JP3681137B2 - Color filter and optical device - Google Patents

Description

【０００９】
（式（１）においてＲ₁ はＮＯ₂ 又はＨを、Ｒ₂ はスルホン基又は、ＳＯ₂ ＮＨ₂ を、Ｒ₃ はＣｌまたはＨを、Ｒ₄ はＮＯ₂ またはＨを、Ｒ₅ はＣｌまたはＨを、Ｒ₆ はＣｌまたはＨを、それぞれ表し、ＸはＨ、Ｎａ、Ｌｉ、Ｋ、又はＮＨ₄ を意味する。）
で示される２：１クロム錯塩染料で着色されていることを特徴とするカラーフィルター、
（２）Ｒ₁ がＮＯ₂ 、Ｒ₂ がスルホン基、Ｒ₃ がＣｌ、Ｒ₄ がＮＯ₂ 、Ｒ₅ がＣｌ、Ｒ₆ がＨである（１）のカラーフィルター、
（３）（１）又は（２）の２：１クロム錯塩染料と他の染料で着色されていることを特徴とする（１）又は（２）のカラーフィルター、
（４）（１）又は（２）の２：１クロム錯塩染料と他の染料の使用割合が、前者１重量部に対し後者４重量部以下である（３）のカラーフィルター、
（５）他の染料が含金イエロー染料又は含金オレンジ染料である（３）又は（４）のカラーフィルター：
（６）含金イエロー染料又は含金オレンジ染料がクロム錯塩染料である（５）のカラーフィルター：
（７）（１）ないし（６）のカラーフィルターを有する光学装置、
に関する。尚、本発明において固着性が良いということは固着処理中の固着液への染料の溶出、次色の着色すべき皮膜を形成する際の溶剤への染料の溶出現像する際の現像液への染料の溶出、次の着色層を設ける際に染料による汚染がみられないことを意味する。
【００１０】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明のカラーフィルターで使用される式（１）で示される含金染料のうち、置換基Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ 及び対イオンＸの好ましい組合せの代表的な具体例を表１にあげる。
【００１１】
【表１】
表１
染料Ｎｏ． Ｒ₁ Ｒ₂ Ｒ₃ Ｒ₄ Ｒ₅ Ｒ₆ Ｘ
１． NO₂ SO₃ H Cl NO₂ Cl H Na
２． H SO₂ NH₂ Cl NO₂ Cl H Na
３． NO₂ SO₃ H Cl H Cl H K
４． NO₂ SO₃ H Cl NO₂ Cl H Li
５． NO₂ SO₃ H H NO₂ H Cl NH₄
【００１２】
本発明のカラーフィルターで使用される式（１）で示される含金染料は、例えば次の方法によって製造される。即ち、下記式（１Ｃ）で示されるモノアゾ染料又は下記式（１Ｆ）で示されるモノアゾ染料のどちらか一方のモノアゾ染料をクロム化剤（例えば、酢酸クロム、クロムサリチル酸等）で通常の方法でクロム化して１：１クロム錯塩を得、次いでこの１：１クロム錯塩に他方のモノアゾ染料を反応せしめて下記式（１Ｇ）で示される非対称型の２：１クロム錯塩を得、必要により酸性化処理、イオン交換処理を施して金属を除き、所望により水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア等のアルカリで処理することによって式（１）の２：１クロム錯塩染料が得られる。下記式（１Ｃ）、式（１Ｆ）、式（１Ｇ）においてＲ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ は前記と同じである。
【００１３】
【化３】

【００１４】
尚、式（１Ｃ）、式（１Ｆ）で示されるモノアゾ染料は、下記式（１Ａ）又は下記式（１Ｄ）で示されるアミン類をジアゾ化し、次いで下記式（１Ｂ）又は下記式（１Ｅ）で示されるピラゾロン類にカップリングすることにより得られる。下記式（１Ａ）、式（１Ｂ）、式（１Ｄ）、式（１Ｅ）においてＲ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ は前記と同じである。
【００１５】
【化４】

【００１６】
本発明のカラーフィルターでは、製造に当たり分光特性の向上を目的として式（１）で示される含金染料と他の染料との混合染料を使用してもよい。混合染料を使用する場合、その混合割合は使用目的に応じ適宜定められるが、例えば式（１）で示される含金染料１重量部に対し他の染料を４重量部以下、０．１から４重量部程度が好ましい。他の染料としては、含金イエロ−染料、含金オレンジ染料等が好ましく、式（１）で示される含金染料と同様のクロム錯塩染料が染色性、相容性の点で好ましい。他の染料としては、例えば下記のクロム錯塩染料があげられる。
【００１７】
【化５】

【００１８】
【化６】

【００１９】
本発明のカラーフィルターの一例について図を用いて説明する。図１（ａ）〜（ｈ）はガラス板（基本）上に異なる色の着色層を積層させた積層方式によるカラーフィルターの製法を示す図である。図１において１はガラス板、２はスピンコートして設けた光硬化性樹脂等の薄膜、２′は２をマスクを介して光硬化させた着色すべき皮膜、２”は着色層、３は不染性保護膜、４はフオトマスク、５は第２の着色層、６は不染性保護膜をそれぞれ示す。
【００２０】
ガラス板１上にゼラチン、カゼイン、グリュー等の蛋白質系天然高分子物質と重クロム酸アンモニウム等の重クロム酸塩との混合物からなる光硬化型組成物またはカチオン性基を有する光硬化性合成樹脂組成物をスピンコーテイング、ローラーコーテイング等の方法によって塗布して、厚さ０．２〜２μの光硬化性薄膜２を設ける（図１（ｂ））。
【００２１】
次に該薄膜上に所定のパターンを有するフオトマスク４を介して紫外光を照射し、露光部を硬化させる。（図１（ｃ））
【００２２】
次に水等で現像し未露光部を除去し所定のパターンの被着色層２′を形成し（図１（ｄ））、第１の色を得るための所定の光学特性を有する染料を用いて染色して第１の着色層２”を形成する（図１（ｅ））。
【００２３】
次に不染性の保護膜３を全面に設け（図１（ｆ））、次に保護膜３の上に前述と同様にして着色すべき層を得るための光硬化性の塗膜層を設け、マスクを介して露光、現像して所定のパターンの着色すべき層を形成させ、第２の色を得るため所定の光学特性を有する染料を用いて染色して第２の着色層５を形成する（図１（ｇ））。
【００２４】
次に不染性の保護膜６を全面に設ける（図１（ｈ））。この操作を繰返し、第３の色の着色層、更には第４の色の着色層を形成することもできる。
【００２５】
固体撮像素子用あるいはカラーセンサー用の直載型色分解カラーフィルターにおいては、基体となる光検知部等が設けられているシリコンウエハ上に平坦化層を設け、その上に前述と同じ操作で着色層を形成することができ、平坦化層には不染性保護膜と同じものを用いることが出来る。
【００２６】
本発明においては、原色系のＲ（赤）の着色層を得るための染料として、前記式（１）で示される含金染料を使用することを必須とするものであり、赤色の着色層の色特性が優れ、カラーフィルターを組込んだデバイスの製造工程で印加される熱に対する耐性及び最終製品に要求される光耐性が良好なため、表示用カラーフィルターとして色バランスのとれたカラー画像を得ることができ、また色分解用カラーフィルターとして忠実な色再現性を得ることができる。
【００２７】
本発明における着色すべき皮膜は、アニオン染料可染性の光硬化型皮膜形成性組成物を基材上に塗布し、紫外線を照射して塗布皮膜を硬化させたものである。着色すべき皮膜としてのゼラチン、カゼイン、グリュー等の蛋白質系天然高分子物質について説明する。ゼラチンはコラーゲンを水と煮沸して非可逆的に水溶性に変えた動物性蛋白質で、動物の骨、皮膚、腱等を原料とし、水と煮沸して抽出される。またカゼインは乳汁の主成分をなす燐蛋白である。これらの天然蛋白質の水溶液に重クロム酸アンモニウム等の重クロム酸塩を添加して光硬化型組成物を得、この組成物をスピンコーテイング、ローラーコーテイング法等でガラス等の基材上に均一に塗布した後紫外線を照射すると塗布層が硬化し、水不溶性の皮膜が形成される。紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。
【００２８】
また、本発明に用いられる被着色材料としてのカチオン性基を有する合成樹脂の例としては側鎖に光反応可能な不飽和基として第４級アンモニウム塩基とを有するポリマーと光重合開始剤及び溶剤より成る樹脂組成物、あるいはカルコン、ケイ皮酸、アジド、スチルバゾール基、エポキシ基等の光架橋基を予めポリマー中に導入したカチオン性基含有ポリマーを水または有機溶媒に溶解させた樹脂組成物、あるいは含窒素モノマーを必須構成成分の一つとして重合して得たポリマーに光架橋剤、例えばジアゾ化合物、アジドあるいはジアジド化合物を添加し、有機溶媒で稀釈した樹脂組成物等が挙げられる。このような光反応性樹脂組成物を基材表面に塗布し紫外線等の活性光線の照射によって硬化し皮膜を得る。紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。
【００２９】
式（１）で示される含金染料を用いて前記の皮膜を染色（着色）するには、例えば浸漬法、印捺法又はインクジェット法等が用いられ、殊に水溶液を用いた浸漬染色法が好都合である。この場合は通常０．１〜３０ｇより好ましくは１〜１０ｇの式（１）の含金染料を水１リットルに溶解した１０〜１００℃の染浴中に前記の皮膜を設けた基材を通常１０秒以上６０分程度浸漬した後取出し、水洗して乾燥する。こうして得られた赤色に着色された皮膜は、カラーフィルターとして好ましい光学特性を示す。
【００３０】
不染性保護膜を設ける方法としては、例えばネガ型のフオトレジスト例えばアクリル系あるいはポリビニルアルコール系ポリマーにジアゾ化合物等の光架橋剤を添加して得た樹脂組成物、あるいはカルコン、ケイ皮膜等の光架橋基を予めアクリル系又はポリビニルアルコール系ポリマーに導入した樹脂組成物等を水または有機溶媒に溶解し、スピンコーテイング法等のコーテイング法によって塗布し紫外線を照射して硬化される方法などが採用される。
【００３１】
本発明において染色すべき皮膜を設ける基材としてはガラス、プラスチックスシートの他、シリコンウエハ等が、必要に応じてシランカップリング剤等により前処理するか又は平坦化層を設けた上で、使用に供される。
【００３２】
本発明のカラーフィルターを有する光学装置としては、例えばＬＣＤ（液晶表示デバイス）、色分解デバイス、カラーセンサー等があげられる。
【００３３】
【実施例】
次に実施例によって本発明を更に詳細に説明する。
【００３４】
実施例１．
光学ガラス上に約０．６μｍの厚さになるように光硬化型のゼラチン膜を形成する。つづいて紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。このパターンの形成された皮膜を有する光学ガラス基板を下記式（３）
【００３５】
【化７】

【００３６】
の化合物の１．０％水溶液中に８０℃×１０分間浸漬して染色し、赤色着色層を設けた。赤色着色部の分光透過率曲線を測定したところ４５０〜５５０ｎｍの領域における透過率は２％以下で透過率５０％を示す波長λ_T ５０は、５８７ｎｍであった。スガ試験機製カーボンアークフェードメーターに２０時間露光した後の濃度変化（ΔＥ）は ５以下で、優れた耐光性を示した。また２２０℃のホットプレ−ト上で３１分間加熱した後の濃度変化（ΔＥ）は３以下で非常に優れた耐熱性を示した。又、固着処理後の固着性についてみると、各工程における染料の溶出は見られず、良好であった。固着処理条件は、まずタンニン酸０．３０％８０℃×５分間処理し、次いで吐酒石 ０．１０％ ７０℃×５分間処理し、最後に１８０℃×５分間処理する方法である。λmax は水中での値である（以下同様）。また耐光性、耐熱性、を表２にあげる。
尚、式（３）の２：１クロム錯塩染料は、６−ニトロ−４−スルホ−２−アミノフェノールをジアゾ化し、１−（３´−クロルフェニル）−３−メチル−５−ピラゾロンとカップリングして得られるモノアゾ染料を通常の方法でクロム化して、１：１クロム錯塩を得、次いでこの１：１クロム錯塩に６ーニトロー４ークロルー２ーアミノフェノールをジアゾ化し、１−フェニル−３−メチルー５ーピラゾロンとカップリングして得られるモノアゾ染料を通常の方法で反応せしめ、反応物を塩析して式（３）のクロム錯塩染料のナトリウム塩を得た。
【００３７】
実施例２．
光学ガラス上にアクリル系アニオン染料可染性、感光性樹脂（日本化薬製、ＣＦＲ−６３３ＤＨＰ）をスピンコートし、膜厚が０．６μｍになるように皮膜を形成する。つづいて紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。このパターンの形成された皮膜を有する光学ガラス基板を前記式（３）の化合物と前記式（２−２）の化合物の５：５混合物の０．５％水溶液中に８０℃×１０分間浸漬して染色し、赤色着色層を設けた。この赤色着色層の分光透過率曲線を測定したところ４５０〜５５０ｎｍの領域における透過率は、２％以下で透過率５０％を示す波長λ_T ＝５０は、５８７ｎｍであった。又、固着処理後の固着性についてみると、各工程における染料の溶出は見られず、良好であった。また耐光性、耐熱性を表２にあげる。
【００３８】
実施例３．
光学ガラス上にアクリル系アニオン染料可染性、感光性樹脂（日本化薬製、ＣＦＲ−６３３ＤＨＰ）をスピンコートし、膜厚が０．６μｍになるように皮膜を形成する。つづいて紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。このパターンの形成された皮膜を有する光学ガラス基板を前記式（３）の化合物と前記式（２−２）の化合物の７：３混合物の０．５％水溶液中に８０℃×１０分間浸漬して染色し、赤色着色層を設けた。この赤色着色層の分光透過率曲線を測定したところ４５０〜５５０ｎｍの領域における透過率は、２％以下で透過率５０％を示す波長λ_T ＝５０は、５８７ｎｍであった。又、固着処理後の固着性についてみると、各工程における染料の溶出は見られず、良好であった。また耐光性、耐熱性を表２にあげる。
【００３９】
実施例４．
光学ガラス上にアクリル系アニオン染料可染性、感光性樹脂（日本化薬製、ＣＦＲ−６３３ＤＨＰ）をスピンコートし、膜厚が０．６μｍになるように皮膜を形成する。つづいて紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。このパターンの形成された皮膜を有する光学ガラス基板を前記式（３）の化合物と前記式（２−２）の化合物の３：７混合物の０．５％水溶液中に７０℃×１０分間浸漬して染色し、赤色着色層を設けた。この赤色着色層の分光透過率曲線を測定したところ４５０〜５５０ｎｍの領域における透過率は、２％以下で透過率５０％を示す波長λ_T ＝５０は、５８２ｎｍであった。又、固着処理後の固着性についてみると、各工程における染料の溶出は見られず、良好であった。また耐光性、耐熱性表２にあげる。
【００４０】
比較例
光学ガラス上にアクリル系アニオン染料可染性、感光性樹脂（日本化薬製、ＣＦＲ−６３３ＤＨＰ）をスピンコートし、膜厚が０．６μｍになるように皮膜を形成する。つづいて紫外線の照射を、マスクを介して行い、現像すると、所定のパターンの着色すべき水不溶性の皮膜が形成される。このパターンの形成された皮膜を有する光学ガラス基板を特開平３−３８６０１記載の式（２）と前記式（２−４）の化合物の９：１混合物の０．５％水溶液中に７０℃×１０分間浸漬して染色し、赤色着色層を設けた。この赤色着色層の分光透過率直線を測定したところ４５０〜５５０ｎｍの領域における透過率は、２％以下で透過率５０％を示す波長λ_T ＝５０は、５８３ｎｍであった。また耐光性、耐熱性熱性を表２にあげる。尚、固着処理後の固着性についてみると、各工程における染料の溶出は見られず、良好であった。
【００４１】
【表２】

【００４２】
耐光性： カーボンアーク ２０時間照射 濃度変化ΔＥで表示
耐熱性： ホットプレート ２２０℃×３１分間熱処理 濃度変化ΔＥで表示
【００４３】
この表２より実施例と比較例を対比すると、実施例の方が比較例よりも耐光性と耐熱性の点で優れている。又、実施例１から４のデ−タから、式（３）の染料と他の染料との使用割合が５：５の実施例２が耐光性、耐熱性が最も優れている。又、その使用割合が３：７の実施例４よりも式（１）の染料を単独で使用する実施例１の方が、耐光性の点で、優れている。これらの結果から一般式（１）の染料と他の染料との使用割合は好ましくは１０：０から２：８、より好ましくは１０：０から３：７、さらに好ましくは１０：０から４：６程度と思われる。
【００４４】
実施例５．
実施例２と同様に感光性樹脂の皮膜を形成した。次に、実施例１の式（３）の錯塩染料と前記式（２−４）の錯塩染料を７：３の割合で混合し、その０．５％水溶液中に、８０℃×１０分間浸漬して染色し赤色着色層を設けた。赤色着色層の分光透過率曲線を測定したところ４４０〜５６０ｎｍの領域における透過率は２％以下でλ_T ＝５０は５８５ｎｍであった。耐光性、耐熱性、固着性は前記の実施例１同様良好であった。
【００４５】
実施例６．
実施例２と同様に感光性樹脂のの皮膜を形成した。次に、下記式（４）で表される化合物の０．５％水溶液中に、７０℃×１０分間浸漬して染色し赤色着色層を設けた。赤色着色層の分光透過率曲線を測定したところ４４０〜５６０ｎｍの領域における透過率は、２％以下で透過率５０％を示す波長λ_T ＝５０は、５８６ｎｍであった。耐光性、耐熱性、固着性は前記の実施例１同様良好であった。
【００４６】
【化８】

【００４７】
【発明の効果】
表示用カラーフィルターとして赤色領域において再現性が良好で、優れた光学特性と耐久性を示すカラーフィルターが得られた。
【図面の簡単な説明】
【図１】図１において（ａ）は基体（ガラス板）を、（ｂ）は光硬化性薄膜の設けられたガラス板を、（ｃ）は光硬化性薄膜にフオトマスクを介して紫外光を照射する工程を、（ｄ）は被着色層の設けられたガラス板を、（ｅ）は被着色層を染色する工程を、（ｆ）は着色層に不染性の保護膜を設ける工程を、（ｇ）は第２の着色層を設ける工程を、（ｈ）は第２の不染性の保護膜を設ける工程をそれぞれ表す。
【符号の説明】
１ ガラス板
２ 光硬化性薄膜
２′ 被着色皮膜
２” 第１着色層
３ 不染料性保護膜
４ フオトマスク
５ 第２着色層
６ 不染性保護膜
７ 現像タンク
８ 染色槽
９ 照射ランプ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a color filter and an optical device. More specifically, the present invention relates to a color filter having excellent optical characteristics used for a liquid crystal display device, a color separation device, a sensor, and the like, and an optical apparatus having the color filter.
[0002]
[Prior art]
A method for producing a color filter by a dyeing method includes a film of a synthetic resin having a transparent cationic group in the form of a thin film such as a stripe or a mosaic (called a pattern) on the surface of a glass or silicon wafer as a substrate, gelatin, casein, The basic principle is to provide a film to be colored by providing a film of a protein-based natural polymer substance such as Grue, and then dye (color) it with a dye. The following three systems are known as specific manufacturing processes for color filters.
[0003]
(1) After providing a film to be colored on the substrate surface, a pattern obtained by exposure and development through a mask is dyed to form a colored layer. Next, a non-colorable protective coat film is provided on the entire surface, and a second film to be colored is provided thereon by the same operation as described above. Thereafter, a colored layer is sequentially laminated as necessary.
(2) After a film to be colored is provided on the surface of the substrate, a pattern obtained by exposure and development through a mask is dyed to form a colored layer, followed by dye fixing and anti-dyeing treatment with tannic acid or the like Apply. A second film to be colored is provided by the same operation. Thereafter, a colored layer is formed on the same substrate surface as necessary.
(3) A film to be colored (colored film) is provided on the substrate surface. After a positive resist layer is provided thereon, exposure and development are performed through a mask to stain the colored film exposed in a pattern, and then the positive resist layer is peeled off to form a colored portion. The operation after the formation of the positive resist layer is repeated, and the same colored film is dyed in a desired pattern into a plurality of colors.
[0004]
The color filter manufactured by the process as described above, except for special ones, is usually R (red), G (green), B (blue) which are the three primary colors, Y (yellow) which is the three primary colors. , M (magenta), C (cyan), and (M may be omitted). The most important characteristic required for the color filter is an optical characteristic, and the spectral characteristic of each colored layer largely determines the value of the final product.
[0005]
In addition, it is highly resistant to heat treatment encountered in the process of manufacturing a liquid crystal display device equipped with a color filter, such as a sputtering process for providing a transparent electrode layer, and to light applied at the time of use as a final product. However, the predetermined optical characteristics must not be impaired. Naturally, the applied dye must have good solubility and solubility in water and be stable in an acidic dye bath for a long time. Furthermore, when a process requiring a fixing process is involved, it is required that the effect of the fixing process be excellent. By the way, protein-based natural polymer substances such as gelatin, casein, and mulberry have a cationic group, and are therefore dyed (colored) with a water-soluble anionic dye. In addition, when using a photocurable synthetic resin substrate instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye in the same manner as a protein-based natural polymer substance. Become so.
[0006]
[Problems to be solved by the invention]
Many water-soluble anionic dyes have been studied in order to obtain a dye having desired color characteristics (optical characteristics) and light resistance, heat resistance, and fixing properties. However, no red dye that satisfies all the above properties has been found. The color characteristic required for a desired red dye has a wavelength (λ _T = 50) giving a 50% transmittance of a colored film dyed so that the transmitted light near 500 nm is 10% or less at 580 to 600 nm. That's what it means.
[0007]
[Means for Solving the Problems]
As a result of various studies, the present inventors have described the above by constructing a thin film layer (red dye layer) of a dyeable polymer material dyed with a 2: 1 chromium complex dye represented by the following general formula (1). It has been found that a red colored layer having good spectral characteristics can be obtained even if a gold-containing yellow dye or a gold-containing orange dye is added to the compound represented by the formula (1). Was completed. That is, the present invention relates to (1) a color filter in which a film colored in a pattern is placed on a substrate, and at least one pattern has the following general formula (1)
[0008]
[Chemical formula 2]

[0009]
(In the formula (1), R ₁ is NO ₂ or H, R ₂ is a sulfone group or SO ₂ NH ₂ , R ₃ is Cl or H, R ₄ is NO ₂ or H, R ₅ is Cl or H, R ₆ represents Cl or H, and X represents H, Na, Li, K, or NH ₄ )
A color filter characterized by being colored with a 2: 1 chromium complex dye represented by
(2) The color filter according to (1), wherein R ₁ is NO ₂ , R ₂ is a sulfone group, R ₃ is Cl, R ₄ is NO ₂ , R ₅ is Cl, and R ₆ is H.
(3) The color filter of (1) or (2), characterized by being colored with a 2: 1 chromium complex dye of (1) or (2) and another dye,
(4) The color filter according to (3), wherein the use ratio of the 2: 1 chromium complex dye of (1) or (2) and the other dye is 4 parts by weight or less with respect to 1 part by weight of the former,
(5) The color filter of (3) or (4), wherein the other dye is a gold-containing yellow dye or a gold-containing orange dye:
(6) The color filter of (5), wherein the gold-containing yellow dye or the gold-containing orange dye is a chromium complex dye:
(7) An optical device having the color filter of (1) to (6),
About. In the present invention, good fixability means that the dye is eluted into the fixing solution during the fixing process, the dye is eluted into the solvent when forming the film to be colored in the next color, and the developer is developed. This means that the dye is not contaminated when the dye is eluted and the next colored layer is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
Among the metal-containing dyes represented by the formula (1) used in the color filter of the present invention, representatives of preferred combinations of the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and the counter ion X Specific examples are listed in Table 1.
[0011]
[Table 1]
Table 1
Dye No. R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ X
1. NO ₂ SO ₃ H Cl NO ₂ Cl H Na
2. H SO ₂ NH ₂ Cl NO ₂ Cl H Na
3. NO ₂ SO ₃ H Cl H Cl HK
4). NO ₂ SO ₃ H Cl NO ₂ Cl H Li
5. NO ₂ SO ₃ HH NO ₂ H Cl NH ₄
[0012]
The gold-containing dye represented by the formula (1) used in the color filter of the present invention is produced, for example, by the following method. That is, either a monoazo dye represented by the following formula (1C) or a monoazo dye represented by the following formula (1F) is converted into chromium by a usual method with a chrominating agent (for example, chromium acetate, chromium salicylic acid, etc.). To obtain a 1: 1 chromium complex salt, and then react this monochromium salt with the other monoazo dye to obtain an asymmetric 2: 1 chromium complex salt represented by the following formula (1G). The 2: 1 chromium complex dye of the formula (1) can be obtained by applying an ion exchange treatment to remove the metal and optionally treating with an alkali such as sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia or the like. In the following formula (1C), formula (1F), and formula (1G), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are the same as described above.
[0013]
[Chemical 3]

[0014]
The monoazo dyes represented by the formulas (1C) and (1F) are diazotized with amines represented by the following formula (1A) or the following formula (1D), and then the following formula (1B) or the following formula (1E). It is obtained by coupling to pyrazolones represented by In the following formula (1A), formula (1B), formula (1D) and formula (1E), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same as described above.
[0015]
[Formula 4]

[0016]
In the color filter of the present invention, a mixed dye of the metal-containing dye represented by the formula (1) and another dye may be used for the purpose of improving the spectral characteristics in production. In the case of using a mixed dye, the mixing ratio is appropriately determined depending on the purpose of use. For example, 4 parts by weight or less of other dyes, 0.1 to 4 parts per 1 part by weight of the metal-containing dye represented by the formula (1) About parts by weight are preferred. Other dyes are preferably a metal-containing yellow dye, a metal-containing orange dye, and the like, and a chromium complex dye similar to the metal-containing dye represented by the formula (1) is preferable in terms of dyeability and compatibility. Examples of other dyes include the following chromium complex dyes.
[0017]
[Chemical formula 5]

[0018]
[Chemical 6]

[0019]
An example of the color filter of the present invention will be described with reference to the drawings. FIGS. 1A to 1H are diagrams showing a method for producing a color filter by a lamination method in which colored layers of different colors are laminated on a glass plate (basic). In FIG. 1, 1 is a glass plate, 2 is a thin film such as a photocurable resin provided by spin coating, 2 'is a film to be colored by photocuring 2 through a mask, 2 "is a colored layer, 3 is Non-stainable protective film, 4 is a photomask, 5 is a second colored layer, and 6 is a non-stainable protective film.
[0020]
A photocurable composition comprising a mixture of a protein-based natural polymer substance such as gelatin, casein, or mulberry and a dichromate such as ammonium dichromate on a glass plate 1 or a photocurable synthetic resin having a cationic group The composition is applied by a method such as spin coating or roller coating to provide a photocurable thin film 2 having a thickness of 0.2 to 2 μm (FIG. 1B).
[0021]
Next, the exposed portion is cured by irradiating the thin film with ultraviolet light through a photomask 4 having a predetermined pattern. (Fig. 1 (c))
[0022]
Next, development is performed with water or the like to remove the unexposed portion, and a colored layer 2 ′ having a predetermined pattern is formed (FIG. 1 (d)), and a dye having a predetermined optical characteristic for obtaining the first color is used. To form a first colored layer 2 ″ (FIG. 1E).
[0023]
Next, a non-stainable protective film 3 is provided on the entire surface (FIG. 1 (f)), and then a photocurable coating layer for obtaining a layer to be colored is formed on the protective film 3 in the same manner as described above. Provided, exposed and developed through a mask to form a layer to be colored in a predetermined pattern, and dyed with a dye having a predetermined optical characteristic to obtain a second color, thereby forming the second colored layer 5 Form (FIG. 1 (g)).
[0024]
Next, a non-stainable protective film 6 is provided on the entire surface (FIG. 1H). By repeating this operation, a colored layer of the third color and further a colored layer of the fourth color can be formed.
[0025]
In direct-mounting color separation color filters for solid-state image sensors or color sensors, a planarizing layer is provided on a silicon wafer on which a photodetecting portion or the like serving as a substrate is provided, and coloring is performed in the same manner as described above. A layer can be formed, and the same layer as the non-dyeing protective film can be used for the planarizing layer.
[0026]
In the present invention, it is essential to use the metal-containing dye represented by the formula (1) as a dye for obtaining a primary color R (red) colored layer. Excellent color characteristics, good resistance to heat applied in the manufacturing process of devices incorporating color filters, and good light resistance required for the final product, resulting in a color image with color balance as a display color filter In addition, faithful color reproducibility can be obtained as a color separation color filter.
[0027]
The film to be colored in the present invention is obtained by applying an anionic dye-dyeable photocurable film-forming composition on a substrate and irradiating with ultraviolet rays to cure the applied film. The protein-based natural high-molecular substances such as gelatin, casein, mulled and the like as the film to be colored will be described. Gelatin is an animal protein that is irreversibly changed to water-soluble by boiling collagen with water. It is extracted from animal bones, skin, tendons, etc. by boiling with water. Casein is a phosphoprotein that is the main component of milk. A photochromic composition is obtained by adding a dichromate such as ammonium dichromate to an aqueous solution of these natural proteins, and this composition is uniformly applied to a substrate such as glass by spin coating, roller coating, or the like. After application, when the ultraviolet ray is irradiated, the applied layer is cured and a water-insoluble film is formed. When ultraviolet rays are irradiated through a mask and developed, a water-insoluble film to be colored having a predetermined pattern is formed.
[0028]
Examples of the synthetic resin having a cationic group as a coloring material used in the present invention include a polymer having a quaternary ammonium base as an unsaturated group capable of photoreaction in a side chain, a photopolymerization initiator, and a solvent. A resin composition comprising, or a cationic group-containing polymer in which a photocrosslinking group such as chalcone, cinnamic acid, azide, stilbazole group, epoxy group or the like is previously introduced into the polymer, is dissolved in water or an organic solvent, Or the resin composition etc. which added the photocrosslinking agent, for example, a diazo compound, an azide, or a diazide compound to the polymer obtained by superposing | polymerizing a nitrogen-containing monomer as one of the essential structural components, and the like are mentioned. Such a photoreactive resin composition is applied to the substrate surface and cured by irradiation with actinic rays such as ultraviolet rays to obtain a film. When ultraviolet rays are irradiated through a mask and developed, a water-insoluble film to be colored having a predetermined pattern is formed.
[0029]
In order to dye (color) the film using the metal-containing dye represented by the formula (1), for example, a dipping method, a printing method, an ink-jet method, or the like is used. In particular, an immersion dyeing method using an aqueous solution is used. Convenient. In this case, a substrate provided with the above film in a dye bath at 10 to 100 ° C. in which 1 to 10 g of a metal-containing dye of the formula (1) is dissolved in 1 liter of water is usually used. After being immersed for about 10 seconds to about 60 minutes, it is taken out, washed with water and dried. The red-colored film thus obtained shows optical characteristics preferable as a color filter.
[0030]
As a method of providing a non-dyeing protective film, for example, a negative photoresist, for example, a resin composition obtained by adding a photo-crosslinking agent such as a diazo compound to an acrylic or polyvinyl alcohol polymer, or a chalcone, a silica film, etc. A resin composition in which a photocrosslinking group is previously introduced into an acrylic or polyvinyl alcohol polymer is dissolved in water or an organic solvent, applied by a coating method such as a spin coating method, and cured by irradiation with ultraviolet rays. Is done.
[0031]
In addition to glass, plastic sheets, silicon wafers, etc., as a base material on which a film to be dyed in the present invention is pretreated with a silane coupling agent or the like as necessary, or after providing a planarizing layer, Provided for use.
[0032]
Examples of the optical apparatus having the color filter of the present invention include an LCD (liquid crystal display device), a color separation device, a color sensor, and the like.
[0033]
【Example】
Next, the present invention will be described in more detail by way of examples.
[0034]
Example 1.
A photocurable gelatin film is formed on the optical glass so as to have a thickness of about 0.6 μm. Subsequently, irradiation with ultraviolet rays is performed through a mask and development is performed, whereby a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having a film on which this pattern is formed is expressed by the following formula (3).
[0035]
[Chemical 7]

[0036]
This was immersed in a 1.0% aqueous solution of the above compound at 80 ° C. for 10 minutes for dyeing to provide a red colored layer. When the spectral transmittance curve of the red colored portion was measured, the transmittance in the region of 450 to 550 nm was 2% or less, and the wavelength λ _T 50 showing the transmittance of 50% was 587 nm. The density change (ΔE) after exposure to a carbon arc fade meter manufactured by Suga Test Instruments for 20 hours was 5 or less, indicating excellent light resistance. The concentration change (ΔE) after heating on a hot plate at 220 ° C. for 31 minutes was 3 or less, indicating very excellent heat resistance. Further, regarding the fixing property after the fixing process, the elution of the dye in each step was not observed, and it was good. The fixing treatment conditions are a method of first treating tannic acid 0.30% at 80 ° C. for 5 minutes, then treating tartarite 0.10% at 70 ° C. for 5 minutes, and finally treating at 180 ° C. for 5 minutes. λmax is a value in water (the same applies hereinafter). Table 2 shows light resistance and heat resistance.
The 2: 1 chromium complex dye of formula (3) is diazotized 6-nitro-4-sulfo-2-aminophenol, and is cupped with 1- (3′-chlorophenyl) -3-methyl-5-pyrazolone. The resulting monoazo dye is chromatated in the usual manner to give a 1: 1 chromium complex salt, which is then diazotized with 6-nitro-4-chloro-2-aminophenol to give 1-phenyl-3- A monoazo dye obtained by coupling with methyl-5-pyrazolone was reacted in the usual manner, and the reaction product was salted out to obtain a sodium salt of a chromium complex dye of formula (3).
[0037]
Example 2
An acrylic anionic dye dyeable and photosensitive resin (manufactured by Nippon Kayaku Co., Ltd., CFR-633DHP) is spin-coated on the optical glass, and a film is formed so as to have a film thickness of 0.6 μm. Subsequently, irradiation with ultraviolet rays is performed through a mask and development is performed, whereby a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having a film on which this pattern is formed is immersed in a 0.5% aqueous solution of a 5: 5 mixture of the compound of formula (3) and the compound of formula (2-2) at 80 ° C. for 10 minutes. And a red colored layer was provided. When the spectral transmittance curve of the red colored layer was measured, the transmittance in the region of 450 to 550 nm was 2% or less, and the wavelength λ _T = 50 indicating the transmittance of 50% was 587 nm. Further, regarding the fixing property after the fixing process, the elution of the dye in each step was not observed, and it was good. Table 2 shows the light resistance and heat resistance.
[0038]
Example 3 FIG.
An acrylic anionic dye dyeable and photosensitive resin (manufactured by Nippon Kayaku Co., Ltd., CFR-633DHP) is spin-coated on the optical glass, and a film is formed so as to have a film thickness of 0.6 μm. Subsequently, irradiation with ultraviolet rays is performed through a mask and development is performed, whereby a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having a film on which this pattern is formed is immersed in a 0.5% aqueous solution of a 7: 3 mixture of the compound of formula (3) and the compound of formula (2-2) at 80 ° C. for 10 minutes. And a red colored layer was provided. When the spectral transmittance curve of the red colored layer was measured, the transmittance in the region of 450 to 550 nm was 2% or less, and the wavelength λ _T = 50 indicating the transmittance of 50% was 587 nm. Further, regarding the fixing property after the fixing process, the elution of the dye in each step was not observed, and it was good. Table 2 shows the light resistance and heat resistance.
[0039]
Example 4
An acrylic anionic dye dyeable and photosensitive resin (manufactured by Nippon Kayaku Co., Ltd., CFR-633DHP) is spin-coated on the optical glass, and a film is formed so as to have a film thickness of 0.6 μm. Subsequently, irradiation with ultraviolet rays is performed through a mask and development is performed, whereby a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having a film on which this pattern is formed is immersed in a 0.5% aqueous solution of a 3: 7 mixture of the compound of formula (3) and the compound of formula (2-2) at 70 ° C. for 10 minutes. And a red colored layer was provided. When the spectral transmittance curve of this red colored layer was measured, the transmittance in the region of 450 to 550 nm was 2% or less, and the wavelength λ _T = 50 indicating 50% transmittance was 582 nm. Further, regarding the fixing property after the fixing process, the elution of the dye in each step was not observed, and it was good. Light resistance and heat resistance are listed in Table 2.
[0040]
Comparative Example An acrylic anionic dye dyeable and photosensitive resin (manufactured by Nippon Kayaku Co., Ltd., CFR-633DHP) is spin-coated on an optical glass, and a film is formed so as to have a film thickness of 0.6 μm. Subsequently, irradiation with ultraviolet rays is performed through a mask and development is performed, whereby a water-insoluble film having a predetermined pattern to be colored is formed. An optical glass substrate having a film on which this pattern was formed was placed at 70 ° C. in a 0.5% aqueous solution of a 9: 1 mixture of the compound of the formula (2) and the formula (2-4) described in JP-A-3-38601. It was dyed by immersion for 10 minutes to provide a red colored layer. When the spectral transmittance straight line of this red colored layer was measured, the transmittance in the region of 450 to 550 nm was 2% or less, and the wavelength λ _T = 50 indicating 50% transmittance was 583 nm. Table 2 shows the light resistance and heat resistance heat resistance. In addition, regarding the fixing property after the fixing treatment, the elution of the dye in each step was not observed, and it was good.
[0041]
[Table 2]

[0042]
Light resistance: Carbon arc 20-hour irradiation Displayed by concentration change ΔE Heat resistance: Hot plate 220 ° C. x 31 minutes heat treatment Displayed by concentration change ΔE
From Table 2, when Examples and Comparative Examples are compared, Examples are superior to Comparative Examples in terms of light resistance and heat resistance. From the data of Examples 1 to 4, Example 2 in which the use ratio of the dye of the formula (3) and other dyes is 5: 5 is most excellent in light resistance and heat resistance. In addition, Example 1 in which the dye of formula (1) is used alone is superior to Example 4 having a use ratio of 3: 7 in terms of light resistance. From these results, the ratio of the dye of the general formula (1) and the other dye is preferably 10: 0 to 2: 8, more preferably 10: 0 to 3: 7, and still more preferably 10: 0 to 4: It seems to be around 6.
[0044]
Example 5 FIG.
A photosensitive resin film was formed in the same manner as in Example 2. Next, the complex salt dye of the formula (3) of Example 1 and the complex salt dye of the formula (2-4) were mixed in a ratio of 7: 3, and immersed in the 0.5% aqueous solution at 80 ° C. for 10 minutes. And dyed to provide a red colored layer. When the spectral transmittance curve of the red colored layer was measured, the transmittance in the region of 440 to 560 nm was 2% or less and λ _T = 50 was 585 nm. The light resistance, heat resistance and adhesion were good as in Example 1.
[0045]
Example 6
A film of photosensitive resin was formed in the same manner as in Example 2. Next, it was immersed in a 0.5% aqueous solution of a compound represented by the following formula (4) at 70 ° C. for 10 minutes for dyeing to provide a red colored layer. When the spectral transmittance curve of the red colored layer was measured, the transmittance in the region of 440 to 560 nm was 2% or less, and the wavelength λ _T = 50 indicating the transmittance of 50% was 586 nm. The light resistance, heat resistance and adhesion were good as in Example 1.
[0046]
[Chemical 8]

[0047]
【The invention's effect】
As a color filter for display, a color filter having good reproducibility in the red region and having excellent optical characteristics and durability was obtained.
[Brief description of the drawings]
1A shows a substrate (glass plate), FIG. 1B shows a glass plate provided with a photocurable thin film, and FIG. 1C shows UV light applied to the photocurable thin film through a photomask. (D) is a glass plate provided with a colored layer, (e) is a step of dyeing the colored layer, and (f) is a step of providing a non-dyeing protective film on the colored layer. (G) represents the step of providing the second colored layer, and (h) represents the step of providing the second non-dyeing protective film.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Glass plate 2 Photocurable thin film 2 'Colored film 2 "1st colored layer 3 Non-dyeing protective film 4 Photomask 5 Second colored layer 6 Non-dyeing protective film 7 Development tank 8 Dyeing tank 9 Irradiation lamp

Claims (7)

In a color filter in which a film colored in a pattern is placed on a substrate, at least one pattern has the following general formula (1)

(In the formula (1), R ₁ is NO ₂ or H, R ₂ is a sulfone group or SO ₂ NH ₂ , R ₃ is Cl or H, R ₄ is NO ₂ or H, R ₅ is Cl or H, R ₆ represents Cl or H, and X represents H, Na, Li, K, or NH ₄ )
A color filter characterized by being colored with a 2: 1 chromium complex dye represented by The color filter according to claim 1, wherein R ₁ is NO ₂ , R ₂ is a sulfone group, R ₃ is Cl, R ₄ is NO ₂ , R ₅ is Cl, and R ₆ is H. The color filter according to claim 1 or 2, which is colored with the 2: 1 chromium complex dye of claim 1 or 2 and another dye. The color filter according to claim 3, wherein the ratio of the 2: 1 chromium complex dye and the other dye according to claim 1 or 2 is 4 parts by weight or less with respect to 1 part by weight of the former. The color filter according to claim 3 or 4, wherein the other dye is a gold-containing yellow dye or a gold-containing orange dye. 6. The color filter according to claim 5, wherein the gold-containing yellow dye or the gold-containing orange dye is a chromium complex dye. An optical device comprising the color filter according to claim 1.

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