JP4040938B2 - Antistatic treatment agent, antistatic film and coated article - Google Patents

Description

（式中、ｍ、ｎは独立に０または１の整数を示す。Ａは、−Ｂ−ＳＯ₃ ^-Ｍで表される置換基を少なくとも一つ有する、炭素数１〜４のアルキレン、アルケニレン基（二重結合は二つ以上有していてもよい。）を示し、該アルキル、アルケニレン基には炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基を置換基として有していてもよい。Ｂは、−（ＣＨ₂）_p−（Ｏ（ＣＨ₂）_q）_r−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される化学構造を含むことを特徴とする［１］〜［４］のいずれかに記載の帯電防止処理剤。
【００２０】
［８］水溶性導電性高分子が、下記一般式（３）、
【００２１】
【化５】

（式中、Ｒ¹〜Ｒ³ は、それぞれ独立に水素原子、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、−Ｂ−ＳＯ₃ ^-Ｍ基を示す。上記のＲ¹、Ｒ²およびＲ³のアルキル基、アルコキシ基またはアルキルエステル基の鎖中には、カルボニル結合、エーテル結合、エステル結合、スルホン酸エステル結合、アミド結合、スルホンアミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合、チオエーテル結合を任意に含有してもよい。Ｂは、−（ＣＨ₂）_p−（Ｏ（ＣＨ₂）_q）_r−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される化学構造を含むことを特徴とする［１］〜［４］のいずれかに記載の帯電防止処理剤。
【００２２】
［９］水溶性導電性高分子が、下記一般式（４）、
【００２３】
【化６】

（式中、Ｒ⁴とＲ⁵は、それぞれ独立にＨ、または炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、−Ｂ−ＳＯ₃ ^-Ｍ 基を示し、Ｒ⁶は、Ｈ、または炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群の一価基を示す。また、上記のＲ⁴とＲ⁵のアルキル基、アルコキシ基またはアルキルエステル基の鎖中には、カルボニル結合、エーテル結合、エステル結合、スルホン酸エステル結合、アミド結合、スルホンアミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合、チオエーテル結合を任意に含有してもよい。Ｂは、−（ＣＨ₂）_p−（Ｏ（ＣＨ₂）_q）_r−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される化学構造を含むことを特徴とする［１］〜［４］のいずれかに記載の帯電防止処理剤。
【００２４】
［１０］水溶性導電性高分子が、化学構造として５−スルホイソチアナフテン−１，３−ジイルを含む重合体であることを特徴とする［１］〜［４］のいずれかに記載の帯電防止処理剤。
【００２５】
［１１］界面活性剤を含むことを特徴とする［１］〜［１０］のいずれかに記載の帯電防止処理剤。
【００２６】
［１２］界面活性剤がフッ素原子を含む界面活性剤であることを特徴とする［１１］に記載の帯電防止処理剤。
【００２７】
［１３］ｐＨが、３．０以上６．０以下であることを特徴とする［１］〜［１１］のいずれかに記載の帯電防止処理剤。
【００２８】
［１４］フッ素化脂肪族アミンの含有量が、水溶性導電性高分子のモノマー単位当たり０．８倍モルから３倍モルであることを特徴とする［１］〜［１３］に記載の帯電防止処理剤。
【００２９】
［１５］水溶性導電性高分子を帯電防止処理剤全体の０．１質量％以上１０質量％以下、フッ素化脂肪族アミンを０．１質量％以上２０質量％以下、水を７０質量％以上９９．８質量％を超えない範囲で含む水溶液であることを特徴とする［１］〜［１４］のいずれかに記載の帯電防止処理剤。
【００３０】
［１６］水溶性導電性高分子およびフッ素化脂肪族アミンを含有することを特徴とする帯電防止膜。
【００３１】
［１７］界面活性剤を含有することを特徴とする［１６］に記載の帯電防止膜。
【００３２】
［１８］界面活性剤がフッ素原子を含む界面活性剤であることを特徴とする［１７］に記載の帯電防止膜。
【００３３】
［１９］［１］〜［１５］のいずれかに記載の帯電防止処理剤を用いて、製造することを特徴とする帯電防止膜。
【００３４】
［２０］化学増幅型レジストの表面を［１６］〜［１９］のいずれかに記載の帯電防止膜で被覆することを特徴とする被覆物品。
【００３５】
［２１］［１６］〜［１９］のいずれかに記載の帯電防止膜を用いることを特徴とするパターン形成方法。
【００３６】
［２２］［１］〜［１５］のいずれかに記載の帯電防止処理剤を使用して製造することを特徴とする半導体素子、フォトマスク、レチクル、ガラス基板、石英基板、ＧＭＲヘッド、磁性体基板。
【００３７】
［２３］［２１］に記載のパターン形成方法を使用して製造することを特徴とする半導体素子、フォトマスク、レチクル、ガラス基板、石英基板、ＧＭＲヘッド、磁性体基板。
【００３８】
【発明の実施の形態】
本発明における帯電防止処理剤とは、水溶性導電性高分子とフッ素化脂肪族アミンを含む水溶液を意味する。帯電防止処理剤を処理した後、放置または乾燥すれば、帯電防止処理剤に含まれている水が揮発等によって減少し、流動性のなくなった半固体あるいは固体となる。この流動性の無くなった状態を帯電防止材と呼び、さらに、帯電防止材が膜状である場合を帯電防止膜と呼ぶ。
【００３９】
水溶性導電性高分子は、一般にブレンステッド酸基を有するπ共役系導電性高分子であることから、ブレンステッド酸基に由来するスルホン酸基、あるいはカルボン酸基等が中和され使用される。化学増幅型レジストに対して悪影響を与えないために施される中和処理において、本発明記載のフッ素化脂肪族アミンで中和を行うことによって緩衝効果が発現し水溶液のｐＨ変動が極端に抑制される。従来のアンモニア、あるいは、有機脂肪族アミンあるいは有機芳香族アミンは塩基性が強いため弱酸性から中性領域でのｐＨ変動が僅かの酸性成分増加によっても大きく影響を受けそのコントロールが困難であった。本発明において含まれるフッ素化脂肪族アミンは、１級塩基化合物でありながら、フッ素で置換されたアルキル基の電子吸引性が該当するアルキル基に比べ強く窒素上の電子密度が低下することから塩基性が低下し緩衝効果を発現する。
【００４０】
また、ブレンステッド酸基の中和に用いる塩基化合物にフッ素原子が含まれることで、帯電防止膜のフッ素含有率が高まり当該固体被膜の表面エネルギ−が小さくなる。一方、化学増幅型レジストは、例えばＣＨ、ＣＨＯ、ＣＨＮＯ、ＣＨＣｌＯ、ＣＨＯＳおよびＣＨＯＮＳ等の表面エネルギ−の大きい元素で構成されているため、当該レジストはその表面エネルギーが大きい。従って、表面エネルギーの小さな帯電防止膜と化学増幅型レジストとの固体同士の親和性あるいは浸透性が低くなり、界面におけるミキシング層の形成を防止することができる。
【００４１】
本発明におけるフッ素化有機脂肪族アミンは、自己ドープ型導電性高分子を脱ドープさせるものでなければ特に限定されない。好ましくは、式（１）
Ｘ−（ＣＦ₂）_mＣＹ₂ＮＨ₂ （１）
（但し、Ｘは、フッ素または水酸基を示し、Ｙは、水素またはフッ素を示し、ｍは１〜１０の整数を示す。）
で表される化合物から選択される少なくとも一つの化合物である。
【００４２】
また、フッ素化脂肪族アミンは、単独で１ｍｏｌ／Ｌの水溶液としたときのｐＨが９．０〜１１．０であるものが好ましい。
【００４３】
フッ素化脂肪族アミンの具体例としては、２，２，２−トリフルオロエチルアミン、２，２，３，３，３−ペンタフルオロプロピルアミン、２，２，３，３，４，４，４−へプタフルオロブチルアミン、２，２，３，３，４，４，５，５，５−ノナフルオロペンチルアミン、２，２，３，３，４，４，５，５，６，６，６−ウンデカフルオロヘキシルアミン、トリフルオロメチルアミン、パーフルオロエチルアミン、パーフルオロプロピルアミン、パーフルオロブチルアミン、パーフルオロペンチルアミン、パーフルオロヘキシルアミン、パーフルオロヘプチルアミン、パーフルオロオクチルアミン、パーフルオロデシルアミン、ジフルオロエタノールアミン等が挙げられる。特に好ましくは、トリフルオロエチルアミン、ペンタフルオロプロピルアミンであり、更に好ましくはトリフルオロエチルアミンである。これらのフッ素化脂肪族アミンは、１種類または２種類以上を混合して用いてもよい。
【００４４】
本発明の帯電防止処理剤に含まれるフッ素化脂肪族アミンは、水溶性導電性高分子の酸性水溶液を中和処理するに際し、当該水溶液のｐＨ値が３から６となる添加量が好ましい。より具体的には、水溶性導電性高分子が含むブレンステッド酸基の総モル数に対して、０．８倍モルから３倍モルのフッ素化脂肪族アミンを含むことが好ましく、０．８倍モルから２倍モルを含むことが特に好ましい。帯電防止処理剤に対する含有量でいうと含まれるフッ素化脂肪族アミンの濃度は、水溶性導電性高分子の種類や濃度によって異なるために一概に規定できないが、０．１質量％から２０質量％である。
【００４５】
本発明で使用される水溶性導電性高分子は、ブレンステッド酸基を有するπ共役系導電性高分子で水溶性であれば、基本的に制限はない。該導電性高分子のブレンステッド酸基は、π電子共役主鎖に直接置換、スペイサーを介して置換、例えばアルキレン側鎖あるいはオキシアルキレン側鎖を介して置換した自己ド−プ型導電性高分子であれば良く、必ずしも化学構造の一次構造には制限されない。具体的なポリマ−としては、ポリ（イソチアナフテンスルホン酸）、ポリ（チオフェンアルカンスルホン酸）、ポリ（チオフェンオキシアルカンスルホン酸）、ポリ（ピロールアルキルスルホン酸）、ポリ（アニリンスルホン酸）等の繰り返し単位を含む共重合体またはこれらの各種塩構造体および置換誘導体等を挙げることができる。
【００４６】
また、前記共重合体におけるスルホン酸基を含む化学構造の繰り返し単位は、通常、重合体の全繰り返し単位の１００モル％〜５０モル％、好ましくは１００モル％〜８０モル％の範囲であり、他のπ共役系化学構造からなる繰り返し単位を含む共重合体であってもよく、２種〜５種の繰り返し単位からなる共重合体組成であってもよい。
【００４７】
なお、本発明において、「繰り返し単位を含む共重合体」とは、必ずしもその単位を連続して含む共重合体に限定されず、π共役系主鎖に基づく所望の導電性が発現される限りにおいてランダムコポリマーのようにπ共役系主鎖に不規則、不連続に繰り返し単位を含む重合体の意味である。
【００４８】
本発明のブレンステッド酸基を有する構造で特に有用構造を例示すると、式（２）、（３）、（４）で表される構造があげられる。導電性高分子としては、前記の様にこれらの単独の重合体でもよいし、共重合体でもよい。
【００４９】
式（２）は、
【００５０】
【化７】

（式中、ｍ、ｎは独立に０または１の整数を示す。Ａは、−Ｂ−ＳＯ₃ ^-Ｍで表される置換基を少なくとも一つ有する、炭素数１〜４のアルキレン、アルケニレン基（二重結合は二つ以上有していてもよい。）を示し、該アルキル、アルケニレン基には炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基を置換基として有していてもよい。Ｂは、−（ＣＨ₂）_p−（Ｏ（ＣＨ₂）_q）_r−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される。
【００５１】
式（３）は、
【００５２】
【化８】

（式中、Ｒ¹〜Ｒ³ は、それぞれ独立に水素原子、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、−Ｂ−ＳＯ₃ ^-Ｍ基を示す。上記のＲ¹、Ｒ²およびＲ³のアルキル基、アルコキシ基またはアルキルエステル基の鎖中には、カルボニル結合、エーテル結合、エステル結合、スルホン酸エステル結合、アミド結合、スルホンアミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合、チオエーテル結合を任意に含有してもよい。Ｂは、−（ＣＨ₂）_p−（Ｏ（ＣＨ₂）_q）_r−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される。
【００５３】
式（４）は、
【００５４】
【化９】

（式中、Ｒ⁴とＲ⁵は、それぞれ独立にＨ、または炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、炭素数１乃至２０の直鎖状もしくは分岐状のアルキルエステル基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、−Ｂ−ＳＯ₃ ^-Ｍ 基を示し、Ｒ⁶は、Ｈ、または炭素数１乃至２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群の一価基を示す。また、上記のＲ⁴とＲ⁵のアルキル基、アルコキシ基またはアルキルエステル基の鎖中には、カルボニル結合、エーテル結合、エステル結合、スルホン酸エステル結合、アミド結合、スルホンアミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合、チオエーテル結合を任意に含有してもよい。Ｂは、−（ＣＨ２）ｐ−（Ｏ（ＣＨ２）ｑ）ｒ−を示し、ｐは０〜５の整数を示し、ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。Ｍ は、Ｈ⁺ 、アルカリ金属イオン、または第４級アンモニウムイオンを示す。）で表される。
【００５５】
ここで、Ｒ¹〜Ｒ⁶として特に有用な例としては、水素原子、アルキル基、アルコキシ基、アルキルエステル基、フェニルおよび置換フェニル基、スルホン酸基が挙げられる。これらの置換基を更に詳しく例示すれば、アルキル基としてはメチル、エチル、プロピル、アリル、イソプロピル、ブチル、１ーブテニル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、エトキシエチル、メトキシエチル、メトキシエトキシエチル、アセトニル、フェナシル等、アルコキシ基としてはメトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、オクチルオキシ、ドデシルオキシ、メトキシエトキシ、メトキシエトキシエトキシ等、アルキルエステル基としては、メトキシカルボニル、エトキシカルボニル、ブトキシカルボニル等のアルコキシカルボニル基、アセトキシ、ブチロイルオキシ等のアシルオキシ基、置換フェニル基としてはフロロフェニル基、クロロフェニル基、ブロモフェニル基、メチルフェニル基、メトキシフェニル基等が挙げられる。上記のＲ¹〜Ｒ⁵のアルキル基、アルコキシ基の鎖中には、カルボニル結合、エーテル結合、エステル結合、スルホン酸エステル結合、アミド結合、スルホンアミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合、チオエーテル結合を任意に含有してもよい。
【００５６】
一般式（３）および一般式（４）のＲ¹〜Ｒ⁵において、前記の置換基の中で、水素原子、炭素数１乃至２０の直鎖状もしくは分岐状のアルキル基、アルコキシ基またはアルキルエステル基が望ましく、また、水素原子、炭素数１乃至２０の直鎖状もしくは分岐状のアルコキシ基が特に望ましい。
【００５７】
一般式（４）のＲ⁶は、水素原子、炭素数１乃至２０の直鎖状もしくは分岐状の飽和もしくは不飽和炭化水素基、フェニル基及び置換フェニル基からなる群の一価基が望ましい。
【００５８】
式中のＢの例としてはブチレン、ペンチレン、ヘキシレン、メチレンジオキシ、エチレンジオキシなどが挙げられる。
【００５９】
式中Ｍは、Ｈ⁺、アルカリ金属イオン、第４級アンモニウムイオンを表すが、これらカチオンを一種類以上含む混合物であっても良い。
【００６０】
アルカリ金属イオンとしては、例えばＮａ⁺、Ｌｉ⁺、Ｋ⁺があげられる。
【００６１】
第４級アンモニウムイオンは、Ｎ（Ｒ⁷）（Ｒ⁸）（Ｒ⁹）（Ｒ¹⁰）⁺で表されるが、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に水素原子、炭素数１乃至３０の直鎖状もしくは分岐状の置換もしくは非置換アルキル基、または置換もしくは非置換アリール基を表わし、アルコキシ基、ヒドロキシル基、オキシアルキレン基、チオアルキレン基、アゾ基、アゾベンゼン基、ｐ−ジフェニレンオキシ基のごとき炭素、水素以外の元素を含む基を含むアルキルまたはアリール基であってもよい。
【００６２】
かかるＮ（Ｒ⁷）（Ｒ⁸）（Ｒ⁹）（Ｒ¹⁰）⁺で表わされる第４級アンモニウムのカチオンとしては、例えばＮＨ₄ ⁺、ＮＨ（ＣＨ₃）₃ ⁺、ＮＨ（Ｃ₆Ｈ₅）₃ ⁺、Ｎ（ＣＨ₃）₂（ＣＨ₂ＯＨ）（ＣＨ₂−Ｚ）⁺等の非置換またはアルキル置換もしくはアリール置換型カチオンが用いられる（但し、Ｚは化学式量が６００以下の任意の置換基を表し、例えば、フェノキシ基、ｐ−ジフェニレンオキシ基、ｐ−アルコキシジフェニレンオキシ基、ｐ−アルコキシフェニルアゾフェノキシ基等の置換基である。）。なお、特定カチオンに変換するために、通常のイオン交換樹脂を用いてもよい。
【００６３】
Ｒ⁷〜Ｒ¹⁰のアルキル基の鎖中には、カルボニル結合、エーテル結合、エステル結合、アミド結合、スルフィド結合、スルフィニル結合、スルホニル結合、イミノ結合等を任意に含んでもよい。
【００６４】
本発明の水溶性導電性高分子を構成するブレンステッド酸を含む構成単位として、使用可能な例をより具体的に例示すれば、式（２）、（３）、（４）に該当しない例として、ポリ（ポリピロールアルカンスルホン酸）、ポリ（ピロールオキシアルカンスルホン酸）、ポリ（カルバゾール−Ｎ−アルカンスルホン酸）、ポリ(フェニレン−オキシアルカンスルホン酸)、ポリ(フェニレンビニレン−アルカンスルホン酸)、ポリ(フェニレンビニレン−オキシアルカンスルホン酸)、ポリ（アニリン−Ｎ−アルカンスルホン酸）、ポリ（チオフェンアルキルカルボン酸）、ポリ（チオフェンオキシアルキルカルボン酸）、ポリ（ポリピロールアルキルカルボン酸）、ポリ（ピロールオキシアルキルカルボン酸）、ポリ（カルバゾール−Ｎ−アルキルカルボン酸）、ポリ(フェニレン−オキシアルキルカルボン酸)、ポリ(フェニレンビニレン−アルキルカルボン酸)、ポリ(フェニレンビニレン−オキシアルキルカルボン酸)、ポリ（アニリン−Ｎ−アルキルカルボン酸）、６−スルホナフト［２，３−ｃ］チオフェン−１，３−ジイル等、もしくはそれらのリチウム塩、ナトリウム塩、アンモニウム塩、メチルアンモニウム塩、エチルアンモニウム塩、ジメチルアンモニウム塩、ジエチルアンモニウム塩、トリメチルアンモニウム塩、トリエチルアンモニウム塩、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩等を挙げることができる。
【００６５】
本発明の式（２）または（３）で表される化学構造の好ましい具体例としては、５−（３´−プロパンスルホ）−４，７−ジオキシシクロヘキサ［２，３−ｃ］チオフェン−１，３−ジイル、５−（２´−エタンスルホ）−４，７−ジオキシシクロヘキサ［２，３−ｃ］チオフェン−１，３−ジイル、５−スルホイソチアナフテン−１，３−ジイル、４−スルホイソチアナフテン−１，３−ジイル、４−メチル−５−スルホイソチアナフテン−１，３−ジイル、６−メチル−５−スルホイソチアナフテン−１，３−ジイル、６−メチル−４−スルホイソチアナフテン−１，３−ジイル、５−メチル−４−スルホイソチアナフテン−１，３−ジイル、６−エチル−５−スルホイソチアナフテン−１，３−ジイル、６−プロピル−５−スルホイソチアナフテン−１，３−ジイル、６−ブチル−５−スルホイソチアナフテン−１，３−ジイル、６−ヘキシル−５−スルホイソチアナフテン−１，３−ジイル、６−デシル−５−スルホイソチアナフテン−１，３−ジイル、６−メトキシ−５−スルホイソチアナフテン−１，３−ジイル、６−エトキシ−５−スルホイソチアナフテン−１，３−ジイル、６−クロロ−５−スルホイソチアナフテン−１，３−ジイル、６−ブロモ−５−スルホイソチアナフテン−１，３−ジイル、６−トリフルオロメチル−５−スルホイソチアナフテン−１，３−ジイル等、もしくはそれらのリチウム塩、ナトリウム塩、アンモニウム塩、メチルアンモニウム塩、エチルアンモニウム塩、ジメチルアンモニウム塩、ジエチルアンモニウム塩、トリメチルアンモニウム塩、トリエチルアンモニウム塩、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩等を挙げることができる。
【００６６】
一般式（４）で表される化学構造の好ましい具体例としては、２−スルホ−１，４−イミノフェニレン、３−メチル−２−スルホ−１，４−イミノフェニレン、５−メチル−２−スルホ−１，４−イミノフェニレン、６−メチル−２−スルホ−１，４−イミノフェニレン、５−エチル−２−スルホ−１，４−イミノフェニレン、５−ヘキシル−２−スルホ−１，４−イミノフェニレン、３−メトキシ−２−スルホ−１，４−イミノフェニレン、５−メトキシ−２−スルホ−１，４−イミノフェニレン、６−メトキシ−２−スルホ−１，４−イミノフェニレン、５−エトキシ−２−スルホ−１，４−イミノフェニレン、２−スルホ−Ｎ−メチル−１，４−イミノフェニレン、２−スルホ−Ｎ−エチル−１，４−イミノフェニレン等、もしくはそのリチウム塩、ナトリウム塩、アンモニウム塩、メチルアンモニウム塩、エチルアンモニウム塩、ジメチルアンモニウム塩、ジエチルアンモニウム塩、トリメチルアンモニウム塩、トリエチルアンモニウム塩、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩等を挙げることができる。
【００６７】
本発明に用いられる自己ドープ型導電性高分子の分子量は、構成する繰り返し単位の化学構造によって異なるため一概に規定することはできないが、本発明の目的に適うものであればよく特に限定されない。通常、主鎖を構成する繰り返し単位数（重合度）によって表せば、通常、５〜２０００、好ましくは１０〜１０００の範囲の重合度のものが挙げられる。
【００６８】
本発明に用いられるブレンステッド酸基を有するπ共役系導電性高分子の特に好ましい具体例としては、５−スルホイソチアナフテン−１，３−ジイルの重合体、５−スルホイソチアナフテン−１，３−ジイルを８０モル％以上含有するランダムコポリマー、ポリ（５−スルホイソチアナフテン−１，３−ジイル−ｃｏ−イソチアナフテン−１，３−ジイル）、２−スルホ−１，４−イミノフェニレンを５０モル％以上含有するランダムコポリマー、ポリ（２−スルホ−１，４−イミノフェニレン−ｃｏ−１，４−イミノフェニレン）等とそれらのリチウム塩、ナトリウム塩、アンモニウム塩、トリエチルアンモニウム塩等を挙げることができる。
【００６９】
本発明の水溶性導電性高分子の濃度は、所望する膜の帯電防止性能によって異なるが、通常は、０．００１〜３０質量％、好ましくは０．０１〜１０質量％である。
【００７０】
本発明の帯電防止処理剤には水と混和し自己ドープ型導電性高分子を脱ドープさせない溶解する溶媒を使用してもよい。例えばより具体的には、１，４−ジオキサンやテトラヒドロフラン等のエーテル類、ジメチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等のカーボネート類、アセトニトリルやベンゾニトリル等のニトリル類、メタノール、エタノール、プロパノール、イソプロパノールなどのアルコール類、Ｎ、Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドンなどの非プロトン性極性溶媒、硫酸等の鉱酸、酢酸などの有機酸等が挙げられ、更にそれらの２種以上の混合溶媒を用いることもできる。
【００７１】
本発明の帯電防止処理剤は、非化学増幅型レジストおよび化学増幅型レジストいずれに対しても使用することができる。
【００７２】
非化学増幅型レジストに対しては、品質変化の少ない、あるいは、ｐＨ値変動の少ない帯電防止処理剤として有効である。具体的には、ノボラック樹脂等のフェノール系樹脂（構成原素：ＣＨＯ）、ポリメチルメタクリレート樹脂、ポリアクリレート樹脂等のアクリル系樹脂（構成元素：ＣＨＯ）、α-メチルスチレンとα−クロロアクリル酸との共重合体系（ＣＨＯＣｌ）等が挙げることができるがこれらに限定されるものではない。
【００７３】
化学増幅型レジストに対しては、ｐＨ値の変動が少ないことからレジストに与える影響を制御できるだけでなく、帯電防止膜中にフッ素化脂肪族アミン由来のフッ素含有率が増加することによって帯電防止膜と化学増幅型レジストとの接触面のミキシング層の形成が防止されることから、化学増幅型レジストの品質変化が防止され、当該化学増幅型レジストの性能を損なうことなく使用することが可能である。
【００７４】
化学増幅型レジストを構成する元素が、ＣＨ、ＣＨＯ、ＣＨＮＯ、ＣＨＣｌＯ、ＣＨＯＳおよびＣＨＮＯＳである場合、帯電防止膜と化学増幅型レジストとの接触面のミキシング層の形成防止がより効果的に認められる。具体的には、フェノール樹脂系（構成原素：ＣＨＯ）、アクリル樹脂系（構成元素：ＣＨＯ）、アジド化合物系（ＣＨＯＮ）等の感光性樹脂、ポリメタクリレート樹脂系（ＣＨＯ）、ポリビニルフェノール系やポリヒドロキシスチレン系（ＣＨＯ）、α-メチルスチレンとα−クロロアクリル酸との共重合体系（ＣＨＯＣｌ）等の感荷電粒子線樹脂を挙げることができるがこれらに限定されるものではない。また、前記感光性樹脂もしくは感荷電粒子線樹脂中に添加剤が加えられていても良い。具体的な添加剤としては、感光剤、アジド化合物、架橋剤、溶解阻害剤、酸発生剤等が挙げられるが、これらに限定されるものではない。レジストを構成する元素としてＣ、Ｈ、Ｏ、Ｃｌ、Ｎに限定されていたとしても、添加剤を構成する元素よりＳ原子が加わりレジスト全体の構成元素としてＳ元素を含んでも良い。
【００７５】
本発明の帯電防止処理剤は、フッ素原子を含む界面活性剤を含んでもよい。本発明の帯電防止処理剤にフッ素原子を含む界面活性剤を含む場合は、帯電防止膜中に含まれるフッ素含有率がフッ素化脂肪族アミンのみを含む場合に比べて増加するため、帯電防止膜と化学増幅型レジストとの接触面のミキシング層の形成がより効果的に防止される。フッ素原子を含む界面活性剤を用いる場合には、該自己ドープ型導電性高分子化合物に対して重量比で０．００１〜９５倍量、望ましくは０．００５〜２０倍量、更に望ましくは０．０１〜５倍量用いる。界面活性剤の量が０．００１倍量未満であると、界面活性剤添加の効果がなくなる場合がある。９５倍量より多いと良好な電子伝導性が確保できない場合がある。
【００７６】
フッ素原子を含む界面活性剤として具体的には、フルオロアルキルスルホン酸、フルオロアルキルカルボン酸、パーフルオロアルキルスルホン酸、パーフルオロカルボン酸、およびその塩類、パーフルオロアルキルスルホンアミド、パーフルオロアルキルスルホンアミドアルキルアンモニウム塩、パーフルオロアルキルベタイン、パーフルオロアルキルアミンオキシド、パーフルオロアルキルエチレンオキシド付加物等を挙げることができる。特に好ましくは、パーフルオロアルキルスルホン酸、パーフルオロカルボン酸、およびその塩類が挙げられる。
【００７７】
本発明の帯電防止処理剤は、フッ素原子を含まない界面活性剤を含むこともできる。フッ素原子を含まない界面活性剤としては、例えば、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤、シリコーン系界面活性剤等をあげることができる。フッ素を含まない界面活性剤を用いる場合には、該自己ドープ型導電性高分子化合物に対して重量比で０．００１〜９５倍量、望ましくは０．００５〜２０倍量、更に望ましくは０．０１〜５倍量用いる。界面活性剤の量が０．００１倍量未満であると、界面活性剤添加の効果がなくなる場合がある。９５倍量より多いと良好な電子伝導性が確保できない場合がある。
【００７８】
界面活性剤は、１種類または２種類以上を含んでいてもよい。
【００７９】
本発明の帯電防止処理剤は、当該溶液中のフッ素化脂肪族アミンの含有量を変化させることにより、酸性〜アルカリ性の間の任意のｐＨの値をとることが可能である。
【００８０】
前記、帯電防止処理剤をレジスト表面に形成する具体的な方法としては、回転塗布が主として使用されているが、その他ディッピング（浸漬する）、あるいは物品に吹きつける、バーコーターによる塗布等の使用目的に応じて様々な方法が挙げられる。
【００８１】
本発明の帯電防止膜が被覆された物品としては、帯電防止膜とレジストが積層された状態の基板であって、基板の材質としてはシリコンウエハー、ガリウム砒素ウエハー、インジウムリンウエハー等の化合物半導体ウエハー、石英基板、磁性体基板等が挙げられるが、これらに限定されるものではない。なお、積層基板は、半導体製造過程、およびフォトマスク、レチクル、ステンシルマスク等の製造過程における一過的な状態の基板も含まれる。
【００８２】
本発明におけるパターン形成方法は、帯電防止膜を化学増幅型レジスト表面に被覆することによって化学増幅型レジストの品質変化、例えば、カブリ、膜減り、Ｔトップや肩落ち等のレジストの形状変化を起こすことがないために、パターンを精度良く形成することができるとともに、帯電防止膜によるチャージアップ防止効果により荷電粒子線を用いた描画工程で位置ズレ防止することができより精度良くパターンを形成することができる。
【００８３】
【実施例】
以下、本発明を実施例および比較例を用いて説明するが、本発明は以下の実施例に制限されるものではない。
【００８４】
水溶液のｐＨは、ガラス電極式水素イオン濃度計ｐＨ ＭＥＴＥＲ Ｆ−１３（（株）堀場製作所製）にて測定した。また、帯電防止処理剤の塗布膜は、スピンナー １Ｈ−ＩＩＩ（協栄セミコンダクター（株）製）を用いて、ガラス基板上に帯電防止処理剤の５ｍｌを滴下した後、１５００ｒｐｍで回転塗布し作製した。塗布膜の表面抵抗値は、表面抵抗測定器メガレスタＭＯＤＥＬ ＨＴ−３０１（シシド静電気（株）製）にて測定した値である。
【００８５】
ミキシング層の形成防止効果は、以下の方法で評価した。
シリコンウエハー上にネガ型の化学増幅系電子線レジストを回転塗布し、プリベーク（各種レジストにより指定された条件で実施した。）により溶剤を除去した。塗布されたレジスト表面に帯電防止処理剤の５ｍｌを滴下した後、１５００ｒｐｍで回転塗布して膜厚０．０２μmの導電性被膜を作成した。導電性被膜をレジストの表面上に回転塗布後３０分間風乾してから、導電性被膜を３０ｍｌの超純水で洗浄除去した。引き続き、加熱処理（各種レジストにより指定された条件で実施した。）を実施してから、２．３８質量％ＴＭＡＨ水溶液によりレジストを溶解除去した。
【００８６】
６インチシリコンウエハー上に塗布されたレジストを２．３８質量％ＴＭＡＨ水溶液でパドル現像する際に、レジストの溶解に伴ってシリコンウエハーのミラー面が一部認められた時点を溶解開始時間とし全面が完全に溶解完了した時点を溶解終了とし、レジストの溶解時間を測定した。
【００８７】
ネガ型のレジストと帯電防止膜との界面でミキシング層の形成が著しく発生したときは、レジストはカブリ現象を起こし２．３８％ＴＭＡＨ水溶液で溶解しなくなる。ミキシング層の形成が抑制されるに従い溶解時間は帯電防止処理剤を塗布していないときのレジストの溶解時間に近づく。
【００８８】
最も好ましくは、帯電防止処理剤を塗布して測定した場合の溶解時間と帯電防止処理剤を塗布していないときのレジストの溶解時間が一致することである。
【００８９】
本実施例で用いた導電性高分子化合物のうち、ポリ（５−スルホイソチアナフテン−1,３−イル）は、特開平７−４８４３６号公報で開示されている方法を参考にして合成した。また、ポリ(２−スルホ−１,４−イミノフェニレン−co−１,４−イミノフェニレン）（５０モル％：５０モル％）は、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ誌、２９巻、３９５０−３９５５頁（１９９６年）記載の方法を参考にして合成した。
【００９０】
［実施例１］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液１００ｍｌに１Ｎ−トリフルオロエチルアミン水溶液２．５ｇを加えて水素イオン濃度（以下ｐＨ値と略す）を４．１に調製し本発明の帯電防止処理剤を得た。本帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値を調べたところ、一ヶ月後ではｐＨ＝４．１、２ヶ月後ではｐＨ＝４．１、３ヵ月後では、ｐＨ＝４．１であった。
【００９１】
［実施例２］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇを添加し２時間攪拌した後、１Ｎ−トリフルオロエチルアミン水溶液２．６ｇを加えてｐＨ値を３．８に調製し本発明の帯電防止処理剤を得た。本発明の帯電防止処理剤５ｍｌをガラス基板に回転塗布した後、乾燥することによってガラス表面に帯電防止膜を作成しＲｓを測定したところ６．０×１０⁵Ω／□であった。上記、帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝３．８、Ｒｓ＝１．８×１０⁶Ω／□、２ヶ月後ではｐＨ＝３．８、Ｒｓ＝３．８×１０⁶Ω／□、３ヵ月後では、ｐＨ＝３．８、Ｒｓ＝４．５×１０⁶Ω／□であった。
【００９２】
［実施例３］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、パーフルオロカプリル酸０．３ｇを添加し２時間攪拌した後、１Ｎ−トリフルオロエチルアミン水溶液を２．９ｇ加えてｐＨ値を３．８に調製し本発明の帯電防止処理剤を得た。本発明の帯電防止処理剤５ｍｌをガラス基板に回転塗布した後、乾燥することによってガラス表面に帯電防止膜を作成しＲｓを測定したところ６．５×１０⁵Ω／□であった。上記、帯電防止剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝３．８、Ｒｓ＝２．１×１０⁶Ω／□、２ヶ月後ではｐＨ＝３．８、Ｒｓ＝４．２×１０⁶Ω／□、３ヵ月後では、ｐＨ＝３．８、Ｒｓ＝４．６×１０⁶Ω／□であった。
【００９３】
［実施例４］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、パーフルオロカプリル酸０．３ｇを添加し２時間攪拌した後、１Ｎ−トリフルオロエチルアミン水溶液を３．５ｇ加えてｐＨ値を５．０に調製し本発明の帯電防止処理剤を得た。本発明の帯電防止処理剤５ｍｌをガラス基板に回転塗布した後、乾燥することによってガラス表面に帯電防止膜を作成しＲｓを測定したところ４．３×１０⁵Ω／□であった。上記、帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝５．０、Ｒｓ＝３．５×１０⁶Ω／□、２ヶ月後ではｐＨ＝５．０、Ｒｓ＝７．８×１０⁶Ω／□、３ヵ月後では、ｐＨ＝４．９、Ｒｓ＝５．１×１０⁷Ω／□であった。
【００９４】
［実施例５］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇ、パーフルオロカプリル酸０．１ｇを添加し２時間攪拌した後、１Ｎ−トリフルオロエチルアミン水溶液を適量加えてｐＨ値を３．８に調製し本発明の帯電防止処理剤を得た。本発明の帯電防止処理剤５ｍｌをガラス基板に回転塗布した後、乾燥することによってガラス表面に帯電防止膜を作成しＲｓを測定したところ７．０×１０⁵Ω／□であった。上記、帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝３．８、Ｒｓ＝２．２×１０⁶Ω／□、２ヶ月後ではｐＨ＝３．８、Ｒｓ＝３．９×１０⁶Ω／□、３ヵ月後では、ｐＨ＝３．８、Ｒｓ＝４．２×１０⁶Ω／□であった。
【００９５】
［実施例６］
ポリ(２−スルホ−１,４−イミノフェニレン−co−１,４−イミノフェニレン）（５０モル％：５０モル％）の０.９質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇ、パーフルオロカプリル酸０．１ｇを添加し２時間攪拌した後、１Ｎ−トリフルオロエチルアミン水溶液を適量加えてｐＨ値を３．８に調製し本発明の帯電防止処理剤を得た。本発明の帯電防止処理剤５ｍｌをガラス基板に回転塗布した後、乾燥することによってガラス表面に帯電防止膜を作成しＲｓを測定したところ１．５×１０⁶Ω／□であった。上記、帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝４．０、Ｒｓ＝５．１×１０⁶Ω／□、２ヶ月後ではｐＨ＝４．０、Ｒｓ＝１．２×１０⁷Ω／□、３ヵ月後では、ｐＨ＝４．０、Ｒｓ＝２．０×１０⁷Ω／□であった。
【００９６】
［実施例７］
ノボラック、感光剤およびブロモメチル基を有する酸発生剤から成るネガ型の化学増幅系電子線レジスト（シプレイ社製商品名ＳＡＬ６０１）を回転塗布し、プリベークにより溶剤を除去した。塗布されたレジスト表面に実施例２記載の本発明の帯電防止処理剤を５ｍｌ滴下した後、１５００ｒｐｍで回転塗布して膜厚０．０２μmの帯電防止膜を作成した。導電性被膜をレジストの表面上に回転塗布後３０分間風乾してから、導電性被膜を３０ｍｌの超純水で洗浄除去した。引き続き、加熱処理を実施してから、２．３８質量％ＴＭＡＨ溶液によりレジストを溶解したところ溶解開始６２秒、溶解終了６７秒であった。なお、帯電防止処理剤を使用しない場合は、溶解開始が６０秒、溶解終了６５秒であった。
【００９７】
［実施例８］
ネガ型の化学増幅系電子線レジスト（住友化学工業（株）社製商品名ＮＥＢ２２）を回転塗布し、プリベークにより溶剤を除去した。塗布されたレジスト表面に実施例３記載の本発明の帯電防止処理剤を５ｍｌ滴下した後、１５００ｒｐｍで回転塗布して膜厚０．０２μmの導電性被膜を作成した。導電性被膜をレジストの表面上に回転塗布後３０分間風乾してから、導電性被膜を３０ｍｌの超純水で洗浄除去した。引き続き、加熱処理を実施してから、２．３８質量％ＴＭＡＨ溶液によりレジストを溶解したところ溶解開始１３秒、溶解終了１５秒であった。なお、帯電防止処理剤を使用しない場合は、溶解開始が１３秒、溶解終了１４秒であった。
【００９８】
［比較例１］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇ、パーフルオロカプリル酸０．１ｇを添加し２時間攪拌した後、１Ｎ−アンモニア水３ｍｌを添加してｐＨを５.２に調製して得られた帯電防止処理剤を用いた以外は実施例１と同様にしてガラス表面に帯電防止剤の薄膜を作成しＲｓを測定したところ５．１×１０⁵Ω／□であった。上記、帯電防止処理剤を冷蔵下（５±３℃）に放置し、経時的にサンプリングしてそのｐＨ値、および上記と同様にガラス塗膜を調べたところ、一ヶ月後ではｐＨ＝４．１、Ｒｓ＝１．１×１０⁶Ω／□、２ヶ月後ではｐＨ＝３．９、Ｒｓ＝１．８×１０⁶Ω／□、３ヵ月後では、ｐＨ＝３．７、Ｒｓ＝２．１×１０⁶Ω／□であった。
【００９９】
［比較例２］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇに１Ｎ−アンモニア水３ｍｌを添加してｐＨを５.０に調製して得られた帯電防止処理剤を用いた以外は実施例７と同様にしてレジストの溶解時間を測定したところ、溶解開始１２０秒、溶解終了１３０秒であった。
【０１００】
［比較例３］
ポリ(５−スルホイソチアナフテン−１,３−ジイル）の０.６質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇに１Ｎ−アンモニア水３ｍｌを添加してｐＨを５.０に調製した帯電防止処理剤を用いた以外は実施例８と同様にしてレジストの溶解時間を測定したところ、レジストは全く溶解しなかった。
【０１０１】
［比較例４］
ポリ(２−スルホ−１,４−イミノフェニレン−co−１,４−イミノフェニレン）（５０モル％：５０モル％）の０.９質量％水溶液９５ｍｌ、ドデシルベンゼンスルホン酸０．１ｇに１Ｎ−アンモニア水３ｍｌを添加してｐＨを５.０に調製して得られた帯電防止処理剤を用いた以外は実施例７と同様にしてレジストの溶解時間を測定したところ、溶解開始７０秒、溶解終了７５秒であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antistatic treatment agent for coating the surface of a chemically amplified resist. In particular, regarding an antistatic treatment agent containing a water-soluble conductive polymer, a fluorinated aliphatic amine, and water, the antistatic treatment agent is excellent in the stability of the hydrogen ion concentration.
[0002]
The present invention also relates to the production of an antistatic film using the antistatic treatment agent. When an antistatic film is produced using the antistatic film, it is difficult to form a mixing layer at the interface between the chemically amplified resist and the antistatic film.
[0003]
[Prior art]
Chemically amplified resist has become an indispensable material as a common lithography technology using charged particle beams such as light, electron beam, or ion beam, but it uses charged particle beams such as electron beam or ion beam. In the chemically amplified resist pattern forming method, it is known that the substrate is charged particularly when the substrate is insulative, and the charged particle beam trajectory is bent by the electric field generated by the substrate charge. In order to prevent the above phenomenon, it is disclosed that a technique of coating a resist surface or a substrate surface with a conductive polymer is effective (see, for example, Patent Document 1).
[0004]
In general, a chemically amplified resist is a compound that is soluble in an organic solvent, and therefore, applying an organic solvent undesirably dissolves the resist. Therefore, it is preferable to coat the resist surface with the conductive polymer in an aqueous solution. Further, if the conductive polymer as the coating material is water-soluble, it can be easily removed by washing with water when it is no longer needed, and an aqueous solution of tetramethylammonium hydroxide (hereinafter abbreviated as TMAH) used in the development process. Development and removal of the coating material can be realized simultaneously.
[0005]
When the surface of the chemically amplified resist is coated with a water-soluble coating material, adverse effects such as dissolving the resist surface do not occur. However, depending on the region of the hydrogen ion concentration (hereinafter abbreviated as pH), the acid generated by exposure is neutralized by the coating material, or it is exposed by the acid supplied from the coating material even though it is not exposed. The hydrogen ion concentration of the aqueous coating material solution is important because the sensitivity of the resist is greatly affected by a slight acid concentration in the coating material, such as the phenomenon of the same state being observed.
[0006]
Water-soluble conductive polymers that are coating materials having antistatic ability include polythiophene derivatives (AOPatil et al., Journal of American Chemical Society, 109, 1858, 1987), sulfonic acid groups directly on the aromatic ring. Substituted polyaniline derivatives (Journal of American Chemical Society, 112, 2800, 1990), isothianaphthene polymers substituted with sulfonic acid groups (JP-A-6-49183 and JP-A-7-48436), etc. It has been known. Among these, aqueous solutions of substituted poly (2,5-thienylene) and substituted poly (sulfo-1,4-iminophenylene) having a cyclic structure at the 2-position and 3-position of thiophene are used in weakly acidic to neutral regions. In order to maintain conductivity, it is considered useful as an antistatic coating material for chemically amplified resists. However, it has been recognized that the pH of such an aqueous conductive polymer solution gradually decreases during storage.
[0007]
As a method for suppressing the pH change of an aqueous solution of a water-soluble conductive polymer, Patent Document 2 discloses a method for removing dissolved oxygen in a solution. However, the deoxygenation treatment requires special measures in terms of the production process and storage in a container. Moreover, although the method of suppressing pH fall using the buffer solution containing a weak acid and an amine is disclosed (for example, refer patent document 3), the weak acid component which does not have electroconductivity is newly added as an additive. Therefore, it is known that the conductivity of the coating film is lowered.
[0008]
[Patent Document 1]
JP-A-4-32848
[Patent Document 2]
JP-A-8-259673
[Patent Document 3]
JP 11-189746 A
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide an antistatic treatment agent excellent in pH stability containing a water-soluble conductive polymer. Another object is to provide a method for using the antistatic treatment agent and a coated article.
[0010]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that an antistatic treatment agent containing a water-soluble conductive polymer, a fluorinated aliphatic amine, and water is excellent in the stability of the hydrogen ion concentration of the aqueous solution. Invented.
[0011]
For example, the present invention includes the following items.
[0012]
[1] An antistatic treatment agent comprising a water-soluble conductive polymer, a fluorinated aliphatic amine, and water.
[0013]
[2] The fluorinated aliphatic amine is represented by the following formula (1)
X- (CF₂)_mCY₂NH₂      (1)
(However, X shows a fluorine atom or a hydroxyl group, Y shows a hydrogen atom or a fluorine atom, and m shows the integer of 1-10.)
The antistatic treatment agent according to [1], wherein the antistatic treatment agent is at least one of at least one of the following.
[0014]
[3] The fluorinated aliphatic amine is a fluorinated aliphatic amine having a pH of 9.0 to 11.0 when the amine is used alone as an aqueous solution having a concentration of 1 mol / L. [1] The antistatic treatment agent according to [1].
[0015]
[4] The antistatic treatment agent according to [1], wherein the fluorinated aliphatic amine is trifluoroethylamine.
[0016]
[5] The antistatic treatment agent according to any one of [1] to [4], wherein the water-soluble conductive polymer is a π-conjugated conductive polymer having a Bronsted acid group.
[0017]
[6] The antistatic treatment agent according to [5], wherein the Bronsted acid group is an aqueous solution of a π-conjugated conductive polymer having a sulfonic acid group.
[0018]
[7] The water-soluble conductive polymer has the following general formula (2):
[0019]
[Formula 4]

(In the formula, m and n each independently represents an integer of 0 or 1. A represents —B—SO._Three ^-1 represents an alkylene or alkenylene group having 1 to 4 carbon atoms and having at least one substituent represented by M (two or more double bonds may be present), and the alkyl or alkenylene group includes carbon. A linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a straight chain having 1 to 20 carbon atoms Or a branched alkyl ester group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, or a substituted phenyl group. B is-(CH₂)_p-(O (CH₂)_q)_r-, P represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. M is H⁺ , An alkali metal ion, or a quaternary ammonium ion. The antistatic treatment agent according to any one of [1] to [4], comprising a chemical structure represented by:
[0020]
[8] The water-soluble conductive polymer has the following general formula (3),
[0021]
[Chemical formula 5]

(Wherein R¹~ R^Three Each independently represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms. C1-C20 linear or branched alkyl ester group, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group, -B-SO_Three ^-M group is shown. R above¹, R²And R^ThreeIn the chain of alkyl group, alkoxy group or alkyl ester group, carbonyl bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, imino bond, thioether Bonds may optionally be included. B is-(CH₂)_p-(O (CH₂)_q)_r-, P represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. M is H⁺ , An alkali metal ion, or a quaternary ammonium ion. The antistatic treatment agent according to any one of [1] to [4], comprising a chemical structure represented by:
[0022]
[9] The water-soluble conductive polymer has the following general formula (4):
[0023]
[Chemical 6]

(Wherein R^FourAnd R^FiveEach independently represents H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms. C1-C20 linear or branched alkyl ester group, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group, -B-SO_Three ^-M represents the group R⁶Represents a monovalent group of the group consisting of H or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group. In addition, the above R^FourAnd R^FiveIn the chain of the alkyl group, alkoxy group or alkyl ester group, carbonyl bond, ether bond, ester bond, sulfonate ester bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, imino bond, thioether Bonds may optionally be included. B is-(CH₂)_p-(O (CH₂)_q)_r-, P represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. M is H⁺ , An alkali metal ion, or a quaternary ammonium ion. The antistatic treatment agent according to any one of [1] to [4], comprising a chemical structure represented by:
[0024]
[10] The water-soluble conductive polymer is a polymer containing 5-sulfoisothianaphthene-1,3-diyl as a chemical structure, according to any one of [1] to [4] Antistatic treatment agent.
[0025]
[11] The antistatic treatment agent according to any one of [1] to [10], which contains a surfactant.
[0026]
[12] The antistatic treatment agent according to [11], wherein the surfactant is a surfactant containing a fluorine atom.
[0027]
[13] The antistatic treatment agent according to any one of [1] to [11], wherein the pH is 3.0 or more and 6.0 or less.
[0028]
[14] The charging according to [1] to [13], wherein the content of the fluorinated aliphatic amine is 0.8 to 3 times mol per monomer unit of the water-soluble conductive polymer. Prevention treatment agent.
[0029]
[15] 0.1% by mass to 10% by mass of the water-soluble conductive polymer, 0.1% by mass to 20% by mass of the fluorinated aliphatic amine, and 70% by mass or more of water. The antistatic treatment agent according to any one of [1] to [14], wherein the antistatic treatment agent is an aqueous solution that does not exceed 99.8% by mass.
[0030]
[16] An antistatic film comprising a water-soluble conductive polymer and a fluorinated aliphatic amine.
[0031]
[17] The antistatic film as described in [16], which contains a surfactant.
[0032]
[18] The antistatic film according to [17], wherein the surfactant is a surfactant containing a fluorine atom.
[0033]
[19] An antistatic film produced using the antistatic treatment agent according to any one of [1] to [15].
[0034]
[20] A coated article, wherein the surface of the chemically amplified resist is coated with the antistatic film according to any one of [16] to [19].
[0035]
[21] A pattern forming method using the antistatic film according to any one of [16] to [19].
[0036]
[22] A semiconductor element, a photomask, a reticle, a glass substrate, a quartz substrate, a GMR head, and a magnetic material, produced using the antistatic treatment agent according to any one of [1] to [15] substrate.
[0037]
[23] A semiconductor element, a photomask, a reticle, a glass substrate, a quartz substrate, a GMR head, and a magnetic substrate manufactured using the pattern forming method according to [21].
[0038]
DETAILED DESCRIPTION OF THE INVENTION
The antistatic treatment agent in the present invention means an aqueous solution containing a water-soluble conductive polymer and a fluorinated aliphatic amine. If the antistatic treatment agent is treated and then allowed to stand or dry, the water contained in the antistatic treatment agent is reduced by volatilization or the like, resulting in a semi-solid or solid with no fluidity. The state where the fluidity is lost is called an antistatic material, and the case where the antistatic material is in a film form is called an antistatic film.
[0039]
Since the water-soluble conductive polymer is generally a π-conjugated conductive polymer having a Bronsted acid group, the sulfonic acid group derived from the Bronsted acid group or the carboxylic acid group is neutralized and used. . In the neutralization treatment to avoid adverse effects on the chemically amplified resist, neutralization with the fluorinated aliphatic amine described in the present invention produces a buffering effect and extremely suppresses pH fluctuations of the aqueous solution. Is done. Conventional ammonia, or organic aliphatic amines or organic aromatic amines have strong basicity, so pH fluctuations from weakly acidic to neutral regions are greatly affected by slight increases in acidic components, making it difficult to control them. . Although the fluorinated aliphatic amine included in the present invention is a primary base compound, the electron withdrawing property of the alkyl group substituted with fluorine is stronger than the corresponding alkyl group, and the electron density on nitrogen is reduced. The sex is lowered and a buffering effect is exhibited.
[0040]
Further, the fluorine compound is contained in the base compound used for neutralizing the Bronsted acid group, so that the fluorine content of the antistatic film is increased and the surface energy of the solid coating is reduced. On the other hand, since the chemically amplified resist is composed of an element having a large surface energy such as CH, CHO, CHNO, CHClO, CHOS, and CHONS, the resist has a large surface energy. Accordingly, the affinity or penetrability between solids of the antistatic film having a small surface energy and the chemically amplified resist is lowered, and the formation of the mixing layer at the interface can be prevented.
[0041]
The fluorinated organic aliphatic amine in the present invention is not particularly limited as long as it does not dedope the self-doped conductive polymer. Preferably, formula (1)
X- (CF₂)_mCY₂NH₂      (1)
(However, X represents fluorine or a hydroxyl group, Y represents hydrogen or fluorine, and m represents an integer of 1 to 10.)
Is at least one compound selected from the compounds represented by:
[0042]
The fluorinated aliphatic amine preferably has a pH of 9.0 to 11.0 when made into a 1 mol / L aqueous solution alone.
[0043]
Specific examples of the fluorinated aliphatic amine include 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,3,3,4,4,4- Heptafluorobutylamine, 2,2,3,3,4,4,5,5,5-nonafluoropentylamine, 2,2,3,3,4,4,5,5,6,6,6- Undecafluorohexylamine, trifluoromethylamine, perfluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluoroheptylamine, perfluorooctylamine, perfluorodecylamine, difluoro Examples include ethanolamine. Particularly preferred are trifluoroethylamine and pentafluoropropylamine, and more preferred is trifluoroethylamine. These fluorinated aliphatic amines may be used alone or in combination of two or more.
[0044]
The fluorinated aliphatic amine contained in the antistatic treatment agent of the present invention is preferably added in such an amount that the pH value of the aqueous solution becomes 3 to 6 when the acidic aqueous solution of the water-soluble conductive polymer is neutralized. More specifically, it preferably contains 0.8 to 3 times moles of a fluorinated aliphatic amine with respect to the total number of Bronsted acid groups contained in the water-soluble conductive polymer. It is particularly preferred to contain a double mole to a double mole. The concentration of the fluorinated aliphatic amine in terms of the content relative to the antistatic treatment agent cannot be defined unconditionally because it varies depending on the type and concentration of the water-soluble conductive polymer, but is 0.1% to 20% by mass. It is.
[0045]
The water-soluble conductive polymer used in the present invention is basically not limited as long as it is a π-conjugated conductive polymer having a Bronsted acid group and is water-soluble. The Bronsted acid group of the conductive polymer is directly substituted on the π-electron conjugated main chain, substituted through a spacer, for example, a self-doped conductive polymer substituted through an alkylene side chain or an oxyalkylene side chain. And the primary structure of the chemical structure is not necessarily limited. Specific polymers include poly (isothianaphthene sulfonic acid), poly (thiophene alkane sulfonic acid), poly (thiopheneoxyalkane sulfonic acid), poly (pyrrole alkyl sulfonic acid), poly (aniline sulfonic acid) and the like. Examples thereof include copolymers containing repeating units, and various salt structures and substituted derivatives thereof.
[0046]
Moreover, the repeating unit of the chemical structure containing a sulfonic acid group in the copolymer is usually in the range of 100 mol% to 50 mol%, preferably 100 mol% to 80 mol% of all repeating units of the polymer, It may be a copolymer containing repeating units composed of other π-conjugated chemical structures, or may be a copolymer composition consisting of 2 to 5 repeating units.
[0047]
In the present invention, the “copolymer containing repeating units” is not necessarily limited to a copolymer containing the units continuously, as long as desired conductivity based on the π-conjugated main chain is expressed. In the meaning, a polymer containing irregularly and discontinuously repeating units in the π-conjugated main chain as in a random copolymer.
[0048]
Examples of particularly useful structures in the structure having a Bronsted acid group of the present invention include structures represented by formulas (2), (3), and (4). The conductive polymer may be a single polymer or copolymer as described above.
[0049]
Equation (2) is
[0050]
[Chemical 7]

(In the formula, m and n independently represent an integer of 0 or 1. A represents —B—SO._Three ^-1 represents an alkylene or alkenylene group having 1 to 4 carbon atoms and having at least one substituent represented by M (two or more double bonds may be present), and the alkyl or alkenylene group includes carbon. A linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a straight chain having 1 to 20 carbon atoms Or a branched alkyl ester group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, or a substituted phenyl group. B is-(CH₂)_p-(O (CH₂)_q)_r-, P represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. M is H⁺ , An alkali metal ion, or a quaternary ammonium ion. ).
[0051]
Equation (3) is
[0052]
[Chemical 8]

(Wherein R¹~ R^Three Each independently represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms. C1-C20 linear or branched alkyl ester group, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group, -B-SO_Three ^-M group is shown. R above¹, R²And R^ThreeIn the chain of the alkyl group, alkoxy group or alkyl ester group, carbonyl bond, ether bond, ester bond, sulfonate ester bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, imino bond, thioether Bonds may optionally be included. B is-(CH₂)_p-(O (CH₂)_q)_r-, P represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. M is H⁺ , An alkali metal ion, or a quaternary ammonium ion. ).
[0053]
Equation (4) is
[0054]
[Chemical 9]

(Wherein R^FourAnd R^FiveEach independently represents H, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated alkoxy group having 1 to 20 carbon atoms. A linear or branched alkyl ester group having 1 to 20 carbon atoms, a linear or branched alkyl ester group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, Phenyl group, substituted phenyl group, -B-SO_Three ^-M represents the group R⁶Represents a monovalent group of the group consisting of H or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group. In addition, the above R^FourAnd R^FiveIn the chain of the alkyl group, alkoxy group or alkyl ester group, carbonyl bond, ether bond, ester bond, sulfonate ester bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, imino bond, thioether Bonds may optionally be included. B represents-(CH2) p- (O (CH2) q) r-, p represents an integer of 0 to 5, q represents an integer of 1 to 3, and r represents an integer of 0 to 3. . M is H⁺ Represents an alkali metal ion or a quaternary ammonium ion. ).
[0055]
Where R¹~ R⁶Particularly useful examples include hydrogen atom, alkyl group, alkoxy group, alkyl ester group, phenyl and substituted phenyl group, and sulfonic acid group. Illustrating these substituents in more detail, examples of the alkyl group include methyl, ethyl, propyl, allyl, isopropyl, butyl, 1-butenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, Ethoxyethyl, methoxyethyl, methoxyethoxyethyl, acetonyl, phenacyl, etc., alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, methoxyethoxy, methoxyethoxyethoxy, etc. Alkyl ester groups include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl, acyloxy groups such as acetoxy and butyroyloxy, Fluorophenyl groups as phenyl group, chlorophenyl group, bromophenyl group, methylphenyl group, methoxyphenyl group and the like. R above¹~ R^FiveIn the chain of alkyl group and alkoxy group, carbonyl bond, ether bond, ester bond, sulfonate ester bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, imino bond, thioether bond are optional. You may contain.
[0056]
R in general formula (3) and general formula (4)¹~ R^FiveIn the above-mentioned substituents, a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group or an alkyl ester group is desirable, and a hydrogen atom or a straight chain having 1 to 20 carbon atoms is preferred. A chain or branched alkoxy group is particularly desirable.
[0057]
R in the general formula (4)⁶Is preferably a monovalent group consisting of a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group.
[0058]
Examples of B in the formula include butylene, pentylene, hexylene, methylenedioxy, ethylenedioxy and the like.
[0059]
Where M is H⁺Represents an alkali metal ion or a quaternary ammonium ion, but may be a mixture containing one or more of these cations.
[0060]
Examples of alkali metal ions include Na⁺, Li⁺, K⁺Can be given.
[0061]
Quaternary ammonium ions are N (R⁷) (R⁸) (R⁹) (R^Ten)⁺Represented by R⁷~ R^TenEach independently represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group, an alkoxy group, a hydroxyl group, an oxyalkylene group, a thioalkylene group. , An azo group, an azobenzene group, a p-diphenyleneoxy group, or an alkyl or aryl group containing a group containing an element other than carbon or hydrogen.
[0062]
N (R⁷) (R⁸) (R⁹) (R^Ten)⁺As the quaternary ammonium cation represented by the formula, for example, NH_Four ⁺, NH (CH_Three)_Three ⁺, NH (C₆H_Five)_Three ⁺, N (CH_Three)₂(CH₂OH) (CH₂-Z)⁺Or an alkyl-substituted or aryl-substituted cation such as Z is an arbitrary substituent having a chemical formula weight of 600 or less. For example, phenoxy group, p-diphenyleneoxy group, p-alkoxydiphenylene And a substituent such as an oxy group or a p-alkoxyphenylazophenoxy group). In addition, in order to convert into a specific cation, you may use a normal ion exchange resin.
[0063]
R⁷~ R^TenThe chain of the alkyl group may optionally contain a carbonyl bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond and the like.
[0064]
More specifically, examples that can be used as the structural unit containing the Bronsted acid constituting the water-soluble conductive polymer of the present invention are examples not corresponding to the formulas (2), (3), and (4). As poly (polypyrrole alkanesulfonic acid), poly (pyrroleoxyalkanesulfonic acid), poly (carbazole-N-alkanesulfonic acid), poly (phenylene-oxyalkanesulfonic acid), poly (phenylene vinylene-alkanesulfonic acid), Poly (phenylene vinylene-oxyalkanesulfonic acid), poly (aniline-N-alkanesulfonic acid), poly (thiophenealkylcarboxylic acid), poly (thiopheneoxyalkylcarboxylic acid), poly (polypyrrolealkylcarboxylic acid), poly (pyrrole) Oxyalkylcarboxylic acid), poly (carbazole-N-alkyl carbonate) Bonic acid), poly (phenylene-oxyalkyl carboxylic acid), poly (phenylene vinylene-alkyl carboxylic acid), poly (phenylene vinylene-oxyalkyl carboxylic acid), poly (aniline-N-alkyl carboxylic acid), 6-sulfonaphtho [ 2,3-c] thiophene-1,3-diyl or the like, or lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt , Tetramethylammonium salt, tetraethylammonium salt and the like.
[0065]
Preferred specific examples of the chemical structure represented by the formula (2) or (3) of the present invention include 5- (3′-propanesulfo) -4,7-dioxycyclohexa [2,3-c] thiophene. -1,3-diyl, 5- (2'-ethanesulfo) -4,7-dioxycyclohexa [2,3-c] thiophene-1,3-diyl, 5-sulfoisothianaphthene-1,3- Diyl, 4-sulfoisothianaphthene-1,3-diyl, 4-methyl-5-sulfoisothianaphthene-1,3-diyl, 6-methyl-5-sulfoisothianaphthene-1,3-diyl, 6 -Methyl-4-sulfoisothianaphthene-1,3-diyl, 5-methyl-4-sulfoisothianaphthene-1,3-diyl, 6-ethyl-5-sulfoisothianaphthene-1,3-diyl, 6-propyl-5-sulfoisothi Naphthene-1,3-diyl, 6-butyl-5-sulfoisothianaphthene-1,3-diyl, 6-hexyl-5-sulfoisothianaphthene-1,3-diyl, 6-decyl-5-sulfoiso Thianaphthene-1,3-diyl, 6-methoxy-5-sulfoisothianaphthene-1,3-diyl, 6-ethoxy-5-sulfoisothianaphthene-1,3-diyl, 6-chloro-5-sulfo Isothianaphthene-1,3-diyl, 6-bromo-5-sulfoisothianaphthene-1,3-diyl, 6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl, or the like Lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium Salts, may be mentioned triethylammonium salt, tetramethylammonium salt, a tetraethylammonium salt.
[0066]
Preferable specific examples of the chemical structure represented by the general formula (4) include 2-sulfo-1,4-iminophenylene, 3-methyl-2-sulfo-1,4-iminophenylene, and 5-methyl-2- Sulfo-1,4-iminophenylene, 6-methyl-2-sulfo-1,4-iminophenylene, 5-ethyl-2-sulfo-1,4-iminophenylene, 5-hexyl-2-sulfo-1,4 -Iminophenylene, 3-methoxy-2-sulfo-1,4-iminophenylene, 5-methoxy-2-sulfo-1,4-iminophenylene, 6-methoxy-2-sulfo-1,4-iminophenylene, 5 -Ethoxy-2-sulfo-1,4-iminophenylene, 2-sulfo-N-methyl-1,4-iminophenylene, 2-sulfo-N-ethyl-1,4-iminophenylene, or the like Lithium salts, sodium salts, ammonium salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethyl ammonium salt, and triethylammonium salt, tetramethylammonium salt, a tetraethylammonium salt.
[0067]
The molecular weight of the self-doped conductive polymer used in the present invention cannot be defined unconditionally because it varies depending on the chemical structure of the repeating unit to be formed, but is not particularly limited as long as it meets the purpose of the present invention. Usually, when expressed in terms of the number of repeating units (polymerization degree) constituting the main chain, those having a polymerization degree in the range of 5 to 2000, preferably 10 to 1000 are mentioned.
[0068]
Particularly preferred specific examples of the π-conjugated conductive polymer having a Bronsted acid group used in the present invention include 5-sulfoisothianaphthene-1,3-diyl polymer, 5-sulfoisothianaphthene-1 , 3-diyl, a random copolymer containing 80 mol% or more, poly (5-sulfoisothianaphthene-1,3-diyl-co-isothianaphthene-1,3-diyl), 2-sulfo-1,4- Random copolymers containing 50 mol% or more of iminophenylene, poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene), etc. and their lithium salts, sodium salts, ammonium salts, triethylammonium salts Etc.
[0069]
The concentration of the water-soluble conductive polymer of the present invention varies depending on the desired antistatic performance of the film, but is usually 0.001 to 30% by mass, preferably 0.01 to 10% by mass.
[0070]
For the antistatic treatment agent of the present invention, a solvent that is miscible with water and does not dedoped the self-doped conductive polymer may be used. For example, more specifically, ethers such as 1,4-dioxane and tetrahydrofuran, carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate, nitriles such as acetonitrile and benzonitrile, methanol, ethanol, propanol, Examples include alcohols such as isopropanol, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, mineral acids such as sulfuric acid, organic acids such as acetic acid, and the like. Two or more kinds of mixed solvents can also be used.
[0071]
The antistatic treatment agent of the present invention can be used for both non-chemically amplified resists and chemically amplified resists.
[0072]
For non-chemically amplified resists, it is effective as an antistatic treatment agent with little change in quality or little change in pH value. Specifically, phenolic resins such as novolak resin (component element: CHO), acrylic resins such as polymethyl methacrylate resin and polyacrylate resin (constituent element: CHO), α-methylstyrene and α-chloroacrylic acid Copolymer system (CHOCl) and the like can be mentioned, but not limited thereto.
[0073]
For chemically amplified resists, not only can the influence on the resist be controlled due to the small fluctuation in pH value, but also the antistatic film can be increased by increasing the fluorine content derived from the fluorinated aliphatic amine in the antistatic film. Is prevented from changing the quality of the chemically amplified resist and can be used without impairing the performance of the chemically amplified resist. .
[0074]
When the elements constituting the chemically amplified resist are CH, CHO, CHNO, CHClO, CHOS, and CHNOS, the formation of a mixing layer on the contact surface between the antistatic film and the chemically amplified resist is more effectively prevented. . Specifically, photosensitive resins such as phenol resin (constituent element: CHO), acrylic resin (constituent element: CHO), azide compound (CHO), polymethacrylate resin (CHO), polyvinyl phenol, Examples thereof include, but are not limited to, polyhydroxystyrene (CHO) and charged particle beam resins such as a copolymer system (CHOCl) of α-methylstyrene and α-chloroacrylic acid. An additive may be added to the photosensitive resin or charged particle beam resin. Specific examples of the additive include, but are not limited to, a photosensitizer, an azide compound, a crosslinking agent, a dissolution inhibitor, and an acid generator. Even if the elements constituting the resist are limited to C, H, O, Cl, and N, S atoms may be added from the elements constituting the additive to include the S element as a constituent element of the entire resist.
[0075]
The antistatic treatment agent of the present invention may contain a surfactant containing a fluorine atom. When the antistatic treatment agent of the present invention contains a surfactant containing fluorine atoms, the fluorine content contained in the antistatic film increases as compared with the case where only the fluorinated aliphatic amine is contained. And the mixing layer on the contact surface between the chemically amplified resist and the resist are more effectively prevented. When a surfactant containing a fluorine atom is used, the weight ratio is 0.001 to 95 times, preferably 0.005 to 20 times, and more preferably 0 to the self-doped conductive polymer compound. Use 0.01 to 5 times the amount. If the amount of the surfactant is less than 0.001 times, the effect of adding the surfactant may be lost. If the amount is more than 95 times, good electron conductivity may not be ensured.
[0076]
Specific examples of the surfactant containing a fluorine atom include fluoroalkylsulfonic acid, fluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, perfluorocarboxylic acid, and salts thereof, perfluoroalkylsulfonamide, perfluoroalkylsulfonamidoalkyl. Examples thereof include ammonium salts, perfluoroalkyl betaines, perfluoroalkylamine oxides, and perfluoroalkylethylene oxide adducts. Particularly preferred are perfluoroalkylsulfonic acid, perfluorocarboxylic acid, and salts thereof.
[0077]
The antistatic treatment agent of the present invention can also contain a surfactant that does not contain fluorine atoms. Examples of the surfactant not containing a fluorine atom include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a silicone surfactant, and the like. When a surfactant containing no fluorine is used, the weight ratio is 0.001 to 95 times, preferably 0.005 to 20 times, and more preferably 0 to the self-doped conductive polymer compound. Use 0.01 to 5 times the amount. If the amount of the surfactant is less than 0.001 times, the effect of adding the surfactant may be lost. If the amount is more than 95 times, good electron conductivity may not be ensured.
[0078]
The surfactant may contain one type or two or more types.
[0079]
The antistatic treatment agent of the present invention can take any pH value between acidic and alkaline by changing the content of the fluorinated aliphatic amine in the solution.
[0080]
As a specific method for forming the antistatic treatment agent on the resist surface, spin coating is mainly used, but other purposes such as dipping (soaking) or spraying on an article, coating with a bar coater, etc. Depending on the method, various methods can be mentioned.
[0081]
The article coated with the antistatic film of the present invention is a substrate in which an antistatic film and a resist are laminated, and the material of the substrate is a compound semiconductor wafer such as a silicon wafer, a gallium arsenide wafer, an indium phosphide wafer, etc. A quartz substrate, a magnetic substrate, and the like can be mentioned, but the invention is not limited to these. Note that the laminated substrate includes a substrate in a transient state in a semiconductor manufacturing process and a manufacturing process of a photomask, a reticle, a stencil mask, and the like.
[0082]
In the pattern forming method of the present invention, the quality of the chemically amplified resist is changed by coating the surface of the chemically amplified resist with the antistatic film, for example, the shape of the resist is changed such as fogging, film reduction, T-top and shoulder drop. Therefore, it is possible to form a pattern with high accuracy, and it is possible to prevent misalignment in a drawing process using a charged particle beam due to the effect of preventing charge-up by an antistatic film. Can do.
[0083]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated using an Example and a comparative example, this invention is not restrict | limited to a following example.
[0084]
The pH of the aqueous solution was measured with a glass electrode type hydrogen ion concentration meter pH METER F-13 (manufactured by Horiba, Ltd.). Further, the coating film of the antistatic treatment agent was prepared by dropping 5 ml of the antistatic treatment agent on a glass substrate using Spinner 1H-III (manufactured by Kyoei Semiconductor Co., Ltd.) and then spin-coating at 1500 rpm. . The surface resistance value of the coating film is a value measured with a surface resistance measuring device Megaresta MODEL HT-301 (manufactured by SHISIDO ELECTRIC CO., LTD.).
[0085]
The effect of preventing the formation of the mixing layer was evaluated by the following method.
A negative type chemically amplified electron beam resist was spin-coated on a silicon wafer, and the solvent was removed by pre-baking (implemented under conditions specified by various resists). 5 ml of the antistatic treatment agent was dropped on the coated resist surface, and then spin coated at 1500 rpm to form a conductive film having a thickness of 0.02 μm. The conductive film was spin-coated on the resist surface and air-dried for 30 minutes, and then the conductive film was washed and removed with 30 ml of ultrapure water. Subsequently, after carrying out heat treatment (implemented under conditions specified by various resists), the resist was dissolved and removed with an aqueous 2.38 mass% TMAH solution.
[0086]
When paddle development is performed on a resist coated on a 6-inch silicon wafer with an aqueous 2.38 mass% TMAH solution, the dissolution start time is when the mirror surface of the silicon wafer is partially recognized as the resist dissolves. The dissolution was completed when the dissolution was completed completely, and the dissolution time of the resist was measured.
[0087]
When the mixing layer is remarkably formed at the interface between the negative resist and the antistatic film, the resist is fogged and is not dissolved in the 2.38% TMAH aqueous solution. As the formation of the mixing layer is suppressed, the dissolution time approaches the dissolution time of the resist when the antistatic treatment agent is not applied.
[0088]
Most preferably, the dissolution time when measured by applying an antistatic treatment and the dissolution time of the resist when no antistatic treatment is applied are the same.
[0089]
Of the conductive polymer compounds used in this example, poly (5-sulfoisothianaphthen-1,3-yl) was synthesized with reference to the method disclosed in JP-A-7-48436. . Poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene) (50 mol%: 50 mol%) is described in Macromolecules, Vol. 29, pages 3950-3955 (1996). The method was synthesized with reference to the method.
[0090]
[Example 1]
To 100 ml of a 0.6% by mass aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl), 2.5 g of 1N-trifluoroethylamine aqueous solution was added, and the hydrogen ion concentration (hereinafter abbreviated as pH value) was 4.1. The antistatic treatment agent of the present invention was obtained. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.) and sampled over time to determine the pH value. After one month, pH = 4.1, after two months, pH = 4. After one or three months, the pH was 4.1.
[0091]
[Example 2]
After adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.1 g of dodecylbenzenesulfonic acid and stirring for 2 hours, 2.6 g of 1N-trifluoroethylamine aqueous solution was added. In addition, the pH value was adjusted to 3.8 to obtain the antistatic treatment agent of the present invention. After 5 ml of the antistatic treatment agent of the present invention was spin-coated on a glass substrate and dried, an antistatic film was formed on the glass surface and Rs was measured to be 6.0 × 10.^FiveIt was Ω / □. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value was examined, and the glass coating film was examined in the same manner as above. 8, Rs = 1.8 × 10⁶Ω / □, after 2 months, pH = 3.8, Rs = 3.8 × 10⁶Ω / □, after 3 months, pH = 3.8, Rs = 4.5 × 10⁶It was Ω / □.
[0092]
[Example 3]
After adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.3 g of perfluorocaprylic acid and stirring for 2 hours, 2.9 g of 1N-trifluoroethylamine aqueous solution was added. In addition, the pH value was adjusted to 3.8 to obtain the antistatic treatment agent of the present invention. After 5 ml of the antistatic treatment agent of the present invention was spin-coated on a glass substrate and dried, an antistatic film was formed on the glass surface and Rs was measured to be 6.5 × 10 6.^FiveIt was Ω / □. The antistatic agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value was examined, and the glass coating film was examined in the same manner as above. After one month, pH = 3.8 , Rs = 2.1 × 10⁶Ω / □, after 2 months, pH = 3.8, Rs = 4.2 × 10⁶Ω / □, after 3 months, pH = 3.8, Rs = 4.6 × 10⁶It was Ω / □.
[0093]
[Example 4]
After adding 95 ml of 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.3 g of perfluorocaprylic acid and stirring for 2 hours, 3.5 g of 1N-trifluoroethylamine aqueous solution was added. In addition, the pH value was adjusted to 5.0 to obtain the antistatic treatment agent of the present invention. After 5 ml of the antistatic treatment agent of the present invention was spin-coated on a glass substrate and dried, an antistatic film was formed on the glass surface and Rs was measured to be 4.3 × 10.^FiveIt was Ω / □. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value was examined, and the glass coating film was examined in the same manner as above. 0, Rs = 3.5 × 10⁶Ω / □ After 2 months, pH = 5.0, Rs = 7.8 × 10⁶Ω / □, after 3 months, pH = 4.9, Rs = 5.1 × 10⁷It was Ω / □.
[0094]
[Example 5]
After adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl), 0.1 g of dodecylbenzenesulfonic acid and 0.1 g of perfluorocaprylic acid, and stirring for 2 hours, 1N- A suitable amount of an aqueous trifluoroethylamine solution was added to adjust the pH value to 3.8 to obtain the antistatic treatment agent of the present invention. After 5 ml of the antistatic treatment agent of the present invention was spin-coated on a glass substrate and dried, an antistatic film was formed on the glass surface and Rs was measured to be 7.0 × 10.^FiveIt was Ω / □. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value was examined, and the glass coating film was examined in the same manner as above. 8, Rs = 2.2 × 10⁶Ω / □, after 2 months, pH = 3.8, Rs = 3.9 × 10⁶Ω / □, after 3 months, pH = 3.8, Rs = 4.2 × 10⁶It was Ω / □.
[0095]
[Example 6]
95 ml of 0.9% by weight aqueous solution of poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene) (50 mol%: 50 mol%), 0.1 g of dodecylbenzenesulfonic acid, perfluoro After adding 0.1 g of caprylic acid and stirring for 2 hours, an appropriate amount of 1N-trifluoroethylamine aqueous solution was added to adjust the pH value to 3.8 to obtain the antistatic treatment agent of the present invention. After 5 ml of the antistatic treatment agent of the present invention was spin-coated on a glass substrate and dried, an antistatic film was formed on the glass surface and Rs was measured.⁶It was Ω / □. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value, and the glass coating film examined in the same manner as above. 0, Rs = 5.1 × 10⁶Ω / □, after two months, pH = 4.0, Rs = 1.2 × 10⁷Ω / □, after 3 months, pH = 4.0, Rs = 2.0 × 10⁷It was Ω / □.
[0096]
[Example 7]
A negative chemical amplification electron beam resist (trade name SAL601, manufactured by Shipley Co., Ltd.) composed of novolak, a photosensitizer and an acid generator having a bromomethyl group was spin-coated, and the solvent was removed by pre-baking. 5 ml of the antistatic treatment agent of the present invention described in Example 2 was dropped on the coated resist surface, and then spin coated at 1500 rpm to form an antistatic film having a thickness of 0.02 μm. The conductive film was spin-coated on the resist surface and air-dried for 30 minutes, and then the conductive film was washed and removed with 30 ml of ultrapure water. Subsequently, after the heat treatment, the resist was dissolved with a 2.38 mass% TMAH solution, and the dissolution was 62 seconds and the dissolution was 67 seconds. When the antistatic treatment agent was not used, the dissolution start was 60 seconds and the dissolution end was 65 seconds.
[0097]
[Example 8]
A negative-type chemically amplified electron beam resist (trade name NEB22 manufactured by Sumitomo Chemical Co., Ltd.) was spin-coated and the solvent was removed by pre-baking. 5 ml of the antistatic treatment agent of the present invention described in Example 3 was dropped on the coated resist surface, and then spin coated at 1500 rpm to form a conductive film having a thickness of 0.02 μm. The conductive film was spin-coated on the resist surface and air-dried for 30 minutes, and then the conductive film was washed and removed with 30 ml of ultrapure water. Subsequently, after the heat treatment was performed, the resist was dissolved by the 2.38 mass% TMAH solution, and the dissolution was 13 seconds and the dissolution was 15 seconds. When the antistatic treatment agent was not used, the dissolution start was 13 seconds and the dissolution end was 14 seconds.
[0098]
[Comparative Example 1]
After adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl), 0.1 g of dodecylbenzenesulfonic acid and 0.1 g of perfluorocaprylic acid, and stirring for 2 hours, 1N- A thin film of antistatic agent was prepared on the glass surface and Rs was measured in the same manner as in Example 1 except that the antistatic treatment agent obtained by adding 3 ml of aqueous ammonia and adjusting the pH to 5.2 was used. However, 5.1 × 10^FiveIt was Ω / □. The antistatic treatment agent was allowed to stand under refrigeration (5 ± 3 ° C.), sampled over time, its pH value, and the glass coating film examined in the same manner as above. 1, Rs = 1.1 × 10⁶Ω / □, after 2 months, pH = 3.9, Rs = 1.8 × 10⁶Ω / □, after 3 months, pH = 3.7, Rs = 2.1 × 10⁶It was Ω / □.
[0099]
[Comparative Example 2]
The pH was adjusted to 5.0 by adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.1 ml of dodecylbenzenesulfonic acid to 3 ml of 1N ammonia water. The dissolution time of the resist was measured in the same manner as in Example 7 except that the obtained antistatic treatment agent was used. The dissolution start time was 120 seconds and the dissolution end time was 130 seconds.
[0100]
[Comparative Example 3]
Charge obtained by adding 95 ml of a 0.6 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.1 g of dodecylbenzenesulfonic acid to 3 ml of 1N ammonia water to adjust the pH to 5.0. When the dissolution time of the resist was measured in the same manner as in Example 8 except that the prevention treatment agent was used, the resist was not dissolved at all.
[0101]
[Comparative Example 4]
95 ml of a 0.9% by weight aqueous solution of poly (2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene) (50 mol%: 50 mol%), 0.1 g of dodecylbenzenesulfonic acid and 1N- The dissolution time of the resist was measured in the same manner as in Example 7 except that the antistatic treatment agent obtained by adding 3 ml of aqueous ammonia to adjust the pH to 5.0 was used. The end was 75 seconds.

Claims (35)

Water-soluble electroconductive polymer, seen containing a fluorinated aliphatic amines and water, wherein the water-soluble electroconductive polymer has the following general formula (2)

(.A shown wherein, m, n and the integers independently 0 or 1, -B-SO ₃ ^- at least one organic substituent represented by M, alkylene, alkenylene group having 1 to 4 carbon atoms (The double bond may have two or more), and the alkyl or alkenylene group is a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, carbon number 1 to 20 linear or branched saturated or unsaturated alkoxy group, 1 to 20 linear or branched alkyl ester group, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group , Phenyl group, and substituted phenyl group may have as a substituent, B represents — (CH ₂ ) _p — (O (CH ₂ ) _q ) _r —, and p represents an integer of 0 to 5. Q represents an integer of 1 to 3, and r represents an integer of 0 to 3. .M is, H ^+, antistatic treatment agent characterized containing Mukoto a chemical structure represented by.) Of an alkali metal ion or a quaternary ammonium ion. Water-soluble electroconductive polymer, seen containing a fluorinated aliphatic amines and water, wherein the water-soluble electroconductive polymer has the following general formula (3)

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched group having 1 to 20 carbon atoms. Saturated or unsaturated alkoxy group, linear or branched alkyl ester group having 1 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group,- B-SO ₃ ^-. showing the M group above alkyl groups R ^1, R ² and R ^3, are in the chain of alkoxy group, or an alkyl ester group, a carbonyl bond, an ether bond, an ester bond, a sulfonate ester bond, amide bond, a sulfonamide bond, a sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, may .B optionally contain a thioether bond, - (CH _{2 p - (O (CH 2)} q) r - indicates, p represents an integer of 0 to 5, q is an integer of 1 to 3, .M r is represents an integer of 0 to 3, H ⁺ , antistatic treatment agent characterized containing Mukoto a chemical structure represented by shown alkali metal ion or a quaternary ammonium ion.). Water-soluble electroconductive polymer, seen containing a fluorinated aliphatic amines and water, said water-soluble conductive polymer, the following general formula (4)

(In the formula, R ⁴ and R ⁵ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched group having 1 to 20 carbon atoms. Saturated or unsaturated alkoxy group, linear or branched alkyl ester group having 1 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group,- B-SO ₃ ^- shows the M group, R ⁶ is, H or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, of the group consisting of phenyl and substituted phenyl group mono-, shows a divalent group. the alkyl group of R ⁴ above and R ^5, are in the chain of alkoxy group, or an alkyl ester group, a carbonyl bond, an ether bond, an ester bond, a sulfonate ester bond, an amide bond, scan Hon'amido bond, sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, good .B optionally contain a thioether _{bond, - (CH 2) p -} (O (CH 2) q) r - indicates, p Represents an integer of 0 to 5, q represents an integer of 1 to 3, r represents an integer of 0 to 3. M represents H ⁺ , an alkali metal ion, or a quaternary ammonium ion. antistatic treatment agent characterized containing Mukoto a chemical structure represented. Water-soluble electroconductive polymer, seen containing a fluorinated aliphatic amines and water, said water-soluble electroconductive polymer is a polymer containing 5-sulfoisothianaphthene-1,3-diyl as a chemical structure A characteristic antistatic treatment agent. Fluorinated aliphatic amine is represented by the following formula (1)
X- (CF ₂ ) _m CY ₂ NH ₂ (1)
(However, X shows a fluorine atom or a hydroxyl group, Y shows a hydrogen atom or a fluorine atom, and m shows the integer of 1-10.)
The antistatic treatment agent according to any one of claims 1 to 4, wherein the antistatic treatment agent is at least one of at least one of the following. Fluorinated aliphatic amines, in any one of claims 1 to 4 pH when an aqueous solution of a concentration of 1 mol / L of the amine alone is a fluorinated aliphatic amine is 9.0 to 11.0 The antistatic processing agent as described. The antistatic treatment agent according to any one of claims 1 to 4, wherein the fluorinated aliphatic amine is trifluoroethylamine. The antistatic treatment agent according to any one of claims 1 to 4 , comprising a surfactant. The antistatic treatment agent according to claim 8 , wherein the surfactant is a surfactant containing a fluorine atom. The antistatic treatment agent according to any one of claims 1 to 4 , having a pH of 3.0 or more and 6.0 or less. The antistatic treatment agent according to any one of claims 1 to 4 , wherein the content of the fluorinated aliphatic amine is from 0.8 to 3 times mol per monomer unit of the water-soluble conductive polymer. The water-soluble conductive polymer is 0.1% by mass to 10% by mass of the whole antistatic treatment agent, the fluorinated aliphatic amine is 0.1% by mass to 20% by mass, and the water is 70% by mass to 99.8%. The antistatic treatment agent according to any one of claims 1 to 4 , wherein the antistatic treatment agent is an aqueous solution that does not exceed mass%. It contains a water-soluble conductive polymer and a fluorinated aliphatic amine, and the water-soluble conductive polymer is represented by the following general formula (2)

(.A shown wherein, m, n and the integers independently 0 or 1, -B-SO ₃ ^- at least one organic substituent represented by M, alkylene, alkenylene group having 1 to 4 carbon atoms (The double bond may have two or more), and the alkyl or alkenylene group is a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, carbon number 1 to 20 linear or branched saturated or unsaturated alkoxy group, 1 to 20 linear or branched alkyl ester group, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group , Phenyl group, and substituted phenyl group may have as a substituent, B represents — (CH ₂ ) _p — (O (CH ₂ ) _q ) _r —, and p represents an integer of 0 to 5. Q represents an integer of 1 to 3, and r represents an integer of 0 to 3. .M is, H ^+, alkali metal ion or a quaternary ammonium shows an ion.) Antistatic film which comprises a chemical structure represented by. It contains a water-soluble conductive polymer and a fluorinated aliphatic amine, and the water-soluble conductive polymer has the following general formula (3)

(Wherein R ^{1 to} R ³ each independently represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched group having 1 to 20 carbon atoms. Saturated or unsaturated alkoxy group, linear or branched alkyl ester group having 1 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group,- B-SO ₃ ^-. showing the M group above alkyl groups R ^1, R ² and R ^3, are in the chain of alkoxy group, or an alkyl ester group, a carbonyl bond, an ether bond, an ester bond, a sulfonate ester bond, amide bond, a sulfonamide bond, a sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, may .B optionally contain a thioether bond, - (CH _{2 p - (O (CH 2)} q) r - indicates, p represents an integer of 0 to 5, q is an integer of 1 to 3, .M r is represents an integer of 0 to 3, H ⁺ , An alkali metal ion or a quaternary ammonium ion) . It contains a water-soluble conductive polymer and a fluorinated aliphatic amine, and the water-soluble conductive polymer has the following general formula (4)

(In the formula, R ⁴ and R ⁵ are each independently H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched group having 1 to 20 carbon atoms. Saturated or unsaturated alkoxy group, linear or branched alkyl ester group having 1 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group, phenyl group, substituted phenyl group,- B-SO ₃ ^- shows the M group, R ⁶ is, H or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, of the group consisting of phenyl and substituted phenyl group mono-, shows a divalent group. the alkyl group of R ⁴ above and R ^5, are in the chain of alkoxy group, or an alkyl ester group, a carbonyl bond, an ether bond, an ester bond, a sulfonate ester bond, an amide bond, scan Hon'amido bond, sulfide bond, a sulfinyl bond, a sulfonyl bond, an imino bond, good .B optionally contain a thioether _{bond, - (CH 2) p -} (O (CH 2) q) r - indicates, p Represents an integer of 0 to 5, q represents an integer of 1 to 3, r represents an integer of 0 to 3. M represents H ⁺ , an alkali metal ion, or a quaternary ammonium ion. An antistatic film comprising the chemical structure represented . It contains a water-soluble conductive polymer and a fluorinated aliphatic amine, and the water-soluble conductive polymer is a polymer containing 5-sulfoisothianaphthene-1,3-diyl as a chemical structure. Antistatic film. The antistatic film according to any one of claims 13 to 16, comprising a surfactant. The antistatic film according to claim 17 , wherein the surfactant is a surfactant containing a fluorine atom. With antistatic treatment agent according to any one of claims 1 to 12 antistatic film, characterized in that to produce. A coated article, wherein the surface of the chemically amplified resist is coated with the antistatic film according to any one of claims 13 to 19. Pattern forming method which comprises using the antistatic film according to any one of claims 13 to 19. Semiconductor device characterized by the manufacture using the antistatic treatment agent as claimed in any one of claims 1 to 12. Photomask characterized by manufactured using antistatic treatment agent as claimed in any one of claims 1 to 12. Reticle, characterized by prepared using antistatic treatment agent as claimed in any one of claims 1 to 12. Glass substrates, characterized in that prepared using the antistatic treatment agent as claimed in any one of claims 1 to 12. Quartz substrate, characterized in that prepared using the antistatic treatment agent as claimed in any one of claims 1 to 12. GMR head is characterized in that prepared using the antistatic treatment agent as claimed in any one of claims 1 to 12. Magnetic substrate, characterized in that prepared using the antistatic treatment agent as claimed in any one of claims 1 to 12.   A semiconductor device manufactured using the pattern forming method according to claim 21.   A photomask manufactured by using the pattern forming method according to claim 21.   A reticle manufactured using the pattern forming method according to claim 21.   It manufactures using the pattern formation method of Claim 21, The glass substrate characterized by the above-mentioned.   A quartz substrate manufactured using the pattern forming method according to claim 21.   A GMR head manufactured by using the pattern forming method according to claim 21.   A magnetic substrate manufactured using the pattern forming method according to claim 21.