【化６】

【００２４】
上記式（３）で示される酸不安定基のうち環状のものとしては、具体的にはテトラヒドロフラン−２−イル基、２−メチルテトラヒドロフラン−２−イル基、テトラヒドロピラン−２−イル基、２−メチルテトラヒドロピラン−２−イル基等が例示できる。式（３）としては、エトキシエチル基、ブトキシエチル基、エトキシプロピル基が好ましい。
【００２５】
次に、式（４）においてＲ¹¹、Ｒ¹²及びＲ¹³は炭素数１〜２０の直鎖状、分岐状もしくは環状のアルキル基等の１価炭化水素基であり、酸素、硫黄、窒素、フッ素などのヘテロ原子を含んでもよく、Ｒ¹¹とＲ¹²、Ｒ¹¹とＲ¹³、Ｒ¹²とＲ¹³とは互いに結合してこれらが結合する炭素原子と共に環を形成してもよい。
【００２６】
式（４）に示される三級アルキル基としては、ｔｅｒｔ−ブチル基、トリエチルカルビル基、１−エチルノルボルニル基、１−メチルシクロヘキシル基、１−エチルシクロペンチル基、２−（２−メチル）アダマンチル基、２−（２−エチル）アダマンチル基、ｔｅｒｔ−アミル基、１，１，１，３，３，３−ヘキサフルオロ−２−メチル−イソプロピル基、１，１，１，３，３，３−ヘキサフルオロ−２−シクロヘキシル−イソプロピル基等を挙げることができる他、下記に示す基を具体的に挙げることができる。
【００２７】
【化７】

【００２８】
ここで、Ｒ¹⁴は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基を示し、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、シクロプロピル基、シクロプロピルメチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等を例示できる。Ｒ¹⁵は炭素数２〜６の直鎖状、分岐状又は環状のアルキル基を示し、具体的にはエチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、シクロプロピル基、シクロプロピルメチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等を例示できる。Ｒ¹⁶及びＲ¹⁷は水素原子、炭素数１〜６のヘテロ原子を含んでもよい１価炭化水素基、又は炭素数１〜６のヘテロ原子を介してもよい１価炭化水素基を示し、これらは直鎖状、分岐状、環状のいずれでもよい。この場合ヘテロ原子としては、酸素原子、硫黄原子、窒素原子を挙げることができ、−ＯＨ、−ＯＲ¹⁸、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−ＮＨ₂、−ＮＨＲ¹⁸、−Ｎ（Ｒ¹⁸）₂、−ＮＨ−、−ＮＲ¹⁸−として含有又は介在することができる。Ｒ¹⁸は炭素数１〜５のアルキル基を示す。Ｒ¹⁶及びＲ¹⁷としては、具体的には、メチル基、ヒドロキシメチル基、エチル基、ヒドロキシエチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、メトキシ基、メトキシメトキシ基、エトキシ基、ｔｅｒｔ−ブトキシ基等を例示できる。
【００２９】
式（１ａ）〜（１ｃ）で表されるモノマーの具体例としては、下記のものが挙げられる。
【００３０】
【化８】

（式中、Ｒ²は上記と同様である。）
【００３１】
本発明のエステル化合物の製造は、例えば下記工程にて行うことができるが、これに限定されるものではない。
【００３２】
【化９】

【００３３】
ここで、Ｒ¹〜Ｒ⁵は上記と同様である。反応は公知の条件にて容易に進行するが、好ましくはジクロロメタンなどの溶媒中、原料のアルコールとピリジン（Ｐｙ）を同時に加え、氷浴下でクロロエタンスルホニルクロリドを滴下することにより目的のモノマーを得ることができる。
【００３４】
【発明の効果】
本発明のスルホン酸エステル化合物をモノマーとして製造したポリマーを用いたレジスト材料は、透明性に優れると共に基板密着性にも優れているため、電子線や遠紫外線、特にＦ₂レーザーによる微細加工に有用である。
【００３５】
【実施例】
以下、合成例及び実施例を示して本発明を具体的に説明するが、本発明は下記実施例に制限されるものではない。
【００３６】
［合成例１］ 下記モノマー１の合成
フラスコ中にジクロロメタン４０ｇ、下記アルコール１を１０ｇ、ピリジン６．９ｇを投入し、フラスコを氷浴に浸した。滴下漏斗にクロロエタンスルホニルクロリド７．１３ｇを入れ、内温を１０℃以下に保ちながらフラスコ中に滴下した。滴下終了後、そのまま一時間撹拌した。通常の反応後処理を行い、得られた油状物質をシリカゲルクロマトグラフィーで精製したところ、８．８ｇの下記モノマー１が得られた。収率は６４％であった。
【００３７】
【化１０】

【００３８】
［合成例２］ 下記モノマー２の合成
フラスコ中にジクロロメタン４０ｇ、下記アルコール２を１０ｇ、ピリジン６．０ｇを投入し、フラスコを氷浴に浸した。滴下漏斗にクロロエタンスルホニルクロリド６．２ｇを入れ、内温を１０℃以下に保ちながらフラスコ中に滴下した。滴下終了後、そのまま一時間撹拌した。通常の反応後処理を行い、得られた油状物質をシリカゲルクロマトグラフィーで精製したところ、８．９ｇの下記モノマー２が得られた。収率は６７％であった。
【００３９】
【化１１】

【００４０】
［合成例３］ 下記モノマー３の合成
フラスコ中にジクロロメタン４０ｇ、下記アルコール３を１０ｇ、ピリジン６．９７ｇを投入し、フラスコを氷浴に浸した。滴下漏斗にクロロエタンスルホニルクロリド７．１９ｇを入れ、内温を１０℃以下に保ちながらフラスコ中に滴下した。滴下終了後、そのまま一時間撹拌した。通常の反応後処理を行い、得られた油状物質をシリカゲルクロマトグラフィーで精製したところ、９．１ｇの下記モノマー３が得られた。収率は６６％であった。
【００４１】
【化１２】

【００４２】
［合成例４］ 下記モノマー４の合成
フラスコ中にジクロロメタン４０ｇ、下記アルコール４を１０ｇ、ピリジン６．０６ｇを投入し、フラスコを氷浴に浸した。滴下漏斗にクロロエタンスルホニルクロリド６．２４ｇを入れ、内温を１０℃以下に保ちながらフラスコ中に滴下した。滴下終了後、そのまま一時間撹拌した。通常の反応後処理を行い、得られた油状物質をシリカゲルクロマトグラフィーで精製したところ、８．１ｇの下記モノマー４が得られた。収率は６１％であった。

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sulfonate compound useful as a monomer for a base material of a resist material suitable for microfabrication technology, particularly a chemically amplified resist material.
[0002]
[Prior art and problems to be solved by the invention]
In recent years, with the high integration and high speed of LSI, there is a demand for finer pattern rules.
[0003]
The background of rapid progress in miniaturization includes higher NA of projection lenses, improved performance of resist materials, and shorter wavelengths. With regard to higher resolution and higher sensitivity of resist materials, chemically amplified positive resist materials catalyzed by acids generated by light irradiation have excellent performance, and have become the mainstream resist materials particularly in deep ultraviolet lithography. (Described in JP-B-2-27660, JP-A-63-27829, etc.).
[0004]
In addition, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change. Resist materials for KrF excimer lasers started with the 0.30 micron process, passed the 0.25 micron rule, The micron rule is being applied to mass production. Furthermore, the investigation below the 0.10 micron rule has begun, and the momentum of miniaturization is further accelerated.
[0005]
In ArF (193 nm), it is expected that the refinement of the design rule will be 0.13 μm or less. However, conventionally used resins such as novolak resins and polyvinylphenols have very strong absorption around 193 nm. Therefore, it cannot be used as a base resin for resist. Therefore, acrylic resins and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and necessary dry etching resistance (Japanese Patent Laid-Open Nos. 9-73173, 10-10739, and 9). -230595 publication, WO97 / 33198).
[0006]
As for F ₂ (157 nm), miniaturization of 0.10 μm or less is expected, but it becomes increasingly difficult to ensure transparency, and acrylic resin, which is a base polymer for ArF, does not transmit light at all, and cycloolefin. Even in the system, those having a carbonyl bond were found to have strong absorption. Further, it was found that polyvinylphenol, which is a base polymer for KrF, has an absorption window at around 160 nm and slightly improves the transmittance, but is far from a practical level.
[0007]
The present invention has been made in view of the above circumstances, and has excellent transmittance in vacuum ultraviolet light of 300 nm or less, particularly F ₂ (157 nm), Kr ₂ (146 nm), KrAr (134 nm), Ar ₂ (126 nm), and the like. An object of the present invention is to provide a sulfonic acid ester compound useful as a monomer as a raw material for a base material of a resist material, particularly a chemically amplified resist material.
[0008]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventor has found that a resin obtained from this ester compound is highly transparent by incorporating a hydrophilic group and a fluorinated alkyl group into the ester side chain of the vinyl sulfonate ester. It has been found that the substrate adhesion and developer compatibility can be ensured without impairing the properties, and the present invention has been achieved.
[0009]
That is, the present invention is selected from a monomer represented by the following general formula, providing a base polymer material for the sulfonate compound of the chemically amplified resist material.
[Chemical formula 2]

[ Wherein, R ² is an acid labile group selected from the groups represented by the following general formulas (2) to (4) , or a linear or branched oxoalkyl group having 1 to 4 carbon atoms.
Embedded image

(In the formula, R ⁷ represents a tertiary alkyl group having 4 to 20 carbon atoms or an oxoalkyl group having 4 to 20 carbon atoms, and b is an integer of 0 to 6. R ⁸ and R ⁹ are hydrogen atoms or A linear, branched or cyclic alkyl group having 1 to 18 carbon atoms , and R ¹⁰ represents a monovalent hydrocarbon group which may have a hetero atom having 1 to 18 carbon atoms, R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring, and in the case of forming a ring, R ⁸ , R ⁹ and R ¹⁰ are straight R ¹¹ , R ¹² and R ¹³ are each a monovalent hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms, R ¹¹ and R ¹² , R ¹¹ and R ¹³ , R ¹² and R ¹³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.)]
[0010]
Hereinafter, the present invention will be described in more detail.
According to the study of the present inventor, as a method for improving the transmittance around 157 nm, it is considered to reduce the number of carbonyl groups and carbon-carbon double bonds as one method. It has been found that introduction of fluorine atoms greatly contributes to the improvement of transmittance. In particular, the present inventor has a conventional fluorine-containing material while a polymer obtained from a sulfonate ester represented by the structure of the following general formulas (1a) to (1c) maintains high transparency around 157 nm. It has been found that it is possible to suppress a decrease in substrate adhesion and repelling of the developer.
[0011]
[Chemical 3]

(Wherein, R ¹ to R ⁵ are as defined above.)
[0012]
In this case, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-propyl group, n-butyl group, sec-butyl group, and tert-butyl group.
[0013]
The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms, and includes a trifluoromethyl group, 2,2,2-trifluoroethyl group, 3, 3, Examples include 3-trifluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, and the like.
[0014]
As the oxoalkyl group having 1 to 4 carbon atoms, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group and the like are used.
[0015]
Next, the acid labile group represented by R ² will be described. As the acid labile group selected from a variety of a group especially represented by the following general formula (2) to (4).
[0016]
[Formula 4]

[0017]
In the formula (2), R ⁷ represents a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, or an oxoalkyl group having 4 to 20 carbon atoms. Specific examples of the tertiary alkyl group include tert. -Butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxane-4-yl. Group, 5-methyl-5-oxooxolan-4-yl group and the like. b is an integer of 0-6.
[0018]
Specific examples of the acid labile group of the above formula (2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.
[0019]
In the formula (3), R ⁸ and R ⁹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group or an ethyl group. Propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ¹⁰ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to ¹⁰ carbon atoms, and is a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.
[0020]
[Chemical formula 5]

[0021]
R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring, and in the case of forming a ring, R ⁸ , R ⁹ and R ¹⁰ are each a carbon number. 1-18, preferably 1-10, represents a linear or branched alkylene group.
[0022]
Of the acid labile groups represented by the above formula (3), the following groups can be specifically exemplified as linear or branched groups.
[0023]
[Chemical 6]

[0024]
Among the acid labile groups represented by the above formula (3), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated. As formula (3), an ethoxyethyl group, a butoxyethyl group, and an ethoxypropyl group are preferable.
[0025]
Next, in the formula (4), R ¹¹ , R ¹² and R ¹³ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, oxygen, sulfur, nitrogen, Hetero atoms such as fluorine may be contained, and R ¹¹ and R ¹² , R ¹¹ and R ¹³ , and R ¹² and R ¹³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.
[0026]
The tertiary alkyl group represented by the formula (4) includes tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- (2-methyl ) Adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group, 1,1,1,3,3,3-hexafluoro-2-methyl-isopropyl group, 1,1,1,3,3 , 3-hexafluoro-2-cyclohexyl-isopropyl group and the like, and the following groups can be specifically mentioned.
[0027]
[Chemical 7]

[0028]
Here, R ¹⁴ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl. Group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. R ¹⁵ is a straight-chain 2 to 6 carbon atoms, an alkyl group branched or cyclic, specifically, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec- butyl group, n- pentyl group N-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. R ¹⁶ and R ¹⁷ represent a hydrogen atom, a monovalent hydrocarbon group that may contain a hetero atom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group that may pass through a hetero atom having 1 to 6 carbon atoms, May be linear, branched or cyclic. In this case, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and —OH, —OR ¹⁸ , —O—, —S—, —S (═O) —, —NH ₂ , —NHR ¹⁸ , —N (R ¹⁸ ) ₂ , —NH—, and —NR ¹⁸ — may be contained or interposed. R ¹⁸ represents an alkyl group having 1 to 5 carbon atoms. Specific examples of R ¹⁶ and R ¹⁷ include methyl group, hydroxymethyl group, ethyl group, hydroxyethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n- Examples include a hexyl group, a methoxy group, a methoxymethoxy group, an ethoxy group, and a tert-butoxy group.
[0029]
Specific examples of the monomer represented by the formula (1a) ~ (1c), it is also the mentioned that following.
[0030]
[Chemical 8]

(Wherein R ² is the same as above)
[0031]
The production of the ester compound of the present invention can be carried out, for example, by the following steps, but is not limited thereto.
[0032]
[Chemical 9]

[0033]
Here, R ^{1 to} R ⁵ are the same as described above. The reaction proceeds easily under known conditions, but preferably the starting alcohol and pyridine (Py) are added simultaneously in a solvent such as dichloromethane and the desired monomer is obtained by dropwise addition of chloroethanesulfonyl chloride in an ice bath. be able to.
[0034]
【The invention's effect】
A resist material using a polymer produced by using the sulfonic acid ester compound of the present invention as a monomer is excellent in transparency and substrate adhesion, and is therefore useful for microfabrication by an electron beam or far ultraviolet light, particularly F ₂ laser. It is.
[0035]
【Example】
EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0036]
[Synthesis Example 1] Into a synthesis flask of the following monomer 1, 40 g of dichloromethane, 10 g of the following alcohol 1 and 6.9 g of pyridine were charged, and the flask was immersed in an ice bath. 7.13 g of chloroethanesulfonyl chloride was put into the dropping funnel and dropped into the flask while keeping the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred as it was for 1 hour. Normal reaction post-treatment was performed, and the resulting oily substance was purified by silica gel chromatography to obtain 8.8 g of the following monomer 1. The yield was 64%.
[0037]
[Chemical Formula 10]

[0038]
[Synthesis Example 2] Into a synthesis flask of the following monomer 2, 40 g of dichloromethane, 10 g of the following alcohol 2 and 6.0 g of pyridine were put, and the flask was immersed in an ice bath. To the dropping funnel, 6.2 g of chloroethanesulfonyl chloride was added and dropped into the flask while maintaining the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred as it was for 1 hour. The usual reaction post-treatment was performed, and the resulting oily substance was purified by silica gel chromatography to obtain 8.9 g of the following monomer 2. The yield was 67%.
[0039]
Embedded image

[0040]
[Synthesis Example 3] Into a synthesis flask of the following monomer 3, 40 g of dichloromethane, 10 g of the following alcohol 3 and 6.97 g of pyridine were put, and the flask was immersed in an ice bath. 7.19 g of chloroethanesulfonyl chloride was placed in the dropping funnel and dropped into the flask while maintaining the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred as it was for 1 hour. Normal reaction post-treatment was performed, and the resulting oily substance was purified by silica gel chromatography to obtain 9.1 g of the following monomer 3. The yield was 66%.
[0041]
Embedded image

[0042]
[Synthesis Example 4] Into a synthesis flask of the following monomer 4, 40 g of dichloromethane, 10 g of the following alcohol 4 and 6.06 g of pyridine were put, and the flask was immersed in an ice bath. 6.24 g of chloroethanesulfonyl chloride was put into the dropping funnel and dropped into the flask while keeping the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred as it was for 1 hour. After usual reaction post-treatment, the resulting oily substance was purified by silica gel chromatography to obtain 8.1 g of the following monomer 4. The yield was 61%.

Claims (1)

Selected from a monomer represented by the following general formula, the base polymer material for the sulfonate compound of the chemically amplified resist material.

[ Wherein, R ² is an acid labile group selected from the groups represented by the following general formulas (2) to (4) , or a linear or branched oxoalkyl group having 1 to 4 carbon atoms.

(In the formula, R ⁷ represents a tertiary alkyl group having 4 to 20 carbon atoms or an oxoalkyl group having 4 to 20 carbon atoms, and b is an integer of 0 to 6. R ⁸ and R ⁹ are hydrogen atoms or the number 1 to 18 linear carbon atoms, an alkyl group branched or cyclic, R ¹⁰ is a .R ⁸ showing a hydrocarbon group which may monovalent to have a hetero atom having 1 to 18 carbon atoms R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring, and in the case of forming a ring, R ⁸ , R ⁹ and R ¹⁰ are straight R ¹¹ , R ¹² and R ¹³ are each a monovalent hydrocarbon group which may contain a hetero atom having 1 to 20 carbon atoms, R ¹¹ and R ¹² , R ¹¹ and R ¹³ , R ¹² and R ¹³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.)]