JP2004176112A - Method of producing thin film, and thin film comprising fine particle, produced by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a uniform thin film having high film strength, at the time of producing a thin film consisting of hydrophobic particles using a micelle electrolytic process, by improving the cohesion between the hydrophobic particles. <P>SOLUTION: In the method of producing a thin film where hydrophobic particles are made soluble by using a micelle formation agent consisting of a ferrocene derivative in an aqueous solvent, and the obtained micelle solution, i.e., dispersion solution is subjected to electrolytic treatment to deposit a thin film of the hydrophobic substance on an electrode, the thin film obtained by the production method is subjected to coagulation treatment. Thus, the uniform thin film having high film strength can be obtained. <P>COPYRIGHT: (C)2004,JPO

Description

また、水性媒体としては、水をはじめ、水とアルコールの混合液、水とアセトンとの混合液など様々な分散媒体を挙げることができる。この際、分散液の平衡濃度としては、疎水性粒子を分散し得る濃度であればよく、特に制限はないが、通常は１０μｇ／ミリリットル以上である。なお、分散液の平衡濃度の上限は、分散剤が水溶媒体に溶解し得る濃度まで可能であり、特に制限はない。
【００５４】
ここで、分散剤の平衡濃度とは、下記の濃度を意味する。通常、分散剤溶液に疎水性粒子を分散させると、分散剤が疎水性粒子表面に吸着する。この吸着により、水溶液中の分散剤濃度が低下する。十分な時間が経過すると吸着が平衡に達し、この分散剤の水溶液中の濃度が一定になる。この状態での水溶液中の分散剤の濃度を平衡状態と称する。平衡濃度の測定は、遠心分離により疎水性粒子を完全に分離し、水溶液中に残存する分散剤の濃度を決定することにより求められる。フェロセン誘導体界面活性剤の濃度は鉄の分析を行えばよい。なお、疎水性粒子の濃度としては、分散できる濃度であればよく、特に制限はない。疎水性粒子の通常の濃度は０．１〜５０．０重量％、好ましくは０．５〜３０．０重量％である。また、この分散液の平衡濃度の調整は、必要に応じて支持塩（支持電解質）を用いても良い。この支持塩を用いれば、水性媒体の電気伝導度を調整することができるからである。支持塩の添加量は、疎水性粒子の分散を妨げない範囲であれば良い。支持塩の通常の添加量としては、上記分散剤の０〜３００倍重量程度の濃度である。好ましくは５０〜２００倍重量程度の濃度である。なお、上記支持塩を用いなくても、電解処理を実行することは可能である。
【００５５】
支持塩を用いない場合には、支持塩を含まない純度の高い薄膜を得ることができる。また、支持塩を用いる場合、その支持塩の種類は、ミセルの形成や電極への疎水性粒子の析出を妨げることなく、水性媒体の電気伝導度を調節しうるものであれば特に制限はない。具体的には、一般に広く支持塩として用いられている硫酸塩（リチウム、カリウム、ナトリウム、ルビジウム、アルミニウム等の塩）、酢酸塩（リチウム、カリウム、ナトリウム、ルビジウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム等の塩）、ハロゲン化物塩（リチウム、カリウム、ナトリウム、ルビジウム、カリウム、マグネシウム、アルミニウム等の塩）、水溶性酸化物塩（リチウム、カリウム、ナトリウム、ルビジウム、カルシウム、マグネシウム、アルミニウム等の塩）が好適である。なお、これらの支持塩は単独で用いてもよく、２種類以上を組み合わせても良い。
【００５６】
また、上述した分散液の調整として支持塩を用いる他に、分散液にイオン交換樹脂を添加し、陽イオン性であるフェロセン誘導体界面活性剤の酸化体を吸着除去する方法がある。さらに、分散液の調整として、分散液に還元剤を添加して酸化体を還元する方法もある。
【００５７】
ここで、平衡濃度のうち酸化体の濃度は、４０μｇ／ｍｌ、好ましくは２０μｇ／ｍｌ以下、還元体の濃度は、５０〜３００μｇ／ｍｌ、好ましくは１００〜２００μｇ／ｍｌである。また、分散液の調整として、イオン交換樹脂と還元剤を併用することもできる。ここで、イオン交換樹脂としては、陽イオン交換樹脂およびキレート樹脂が使用できるが、フェロセン誘導体界面活性剤の酸化体を選択的に吸着し、還元体をあまり吸着しないものが好ましい。
【００５８】
具体的に陽イオン交換樹脂としては、メタクリル系およびアクリル系の弱酸性陽イオン交換樹脂、キレート系交換樹脂としてはイミノジ酢酸型キレート樹脂が好ましく、これらはリチウム型に置換して使用する。これは特に分散液が酸性の場合は、水素イオンが選択的に除去されることにより、フェロセンの酸化錫が抑制され分散液の長期安定性に寄与するためである。
【００５９】
還元剤としては、水溶性の還元剤が好ましく、具体的にはチオ硫酸塩、亜硫酸塩、亜リン酸塩、シュウ酸塩、クエン酸塩等が使用できる。なお、フェロセン誘導体界面活性剤の酸化体が還元されることにより還元体の濃度が過剰になりすぎ場合には、吸着剤を添加して過剰なフェロセン誘導体界面活性剤を吸着除去することが可能である。ここで使用される吸収剤としては、例えばシリカ、アルミナ、活性炭、スチレン、ジビニルベンゼン共重合体等のポリマー架橋体が使用できるが、特に分散液の安定性に影響を与えず少量の添加でフェロセン誘導体界面活性剤を吸着除去可能な、無極性の比表面積２００ｍ^２／ｇ以上の架橋構造を持つポリスチレン系の合成吸着剤が非常に好ましい。
【００６０】
次に、このようにして調整した疎水性粒子の分散液を、疎水性粒子濃度が所定の範囲にあれば、ミセル電解に利用する。ただし、疎水性粒子の濃度が所定の範囲より高ければ、水性媒体で希釈して疎水性粒子濃度を所定の範囲に調整したのち、これに吸着剤を添加して余剰なフェロセン誘導体界面活性剤を吸着させ、フェロセン誘導体界面活性剤の平衡濃度を所定の範囲に調整する。
【００６１】
次に、遠心分離などの公知手段によって、上記分散液中の吸着剤および粗大疎水性粒子を除去することにより、目的の分散液を製造することができる。
【００６２】
このようにして製造された分散液中の疎水性粒子濃度は、好ましくは０．２〜１０．０重量％、より好ましくは０．５〜５．０重量％の範囲である。また、フェロセン誘導体界面活性剤の還元体の濃度は、好ましくは５０〜３００μｇ／ｍｌ、より好ましくは１００〜２００μｇ／ｍｌの範囲である。
【００６３】
これまでのように、平衡濃度のを後で調整できない場合には、作成時の濃度で、作成する疎水性粒子の濃度を調整しなくてはならなかった。その理由は、疎水性粒子濃度を上げて分散させる場合は、過剰量の分散剤が必要であり、疎水性粒子濃度を所定値に合わせるために後で希釈する際、平衡濃度も希釈され、所定値になると考えられる。しかし、現実にはそれ以上の分散液を過剰に添加しないと、分散処理中に疎水性粒子が凝集して、分散できないからである。
【００６４】
なお、分散剤の平衡濃度は、下記の▲１▼染料可溶化法、▲２▼電気化学的法、▲３▼プラズマ発光分析法によって測定することができる。
【００６５】
▲１▼染料可溶化法
染料可溶化法においては、まず、疎水性粒子分散液を遠心分離処理したのち、その上澄み液を採取し、溶液の吸収スペクトルを測定する。次に、その溶液に染料を添加して溶解させたのち、余剰な染料を除去した上澄み液を分取する。この上澄みの吸収スペクトルを測定し、染料添加前に測定した溶液の吸収スペクトルとの差スペクトルを算出する。
【００６６】
一方、別途、染料を既知量の分散液（疎水性粒子の分散に使用したもの）で可溶化した溶液を調整し、この溶液の分散剤濃度と吸収スペクトルとの関係を示す検量線データと先に測定した差スペクトルから、分散剤の平衡濃度を算出する。この際、使用する染料としては、分散剤で可溶化可能な染料であればよく、特に制限されず、例えばアゾ系やフタロシアニン系などを用いることができる。
【００６７】
また、遠心分離処理における遠心力としては、疎水性粒子の比重にもよるが、疎水性粒子が沈降し、かつ平衡濃度の分散剤が沈降しないような遠心力であればよく、特に制限はない。
【００６８】
▲２▼電気化学的法
電気化学的法においては、まず、上記▲１▼の染料可溶化法と同様にして、遠心分散後の上澄みを採取し、微分パルスボルタンメトリー測定を行う。次に、この測定結果と、既知量の分散剤で微分パルスボルタンメトリーの測定を行って作成した検量線データとから、分散剤の平衡濃度を算出する。なお、この微分パルスボルタンメトリーの測定において、酸化性物質のピークの有無が確認できるので、イオン交換樹脂の適正な添加量を確認することもできる。
【００６９】
▲３▼プラズマ発光分析法
プラズマ発光分析法とは、上記▲１▼の染料可溶化法と同様にして遠心分離後の上澄みを採取し、プラズマ発光分析を行い、予め、作成しておいた検量線のデータから分散剤の平衡濃度を算出する方法である。このようにして製造された疎水性粒子の分散液を用いて、電解処理法により基板上に薄膜を形成させるには、上記分散液中にパターニングされた電極を侵漬し、この電極に通電し、電解処理すればよい。これにより、導電性基板上に疎水性粒子の薄膜が形成される。
【００７０】
この際の電解条件は、各種状況に応じて適宜選定すればよいが、通常は液温０〜５０℃、好ましくは５〜２５℃、電圧０．３〜１．５Ｖ、好ましくは０．４〜１．０Ｖである。なお、図１（１）Ｓ１−１に示されている本発明の電解成膜方法は、図２（２）Ｓ２−１に示されている従来方法の電解成膜方法とほぼ同様の内容である。
【００７１】
（２）弱水洗
前述の成膜後、必要な部分以外についている分散液を洗い流す。このとき、不要な分散液の除去は、導電性基板を水中に侵浸し、水流を当てて洗い流したり、空中でシャワー水流や、カーテン上の水流を当てることで達成される。ただし、この状態での成膜された薄膜の密着性は弱いため、基板付近での水流は５ｍ／秒以下、好ましくは１ｍ／以下、さらに好ましくは０．１ｍ／秒〜０．８ｍ／秒以下が望ましい。
【００７２】
さらに、洗い流した分散液が再度基板に付着しないように速やかに基板から離れる流れを作っておくことが望ましい。このとき使用する洗浄水の成分は、何も添加していない純水や超純水であってもよく、また、炭酸ガスやイオン性溶質、非イオン性溶質を溶かして水の導電性を高め、静電気が生じないようにし、静電気を帯びた粒子が基板に付着しにくくする効果を持たせても良い。
【００７３】
また、この洗浄中に、薄膜表面に気液界面が存在するとその部分で薄膜が乱れるために気液界面を生じさせない工夫が必要である。気液界面を生じさせない工夫としては、例えば、洗浄を完全に水中で行うことや、湿度１００％の水ミスト中で行うことが有効である。
【００７４】
また、次の凝集処理へ受け渡すときにも薄膜表面に気液界面を作らない工夫が必要である。弱洗水処理から凝集処理へ移行する際の薄膜表面に気液界面を作らない工夫としては、弱洗水処理後、基板上に水が残っている間に、次の段階である凝集処理へ移行することである。なお、薄膜を洗浄する洗浄水の温度は、５０度以下であることが望ましい。
【００７５】
なお、図１（１）Ｓ１−２に示されている本発明の弱水洗方法は、図２（２）Ｓ２−２に示されている従来方法の弱水洗方法とほぼ同様の内容であるが、気液界面を作らない点で従来方法と大きく異なる。
【００７６】
（３）凝集処理
次に、薄膜の密着強度を向上させるために、下記の凝集処理▲１▼〜▲３▼までのいずれか一つもしくは複数の組み合わせを選ぶことができる。また、凝集処理を行う際に薄膜上に気液界面が存在するとその部分での薄膜の乱れが生じるため、凝集処理はすべて水中で行うか、又は水ミスト中で実行することが有効である。
【００７７】
凝集処理▲１▼
界面活性剤が溶けていない水を使用した上記弱水洗は、微粒子に吸着した界面活性剤を取り除く効果があり、弱い凝集促進効果もある。しかし、さらに凝集を促進させるためには、水洗後の基板を昇温処理する。この昇温処理が、凝集処理▲１▼である。方法は、ＩＲ加熱や熱風による加熱など方法は問わない。
【００７８】
ただし、薄膜が気液界面にさらされると膜が乱れる恐れがあるため、５０℃以上の温水に薄膜をさらす処理が望ましい。このときの温度は、微粒子の凝集を促進させる目的であるため、７０℃以上がさらに望ましく、上限として水が沸騰しない範囲で好適に処理が可能である。この処理時間は、１０分以下であり、望ましくは５分以下であることも好ましい。また場合によっては、３０秒以下で処理することも可能である。
【００７９】
密着性向上の原理は、昇温により分散液の平衡が微粒子析出側に大きく傾くことによる。特に、非イオン性の界面活性剤は、温度が上がるとポリオキシエチレン基の水分子との水素結合が離れ、相分離を起こすことが知られており、界面活性剤の分散能力喪失が膜の凝集促進を引き起こし、ひいては密着性向上に大きく寄与する機構の一つとなっている。
【００８０】
凝集処理▲２▼
また、密着強度を向上させるために、弱水洗洗浄水のｐＨが３．０〜７．０の酸性水を用いて、分散している微粒子の電荷を変化させることで凝集を促進させることもできる。この弱水洗洗浄水のｐＨが３．０〜７．０の酸性水を用いる処理が、凝集処理▲２▼である。
【００８１】
上記処理時間は、１０分以下であり、望ましくは５分以下である。場合によっては、３０秒以下で処理が可能である。このときの弱水洗洗浄水のｐＨは、透明電極を変化させないルイス酸を任意に選択することができる。例えば、リン酸二水素アンモニウムや、ホウ酸、酢酸、酒石酸、蟻酸等が好適に使用できる。
【００８２】
凝集処理▲３▼
また、密着強度を向上させるために、薄膜を分散液より浸透圧の高い水溶液に浸す処理を行うこともできる。この浸透圧の高い水溶液を用いる処理が、凝集処理▲３▼である。
【００８３】
上記凝集処理▲３▼の結果、薄膜中の水分が急速に排出され、薄膜の凝集が進み、密着強度が増す。この処理の時間は、１０分以下で十分な凝集処理が得られる場合が多い。しかし、５分以下で十分な凝集処理が実施できることが好ましい。また場合によっては、３０秒以下で処理が可能なこともある。
【００８４】
浸透圧を高める方法として、水に溶質を添加する方法が一般的である。浸透圧は、一定体積の溶液に含まれる溶質の種類やモル数が等しければ、溶質の種類に関係なく同じ値を示す束一的な性質を示す。このように、上記水溶液に溶質イオンが存在する場合には、分散微粒子の電荷をキャンセルする働きもあり、分散安定性を失う。このことは、凝集力を強め薄膜の密着性を向上する働きが存在することを意味する。
【００８５】
一般的に電解質は、水中で電離をするため、解離したイオン数に相関して、浸透圧が増幅される傾向が高い。分散液を作るときに混合した溶質成分より多くの溶質成分、又は解離イオンを溶かした水溶液で作り、薄膜に作用させることで凝集処理ができる。
【００８６】
また、ここで用いる溶質は、水に溶解する溶質であればどのようなものでも良いし、また、分散液成分と同じものであっても、違っても良く、また、塩化ナトリウムのような無機物でも良い。例えば、酒石酸ナトリウムなどの有機物でも使用可能である。また、上記溶質は固体ばかりでなく、アルコールやグリセリンのように水溶性の常温で液体の物質でも良い。
【００８７】
分散液と処理液の浸透圧の差を調べるためには、図２のような装置で簡便に調べることができる。半透膜３２によって隔てられた容器に処理液２８を入れ、分散液３０の水面と処理液２８の水面を合わせる。処理液２８の浸透圧が分散液３０の浸透圧より高い場合は、処理液２８の水面が上昇する。なお、処理液３０に１０％ＮａＣｌ水溶液を選択した場合、水面が上昇し、分散液３０より浸透圧が高いことがわかった。また、０．１％ＮａＣｌ水溶液を選択した場合、水面は、やや下がったため、本発明の実施の形態の分散液３０より浸透圧が低いことがわかった。なお、図１（１）Ｓ１−３に示されている凝集処理行程が、上記凝集処理▲１▼〜▲３▼に相当する。また、図１（１）Ｓ１−３に示されている凝集処理行程、および上記凝集処理▲１▼〜▲３▼は従来の薄膜製造方法にはなかった本発明に特徴的な処理である。
【００８８】
（４）乾燥
上記凝集処理の次に乾燥工程を実行する。密着強度が増した薄膜は、乾燥工程を経ると凝集がさらに進み、微粒子同士の密着性が高まる。具体的な乾燥工程としては、熱風による乾燥や、エアーナイフによる水切り等による処理が好適に使用可能である。また、乾燥行程を実行する際には、薄膜の水分を均一に、かつ速やかに除くことが、均一な薄膜を得るために望ましい。
なお、図１（１）Ｓ１−４に示されている乾燥処理は、上記乾燥工程を意味し、図２（２）Ｓ２−３に示されている従来方法の乾燥処理とほぼ同様の内容である。
【００８９】
（５）応力除去
次に、薄膜に生じた応力を除去するために、以下に示す応力除去行程▲１▼、▲２▼中、一つもしくは２つを選択して実行する。
【００９０】
応力除去▲１▼
電解処理により形成された薄膜は、上記凝集処理と上記乾燥処理によって、高い密着性を得ることができる。しかし、急激な凝集行程を経るため、薄膜にはストレスが蓄積される場合がある。また、薄膜を乾燥させた直後に水をかけると、ストレスによる剥離が生じる場合がある。そこで、上記凝集処理と乾燥処理により生じるストレスを効率よく開放する方法として、溶媒の湿澗処理が有効である。また、溶媒の蒸気にさらすことによる処理も有効である。この溶媒による湿澗処理又は蒸気にさらす処理が応力除去行程▲１▼である。
【００９１】
上記湿澗処理および蒸気にさらす処理をする際に使用可能な溶媒としては、薄膜となる微粒子に親和性が高いものであれば自由に選択できる。特にアルコールやケトンが望ましく、さらに望ましくはエタノールやメタノールが良い。
【００９２】
応力除去▲２▼
電解処理により形成された薄膜は、上記凝集処理と上記乾燥処理によって、高い密着性を得ることができる。しかし、このようにして作られた薄膜は、熱を受けることで、熱膨張をする場合がある。このとき、基板との熱膨張係数の違い等により薄膜にストレスが生じる場合がある。そこで、薄膜に生じた力を逆に利用して応力を除去する。この薄膜に生じた力を利用する処理が応力除去行程▲２▼である。
【００９３】
処理温度は、薄膜が受けた熱履歴より高い温度であればよく、望ましくは１００℃以上、さらに望ましくは１５０℃以上２００℃以下の温度が好適である。処理温度が、２００℃を超えると、微粒子が空気酸化を受けやすくなるため注意が必要である。なお、この応力除去行程▲２▼は請求の範囲に記載されている熱アニール処理の一例に相当する。
【００９４】
また、図１（１）Ｓ１−５に示されている応力除去行程処理および上記応力除去行程▲１▼・▲２▼は、従来の薄膜製造方法にはなかった本発明に特徴的な処理方法である。
【００９５】
（６）強水洗
このようにして、上記電解成膜、弱水洗、凝集処理、乾燥、応力除去を経て形成された薄膜は、次の行程である２色目、３色目、あるいは保護膜塗布行程へと進む前に、本水洗を行う。これを強水洗と呼ぶ。すなわち、強い水流により薄膜上の異物等を洗い流すことである。
【００９６】
なお、図１（１）Ｓ１−６に示されている本発明の強水洗処理は、従来の薄膜製造方法にはなかった特徴的な処理方法である。
【００９７】
（７）その他（ガラス基板および顔料。特にカラーフィルタに関する。）
導電性基板としては、アルミニウム等の金属基板、あるいはガラス（無アルカリガラス、石英ガラス、ソーダライムガラス等）、プラスチック、セラミックス等の絶縁性基板上に、ＩＴＯ（インジウムチンオキシド）、二酸化錫、白金、グラファイト、クロム、ニッケル、酸化アンチモン等の導電性薄膜を設けたものを用いることができる。このようにして導電性基板上に形成された疎水性粒子の薄膜には、必要に応じて、後処理として平坦膜剤を用いて保護膜が形成され、その表面は保護される。 薄膜に保護膜を形成するには、まず、薄膜が形成された基板をスピンコーターにセットし、ディスペンサーを用いて平坦膜剤を基板表面に滴下後、基板を高速で回転させ均一に平坦膜剤を塗布する。
【００９８】
次に、所定温度で所定時間ベーク（焼成）し硬化させることにより薄膜に保護膜を形成することができる。
【００９９】
カラーフィルタは、疎水性粒子として有機顔料粒子を用い、上記のようにして、製造した疎水性粒子の分散液を使用し、透明基板上に、三原色であるＲＧＢ（Ｒ：赤色、Ｇ：緑色、Ｂ：青色）の顔料薄膜を形成したものである。
【０１００】
カラーフィルタの製造するには、透明基板として、パターニングされた透明電極を有する透明基板が用いられる。
【０１０１】
このような基板としては、ディスプレイを形成する画素形状に合わせてパターニングされたＩＴＯ電極を有するガラス基板が好適である。
【０１０２】
また、ＲＧＢの有機顔料としては、耐光性、耐熱性、耐薬品性に優れたものが好ましく単独又は２種類以上を混合して任意に用いることができる。
【０１０３】
代表的な有機顔料の具体例として、カラーインディクスナンバー（ＣＩ）で示すと、ピグメントレッド９，８１，９７，１２２，１２３，１４４，１４６，１４９，１６６，１６８，１６９，１７７，１８０，１９２，２０９，２１５，２１６，２１７，２２０，２２３，２２４，２２６，２２７，２２８，２４０，２５４の赤色顔料、ピグメントイエロー１，３，１２，１３，１４，１７，２０，２４，３４，５５，７４，８１，８３，８６，９３，１０１，１１３，１１７，１２５，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５２，１５３，１５４，１６６，１６８，１７３，１８１，１８５，１９９の黄色顔料、ピグメントオレンジ１３，３１，３６，３８，４０，４２，４３，５１，５５，５９，６１，６４，６５，７１の橙色顔料、ピグメントグリーン７，３６の緑色顔料、ピグメントブルー１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４の青色顔料、ピグメントバイオレット１９，２３，２９，３０，３７，４０，５０の紫色顔料等が挙げられる。これらの有機顔料には、薄膜の導電性や誘電率を制御するために導電性粒子や高誘電率粒子を混合分散しても良い。
【０１０４】
本発明において用いられる導電性粒子としては、ＩＴＯ、導電性酸化錫（ＳｎＯ_２、ＳｎＯ_２・Ｓｂ）、導電性酸化亜鉛（Ａｌドーブ酸化亜鉛、アンチモン酸亜鉛、（ＺｎＯ・Ｓｂ_２Ｏ_５））、さらにはＳｉＯ_２、ＴｉＯ_２や硫酸バリウムを導電酸化錫でコートした複合粒子等が使用でき、これらはカップリング剤やポリマー処理により表面を疎水科して使用する。
【０１０５】
高誘電率粒子としてはチタン酸バリウム等を用いることができる。また、場合によっては、膜厚調整を目的として、成膜する際に上記導電性粒子と同時に使用される粒子として、ＳｉＯ_２、ＴｉＯ_２ 、ＺｎＯ、Ａｌ_２Ｏ_３ 等の超微粒子を疎水化処理したものが挙げられる。上記導電性粒子は単独で用いてもよく、二種以上を組み合わせて用いても良い。
カラーフィルタを構成する三原色の有機顔料薄膜を形成するには、赤色、緑色、および青色の有機顔料のいずれか一つを含む分散液を用い、上述の薄膜製造方法における操作により、所望色調の薄膜を所望のパターンで形成する。
【０１０６】
次に、有機顔料の種類を変えて上述の操作を繰り返し行えば、ＲＧＢのカラーフィルタの薄膜を得ることができる。このようにして得られたＲＧＢのカラーフィルタには、必要に応じて、後処理として、保護膜が形成される。その保護膜を形成するに当たっては、上記の薄膜のときと同様にして保護膜を形成しても良いし、常法であるスピンコートを用いて保護膜を形成しても良い。このようにしてＲＧＢのカラーフィルタの表面を保護する。ただし、導電性のカラーフィルタの場合は、保護膜は液晶を駆動するのに十分な電圧を通す印加できる厚さにしなければならない。
【０１０７】
次に、上記の薄膜のときと同様にして保護膜を形成し、ＲＧＢのカラーフィルタの表面を保護する。
【０１０８】
また、薄膜に導電性がない場合は、このＲＧＢのカラーフィルタの上から常法によりＩＴＯ薄膜を形成することによりカラーフィルタを製造することができる。
【０１０９】
本発明の好適な実施例について説明する。
【０１１０】
【実施例１】
（１）顔料分散液の製造
赤色有機顔料分散液の調製は、フェロセン誘導体界面活性剤として上記に示す「化１」の式で表されるＩＤＦＥ８．２重量部、疎水性粒子として赤色顔料Ｃ．Ｉ．ピグメントレッド１７７ ５０．０重量部、リチウムブロマイド１ 水和物１．０５重量部を純水１０００重量部に加え混合し、超音波ホモジナイサーを用いて分散した。その後、１００００ｒｐｍで遠心分離して粗大粒子を除去した。
【０１１１】
次に、この分散・分級処理した顔料分散液の固形分濃度および平衡濃度を測定した。その後、固形分濃度が２．０重量％になるように、ＩＤＦＥ濃度が１５０μｇ／ｍｌのリチウムブロマイド０．０１ｍｏｌ／ｌ水溶液で希釈し、Ｃ．Ｉ．ピグメントレッド１７７顔料分散液を調製した。
【０１１２】
また、ＩＤＦＥ９．４５重量部、疎水性粒子として黄色顔料Ｃ．Ｉ．ピグメントイエロー８３ ５０．０重量部、リチウムブロマイド１ 水和物１．０５重量部を純水１０００重量部に加え混合し、超音波ホモジナイサーを用いて分散した。その後、１００００ｒｐｍで遠心分離して粗大粒子を除去した。
【０１１３】
次に、この分散・分級処理した顔料分散液の固形分濃度および平衡濃度を測定した後、固形分濃度が２．０重量％になるようにＩＤＦＥ濃度１５０μｇ／ｍｌのリチウムブロマイド０．０１ｍｏｌ／ｌ水溶液で希釈し、Ｃ．Ｉ．ピグメントイエロー８３顔料分散液を調製した。
【０１１４】
このように、得られたＣ．Ｉ．ピグメントレッド１７７ 顔料分散液７５重量部と、Ｃ．Ｉ．ピグメントイエロー８３ 顔料分散液２５重量部とを混合し、赤色顔料分散液を調製した。
【０１１５】
（２）顔料薄膜の電解成膜
まず、顔料分散液に、ＩＴＯ（インジウム錫酸化物）透明電極の付いたガラス基板を浸漬した。次に、対向電極は、ＩＴＯ電極面積の１．２倍以上の表面積を持つステンレス板を使用した。ここで、参照極は、東亜ＤＫＫ社製のＡｇ／ＡｇＣｌ（銀／塩化銀）電極を用いた。また、電源は、北斗電工株式会社製造のポテンショスタット／ガルバノスタットＨＡ−１５１を用いた。
【０１１６】
次に、ＩＴＯ電極（＋）とＳＵＳ電極（−）と参照極（ＲＥ）とを接続し、ＩＴＯ電極に参照極基準として、０．５Ｖを１０分印加した。ここで、ＳＵＳ電極（−）とは、ステンレス板を使用した電極である。
【０１１７】
次に、電極上に顔料薄膜を形成し、実施例・比較実施例に示した実験に供した。
【０１１８】
（３）曇値の測定
成膜した顔料膜の均一性の測定はＨＡＺＥにより評価した。なお、この表中、ＨＡＺＥとは、製造した薄膜の透明性を示す指標であり、以下の式で表せる。
【０１１９】
【数１】
ＨＡＺＥ＝［（拡散した光の通過率）／（通過した光の透過率）］×１００
このＨＡＺＥの値は小さいほど、透明性が高いことを意味する。具体的には、ＨＡＺＥの値が１０未満が望ましく、さらに望ましくは５以下である。
【０１２０】
ＨＡＺＥの値は、ＨＡＺＥメータを用いて測定する。用いたＨＡＺＥメータは、スガ試験機株式会社製のＨＧＭ−２ＤＰ型のＨＡＺＥメータである。この装置は、全自動直読ヘーズコンピュータであり、その測定スポットサイズは７ｍｍφにセットした。また、実際の測定の際には、一枚の基板中の３カ所を測定し、その平均値を最終的な測定として採用し、表１、表２，表３、表４中に記載した。
【０１２１】
（４）顔料薄膜の形成
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１２２】
次に、基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０℃の温水に１５秒間、純水により洗浄した顔料薄膜付基板を浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて、顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、上記乾燥窒素を用いることによって目視で瞬時に乾燥していることが確認できた。
【０１２３】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて、基板上に顔料薄膜を得た。このようにして得られた顔料薄膜は、非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例１の結果が表１、表２、表３、表４中に示されている。
【０１２４】
【表１】

【表２】

【表３】

【表４】

【実施例２】
以下に述べる実施例２においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１２５】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１２６】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、純水により洗浄した顔料薄膜付基板を、７０℃の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて、顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できた。
【０１２７】
次に、顔料薄膜をエタノールに１５秒間浸漬した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて、基板上に顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例２の結果が表２中に示されている。
【０１２８】
【実施例３】
以下に述べる実施例３においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１２９】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１３０】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、５％ＮａＣｌ水溶液（塩化ナトリウム）に浸して凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて、顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１３１】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは５であった。なお、実施例３の結果が表２中に示されている。
【０１３２】
【実施例４】
以下に述べる実施例４においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１３３】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１３４】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、ｐＨ５の酸性水に浸して凝集処理を行った。なお、酸性水は、０．１モル／リットル酢酸水溶液と０．１モル／リットル酢酸ナトリウム水溶液の割合が、酢酸が１に対し、酢酸ナトリウムが２となるような体積比で混合したものを用いた。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて、顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。次に、顔料薄膜付基板をエタノールに１５秒間浸浸した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例４の結果が表２中に示されている。
【０１３５】
【実施例５】
以下に述べる実施例５においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１３６】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１３７】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、顔料薄膜付基板をほぼ垂直に立てかけ、重力によりゆっくりと水を切り、１２０度に設定したホットプレートに載せて５分間乾燥した。次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは５であった。なお、実施例５の結果が表３中に示されている。
【０１３８】
【実施例６】
以下に述べる実施例６においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１３９】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１４０】
次に、顔料薄膜付基板表面に水が残っている間に、基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、水滴が顔料薄膜付基板表面に残らないようにゆっくりと洗浄水槽の中から引き上げ、１２０度に設定したホットプレートに載せて５分間乾燥した。次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは４であった。なお、実施例６の結果が表３中に示されている。
【０１４１】
【実施例７】
以下に述べる実施例７においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１４２】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１４３】
次に、顔料薄膜付基板表面に水が残っている間に、基板表面に気液界面が生じないように速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１４４】
次に、顔料薄膜付基板をメタノールに１５秒間浸漬した。次に、メタノールに浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例７の結果が表４中に示されている。
【０１４５】
【実施例８】
以下に述べる実施例８においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１４６】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１４７】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１４８】
次に、顔料薄膜付基板をＩＰＡ（イソプロピルアルコール）に１５秒間浸漬した。次に、ＩＰＡ（イソプロピルアルコール）に浸漬した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは４であった。なお、実施例８の結果が表４中に示されている。
【０１４９】
【実施例９】
以下に述べる実施例９においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１５０】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１５１】
次に、顔料薄膜付基板表面に水が残っている間に、基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１５２】
次に、顔料薄膜付基板をエタノール蒸気が充満するビーカー中に１５秒〜２０秒入れた。次に、エタノール蒸気が充満するビーカーから顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一あった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例９の結果が表４中に示されている。
【０１５３】
【実施例１０】
以下に述べる実施例１０においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１５４】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１５５】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１５６】
次に、顔料薄膜付基板を水蒸気が充満する十分に保温されたビーカー中に１５秒〜２０秒入れた。次に、水蒸気が充満するビーカーから顔料薄膜付基板を取り出し、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは５であった。なお、実施例１０の結果が表４中に示されている。
【０１５７】
【実施例１１】
以下に述べる実施例１１においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１５８】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。まず、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１５９】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１６０】
次に、顔料薄膜付基板を１５０度に昇温されたホットプレート上に５分間載せた。次に、ホットプレート上に載せた顔料薄膜付基板を取り出し、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例１１の結果が表４中に示されている。
【０１６１】
【実施例１２】
以下に述べる実施例１２においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１６２】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１６３】
次に、顔料薄膜付基板表面に水が残っている間に、顔料薄膜付基板表面に気液界面が生じないよう速やかに、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。
【０１６４】
次に、上記顔料薄膜付基板を１００度に昇温されたホットプレート上に５分間載せた。次に、ホットプレート上の顔料薄膜付基板を取り出し、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は非常に透明で均一であった。また、顔料薄膜の乱れは観察されず、ＨＡＺＥは３であった。なお、実施例１２の結果が表４中に示されている。
【０１６５】
【比較実施例１】
以下に述べる比較実施例１においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１６６】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１６７】
次に、顔料薄膜付基板を立てかけて、顔料薄膜付基板上の水を緩やかに除いた。顔料薄膜付基板上の水を取り除いた。従来は、上記水が排出される過程で、顔料薄膜付基板表面に気液界面が生じていた。次に、顔料薄膜付基板上の水がなくなった時点で１２０度に昇温したオーブンに入れ、１５分間乾燥を行った。このようにして得られた顔料薄膜は、顔料薄膜の乱れが観察され、ＨＡＺＥは１５であった。また、気液界面に起因するムラが確認できた。
【０１６８】
なお、比較実施例１の結果が表１、表２、表３、表４中に示されている。また、比較実施例１は従来技術を意味するが、便宜上、「実施例」の語を用いた。これに対して、以下に示す比較実施例２〜１２は本発明における実施例１〜１２と比較すべく設けられた本発明の他の実施例であり、従来技術を意味するものではない。
【０１６９】
【比較実施例２】
以下に述べる比較実施例２においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１７０】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、８０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。しかし、エアーナイフの風圧で顔料薄膜の乱れが観察された。
【０１７１】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸した顔料薄膜を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で表面を洗い流した。そして最後に、表面を乾燥させて顔料薄膜付基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、顔料薄膜表面および顔料薄膜付基板の裏面に顔料分散液の凝集物がうっすらとかつ不定形に堆積した顔料薄膜が得られた。なお、ＨＡＺＥは２２であった。また、比較実施例２の結果が表１中に示されている。
【０１７２】
【比較実施例３】
以下に述べる比較実施例３においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１７３】
まず、上記方法にて電解成膜した顔料薄膜付基板を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、顔料薄膜付基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１７４】
次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。しかし、エアーナイフの風圧で顔料薄膜の乱れが観察された。
【０１７５】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸した顔料薄膜を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて顔料薄膜付基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、エアーナイフによる顔料薄膜の乱れをそのまま残した膜が得られた。なお、ＨＡＺＥは２０であった。 なお、比較実施例３の結果が表１中に示されている。
【０１７６】
【比較実施例４】
以下に述べる比較実施例４においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１７７】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１７８】
次に、８０温度の温水に１５秒浸し凝集処理を行った。次に、顔料薄膜付基板をエタノールに１５秒浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、アルコールにより顔料膜の溶解が起こり、膜の乱れが多い膜が得られた。なお、ＨＡＺＥは１８であった。また、比較実施例４の結果が表１中に示されている。
【０１７９】
【比較実施例５】
以下に述べる比較実施例５においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１８０】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１８１】
次に、上記顔料薄膜付基板を８０温度の温水に１５秒浸し凝集処理を行った。
次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素により水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できた。
【０１８２】
次に、顔料薄膜付基板を１５ｍ／ｓｅｃの強い流速の水で表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、強い水流で生じた顕微鏡で観察できる無数の小さなクラックが観察され、顔料薄膜の面積の半分以上が剥離した。なお、ＨＡＺＥは膜の剥離のため測定できなかった。なお、比較実施例５の結果が表１、表４中に示されている。
【０１８３】
【比較実施例６】
以下に述べる比較実施例６においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１８４】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１８５】
次に、顔料薄膜付基板上に洗浄水と空気の気液界面を数回作った。次に、顔料薄膜付基板を８０温度の温水に１５秒浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できた。
【０１８６】
次に、顔料薄膜付基板をエタノールに１５秒浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、気液界面による膜の乱れが観察された。なお、ＨＡＺＥは９であった。また、比較実施例６の結果が表１中に示されている。
【０１８７】
【比較実施例７】
以下に述べる比較実施例７においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１８８】
上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１８９】
次に、上記顔料薄膜付基板を８０度の温水に１５秒浸し凝集処理を行った。このとき、顔料薄膜付基板を温水から数回引き上げ、顔料薄膜上に温水と空気の気液界面を数回作った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素により水を均一に取り除いた。なお、顔料薄膜付基板は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できた。
【０１９０】
次に、顔料薄膜付基板をエタノールに１５秒浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、気液界面による膜の乱れが観察された。なお、ＨＡＺＥは１０であった。また、比較実施例８の結果が表１中に示されている。
【０１９１】
【比較実施例８】
以下に述べる比較実施例８においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１９２】
次に、顔料薄膜付基板を４０度の温水に１５秒間浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できが、エアーナイフの風圧で顔料薄膜の乱れが観察された。
【０１９３】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、エアーナイフによる顔料薄膜の乱れをそのまま残した膜であった。なお、ＨＡＺＥは１２であった。なお、比較実施例８の結果が表２中に示されている。
【０１９４】
【比較実施例９】
以下に述べる比較実施例９においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１９５】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０１９６】
次に、顔料薄膜付基板をｐＨ７．４のリン酸塩ｐＨ標準液（ＪＩＳ Ｋ ００２３）に浸して凝集処理を行った。しかし、上記ｐＨ７．４のリン酸塩ｐＨ標準液（ＪＩＳ Ｋ ００２３）はやや塩基性であり、上記ｐＨ水溶液では十分な凝集処理が起こらなかった。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できが、エアーナイフの風圧で顔料膜の乱れが観察された。
【０１９７】
次に、顔料薄膜付基板をエタノールに１５秒間浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、エアーナイフによる顔料膜の乱れをそのまま残した膜であった。なお、ＨＡＺＥは１５であった。なお、比較実施例９の結果が表２中に示されている。
【０１９８】
【比較実施例１０】
以下に述べる比較実施例３においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０１９９】
上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０２００】
次に、顔料薄膜付基板を０．１％ＮａＣｌ（塩化ナトリウム）水溶液に浸して凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素を用いて顔料薄膜付基板上の水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できが、エアーナイフの風圧で顔料薄膜の乱れが観察された。
【０２０１】
次に、上記顔料薄膜付基板をエタノールに１５秒浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、エアーナイフによる顔料薄膜の乱れをそのまま残した膜であった。なお、ＨＡＺＥは１４であった。なお、比較実施例１０の結果が表２中に示されている。
【０２０２】
【比較実施例１１】
以下に述べる比較実施例１１においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０２０３】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０２０４】
次に、顔料薄膜付基板を８０度の温水に１５秒浸し凝集処理を行った。次に、エアーガンにより手動で乾燥窒素を上記顔料薄膜に吹きつけ、上記顔料薄膜付基板の水を取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥していることが確認できた。しかし、エアーガンから噴出する窒素は一度に顔料薄膜付基板の一部分しか覆うことができず、一度に顔料薄膜付基板全体を乾燥することはできなかった。その結果、顔料薄膜が乱れた。
【０２０５】
次に、顔料薄膜付基板をエタノールに１５秒浸漬した。次に、エタノールに浸した顔料薄膜付基板を引き上げ、アルコールが乾く前に、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、エアーガンによる薄膜の乱れをそのまま残した膜になった。なお、ＨＡＺＥは１１であった。なお、比較実施例１１の結果が表３中に示されている。
【０２０６】
【比較実施例１２】
以下に述べる比較実施例１２においては、（１）顔料分散液の製造、（２）顔料薄膜の電解成膜、（３）膜の均一性の測定については、実施例１と同様である。以下、（４）顔料薄膜の形成について実施例１と異なる点を述べる。
【０２０７】
まず、上記方法にて電解成膜した顔料薄膜を、顔料分散液から速やかに引き上げ、純水により洗浄した。なお、基板に当たる水の流速は０．５ｍ／ｓｅｃであった。
【０２０８】
次に、顔料薄膜付基板を８０度の温水に１５秒浸し凝集処理を行った。次に、エアーナイフ（スリット幅０．０５ｍｍ、窒素圧０．２ｋｇ／ｃｍ^２）の乾燥窒素により水を均一に取り除いた。なお、顔料薄膜付基板表面は、乾燥窒素を用いたため目視で瞬時に乾燥されていることが確認できた。
【０２０９】
次に、上記顔料薄膜付基板を８０度に昇温されたホットプレート上に５分間載せ、取り出し、１５ｍ／ｓｅｃの強い流速の水で顔料薄膜付基板表面を洗い流した。そして最後に、顔料薄膜付基板表面を乾燥させて基板上の顔料薄膜を得た。このようにして得られた顔料薄膜は、強い水流で生じた顕微鏡で観察できる小さなクラックが観察され、顔料薄膜の面積の一部が剥離していた。なお、剥離した部分を除いた顔料薄膜のＨＡＺＥは９であった。また、比較実施例１２の結果が表４中に示されている。
【０２１０】
【発明の効果】
以上、詳細に説明したように、本発明においては、疎水性粒子を水性溶媒中でフェロセン誘導体よりなるミセル化剤を用いて可溶化し、得られたミセル溶液を電解処理し、電極上に前記疎水性粒子の薄膜を形成し、前記電解処理により形成した薄膜の凝集処理を施したので、高強度かつ均一性の高い膜を製造できることができる。
【０２１１】
また、上記疎水性粒子に顔料粒子を用いた場合には、透明性、色特性に優れた膜が得ることができる。
【０２１２】
また、本発明の製造方法によれば、上記のような効果が得られる微粒子を成分とする薄膜を製造することができる。
【０２１３】
【図面の簡単な説明】
【図１】本発明と従来技術との比較図である。
【図２】本実施の形態における分散液と処理液の浸透圧の差を調べる装置の図である。
【符号の説明】
１０ Ｓ１−１ 電解成膜
１２ Ｓ１−２ 弱水洗
１４ Ｓ１−３ 凝集処理
１６ Ｓ１−４ 乾燥
１８ Ｓ１−５ 応力除去
２０ Ｓ１−６ 強洗水
２２ Ｓ２−１ 電解成膜
２４ Ｓ２−２ 弱洗水
２６ Ｓ２−３ 乾燥
２８ 処理液
３０ 分散液
３２ 半透膜[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a thin film. In particular, the present invention relates to a method for producing a thin film using a micelle electrolysis method.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, micelle electrolysis has been intensively researched and developed as a method of manufacturing a thin film used for a liquid crystal color filter, a solar cell, and the like, and has been targeted for development. In particular, thin films produced by the micellar electrolysis method have attracted attention because they are used for color filters for liquid crystals. The following is a reason why the micellar electrolysis method is receiving attention.
[0003]
(1) A large voltage is not required for forming the color filter layer.
[0004]
According to the micellar electrolysis method, a color filter film can be formed with a voltage of less than 1 volt based on a silver / silver chloride reference electrode.
[0005]
(2) Positioning (alignment) of the red, blue, and green color filter layers is easy.
[0006]
One of the classic methods of forming a color filter is a method (photolithography) in which a mask is made of a photoresist for each color, and a pigment of a color corresponding to each color is laminated using the mask. Such a method tends to be a very complicated operation when making a pattern with a photoresist, and often the mask position is shifted. On the other hand, in the micellar electrolysis method, the electrode for applying a voltage to the liquid crystal can be used as it is as the electrode in the micelle electrolysis method. Pigment can be accumulated.
[0007]
(3) It is easy to imagine that it is technically difficult to maintain high accuracy with a photolithography apparatus that is enlarged according to the substrate size.
[0008]
At present, the size of a glass substrate for a display (mother glass) has been steadily expanding, and in a category called the fifth generation, the size of the glass substrate has exceeded 1 m on a side. In addition, in the sixth generation, a standard with one side exceeding 1.5 m has appeared. The size of a unit component constituting a pixel of a liquid crystal display needs to be aligned with an accuracy of micron to submicron. However, in the micelle electrolysis method, since a film is formed by an electrochemical reaction that occurs along an underlying electrode pattern, a decrease in positional accuracy due to an increase in substrate size is an excellent method that does not occur in principle. As described above, the micelle electrolysis method has very favorable characteristics for forming a color filter.
[0009]
Here, the micelle electrolysis method is to solubilize a hydrophobic substance using a micellizing agent comprising a ferrocene derivative in an aqueous solvent, subject the resulting micelle solution to electrolytic treatment, and deposit a thin film of the hydrophobic substance on an electrode. It is a method of forming. This micelle electrolysis method is disclosed in Patent Document 1, for example.
[0010]
Patent Document 2 discloses a micelle dispersion liquid suitable for producing a color filter and a method for producing the same. The micelle dispersion has the same meaning as the micelle solution.
[0011]
Further, Patent Document 3 describes a method for manufacturing a color filter for a liquid crystal display using a micellar electrolysis method. This document describes a method in which a transparent electrode is formed on a transparent substrate, and a color filter using a coloring agent is formed on the transparent electrode by micellar electrolysis. In particular, a method using a micellar electrolysis method using a micelle solution containing a pigment as a colorant and transparent conductive particles having a hydrophobic surface is described. According to such a method, the color filter can be made conductive, and the voltage from the transparent electrode can be efficiently applied to the liquid crystal.
However, the pigment film immediately after electrolytic film formation by the conventional micellar electrolysis method is soft because the adhesion force of the pigment particles is weak, and may be easily peeled off in a washing step after film formation.
[0012]
Various measures have been conventionally devised for such a problem.
[0013]
For example, Patent Literature 4 described below discloses a method of controlling the surface tension of cleaning water to prevent film peeling in the cleaning step to prevent film peeling.
[0014]
Patent Document 5 also discloses a method for improving the strength of a pigment film using a film structure reinforcing agent.
[0015]
[Patent Document 1]
JP-A-63-243298
[Patent Document 2]
JP-A-2000-256894
[Patent Document 3]
Patent No. 3044788 (International application number: PCT / JP94 / 00780)
[Patent Document 4]
Patent No. 3290131
[Patent Document 5]
Patent No. 1864226
[0016]
[Problems to be solved by the invention]
However, in the method disclosed in Patent Document 4, handling may be difficult because the original strength of the pigment film is not improved.
[0017]
Further, in the method disclosed in Patent Document 5 described above, in the current trend of increasing the size of glass substrates and shortening the process time, a large amount of substrates must be processed in a short time. In some cases, the cleaning of the substrate cannot be completed. As described above, in the method disclosed in Patent Literature 5, it may not be possible to expect a pigment film that withstands strong detergency, that is, a further improvement in film strength.
[0018]
As for the above problems, the present inventors have conducted intensive studies and found that the hydrophobic particles were solubilized in an aqueous solvent using a micellizing agent comprising a ferrocene derivative, and the obtained micelle solution, that is, the dispersion was subjected to electrolytic treatment. In the method for producing a thin film of a hydrophobic substance on an electrode, it has been found that excellent results can be obtained by performing an aggregation treatment in order to improve the adhesion of the obtained pigment thin film. Specifically, it has been found that by employing the above method, the adhesion strength of the pigment film is remarkably improved, and the handling becomes easy.
That is, an object of the present invention is to provide a method for improving the strength of a pigment film immediately after film formation and quickly producing a pigment thin film of stable quality.
[0019]
Means to be Solved by the Invention
1. The present invention provides a method for solubilizing hydrophobic particles using a micellizing agent comprising a ferrocene derivative in an aqueous solvent, and subjecting the resulting micelle solution, that is, a dispersion, to electrolytic treatment to form a thin film of the hydrophobic substance on an electrode. In the method for producing a thin film, the obtained pigment thin film is subjected to a coagulation treatment.
[0020]
According to such a configuration, the adhesion of the thin film is improved.
[0021]
2. The present invention is characterized in that the aggregation treatment is a treatment at a temperature of 50 ° C. or more and a boiling point of water or less.
[0022]
This is because when the film formed by the electrolytic treatment is immersed under the condition that the water temperature is 50 ° C. or lower, a high strength and uniform film may not be obtained. A more preferable water temperature is 70 ° C. or higher.
[0023]
Next, the time for immersing the film formed by the electrolytic treatment under the condition that the water temperature is 50 ° C. or higher is preferably 5 to 600 seconds. If the treatment time is 600 seconds or longer, the film formed by the electrolytic treatment may be strained. Also, if the processing time is 5 seconds or less, a sufficient effect cannot be obtained, and a high-strength and uniform film may not be obtained. However, if the heat of the warm water is efficiently transmitted to the thin film by devising the water flow, a processing time of 5 seconds or less is possible. Further, a more preferable immersion treatment time is 15 seconds to 100 seconds.
[0024]
3. The present invention is characterized in that the coagulation treatment is performed with an acidic aqueous solution having a pH in a range of 7.0 to 3.0.
[0025]
The time for immersing the film formed by the electrolytic treatment in an acidic aqueous solution having a pH of 7.0 to 3.0 is preferably 5 to 600 seconds. However, if the heat of the warm water is efficiently transmitted to the thin film by devising the water flow, a processing time of 5 seconds or less is possible. Further, a more preferable immersion treatment time is 15 seconds to 100 seconds.
[0026]
The acidic aqueous solution is not particularly limited as long as it is a Lewis Acid which does not affect the transparent electrode. For example, ammonium dihydrogen phosphate, boric acid, acetic acid, tartaric acid, formic acid and the like can be suitably used.
[0027]
4. The present invention is characterized in that the aggregation treatment is performed with an aqueous solvent having an osmotic pressure higher than that of the dispersion.
[0028]
The aqueous solvent is not particularly limited as long as the aqueous solution has a high osmotic pressure and does not affect the thin film. Preferably, the aqueous solvent is an aqueous solution in which an inorganic substance such as sodium chloride or an organic substance such as sodium tartrate is dissolved.
[0029]
The time for treating the membrane formed by the electrolytic treatment with the aqueous solution medium having a high osmotic pressure with the micelle solution is preferably from 5 to 600 seconds. However, if the heat of the warm water is efficiently transmitted to the thin film by devising the water flow, a processing time of 5 seconds or less is possible. Further, a more preferable processing time is 15 seconds to 100 seconds.
[0030]
By executing the processes described in the above-mentioned means 1 to 4, strain stress may be generated in the film. Therefore, it is preferable to further execute the processing described in the following means 5 to 8 in order to remove the strain stress generated in the film.
[0031]
5. The present invention is characterized in that after the aggregation treatment, a drying step of the pigment thin film in the film formed by the electrolytic treatment is performed, and further, a stress removing step of the pigment thin film is performed.
[0032]
6. The present invention is characterized in that the stress relieving step is performed by direct wet treatment of the solvent or exposure to the vapor of the solvent.
[0033]
7. The present invention is characterized in that the solvent is a solvent containing alcohol and / or ketone.
[0034]
The solvent containing alcohol and / or ketone is preferably a solvent containing ethanol, 2-propanol and acetone.
[0035]
8. The present invention is characterized in that the stress removing step is a thermal annealing process.
[0036]
9. The present invention is characterized in that the method includes a step of performing a water-washing treatment at a water temperature of 50 ° C. or less on the thin film before the aggregation treatment.
[0037]
Here, the reason why the film formed by the above electrolytic treatment is washed with water at 50 ° C. or less before the aggregation treatment is to prevent the pigment dispersion liquid from being aggregated by the aggregation treatment and disturbing the substrate and the thin film. It is. Another reason is to remove the ferrocene derivative surfactant taken in the film formed by the electrolytic treatment.
[0038]
By removing the ferrocene derivative surfactant, a uniform film having high film strength can be manufactured.
[0039]
10. According to the present invention, in the method for producing a thin film, wherein the thin film is aggregated after the water washing process, a gas-liquid interface is not formed on the thin film when the water washing process is performed.
[0040]
By not forming a gas-liquid interface, disturbance of the thin film can be prevented.
[0041]
11. In the method for producing a thin film, wherein the aggregation treatment of the thin film is performed after the water washing process, a gas-liquid interface is not formed on the thin film when the process shifts from the water washing treatment to the aggregation treatment.
[0042]
Similarly, by not forming a gas-liquid interface on the thin film, disturbance of the thin film can be prevented.
[0043]
12. In the method of manufacturing a thin film, wherein the aggregation treatment of the thin film is performed after the water washing treatment, a gas-liquid interface is not formed on the thin film when the aggregation treatment is performed.
[0044]
Similarly, by not forming a gas-liquid interface on the thin film, the disturbance of the thin film can be prevented.
[0045]
13. The present invention is a thin film containing fine particles as a component, which is manufactured by the thin film manufacturing method described above.
[0046]
Here, the thin film containing fine particles as components has the same function and effect as the thin film manufactured by the above-described thin film manufacturing method.
[0047]
BEST MODE FOR CARRYING OUT THE INVENTION
A preferred embodiment of the present invention will be described.
[0048]
Note that a flowchart of the embodiment of the present invention is shown in FIG. 1 (1) in comparison with the conventional method of FIG. 2 (2).
[0049]
(1) Electrolytic film formation
In the present invention, first, hydrophobic particles and conductive particles are dispersed in an aqueous medium containing a ferrocene derivative surfactant as a dispersant.
[0050]
Here, the hydrophobic substance used in the present invention is not particularly limited as long as it is a particle whose surface shows hydrophobicity, and various substances can be used. The hydrophobic particles can be divided into hydrophobic organic particles and inorganic particles.
Examples of the hydrophobic organic particles include organic pigments, organic fluorescent materials, organic luminescent materials, organic photosensitive materials, and organic polymers. These particles are not particularly limited.
[0051]
Examples of the hydrophobic inorganic particles include inorganic particles obtained by subjecting the particle surface to a hydrophobic treatment, for example, conductive particles of ITO (indium tin oxide), tin oxide, zinc, or zinc oxide, titanium oxide, silica, and alumina. Can be The shape and size of the hydrophobic organic or inorganic particles are not particularly limited, but are preferably powders having a particle size of 10 μm or less.
[0052]
The ferrocene-based surfactant used is a surfactant containing a ferrocene derivative as an active ingredient, and includes various types such as nonionic, cationic, and anionic. Specifically, ammonium ferrocene derivatives as described in Japanese Patent Application No. 62-075930, ether ferrocene derivatives and ester ferrocene derivatives as described in International Application POT / JP88 / 00855, Japanese Patent Application No. No. 63-052696, and a pyridinium-type ferrocene derivative, as well as Japanese Patent Application Nos. 63-233798, 63-231745, 63-248601, and 01-04370. Japanese Patent Application No. 01-054956, Japanese Patent Application No. 01-070680, Japanese Patent Application No. 01-070681, Japanese Patent Application No. 01-076498, Japanese Patent Application No. 01-076498, Japanese Patent Application No. 01-076499, Japanese Patent Application No. Various ferrocene derivatives as disclosed in Japanese Patent Application No. 02-126616 and Japanese Patent Application No. 05-175058. It can be. Among these ferrocene-based surfactants, the following compounds are generally preferably used.
[0053]
Embedded image

Examples of the aqueous medium include various dispersion media such as water, a mixed liquid of water and alcohol, and a mixed liquid of water and acetone. At this time, the equilibrium concentration of the dispersion is not particularly limited as long as it is a concentration capable of dispersing the hydrophobic particles, and is usually 10 μg / ml or more. The upper limit of the equilibrium concentration of the dispersion can be up to a concentration at which the dispersant can be dissolved in the aqueous medium, and is not particularly limited.
[0054]
Here, the equilibrium concentration of the dispersant means the following concentration. Usually, when hydrophobic particles are dispersed in a dispersant solution, the dispersant is adsorbed on the surface of the hydrophobic particles. This adsorption reduces the concentration of the dispersant in the aqueous solution. After a sufficient time, the adsorption reaches equilibrium and the concentration of the dispersant in the aqueous solution becomes constant. The concentration of the dispersant in the aqueous solution in this state is called an equilibrium state. The equilibrium concentration can be determined by completely separating the hydrophobic particles by centrifugation and determining the concentration of the dispersant remaining in the aqueous solution. The concentration of the ferrocene derivative surfactant may be determined by analyzing iron. The concentration of the hydrophobic particles is not particularly limited as long as it can be dispersed. Typical concentrations of hydrophobic particles are 0.1-50.0% by weight, preferably 0.5-30.0% by weight. For adjusting the equilibrium concentration of the dispersion, a supporting salt (supporting electrolyte) may be used as necessary. This is because the use of this supporting salt makes it possible to adjust the electric conductivity of the aqueous medium. The amount of the supporting salt added may be within a range that does not hinder the dispersion of the hydrophobic particles. The usual addition amount of the supporting salt is about 0 to 300 times the weight of the dispersant. Preferably, the concentration is about 50 to 200 times the weight. The electrolytic treatment can be performed without using the above supporting salt.
[0055]
In the case where the supporting salt is not used, a thin film having a high purity containing no supporting salt can be obtained. When a supporting salt is used, the type of the supporting salt is not particularly limited as long as the electric conductivity of the aqueous medium can be adjusted without hindering formation of micelles and precipitation of hydrophobic particles on the electrode. . Specifically, sulfates (salts such as lithium, potassium, sodium, rubidium and aluminum) and acetates (lithium, potassium, sodium, rubidium, beryllium, magnesium, calcium, strontium, Salts of barium, aluminum, etc., halide salts (salts of lithium, potassium, sodium, rubidium, potassium, magnesium, aluminum, etc.), water-soluble oxide salts (lithium, potassium, sodium, rubidium, calcium, magnesium, aluminum, etc.) Are preferred. These supporting salts may be used alone or in combination of two or more.
[0056]
In addition to the use of a supporting salt to adjust the above-mentioned dispersion, there is a method of adding an ion-exchange resin to the dispersion and adsorbing and removing an oxidized form of a cationic ferrocene derivative surfactant. Further, as a method for preparing a dispersion, there is a method in which a oxidant is reduced by adding a reducing agent to the dispersion.
[0057]
Here, of the equilibrium concentrations, the concentration of the oxidant is 40 μg / ml, preferably 20 μg / ml or less, and the concentration of the reductant is 50 to 300 μg / ml, preferably 100 to 200 μg / ml. In addition, an ion exchange resin and a reducing agent can be used in combination for adjusting the dispersion liquid. Here, as the ion exchange resin, a cation exchange resin and a chelate resin can be used, but those which selectively adsorb the oxidized form of the ferrocene derivative surfactant and do not adsorb much the reduced form are preferable.
[0058]
Specifically, the cation exchange resin is preferably a methacrylic or acrylic weakly acidic cation exchange resin, and the chelate exchange resin is preferably an iminodiacetic acid type chelate resin, which is replaced with a lithium type. This is because, particularly when the dispersion is acidic, by selectively removing hydrogen ions, tin oxide of ferrocene is suppressed and contributes to the long-term stability of the dispersion.
[0059]
As the reducing agent, a water-soluble reducing agent is preferable, and specifically, thiosulfate, sulfite, phosphite, oxalate, citrate and the like can be used. If the oxidized form of the ferrocene derivative surfactant is reduced so that the concentration of the reduced form becomes excessive, it is possible to add an adsorbent to adsorb and remove the excess ferrocene derivative surfactant. is there. As the absorbent used herein, for example, a crosslinked polymer such as silica, alumina, activated carbon, styrene, and divinylbenzene copolymer can be used, but ferrocene can be added in a small amount without affecting the stability of the dispersion. Non-polar specific surface area 200m capable of adsorbing and removing derivative surfactant²A polystyrene-based synthetic adsorbent having a crosslinked structure of at least / g is very preferred.
[0060]
Next, the dispersion liquid of the hydrophobic particles thus adjusted is used for micellar electrolysis when the concentration of the hydrophobic particles is within a predetermined range. However, if the concentration of the hydrophobic particles is higher than a predetermined range, the concentration of the hydrophobic particles is adjusted to a predetermined range by diluting with an aqueous medium, and then an adsorbent is added thereto to remove excess ferrocene derivative surfactant. Then, the equilibrium concentration of the ferrocene derivative surfactant is adjusted to a predetermined range.
[0061]
Next, by removing the adsorbent and the coarse hydrophobic particles in the dispersion by known means such as centrifugation, the target dispersion can be produced.
[0062]
The concentration of hydrophobic particles in the dispersion thus produced is preferably in the range of 0.2 to 10.0% by weight, more preferably 0.5 to 5.0% by weight. The concentration of the reduced form of the ferrocene derivative surfactant is preferably in the range of 50 to 300 μg / ml, more preferably 100 to 200 μg / ml.
[0063]
As before, when the equilibrium concentration cannot be adjusted later, the concentration of the hydrophobic particles to be prepared has to be adjusted by the concentration at the time of preparation. The reason is that when dispersing by increasing the hydrophobic particle concentration, an excessive amount of a dispersant is necessary, and when the hydrophobic particle concentration is later diluted to match the predetermined value, the equilibrium concentration is also diluted, and the It is considered to be a value. However, in reality, if the dispersion liquid is not excessively added, the hydrophobic particles aggregate during the dispersion treatment and cannot be dispersed.
[0064]
The equilibrium concentration of the dispersant can be measured by the following (1) dye solubilization method, (2) electrochemical method, and (3) plasma emission analysis method.
[0065]
(1) Dye solubilization method
In the dye solubilization method, first, a hydrophobic particle dispersion is subjected to a centrifugal separation treatment, and then the supernatant is collected, and the absorption spectrum of the solution is measured. Next, after adding and dissolving the dye to the solution, the supernatant liquid from which the excess dye has been removed is separated. The absorption spectrum of the supernatant is measured, and the difference spectrum from the absorption spectrum of the solution measured before addition of the dye is calculated.
[0066]
On the other hand, a solution prepared by separately solubilizing a dye with a known amount of a dispersion liquid (used for dispersing hydrophobic particles) was prepared, and calibration curve data indicating the relationship between the dispersant concentration of this solution and the absorption spectrum were prepared. The equilibrium concentration of the dispersant is calculated from the difference spectrum measured in (1). At this time, the dye to be used is not particularly limited as long as it is a dye that can be solubilized with a dispersant, and for example, an azo type or a phthalocyanine type can be used.
[0067]
Further, the centrifugal force in the centrifugal separation process depends on the specific gravity of the hydrophobic particles, but may be any centrifugal force such that the hydrophobic particles settle, and the dispersant of the equilibrium concentration does not settle, and is not particularly limited. .
[0068]
(2) Electrochemical method
In the electrochemical method, first, the supernatant after centrifugal dispersion is collected and subjected to differential pulse voltammetry measurement in the same manner as in the dye solubilization method (1). Next, the equilibrium concentration of the dispersant is calculated from the measurement results and calibration curve data created by performing differential pulse voltammetry measurement with a known amount of the dispersant. In this differential pulse voltammetry measurement, the presence or absence of the peak of the oxidizing substance can be confirmed, so that the appropriate addition amount of the ion exchange resin can also be confirmed.
[0069]
(3) Plasma emission spectrometry
Plasma emission spectroscopy is a method in which the supernatant after centrifugation is collected in the same manner as in the dye solubilization method (1) above, plasma emission analysis is performed, and the dispersing agent is determined from the data of the previously prepared calibration curve. This is a method for calculating the equilibrium concentration. In order to form a thin film on a substrate by an electrolytic treatment method using the dispersion liquid of hydrophobic particles manufactured in this manner, a patterned electrode is immersed in the dispersion liquid, and a current is applied to this electrode. , Electrolytic treatment may be performed. As a result, a thin film of hydrophobic particles is formed on the conductive substrate.
[0070]
The electrolysis conditions at this time may be appropriately selected according to various situations, but usually the solution temperature is 0 to 50 ° C, preferably 5 to 25 ° C, and the voltage is 0.3 to 1.5 V, preferably 0.4 to 500 ° C. 1.0V. The electrolytic film forming method of the present invention shown in FIG. 1 (1) S1-1 has substantially the same contents as the conventional electrolytic film forming method shown in FIG. 2 (2) S2-1. is there.
[0071]
(2) weak washing
After the above-described film formation, the dispersion liquid remaining outside the necessary portions is washed away. At this time, the unnecessary dispersion is removed by infiltrating the conductive substrate into water and rinsing it by applying a water flow, or applying a shower water flow or a water flow on a curtain in the air. However, since the adhesion of the formed thin film in this state is weak, the water flow near the substrate is 5 m / sec or less, preferably 1 m / sec or less, more preferably 0.1 m / sec to 0.8 m / sec or less. Is desirable.
[0072]
Furthermore, it is desirable to make a flow that quickly separates from the substrate so that the washed-out dispersion liquid does not adhere to the substrate again. The component of the washing water used at this time may be pure water or ultrapure water to which nothing is added, and also enhances the conductivity of water by dissolving carbon dioxide gas, ionic solutes and nonionic solutes. Alternatively, an effect may be provided in which static electricity is prevented from being generated, and particles having the static electricity are hardly attached to the substrate.
[0073]
In addition, if a gas-liquid interface is present on the surface of the thin film during this cleaning, the thin film is disturbed at that portion, so it is necessary to take measures to prevent the gas-liquid interface from occurring. As a device that does not cause a gas-liquid interface, for example, it is effective to perform the cleaning completely in water or to perform the cleaning in a water mist with a humidity of 100%.
[0074]
In addition, it is necessary to devise a method that does not form a gas-liquid interface on the surface of the thin film when transferring to the next aggregation treatment. As a measure to prevent the formation of a gas-liquid interface on the surface of the thin film when shifting from the weak washing process to the coagulation process, after the weak washing process, while the water remains on the substrate, proceed to the next stage of the coagulation process. Is to move. Note that the temperature of the cleaning water for cleaning the thin film is desirably 50 degrees or less.
[0075]
The weak water washing method of the present invention shown in FIG. 1 (1) S1-2 has substantially the same contents as the conventional weak water washing method shown in FIG. 2 (2) S2-2. The method differs greatly from the conventional method in that no gas-liquid interface is formed.
[0076]
(3) Aggregation treatment
Next, in order to improve the adhesion strength of the thin film, any one or a combination of the following aggregation treatments (1) to (3) can be selected. Further, if a gas-liquid interface is present on the thin film when performing the agglomeration treatment, the thin film will be disturbed at that part. Therefore, it is effective to perform all the agglomeration treatment in water or in a water mist.
[0077]
Coagulation treatment (1)
The weak washing using water in which the surfactant is not dissolved has an effect of removing the surfactant adsorbed on the fine particles, and also has a weak aggregation promoting effect. However, in order to further promote the aggregation, the substrate after the water washing is subjected to a temperature increasing treatment. This heating process is the coagulation process (1). The method does not matter, such as IR heating or heating with hot air.
[0078]
However, when the thin film is exposed to the gas-liquid interface, the film may be disturbed. Therefore, it is desirable to perform the treatment of exposing the thin film to warm water of 50 ° C. or higher. The temperature at this time is more preferably 70 ° C. or more because the purpose is to promote the aggregation of the fine particles, and the treatment can be suitably performed within a range where water does not boil as an upper limit. This processing time is 10 minutes or less, preferably 5 minutes or less. In some cases, processing can be performed in 30 seconds or less.
[0079]
The principle of the improvement of the adhesion is based on the fact that the equilibrium of the dispersion is greatly inclined to the fine particle deposition side by increasing the temperature. In particular, nonionic surfactants are known to lose phase hydrogen bonding with water molecules of polyoxyethylene groups when the temperature rises, causing phase separation. It is one of the mechanisms that promotes coagulation and thus greatly contributes to the improvement of adhesion.
[0080]
Coagulation treatment (2)
In addition, in order to improve the adhesion strength, aggregation can be promoted by changing the electric charge of the dispersed fine particles using acidic water having a pH of 3.0 to 7.0 for weak washing water. . The treatment using acidic water having a pH of 3.0 to 7.0 for the weak washing water is the coagulation treatment (2).
[0081]
The processing time is 10 minutes or less, preferably 5 minutes or less. In some cases, processing can be performed in 30 seconds or less. The pH of the weak washing water at this time can be arbitrarily selected from Lewis acids that do not change the transparent electrode. For example, ammonium dihydrogen phosphate, boric acid, acetic acid, tartaric acid, formic acid and the like can be suitably used.
[0082]
Coagulation treatment (3)
Further, in order to improve the adhesion strength, a treatment of immersing the thin film in an aqueous solution having a higher osmotic pressure than the dispersion liquid can be performed. The treatment using the aqueous solution having a high osmotic pressure is the coagulation treatment (3).
[0083]
As a result of the coagulation treatment (3), the moisture in the thin film is rapidly discharged, the coagulation of the thin film proceeds, and the adhesion strength increases. In many cases, a sufficient coagulation treatment can be obtained with a treatment time of 10 minutes or less. However, it is preferable that a sufficient coagulation treatment can be performed in 5 minutes or less. In some cases, processing can be performed in 30 seconds or less.
[0084]
As a method of increasing the osmotic pressure, a method of adding a solute to water is general. The osmotic pressure shows a uniform property that shows the same value regardless of the type of solute if the type and the number of moles of the solute contained in a fixed volume of solution are equal. As described above, when the solute ion is present in the aqueous solution, it also has a function of canceling the electric charge of the dispersed fine particles, and loses the dispersion stability. This means that there is a function of increasing the cohesive force and improving the adhesion of the thin film.
[0085]
Generally, the electrolyte is ionized in water, and therefore, the osmotic pressure tends to be amplified in correlation with the number of dissociated ions. When a dispersion is prepared, an aqueous solution in which more solute components or dissociated ions are dissolved than the mixed solute components is prepared, and agglomeration treatment can be performed by acting on the thin film.
[0086]
The solute used here may be any solute that dissolves in water, or may be the same as the dispersion component, or may be different, and may be an inorganic substance such as sodium chloride. But it's fine. For example, organic substances such as sodium tartrate can be used. The solute may be not only a solid but also a water-soluble, room temperature liquid substance such as alcohol or glycerin.
[0087]
In order to check the difference in osmotic pressure between the dispersion liquid and the processing liquid, the difference can be easily checked using an apparatus as shown in FIG. The processing liquid 28 is placed in a container separated by the semipermeable membrane 32, and the water surface of the dispersion liquid 30 and the water surface of the processing liquid 28 are matched. When the osmotic pressure of the processing liquid 28 is higher than the osmotic pressure of the dispersion liquid 30, the water level of the processing liquid 28 rises. When a 10% aqueous solution of NaCl was selected as the treatment liquid 30, the water level rose and the osmotic pressure was higher than that of the dispersion liquid 30. Also, when the 0.1% NaCl aqueous solution was selected, the water surface was slightly lowered, and thus it was found that the osmotic pressure was lower than that of the dispersion liquid 30 according to the embodiment of the present invention. The aggregation processing step shown in S1-3 of FIG. 1A corresponds to the aggregation processing (1) to (3). In addition, the aggregating process shown in S1-3 of FIG. 1 (1) and the aggregating processes (1) to (3) are processes unique to the present invention, which are not included in the conventional thin film manufacturing method.
[0088]
(4) Drying
A drying step is performed after the aggregation processing. The thin film having the increased adhesion strength is further agglomerated after the drying step, and the adhesion between the fine particles is enhanced. As a specific drying step, drying by hot air, treatment by draining with an air knife, or the like can be suitably used. When performing the drying step, it is desirable to uniformly and promptly remove moisture from the thin film in order to obtain a uniform thin film.
The drying process shown in S1-4 of FIG. 1 (1) means the above-described drying process, and has substantially the same contents as the drying process of the conventional method shown in S2-3 of FIG. 2 (2). is there.
[0089]
(5) Stress relief
Next, in order to remove the stress generated in the thin film, one or two of the following stress removing steps (1) and (2) are selected and executed.
[0090]
Stress relief ▲ 1 ▼
The thin film formed by the electrolytic treatment can have high adhesion by the aggregation treatment and the drying treatment. However, stress may be accumulated in the thin film due to a rapid aggregation process. If water is applied immediately after the thin film is dried, peeling may occur due to stress. Therefore, as a method for efficiently releasing the stress caused by the coagulation treatment and the drying treatment, a wet treatment with a solvent is effective. In addition, treatment by exposing to solvent vapor is also effective. The wetting treatment with the solvent or the treatment with the steam is the stress removing step (1).
[0091]
A solvent that can be used for the above-mentioned wet treatment and exposure to steam can be freely selected as long as it has a high affinity for the fine particles to be formed into a thin film. Particularly, alcohol and ketone are desirable, and ethanol and methanol are more desirable.
[0092]
Stress relief ▲ 2 ▼
The thin film formed by the electrolytic treatment can have high adhesion by the aggregation treatment and the drying treatment. However, the thin film thus formed may undergo thermal expansion by receiving heat. At this time, stress may occur in the thin film due to a difference in thermal expansion coefficient from the substrate. Therefore, the stress is removed by using the force generated in the thin film in reverse. The process utilizing the force generated in the thin film is the stress removal step (2).
[0093]
The processing temperature may be higher than the thermal history of the thin film, and is preferably 100 ° C. or higher, more preferably 150 ° C. or higher and 200 ° C. or lower. Care must be taken when the processing temperature exceeds 200 ° C., because the fine particles are easily susceptible to air oxidation. This stress removal step (2) corresponds to an example of the thermal annealing treatment described in the claims.
[0094]
In addition, the stress removal process shown in S1-5 of FIG. 1 (1) and the stress removal processes (1) and (2) are a processing method characteristic of the present invention which was not present in the conventional thin film manufacturing method. It is.
[0095]
(6) Strong washing
In this manner, the thin film formed through the above-described electrolytic film formation, weak water washing, coagulation treatment, drying, and stress removal, before proceeding to the next step of the second color, the third color, or the protective film coating step, Perform main water washing. This is called strong washing. That is, the foreign matter on the thin film is washed away by a strong water flow.
[0096]
The strong water washing treatment of the present invention shown in FIG. 1 (1) S1-6 is a characteristic treatment method which has not been provided in the conventional thin film manufacturing method.
[0097]
(7) Others (glass substrates and pigments, especially color filters)
As the conductive substrate, a metal substrate such as aluminum, or an insulating substrate such as glass (alkali-free glass, quartz glass, soda lime glass, etc.), plastic, ceramics, etc., ITO (indium tin oxide), tin dioxide, platinum One provided with a conductive thin film of graphite, chromium, nickel, antimony oxide or the like can be used. A protective film is formed on the thin film of hydrophobic particles thus formed on the conductive substrate by using a flattening agent as a post-treatment, if necessary, and the surface is protected. To form a protective film on a thin film, first set the substrate on which the thin film has been formed on a spin coater, drop a flat film agent onto the substrate surface using a dispenser, and rotate the substrate at high speed to uniformly coat the flat film agent. Is applied.
[0098]
Next, the protective film can be formed on the thin film by baking (firing) at a predetermined temperature for a predetermined time and curing.
[0099]
The color filter uses organic pigment particles as the hydrophobic particles, and uses the dispersion liquid of the hydrophobic particles produced as described above. On the transparent substrate, the three primary colors RGB (R: red, G: green, B: blue).
[0100]
To manufacture a color filter, a transparent substrate having a patterned transparent electrode is used as the transparent substrate.
[0101]
As such a substrate, a glass substrate having an ITO electrode patterned in accordance with the shape of a pixel forming a display is preferable.
[0102]
As the RGB organic pigments, those excellent in light resistance, heat resistance, and chemical resistance are preferable, and they can be used alone or in combination of two or more.
[0103]
As specific examples of typical organic pigments, Pigment Red 9, 81, 97, 122, 123, 144, 146, 149, 166, 168, 169, 177, 180, 192 can be represented by a color index number (CI). , 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, Pigment Yellow 1, 3, 12, 13, 13, 14, 17, 20, 24, 34, 55, 74, 81, 83, 86, 93, 101, 113, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 152, 153, 154, 166, 168, 173, 181, 185 Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61 64, 65, 71 orange pigment, pigment green 7, 36 green pigment, pigment blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64 blue pigment And violet pigments such as CI Pigment Violet 19, 23, 29, 30, 37, 40, and 50. These organic pigments may be mixed and dispersed with conductive particles and high dielectric constant particles in order to control the conductivity and dielectric constant of the thin film.
[0104]
The conductive particles used in the present invention include ITO and conductive tin oxide (SnO).₂, SnO₂Sb), conductive zinc oxide (Al-doped zinc oxide, zinc antimonate, (ZnO.Sb₂O₅)) And even SiO₂, TiO₂Or composite particles obtained by coating barium sulfate with conductive tin oxide can be used, and these are used after the surface is hydrophobicized by a coupling agent or polymer treatment.
[0105]
Barium titanate or the like can be used as the high dielectric constant particles. In some cases, for the purpose of adjusting the film thickness, SiO 2 may be used as the particles used simultaneously with the conductive particles at the time of film formation.₂, TiO₂  , ZnO, Al₂O₃  And the like, which are obtained by subjecting ultrafine particles to hydrophobic treatment. The above conductive particles may be used alone or in combination of two or more.
To form a three-primary-color organic pigment thin film constituting a color filter, a dispersion containing any one of red, green, and blue organic pigments is used. Is formed in a desired pattern.
[0106]
Next, by repeating the above operation while changing the type of the organic pigment, a thin film of an RGB color filter can be obtained. A protective film is formed on the RGB color filters obtained as described above, as necessary, as post-processing. In forming the protective film, the protective film may be formed in the same manner as in the case of the thin film described above, or the protective film may be formed by using ordinary spin coating. Thus, the surface of the RGB color filter is protected. However, in the case of a conductive color filter, the protective film must be thick enough to apply a voltage sufficient to drive the liquid crystal.
[0107]
Next, a protective film is formed in the same manner as in the case of the above-mentioned thin film to protect the surface of the RGB color filter.
[0108]
When the thin film has no conductivity, a color filter can be manufactured by forming an ITO thin film on the RGB color filter by a conventional method.
[0109]
A preferred embodiment of the present invention will be described.
[0110]
Embodiment 1
(1) Production of pigment dispersion
The red organic pigment dispersion was prepared by adding 8.2 parts by weight of IDFE represented by the above formula (1) as a ferrocene derivative surfactant and red pigment C.I. as a hydrophobic particle. I. Pigment Red 177 (50.0 parts by weight) and lithium bromide monohydrate (1.05 parts by weight) were added to pure water (1000 parts by weight), mixed, and dispersed using an ultrasonic homogenizer. Thereafter, coarse particles were removed by centrifugation at 10,000 rpm.
[0111]
Next, the solid content concentration and the equilibrium concentration of the dispersion / classification-treated pigment dispersion were measured. Thereafter, the mixture was diluted with a 0.01 mol / l aqueous solution of lithium bromide having an IDFE concentration of 150 μg / ml so that the solid concentration became 2.0% by weight. I. Pigment Red 177 pigment dispersion was prepared.
[0112]
Also, 9.45 parts by weight of IDFE and yellow pigment C.I. I. Pigment Yellow 83 (50.0 parts by weight) and lithium bromide monohydrate (1.05 parts by weight) were added to pure water (1000 parts by weight), mixed, and dispersed using an ultrasonic homogenizer. Thereafter, coarse particles were removed by centrifugation at 10,000 rpm.
[0113]
Next, after measuring the solid concentration and the equilibrium concentration of the pigment dispersion liquid subjected to the dispersion and classification treatment, 0.01 mol / l of lithium bromide having an IDFE concentration of 150 μg / ml was adjusted so that the solid concentration became 2.0% by weight. Diluted with an aqueous solution, and C.I. I. Pigment Yellow 83 pigment dispersion was prepared.
[0114]
Thus, the obtained C.I. I. Pigment Red 177, 75 parts by weight of a pigment dispersion, and C.I. I. Pigment Yellow 83 and 25 parts by weight of a pigment dispersion to prepare a red pigment dispersion.
[0115]
(2) Electrolytic deposition of pigment thin film
First, a glass substrate provided with an ITO (indium tin oxide) transparent electrode was immersed in the pigment dispersion. Next, a stainless plate having a surface area equal to or more than 1.2 times the area of the ITO electrode was used as the counter electrode. Here, an Ag / AgCl (silver / silver chloride) electrode manufactured by Toa DKK was used as a reference electrode. The power supply used was a potentiostat / galvanostat HA-151 manufactured by Hokuto Denko Corporation.
[0116]
Next, the ITO electrode (+), the SUS electrode (-), and the reference electrode (RE) were connected, and 0.5 V was applied to the ITO electrode as a reference electrode reference for 10 minutes. Here, the SUS electrode (-) is an electrode using a stainless steel plate.
[0117]
Next, a pigment thin film was formed on the electrode, and subjected to the experiments shown in Examples and Comparative Examples.
[0118]
(3) Measurement of haze value
The uniformity of the formed pigment film was measured by HAZE. In this table, HAZE is an index indicating the transparency of the manufactured thin film, and can be expressed by the following equation.
[0119]
(Equation 1)
HAZE = [(Transmittance of diffused light) / (Transmittance of transmitted light)] × 100
The smaller the value of HAZE, the higher the transparency. Specifically, the value of HAZE is preferably less than 10, more preferably 5 or less.
[0120]
The value of HAZE is measured using a HAZE meter. The Haze meter used was a HGM-2DP type Haze meter manufactured by Suga Test Instruments Co., Ltd. This apparatus was a fully automatic direct reading haze computer, and the measurement spot size was set to 7 mmφ. In the actual measurement, three points in one substrate were measured, and the average value was adopted as the final measurement, and is shown in Tables 1, 2, 3 and 4.
[0121]
(4) Formation of pigment thin film
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0122]
Next, while the water remains on the substrate surface, the substrate with the pigment thin film washed with pure water for 15 seconds is immersed in warm water of 80 ° C. immediately so that a gas-liquid interface does not occur on the surface of the substrate with the pigment thin film, and agglomerated. Processing was performed. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried by using the above-mentioned dry nitrogen.
[0123]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec. Finally, the surface of the substrate with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 1 are shown in Tables 1, 2, 3, and 4.
[0124]
[Table 1]

[Table 2]

[Table 3]

[Table 4]

Embodiment 2
In Example 2 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0125]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0126]
Next, while the water remains on the surface of the substrate with the pigment thin film, the substrate with the pigment thin film washed with pure water is quickly placed in hot water at 70 ° C. so that no gas-liquid interface is formed on the surface of the substrate with the pigment thin film. It was immersed for 2 seconds to perform a coagulation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate provided with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0127]
Next, the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec. Finally, the surface of the substrate with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 2 are shown in Table 2.
[0128]
Embodiment 3
In Example 3 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0129]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0130]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in a 5% aqueous NaCl solution (sodium chloride) immediately so that a gas-liquid interface did not occur on the surface of the substrate with the pigment thin film. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0131]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 5. The results of Example 3 are shown in Table 2.
[0132]
Embodiment 4
In Example 4 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0133]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0134]
Next, while water remained on the surface of the substrate with the pigment thin film, coagulation treatment was performed by immersing the substrate in the acidic water of pH 5 immediately so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. The acidic water used is a mixture of a 0.1 mol / l acetic acid aqueous solution and a 0.1 mol / l sodium acetate aqueous solution in a volume ratio such that sodium acetate is 2 with respect to 1 for acetic acid. Was. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used. Next, the substrate with a pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 4 are shown in Table 2.
[0135]
Embodiment 5
In Example 5 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0136]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0137]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in warm water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. Next, the substrate with the pigment thin film was placed almost vertically, water was slowly drained by gravity, and the substrate was placed on a hot plate set at 120 degrees and dried for 5 minutes. Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent. No disturbance of the pigment thin film was observed, and HAZE was 5. The results of Example 5 are shown in Table 3.
[0138]
Embodiment 6
In Example 6 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0139]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0140]
Next, while water remained on the surface of the substrate with the pigment thin film, coagulation treatment was performed by immersing the substrate in hot water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the substrate surface. Next, it was slowly pulled out of the washing water tank so that water droplets did not remain on the surface of the substrate with the pigment thin film, placed on a hot plate set at 120 degrees, and dried for 5 minutes. Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 4. The results of Example 6 are shown in Table 3.
[0141]
Embodiment 7
In Example 7 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0142]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0143]
Next, while water remained on the surface of the substrate provided with the pigment thin film, coagulation treatment was performed by immersing the substrate in hot water of 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the substrate surface. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0144]
Next, the substrate with the pigment thin film was immersed in methanol for 15 seconds. Next, the substrate with the pigment thin film immersed in methanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 7 are shown in Table 4.
[0145]
Embodiment 8
In Example 8 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0146]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0147]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in warm water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0148]
Next, the substrate with the pigment thin film was immersed in IPA (isopropyl alcohol) for 15 seconds. Next, the substrate with the pigment thin film immersed in IPA (isopropyl alcohol) was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 4. The results of Example 8 are shown in Table 4.
[0149]
Embodiment 9
In Example 9 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0150]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0151]
Next, while water remained on the surface of the substrate with the pigment thin film, coagulation treatment was performed by immersing the substrate in hot water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the substrate surface. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, since the surface of the substrate with the pigment thin film was dried with nitrogen, it was confirmed that the substrate was instantaneously dried.
[0152]
Next, the substrate with the pigment thin film was placed in a beaker filled with ethanol vapor for 15 to 20 seconds. Next, the substrate with the pigment thin film was pulled up from a beaker filled with ethanol vapor, and the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 9 are shown in Table 4.
[0153]
Embodiment 10
In Example 10 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0154]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0155]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in warm water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0156]
Next, the substrate with the pigment thin film was placed in a sufficiently warm beaker filled with water vapor for 15 seconds to 20 seconds. Next, the substrate with the pigment thin film was taken out of the beaker filled with water vapor, and the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 5. The results of Example 10 are shown in Table 4.
[0157]
Embodiment 11
In Example 11 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0158]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. First, the flow rate of water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0159]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in warm water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0160]
Next, the substrate with the pigment thin film was placed on a hot plate heated to 150 ° C. for 5 minutes. Next, the substrate with the pigment thin film placed on the hot plate was taken out, and the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 11 are shown in Table 4.
[0161]
Embodiment 12
In Example 12 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0162]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0163]
Next, while water remained on the surface of the substrate with the pigment thin film, aggregation treatment was performed by immersing the substrate in warm water at 80 ° C. for 15 seconds so that a gas-liquid interface was not generated on the surface of the substrate with the pigment thin film. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0164]
Next, the substrate with a pigment thin film was placed on a hot plate heated to 100 ° C. for 5 minutes. Next, the substrate with the pigment thin film on the hot plate was taken out, and the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was very transparent and uniform. No disturbance of the pigment thin film was observed, and HAZE was 3. The results of Example 12 are shown in Table 4.
[0165]
[Comparative Example 1]
In Comparative Example 1 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0166]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0167]
Next, the substrate with the pigment thin film was set up, and water on the substrate with the pigment thin film was slowly removed. Water on the substrate with the pigment thin film was removed. Conventionally, in the process of discharging the water, a gas-liquid interface has been formed on the surface of the substrate with the pigment thin film. Next, when the water on the substrate with the pigment thin film was exhausted, the substrate was placed in an oven heated to 120 ° C. and dried for 15 minutes. In the pigment thin film thus obtained, disturbance of the pigment thin film was observed, and HAZE was 15. In addition, unevenness due to the gas-liquid interface was confirmed.
[0168]
The results of Comparative Example 1 are shown in Tables 1, 2, 3, and 4. Further, Comparative Example 1 means a conventional technique, but for convenience, the term "Example" is used. On the other hand, Comparative Examples 2 to 12 shown below are other examples of the present invention provided for comparison with Examples 1 to 12 of the present invention, and do not mean the prior art.
[0169]
[Comparative Example 2]
In Comparative Example 2 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0170]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion, immersed in 80 ° C. hot water for 15 seconds, and subjected to a coagulation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used. However, the turbulence of the pigment thin film was observed due to the wind pressure of the air knife.
[0171]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the pigment thin film immersed in ethanol was pulled up, and the surface was washed away with water having a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the surface was dried to obtain a pigment thin film on the substrate provided with the pigment thin film. In the pigment thin film thus obtained, a pigment thin film in which agglomerates of the pigment dispersion were slightly and irregularly deposited on the surface of the pigment thin film and the back surface of the substrate provided with the pigment thin film was obtained. In addition, HAZE was 22. Table 1 shows the results of Comparative Example 2.
[0172]
[Comparative Example 3]
In Comparative Example 3 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0173]
First, the substrate with the pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate with the pigment thin film was 0.5 m / sec.
[0174]
Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used. However, the turbulence of the pigment thin film was observed due to the wind pressure of the air knife.
[0175]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the pigment thin film immersed in ethanol was pulled up, and before the alcohol was dried, the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the surface of the substrate with the pigment thin film was dried to obtain a pigment thin film on the substrate with the pigment thin film. As the pigment thin film thus obtained, a film was obtained in which the disturbance of the pigment thin film by the air knife was left as it was. In addition, HAZE was 20. The results of Comparative Example 3 are shown in Table 1.
[0176]
[Comparative Example 4]
In Comparative Example 4 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0177]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0178]
Next, it was immersed in warm water of 80 temperature for 15 seconds to perform a coagulation treatment. Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. In the pigment thin film thus obtained, the pigment film was dissolved by the alcohol, and a film with much disorder was obtained. In addition, HAZE was 18. Table 1 shows the results of Comparative Example 4.
[0179]
[Comparative Example 5]
In Comparative Example 5 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0180]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow rate of the water hitting the substrate was 0.5 m / sec.
[0181]
Next, the above-mentioned substrate with a pigment thin film was immersed in warm water at a temperature of 80 for 15 seconds to perform an aggregation treatment.
Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water was uniformly removed by dry nitrogen. In addition, it was confirmed that the surface of the substrate provided with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0182]
Next, the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. In the pigment thin film thus obtained, countless small cracks observed by a microscope generated by strong water flow were observed, and more than half of the area of the pigment thin film was peeled off. In addition, HAZE could not be measured due to peeling of the film. The results of Comparative Example 5 are shown in Tables 1 and 4.
[0183]
Comparative Example 6
In Comparative Example 6 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0184]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0185]
Next, a gas-liquid interface between washing water and air was formed several times on the substrate with the pigment thin film. Next, the substrate with the pigment thin film was immersed in warm water of 80 temperature for 15 seconds to perform a coagulation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, it was confirmed that the surface of the substrate provided with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0186]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface was washed away with water having a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. In the pigment thin film obtained in this way, film disturbance due to the gas-liquid interface was observed. In addition, HAZE was 9. Table 1 shows the results of Comparative Example 6.
[0187]
Comparative Example 7
In Comparative Example 7 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0188]
The pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0189]
Next, the above-mentioned substrate with a pigment thin film was immersed in warm water of 80 degrees for 15 seconds to perform a coagulation treatment. At this time, the substrate with the pigment thin film was pulled out of the hot water several times, and a gas-liquid interface between the hot water and air was formed on the pigment thin film several times. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water was uniformly removed by dry nitrogen. In addition, it was confirmed that the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0190]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface was washed away with water having a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. In the pigment thin film obtained in this way, film disturbance due to the gas-liquid interface was observed. In addition, HAZE was 10. Table 1 shows the results of Comparative Example 8.
[0191]
Comparative Example 8
In Comparative Example 8 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0192]
Next, the substrate with the pigment thin film was immersed in warm water of 40 ° C. for 15 seconds to perform an aggregation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, since the surface of the substrate with the pigment thin film was dried using dry nitrogen, it could be visually confirmed that the substrate was instantaneously dried. However, disturbance of the pigment thin film was observed by the air pressure of the air knife.
[0193]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was a film in which the disturbance of the pigment thin film by the air knife was left as it was. In addition, HAZE was 12. The results of Comparative Example 8 are shown in Table 2.
[0194]
Comparative Example 9
In Comparative Example 9 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0195]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0196]
Next, the substrate with the pigment thin film was immersed in a phosphate pH standard solution having a pH of 7.4 (JIS K0023) to perform an aggregation treatment. However, the phosphate pH standard solution having a pH of 7.4 (JIS K0023) was slightly basic, and a sufficient aggregation treatment did not occur with the pH aqueous solution. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water of the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). In addition, since the surface of the substrate with the pigment thin film was dried using nitrogen, it could be visually confirmed that the substrate was instantaneously dried. However, disturbance of the pigment film was observed by the wind pressure of the air knife.
[0197]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was a film in which the disturbance of the pigment film by the air knife was left as it was. In addition, HAZE was 15. The results of Comparative Example 9 are shown in Table 2.
[0198]
Comparative Example 10
In Comparative Example 3 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0199]
The pigment thin film electrolytically formed by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0200]
Next, the substrate with the pigment thin film was immersed in a 0.1% NaCl (sodium chloride) aqueous solution to perform an aggregation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water on the substrate with the pigment thin film was uniformly removed using the dry nitrogen of (1). The surface of the substrate with the pigment thin film was dried instantaneously because dry nitrogen was used. However, the pigment thin film was disturbed by the wind pressure of the air knife.
[0201]
Next, the substrate with a pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was a film in which the disturbance of the pigment thin film by the air knife was left as it was. In addition, HAZE was 14. The results of Comparative Example 10 are shown in Table 2.
[0202]
[Comparative Example 11]
In Comparative Example 11 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as those in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0203]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0204]
Next, the substrate with the pigment thin film was immersed in warm water of 80 degrees for 15 seconds to perform a coagulation treatment. Next, dry nitrogen was manually sprayed on the pigment thin film with an air gun to remove water from the substrate with the pigment thin film. In addition, it was confirmed that the surface of the substrate with the pigment thin film was instantaneously dried because dry nitrogen was used. However, the nitrogen ejected from the air gun can cover only a part of the substrate with the pigment thin film at a time, and the entire substrate with the pigment thin film cannot be dried at one time. As a result, the pigment thin film was disturbed.
[0205]
Next, the substrate with the pigment thin film was immersed in ethanol for 15 seconds. Next, the substrate with the pigment thin film immersed in ethanol was pulled up, and the surface of the substrate with the pigment thin film was washed away with water at a strong flow rate of 15 m / sec before the alcohol was dried. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. The pigment thin film thus obtained was a film in which the disturbance of the thin film due to the air gun was left as it was. In addition, HAZE was 11. The results of Comparative Example 11 are shown in Table 3.
[0206]
Comparative Example 12
In Comparative Example 12 described below, (1) production of a pigment dispersion, (2) electrolytic deposition of a pigment thin film, and (3) measurement of film uniformity are the same as in Example 1. Hereinafter, (4) a point different from Example 1 in forming a pigment thin film will be described.
[0207]
First, a pigment thin film electrolytically deposited by the above method was quickly pulled up from the pigment dispersion and washed with pure water. The flow velocity of the water hitting the substrate was 0.5 m / sec.
[0208]
Next, the substrate with the pigment thin film was immersed in warm water of 80 degrees for 15 seconds to perform a coagulation treatment. Next, an air knife (slit width 0.05 mm, nitrogen pressure 0.2 kg / cm²The water was uniformly removed by dry nitrogen. In addition, it was confirmed that the surface of the substrate provided with the pigment thin film was instantaneously dried because dry nitrogen was used.
[0209]
Next, the substrate with the pigment thin film was placed on a hot plate heated to 80 ° C. for 5 minutes, taken out, and the surface of the substrate with the pigment thin film was washed away with water having a strong flow rate of 15 m / sec. Finally, the substrate surface with the pigment thin film was dried to obtain a pigment thin film on the substrate. In the pigment thin film thus obtained, small cracks generated by a strong water flow and observable with a microscope were observed, and a part of the area of the pigment thin film was peeled off. In addition, HAZE of the pigment thin film excluding the peeled portion was 9. The results of Comparative Example 12 are shown in Table 4.
[0210]
【The invention's effect】
As described in detail above, in the present invention, the hydrophobic particles are solubilized in an aqueous solvent using a micellizing agent composed of a ferrocene derivative, the obtained micelle solution is subjected to electrolytic treatment, and the Since a thin film of the hydrophobic particles is formed and the thin film formed by the electrolytic treatment is subjected to the aggregation treatment, a film having high strength and high uniformity can be manufactured.
[0211]
When pigment particles are used as the hydrophobic particles, a film having excellent transparency and color characteristics can be obtained.
[0212]
Further, according to the production method of the present invention, it is possible to produce a thin film containing fine particles as components, which can achieve the above-described effects.
[0213]
[Brief description of the drawings]
FIG. 1 is a comparison diagram between the present invention and a conventional technique.
FIG. 2 is a diagram of an apparatus for examining a difference in osmotic pressure between a dispersion liquid and a processing liquid in the present embodiment.
[Explanation of symbols]
10 S1-1 electrolytic film formation
12 S1-2 Weak washing
14 S1-3 Coagulation treatment
16 S1-4 Drying
18 S1-5 Stress relief
20 S1-6 Strong washing water
22 S2-1 Electrolytic film formation
24 S2-2 Weak washing water
26 S2-3 Drying
28 Treatment liquid
30 dispersion
32 semi-permeable membrane

Claims (13)

The hydrophobic particles are solubilized using a micellizing agent comprising a ferrocene derivative in an aqueous solvent, and the resulting micelle solution, that is, a dispersion is subjected to electrolytic treatment to form a thin film of the hydrophobic substance on an electrode. In the manufacturing method,
A method for producing a thin film, comprising subjecting a thin film obtained by the production method to an agglomeration treatment. The method for producing a thin film according to claim 1, wherein the coagulation treatment is a treatment at a temperature of 50 ° C. or more and a boiling point of water or less. The method for producing a thin film according to claim 1, wherein the coagulation treatment is performed with an acidic aqueous solution having a pH in a range of 7.0 to 3.0. The method for producing a thin film according to claim 1, wherein the coagulation treatment is performed with an aqueous solvent having a higher osmotic pressure than the dispersion liquid. The method according to any one of claims 1 to 4, wherein after the aggregation treatment, a drying step of the pigment thin film in the film formed by the electrolytic treatment is performed, and further, a stress removing step of the pigment thin film is performed. Production method of thin film. The method for producing a thin film according to claim 5, wherein in the stress removing step, a direct wetting treatment of the solvent or exposure to a vapor of the solvent is performed. The method according to claim 6, wherein the solvent is a solvent containing an alcohol and / or a ketone. 6. The method according to claim 5, wherein the stress removing step is a thermal annealing process. The method for producing a thin film according to any one of claims 1 to 8, further comprising a step of performing a water washing treatment on the thin film at a water temperature of 50 ° C or less before the aggregation treatment. The method for producing a thin film according to claim 9, wherein in the method for producing a thin film, wherein the thin film is subjected to the aggregation treatment after the water washing treatment, a gas-liquid interface is not formed on the thin film when the water washing treatment is performed. Method. The method according to claim 9, wherein in the method for producing a thin film in which the aggregation treatment of the thin film is performed after the water washing treatment, a gas-liquid interface is not formed on the thin film when the washing treatment is shifted to the aggregation treatment. Manufacturing method of thin film. The method for producing a thin film according to claim 9, wherein in the method for producing a thin film, wherein the aggregation treatment of the thin film is performed after the water washing treatment, a gas-liquid interface is not formed on the thin film when the aggregation treatment is performed. Method. A thin film comprising fine particles as a component, which is manufactured by the method for manufacturing a thin film according to claim 1.

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