JP3556835B2

JP3556835B2 - Image recording coloring composition and method for producing the same

Info

Publication number: JP3556835B2
Application number: JP16782198A
Authority: JP
Inventors: 千豊鷹取; 正行中野; 宣明関根; 行雄神原; 啓二中島; 研大倉; 道衛中村
Original assignee: Dainichiseika Color and Chemicals Mfg Co Ltd
Current assignee: Dainichiseika Color and Chemicals Mfg Co Ltd
Priority date: 1997-06-02
Filing date: 1998-06-02
Publication date: 2004-08-25
Anticipated expiration: 2018-06-02
Also published as: JPH1149998A

Description

【０００１】
【発明の属する技術分野】
本発明は、電子写真、電子印刷、静電記録、インクジェット記録及び熱転写記録等の画像記録における記録剤或いはその製造に使用される高濃度着色組成物及び該画像記録用記録剤に使用された画像記録用着色組成物及びそれらの製造方法に関する。
【０００２】
更に詳しくは本発明は、顔料及び樹脂を含有する画像記録用記録剤において、顔料として優れた各種堅牢性及び微細な粒子径を有するジメチルキナクリドン顔料と無置換キナクリドン顔料との混合顔料、ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料、或はジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料とジメチルキナクリドン顔料及び／又は無置換キナクリドン顔料との混合顔料を含有する鮮明なマゼンタ色の画像記録用着色組成物及びその製造方法を提供するものである。
【０００３】
【従来の技術】
従来、フルカラー又はモノカラーの電子写真、静電印刷、静電記録、インクジェット記録及び熱転写記録等の画像記録に使用されるマゼンタ色記録剤に使用される赤色顔料としては、赤色の油溶性染料、分散染料、チオインジゴ系顔料、溶性アゾレーキ系顔料、不溶性アゾ系顔料、ジメチルキナクリドン顔料等が使用されてきている。
【０００４】
【発明が解決しようとしている課題】
上記したマゼンタ色画像記録剤に使用する赤色顔料としてはマゼンタ色顔料として著名なジメチルキナクリドン顔料が使用されることが多いが、単独ではマゼンタ色としては青みが強過ぎるため、多くの場合それより黄味の赤色色素を混合調色して所望のマゼンタ色として使用している。
【０００５】
しかしながら、これらに使用される赤色色素についてみると、油溶性染料、分散染料等は樹脂媒体に溶解的に着色できるため着色力は高いが、耐光性、耐熱性、耐溶剤性、耐薬品性等の諸堅牢性に劣るという欠点がある。又、チオインジゴ系顔料、溶性アゾレーキ系顔料、不溶性アゾ系顔料も染料類よりは優れているが、耐光性、耐熱性等の諸堅牢性が不十分である。従って、上記した如き染料や顔料は、各種の堅牢性を要求される記録剤用のマゼンタ色用に使用される色素としては不十分であり、優れた物性を有する記録剤用のマゼンタ色に使用される顔料の開発が要望されている。
【０００６】
本発明者らは、上記の従来のマゼンタ色記録剤用の色素の欠陥を解決し、諸堅牢性を満足させ得る赤色顔料の開発について種々研究した結果、特定のキナクリドン系顔料、即ち、γ型の結晶形を示す無置換キナクリドン顔料やジメチルキナクリドン顔料とγ型、β型無置換キナクリドン顔料との固溶体顔料等がこの用途に適切な高堅牢性等の物性を有するとともに鮮明で透明な黄味赤色の色相をもたらすことができることを見い出した。
【０００７】
上記の知見から、マゼンタ色記録剤に使用される顔料としてジメチルキナクリドン顔料と無置換キナクリドン顔料との混合顔料、ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料、或はジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料とジメチルキナクリドン顔料及び／又は無置換キナクリドン顔料との混合顔料（以下、ジメチルキナクリドン−無置換キナクリドン調色顔料と総称する）が、適切なマゼンタ色の色相を有し、耐光性、耐溶剤性、耐熱性、耐薬品性等の諸堅牢性に優れ、更に、従来の塗料やプラスチック着色等の用途に使用されている顔料に比べ粒子径を小さくすることにより、色相の鮮明性及び冴え、透明性等に優れた性質を発揮することができ、これを着色剤として使用することにより優れた画像記録用記録剤が得られることを見い出し本発明を完成した。
【０００８】
【課題を解決するための手段】
即ち、本発明は、顔料及び樹脂バインダーを含む画像記録用着色組成物において、該顔料が、ジメチルキナクリドン顔料とβ型及びγ型無置換キナクリドン顔料との固溶体顔料とジメチルキナクリドン顔料及び／又はγ型無置換キナクリドン顔料との混合顔料であることを特徴とする画像記録用着色組成物及びその製造方法である。
【０００９】
本発明の画像記録用着色組成物は、その顔料成分としてジメチルキナクリドン−無置換キナクリドン調色顔料を使用しているものであるが、この赤色顔料は耐光性、耐熱性、耐溶剤性、耐薬品性、耐水性等の諸堅牢性に優れ、更に高い着色力、鮮明性、冴え、透明性を有するものであり、高濃度着色組成物の製造に際しても加工温度を１２０℃以下で行うような分散加工方法を取ること等によって着色物の製造の工程においても安定に製造することができ、又、最終的に画像記録用記録剤として使用される際にも鮮明で冴えた、透明感の高い画像を安定して記録することができるものである。又、液体記録剤として使用するに際にも、長期間安定に記録することができるものである。従って、得られた画像は色相に優れ、鮮明性、透明性に優れるとともに上記した諸堅牢性に優れた性質を示す。
【００１０】
【発明の実施の形態】
本発明を更に詳細に説明すると、本発明で使用し主として本発明を特徴づけるジメチルキナクリドン−無置換キナクリドン調色顔料を調製し、それを使用して画像記録用着色組成物とする方法としては、顔料の製造工程で混合調色を行った微粉顔料を用いて直接着色組成物を製造する方法と、微粉顔料を予めロールミル又は押出機等の加熱混練機を使用して、或は顔料の水性プレスケーキを加熱ニーダー等を使用して高濃度着色剤を製造し、それを用いて着色組成物を製造する方法がある。
【００１１】
具体的な調色顔料及び該調色顔料を含む高濃度着色剤としては、例えば、下記の如きものが挙げられる。
（Ａ）ジメチルキナクリドン顔料と無置換キナクリドン顔料との混合顔料及びその高濃度着色剤。
（ａ）両顔料をそれぞれ単独で乾燥し、衝撃粉砕又は磨砕された微粉顔料での混合物及び高濃度着色剤。
（ｂ）両顔料の水性プレスケーキを混合し、乾燥後、衝撃粉砕又は磨砕された微粉混合顔料及び高濃度着色剤。
（ｃ）両顔料の水性プレスケーキをそれぞれ単独で加熱ニーダー等に仕込み、溶融フラッシング法等により製造した高濃度着色剤。
（ｄ）両顔料の水性プレスケーキを混合し同様にして製造した高濃度着色剤。
【００１２】
（Ｂ）ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料及びその高濃度着色剤。
（ａ）ジメチルキナクリドン顔料とγ型無置換キナクリドン顔料の固溶体を乾燥し、衝撃粉砕又は磨砕された微粉顔料及び高濃度着色剤。
（ｂ）ジメチルキナクリドン顔料とγ型無置換キナクリドン顔料及びβ型無置換キナクリドン顔料の固溶体を乾燥し、衝撃粉砕又は磨砕された微粉顔料及び高濃度着色剤。
（ｃ）上記（ａ）、（ｂ）の固溶体顔料の水性プレスケーキをそれぞれ単独で加熱ニーダー等に仕込み、溶融フラッシング法等により製造した高濃度着色剤。
（ｄ）上記（ａ）、（ｂ）の固溶体顔料の水性プレスケーキを混合し同様にして製造した高濃度着色剤。
【００１３】
（Ｃ）ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料と、ジメチルキナクリドン顔料及び／又は無置換キナクリドン顔料との混合顔料及びその高濃度着色剤。
（ａ）ジメチルキナクリドン顔料とγ型無置換キナクリドン顔料の固溶体の微粉顔料と、γ型無置換キナクリドン微粉顔料との調色顔料及び高濃度着色剤。
（ｂ）ジメチルキナクリドン顔料とγ型無置換キナクリドン顔料及びβ型無置換キナクリドン顔料の固溶体の微粉顔料とγ型無置換キナクリドン微粉顔料との調色顔料及び高濃度着色剤。
（ｃ）上記（ａ）、（ｂ）の固溶体顔料の水性プレスケーキをそれぞれ単独で加熱ニーダー等に仕込み、溶融フラッシング法等により製造した高濃度着色剤。
（ｄ）上記（ａ）、（ｂ）の固溶体顔料の水性プレスケーキを混合し同様にして製造した高濃度着色剤。
【００１４】
上記において、ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料とは、ジメチルキナクリドン顔料及び無置換キナクリドン顔料の混合顔料を下記するような顔料化処理をすることにより固溶体の状態にし、色相の鮮明性、冴え、透明性を向上させることを目的としている。混合顔料を固溶体にする方法は従来公知の方法に準ずる。例えば、固溶体にする複数の顔料を配合し、酸ペースト処理ないし磨砕工程を経て固溶体粗結晶を得、有機溶剤等で処理することによって達成される。
【００１５】
本発明に使用するジメチルキナクリドン−無置換キナクリドン調色顔料、即ち、ジメチルキナクリドン顔料と無置換キナクリドン顔料との混合顔料（Ａ）中の両者の混合比率、ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料（Ｂ）中の両者の組成比率、或いは該固溶体顔料（Ｂ）とジメチルキナクリドン顔料及び／又は無置換キナクリドン顔料との混合物顔料（Ｃ）中の合計のジメチルキナクリドン顔料と無置換キナクリドン顔料の比率（重量）は、希望する画像の色相によって決められるものであり、約９９：１〜１：９９の範囲であって、好ましくは９０：１０〜３０：７０の範囲である。
【００１６】
無置換キナクリドン顔料としては、黄味の赤色を示すγ型無置換キナクリドン顔料及び紫味の赤色を示すβ型無置換キナクリドン顔料が使用される。ジメチルキナクリドン顔料と無置換キナクリドン顔料との固溶体顔料において、明るい鮮明な黄味のマゼンタ色を得るためには、ジメチルキナクリドン顔料とγ型及びβ型無置換キナクリドン顔料の合計の対比（重量比）は約５０：５０〜２０：８０で、無置換キナクリドン顔料としては黄味のγ型無置換キナクリドン顔料を多く使用することが好ましい。β型無置換キナクリドン顔料は少量使用する時は非常に冴えた色を示すが、多く使用すると紫味になるので固溶体顔料全体に対して約３０重量％以下の量に抑えるのが好ましい。
【００１７】
β型無置換キナクリドン顔料を比較的多く使用した、ジメチルキナクリドン顔料とγ型及びβ型無置換キナクリドン顔料との固溶体顔料に更に黄味のγ型無置換キナクリドン顔料を加えて調色することによって明るい鮮明な黄味のマゼンタ色を得ることができる。
【００１８】
本発明に使用する上記したジメチルキナクリドン−無置換キナクリドン調色顔料顔料を使用して優れた画像の色の透明性、冴え、鮮明性等の性質や物性にもたらすために、顔料の結晶を整えたり、顔料粒子の形状や粒子径を所望の範囲に整えたりする等の後処理が通常の方法に準じて行われる。
【００１９】
一般にジメチルキナクリドン顔料や無置換キナクリドン顔料等のキナクリドン系顔料が塗料或いはプラスチック等の着色の用途に使用される場合には、顔料に隠蔽力、媒体への分散の容易さ、耐候性、耐加熱加工性等の性能を持たせるため顔料の平均粒子径は大きく、例えば、約５００〜７００ｎｍの大きさに調整している。
【００２０】
しかし、この粗大な顔料を画像記録剤の着色剤として使用した場合には、色相の透明性、冴え及び鮮明性に欠けるという問題がある。特に、フルカラー記録剤の着色剤として使用する場合には、色相の透明性、冴え、鮮明性を有していることが好まい。そのためには、本発明に使用する上記したジメチルキナクリドン−無置換キナクリドン調色顔料は画像記録用着色組成物を製造するフラッシング、混練或は湿式分散等の通常の分散方法で分散することによって平均粒子径が約２００ｎｍ以下、好ましくは約１５０ｎｍ以下になるように調製することが好ましい。
【００２１】
顔料を微粒子化する方法としては衝撃粉砕による方法や磨砕による方法等が挙げられる。衝撃粉砕法としてはボールミルや振動ミルを用いるドライミリング法がその代表的方法であり、従来公知のスチールボール、スチールロッド等の粉砕媒体が使用され、磨砕助剤として無機塩が併せて使用することが好ましい。磨砕法としてソルトミリング法やソルベントソルトミリング法がその代表的方法であり、無水芒硝、塩化ナトリウム、硫酸アルミニウム等の磨砕助剤が併せて使用される。粉砕或いは磨砕の工程の後処理として金属系の不純物の除去のために希酸水溶液で洗浄後充分水洗したり、水溶性塩類を水で除去して後充分水洗する。このようにして得られた微粒子顔料は色相の鮮明性、冴え、透明性を有し、又、耐光性、耐熱性、耐溶剤性、耐薬品性、耐水性等の諸堅牢性に優れた性質を示した。
【００２２】
本発明において使用される樹脂は、固体状の着色組成物にあっては分散媒体であり、液体の着色組成物にあっては顔料の分散剤として機能するものであり、又、実際に記録剤として使用されたときは顔料の固着剤として作用するものである。このような目的で使用される樹脂としては、電子写真、静電印刷、静電記録等の乾式現像剤及び湿式現像剤、油性及び水性インクジェットインク、熱転写インクリボン及びフイルム等の画像記録剤に通常使用されているいずれの樹脂であってもよい。又、それぞれの用途に合わせて、必要に応じて従来公知の添加剤、例えば、帯電制御剤、流動化剤等、或いは媒体として溶剤、水系媒体が使用される。
【００２３】
本発明の画像記録用着色組成物はその目的により種々の使い方がなされる。その一つは高濃度着色組成物であって、顔料を高濃度に含み、予め充分に練肉して顔料を分散させたり、調色を行っておくことにより、後の工程を容易にするためのものであり、粗粒、粗粉、微粉、シート状、小塊状等の固体状、或いはペースト状又は液状のいずれの形状にても使用される。
【００２４】
又、本発明の画像記録用着色組成物として、目的の画像記録剤として使用される組成のものが挙げられ、いわゆる微細粉体状乾式現像剤、液状湿式現像剤、静電記録剤、インクジェット記録用インキ、フイルム、紙等の基材に塗布された熱転写インクリボン及びフイルム等である。
【００２５】
本発明で使用されるマゼンタ色に調色されたジメチルキナクリドン−無置換キナクリドン調色顔料の、樹脂やその他の添加剤或いは媒体を含む着色組成物中における含有量は、上記したような使用する目的によって異なるものである。
顔料の高濃度着色組成物では、その含有量は約７０重量％〜１０重量％、好ましくは６０重量％〜２０重量％程度である。
【００２６】
又、目的の画像記録剤中の顔料の含有量としては記録剤の種類によって異なり、電子写真用乾式現像剤等においては顔料の含有量としては約１５重量％〜２重量％、好ましくは１０重量％〜３重量％程度であり、静電記録用湿式現像剤等においては濃厚原液で約１重量％〜２０重量％、好ましくは３重量％〜１０重量％程度であり、通常は希釈液で１０〜３０容量倍に希釈して使用される。熱転写インクリボン若しくはフイルムの着色剤として使用される場合には、１５重量％〜４重量％、好ましくは１０重量％〜６重量％程度であり、インクジェット記録用インクでは３重量％〜２０重量％、好ましくは５重量％〜１０重量％程度であり、それぞれ使用する目的に応じて最も好ましい含有量で使用される。
【００２７】
前記した顔料の高濃度着色組成物の製造方法として乾式の加熱混練分散法とセラミックビーズ、ガラスビーズ、スチールボール等を用いる湿式の媒体分散法がある。特に顔料を樹脂中に高濃度に分散する方法としては二本ロール、三本ロール、加熱ニーダー、加圧加熱ニーダー、一軸押出機、二軸押出機等の混練分散機を使用して樹脂を溶融して顔料を混練分散する方法がとられる。
【００２８】
これらのいずれの場合においても混練分散加工は１２０℃以下の温度で行なわれることが望ましい。この比較的低温の加工温度条件で行うことによって予め微細に調製された顔料の粒子径がそのまま保たれ、引き続き行われる記録剤製造の加工工程においても同様に行うことにより、画像記録剤として色相の鮮明性、冴え、透明性が示されるのである。
【００２９】
この顔料の高濃度分散方法として最も好ましい方法は、顔料の水性ペーストを溶融した樹脂でフラッシングする方法（常圧溶融フラッシング法）であり、例えば、特開平２−１７５７７０号公報で提案されている方法等である。具体的には、溶剤は全く使用せずに顔料の水性プレスケーキと樹脂バインダーとを蒸気加熱可能なニーダー又はフラッシャーに仕込み、樹脂の融点又は軟化点未満の温度で常圧で混練して水性相の顔料を樹脂相に移行させ、分離した水を除去し、更に残存している水分を混練蒸発させる方法である。水性プレスケーキを使用することでプレスケーキの顔料粒子をそのまま樹脂中に移行させることができ、又、混練分散加工も水が存在する間は１００℃以下で進めることができるという特徴を有している。
【００３０】
又、高濃度顔料分散工程として、粉末顔料、樹脂バインダーに分散剤として水を加えて、同様にして常圧で溶剤の不存在下、加工温度を１２０℃以下で該樹脂の融点又は軟化点未満の温度で混練して顔料を樹脂相に移行させ、分離水は除去し、残存水は混練蒸発させる方法によっても高濃度分散着色組成物を得ることができる。
【００３１】
本発明の画像記録用着色組成物においては、電子写真、静電印刷、静電記録等の乾式現像剤及び湿式現像剤、水性、油性及びソリッド状インクジェットインク、熱転写インクリボン及び熱転写インクフイルム等の画像記録剤は、上記のジメチルキナクリドン−無置換キナクリドン調色顔料をそのまま或は前記した顔料の高濃度着色組成物の形で使用して、樹脂バインダー、樹脂溶液或は付加重合性単量体中に分散或は希釈再分散し、それぞれの画像記録剤の製造の常法に従い、その際に必要に応じて従来公知の帯電制御剤、流動化剤、強磁性材料、溶剤媒体、水系媒体等を添加して製造される。
【００３２】
電子写真、静電印刷、静電記録等に使用される画像記録用記録剤について述べると、乾式記録剤としては粉砕法及び重合法と呼ばれる懸濁重合法、乳化重合液凝集法等の製造方法によって製造される微細粉体状乾式現像剤が使用される。粉砕法は顔料、樹脂バインダー、帯電制御剤等を加熱混練し、冷却後、粉砕、所定の粒度に分級する製造方法であり、懸濁重合法は顔料、帯電制御剤等を分散させた付加重合性単量体を液滴の粒径を制御したＯ／Ｗ型エマルジョンとし、懸濁重合法により着色微粒子重合体とする方法であり、又、乳化重合液凝集法は乳化重合液に顔料や電荷制御剤の微分散液を混合し、得られた着色乳化重合液を加熱し、融着及び凝集させることにより重合体粒子に顔料や帯電制御剤を共沈或は吸着させるとともに、所定の粒度に微粒子化する方法である。それぞれ更に必要に応じて従来公知の流動化剤や強磁性材料等の添加剤が添加される。
【００３３】
又、湿式記録剤としては、顔料を樹脂バインダー、分散安定剤、帯電制御剤等とともに溶剤媒体中で湿式媒体分散機を用いて分散させる方法、或は顔料、樹脂バインダー、帯電制御剤等よりなる着色樹脂微粒子を同様にして分散安定剤或は更に帯電制御剤とともに、溶剤媒体中で湿式媒体分散機を用いて分散させる方法によって製造される液状湿式現像剤が使用される。
【００３４】
又、本発明の画像記録用着色組成物はマゼンタ色の画像記録剤として単色ないし二色カラー、多色カラー等の個別色で使用される外、フルカラー記録システムとしてシアン色、イエロー色或いは更にブラック色の画像記録剤とセットになって一緒に使用され得ることは勿論である。これらの有機顔料、無機顔料の例としては、フタロシアニン系、アゾ系、ポリ縮合アゾ系、アゾメチンアゾ系、アンスラキノン系、ペリノン・ペリレン系、インジゴ・チオインジゴ系、ジオキサジン系、イソインドリノン系、ピロロピロール系顔料等、カーボンブラック顔料、酸化チタン系、酸化鉄系、焼成顔料系、体質顔料等従来使用されている顔料である。
【００３５】
特にフルカラー記録剤に使用される顔料としては、シアン色の顔料としてフタロシアニン系ブルー顔料であり、イエロー色としてはアゾ系、ポリ縮合アゾ系、アンスラキノン系、イソインドリノン系のそれぞれの黄色顔料であり、ブラック色としてはカーボンブラック顔料、アゾメチンアゾ系黒色顔料、各色の顔料の調色による黒色顔料等がその代表的なものとして挙げられる。
【００３６】
これらの各種の顔料も前記したジメチルキナクリドン−無置換キナクリドン調色顔料と同様に、画像記録用着色組成物を製造するフラッシング、混練或は湿式分散等の通常の分散方法で分散することによって、平均粒子径が約２００ｎｍ以下、好ましくは約１５０ｎｍ以下になるように調製された顔料を使用することが好ましい。
【００３７】
【実施例】
次に顔料製造例及び実施例を挙げて本発明を更に具体的に説明する。尚、文中部又は％とあるのは重量基準である。
顔料製造例１
ジメチルキナクリドンの粗顔料１０部、塩化ナトリウム１００部及び高沸点脂環式炭化水素１部をボールミルに充填し、１０時間磨砕を行った。顔料化、濾過及び洗浄等の後処理を行ない、プレスケーキを得た。ジメチルキナクリドン顔料としての固形分は３０％であった。得られたプレスケーキを乾燥及び粉砕してジメチルキナクリドン顔料を得た。このようにして製造された顔料を分散させたときの平均粒子径は約２００ｎｍ以下を示し、色相は青味の赤色を示した。
【００３８】
別にγ型無置換キナクリドンの粗顔料１０部、無水芒硝９０部及び塩素化脂肪族炭化水素１部をボールミルに充填し、１０時間磨砕を行った。顔料化、濾過及び洗浄等の後処理を行ない、プレスケーキを得た。γ型無置換キナクリドン顔料としての固形分は３０％であった。得られたプレスケーキを乾燥及び粉砕してγ型無置換キナクリドン顔料を得た。このようにして製造された顔料を分散させたときの平均粒子径は約２００ｎｍ以下を示し、色相は黄味の赤色を示した。
【００３９】
顔料製造例２
顔料製造例１で得たジメチルキナクリドン顔料の水性プレスケーキを固形分で７０部を採り、γ型無置換キナクリドン顔料の水性プレスケーキの固形分３０部と混合し、乾燥及び粉砕してジメチルキナクリドン顔料及びγ型キナクリドン顔料の混合物顔料を得た。色相はマゼンタ色を示した。混合物顔料を分散させたときの平均粒子径は約２００ｎｍ以下であった。
【００４０】
顔料製造例３
５０部のジメチルキナクリドン顔料に５０部のγ型無置換キナクリドン顔料のクルードを添加し、摩砕し、固溶体粗結晶を得て、有機溶剤処理による顔料化を行い、濾過及び洗浄後、乾燥及び粉砕してジメチルキナクリドン−γ型キナクリドン（重量比５０：５０）固溶体顔料を得た。色相は黄味の赤色を示した。赤色固溶体顔料を分散させたときの平均粒子径は約２００ｎｍ以下であった。
【００４１】
顔料製造例４
３５部のジメチルキナクリドン顔料に５０部のγ型無置換キナクリドン顔料及び１５部のβ型無置換キナクリドン顔料のクルードを添加し、摩砕し、固溶体粗結晶を得て、有機溶剤処理による顔料化を行い、濾過及び洗浄後、乾燥及び粉砕してジメチルキナクリドン−γ型キナクリドン−β型無置換キナクリドン（重量比３５：５０：１５）固溶体顔料を得た。色相は黄味の赤色を示した。赤色固溶体顔料を分散させたときの平均粒子径は約２００ｎｍ以下であった。
【００４２】
顔料製造例５
３５部のジメチルキナクリドン顔料に２０部のγ型無置換キナクリドン顔料及び１５部のβ型無置換キナクリドン顔料のクルードを添加し、摩砕し、固溶体粗結晶を得て、有機溶剤処理による顔料化を行い、濾過及び洗浄後、乾燥及び粉砕してジメチルキナクリドン−γ型無置換キナクリドン−β型キナクリドン（重量比３５：２０：１５）固溶体顔料を得た。色相は黄味の赤色を示した。赤色固溶体顔料を分散させたときの平均粒子径は約２００ｎｍ以下であった。
【００４３】
顔料製造例６
顔料製造例５で得たジメチルキナクリドン−γ型無置換キナクリドン−β型キナクリドン（重量比３５：２０：１５）固溶体顔料の水性プレスケーキを固形分で７０部を採り、顔料製造例１で得たジメチルキナクリドン顔料の水性プレスケーキの固形分３０部と混合し、乾燥及び粉砕してジメチルキナクリドン−γ型無置換キナクリドン−β型キナクリドン固溶体顔料及びジメチルキナクリドン顔料の混合物顔料を得た。色相はマゼンタ色を示した。混合物顔料を分散させたときの平均粒子径は約２００ｎｍ以下であった。
【００４４】
参考例１
特開平２−１７５７７０号公報で提案された顔料の常圧溶融フラッシング法に従って、顔料製造例１で得たジメチルキナクリドン顔料のプレスケーキ８４部（顔料固形分２５％）、γ型無置換キナクリドン顔料のプレスケーキ３０部（顔料固形分３０％）及びスチレン−メタクリル系共重合樹脂（軟化点約１１０℃、ガラス転移点約５６℃、ＧＰＣ法重量平均分子量約９万）７０部を加熱型ニーダーに仕込み、混合しつつ蒸気加熱を行い、溶融フラッシングを行った。混練樹脂の温度を９０〜９５℃にし、フラッシングを続け、水分を分離させた。分離水を排出し更に残存している水分を加熱混練しつつ蒸発させ除去した。更に混練を続けた後、ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００４５】
次に、このようにして得たマゼンタ色混合顔料を含む高濃度着色組成物１４．７部及びクロム錯塩系負帯電制御剤３部を上記で使用したスチレン−メタクリル系共重合樹脂８２．３部と常法に従って混練し、冷却後、粗砕して後、ジェットミルで微粉砕し、更に分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得た。常法に従い流動化剤としてコロイダルシリカを添加して充分に混合し、次いでキャリアの磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。
【００４６】
これを負電荷フルカラー現像用電子写真複写機に仕込み、紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈し、耐光性等の諸物性に優れた堅牢性を示した。又、オーバーヘッドプロジェクター（以下ＯＨＰとする）用のポリエステルシートに複写すると透明な画像を呈し、ＯＨＰスクリーンに鮮明なマゼンタ色の映像を示した。
【００４７】
又、シアン色顔料としてＣ．Ｉ．ピグメントブルー１５：３（以下現像剤中の顔料含有率を示す：３．５％）、黄色顔料としてＣ．Ｉ．ピグメントイエロー９３（４．４％）、ブラック色顔料としてＣ．Ｉ．ピグメントブラック７（３．５％）のそれぞれ平均粒子径が約２００ｎｍ以下になるように分散できる顔料を用いて、上記と同様にしてそれぞれシアン色現像剤、イエロー色現像剤、ブラック色現像剤とし、上記で得たマゼンタ色現像剤とともに四色フルカラー複写を行ない、鮮明なフルカラー画像を得た。又、ＯＨＰシートに複写し、ＯＨＰスクリーンに鮮明なフルカラー映像を映すフルカラー画像を得た。
【００４８】
参考例２
顔料製造例１で得たジメチルキナクリドン顔料２１部及びγ型無置換キナクリドン顔料９部と参考例１で使用したスチレン−メタクリル系共重合樹脂７０部と水１００部を加熱型ニーダーに仕込み、混合しつつ蒸気加熱を行い、充分混練を行った。混練樹脂の温度を９０〜９５℃にし、水分を分離させた。分離水を排出し更に残存している水分を加熱混練しつつ蒸発させ除去した。更に混練を続けた後、ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００４９】
参考例１と同様にして、マゼンタ色混合顔料を含む高濃度着色組成物及びクロム錯塩系負帯電制御剤をスチレン−メタクリル系共重合樹脂と混練し、粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、コロイダルシリカを添加し、磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。
【００５０】
又、参考例１で使用したシアン色、イエロー色及びブラック色の現像剤を上記のマゼンタ色現像剤とともに、紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００５１】
参考例３
顔料製造例２で得たジメチルキナクリドン顔料及びγ型無置換キナクリドン顔料の混合物顔料３０部を参考例１で使用したスチレン−メタクリル系共重合樹脂７０部と三本ロールにて充分混練し、顔料を分散させた。冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。参考例１で示した方法に従って、このようにして得たマゼンタ色混合顔料を含む高濃度着色組成物１４．７部及びクロム錯塩系負帯電制御剤３部を上記で使用したスチレン−メタクリル系共重合樹脂８２．３部と混練し、冷却後、粗砕、微粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、コロイダルシリカを添加し、磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。
【００５２】
又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。又、参考例１で使用したシアン色、イエロー色及びブラック色の現像剤を上記のマゼンタ色現像剤とともに、紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００５３】
参考例４
参考例１で示した顔料の常圧溶融フラッシング法に従って、顔料製造例１で得たジメチルキナクリドン顔料のプレスケーキ５０部（顔料固形分３０％）と顔料製造例３で得たジメチルキナクリドン−γ型キナクリドン（５０：５０）固溶体顔料のプレスケーキ５３．６部（顔料固形分２８％）及び実施例１で使用したスチレン−メタクリル系共重合樹脂７０部を加熱型ニーダーに仕込み、混合し、溶融フラッシングを行った。分離した水を排出し更に残存している水分を加熱混練しつつ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００５４】
参考例１と同様にして上記で得たマゼンタ色混合顔料を含む高濃度着色組成物及びクロム錯塩系負帯電制御剤をスチレン−メタクリル系共重合樹脂と混練し、粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、コロイダルシリカを添加し、磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。
【００５５】
又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。又、参考例１で使用したシアン色、イエロー色及びブラック色の現像剤を上記のマゼンタ色現像剤とともに紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００５６】
実施例１
参考例１に記載の顔料の溶融フラッシング法に従って、顔料製造例１で得たジメチルキナクリドン顔料のプレスケーキ５０部（顔料固形分３０％）と顔料製造例４で得たジメチルキナクリドン−γ型キナクリドン−β型キナクリドン（重量比３５：５０：１５）固溶体顔料のプレスケーキ５３．６部（顔料固形分２８％）及び負電荷用ビスフェノール型ポリエステル樹脂（軟化点約１００℃）と加熱型ニーダーに仕込み、混合し、溶融フラッシングを行った。分離した水を排出し更に残存している水分を加熱及び蒸発しつつ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００５７】
次に、参考例１に記載の方法に従って、このようにして得たマゼンタ色混合顔料を含む高濃度着色組成物１４．７部及びクロム錯塩系負帯電制御剤３部を上記で使用したビスフェノール型ポリエステル樹脂８２．３部と混練し、冷却後、粗砕、微粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、流動化剤としてコロイダルシリカを添加し、磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。
【００５８】
又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。又、参考例１で使用したシアン色、イエロー色及びブラック色の現像剤を上記のマゼンタ色現像剤とともに紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００５９】
実施例２
参考例１に記載の顔料の溶融フラッシング法に従って、顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（重量比７０：３０）混合顔料の水性プレスケーキ１０７．２部（顔料固形分２８％）及び正電荷用三級アミノ基を有するスチレン−メタクリル系共重合樹脂７０部とを加熱型ニーダーに仕込み、混合し、溶融フラッシングを行った。分離した水を排出し更に残存している水分を加熱混練しつつ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００６０】
参考例１に記載の方法に従って、マゼンタ色混合顔料を含む高濃度着色組成物１４．７部及び上記で使用したスチレン−メタクリル系共重合樹脂８５．３部と混練し、冷却後、粗砕、微粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、流動化剤としてコロイダルシリカを添加し、磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。正電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。
【００６１】
又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。又、上記と同様にして参考例１で使用した青色、黄色及び黒色顔料を用いてシアン色、イエロー色及びブラック色の現像剤とし、上記のマゼンタ色現像剤とともに正電荷フルカラー現像用電子写真複写機にて紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００６２】
実施例３
参考例１で示された顔料の溶融フラッシング法に従って、顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（重量比３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（重量比７０：３０）混合顔料の水性プレスケーキ１０７．２部（顔料固形分２８％）及び負電荷用ビスフェノール型ポリエステル樹脂７０部とを加熱型ニーダーに仕込み、混合し、溶融フラッシングを行った。分離した水を排出し更に残存している水分を加熱混練しつつ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００６３】
実施例１と同様にして上記で得たマゼンタ色混合顔料を含む高濃度着色組成物及びクロム錯塩系負帯電制御剤を上記で使用したビスフェノール型ポリエステル樹脂と混練し、粉砕及び分級して５〜２０μｍのマゼンタ色樹脂組成物の微粉末を得、コロイダルシリカを添加し、キャリアの磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。
【００６４】
又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。又、上記と同様にして参考例１で使用した青色、黄色及び黒色顔料を用いてシアン色、イエロー色及びブラック色の現像剤とし、上記のマゼンタ色現像剤とともに負電荷フルカラー現像用電子写真複写機にて紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００６５】
実施例４
マレイン酸ジエチル５０部を容器に採り、スチレン−メタクリル酸ベンジル−メタクリル酸２−エチルヘキシル（共重合モル比７０：２０：１０）共重合体２０部を加えて溶解させ、そこに顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（重量比３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（重量比７０：３０）混合顔料２５．５部及びフタルイミドメチル化ジメチルキナクリドン４．５部を混合し、連続式横形湿式ビーズ媒体分散機を用いて充分に微細に分散し、マゼンタ色顔料高濃度単量体分散液を得た。同様にしてマレイン酸ジエチル５０部に上記のスチレン−メタクリル酸エステル共重合体２０部を溶解させ、クロム錯塩系負電荷制御剤３０部を加え、混合し、連続式横形湿式ビーズ媒体分散機を用いて微細に分散し負電荷制御剤の高濃度単量体分散液を得た。
【００６６】
上記で得たマゼンタ色顔料の高濃度単量体分散液１６．７部と負電荷制御剤の高濃度単量体分散液１０．０部及びメタクリル酸ブチル１２．６部、スチレン６０．７部、ラウリルメルカプタン１．５部及びアゾイソブチロニトリル２．０部を添加し、均一になるように充分に撹拌及び混合した。４％コロイダルシリカ水分散液を２００部を準備し、高剪断力高速攪拌機で攪拌しつつ上記で得た顔料及び電荷制御剤を含む単量体分散液１０３．５部を徐々に添加し、水中油滴型のエマルジョンを調製した。エマルジョンの油滴の大きさが約７〜９μｍ位になるように攪拌の速度及び攪拌時間を調整した。
【００６７】
攪拌機、温度計、窒素ガス導入管、蛇管コンデンサー及び滴下濾斗を備えた重合反応装置に４％コロイダルシリカ水分散液２００部及び上記で得たマゼンタ色エマルジョン２０３．５部の約３分の１を仕込み、７５〜８０℃にて２時間重合反応を行った。次いで、残りの約３分の２のエマルジョンを滴下濾斗より３時間かけて滴下し、更に１時間攪拌を続け、次いで３０分間かけて８５℃に昇温し１時間攪拌して重合反応を完結させた。生成した重合物を濾別し、水酸化ナトリウム水溶液で洗浄してシリカを除去し、充分水洗した後、乾燥して平均粒子径約８μｍのマゼンタ色重合体の微粉末を得た。コロイダルシリカを添加し、キャリアの磁性鉄粉と混合し、マゼンタ色電子写真乾式現像剤とした。負電荷フルカラー現像用電子写真複写機にて紙に複写した。複写画像は鮮明で冴えたマゼンタ色を呈した。又、ＯＨＰ用のポリエステルシートに複写すると透明な画像を呈し、スクリーンに鮮明なマゼンタ色の映像を示した。
【００６８】
又、上記と同様にしてＣ．Ｉ．ピグメントブルー１５：３（以下現像剤中の顔料の含有率を示す：３．４０％）及びフタルイミドメチル銅フタロシアニン（０．６０％）を用いてシアン色現像剤、Ｃ．Ｉ．ピグメントイエロー９３（４．２５％）及びフタルイミドメチルジアンスラキノニル−モノフェニルアミノ−ｓ−トリアジン（０．７５％）を用いてイエロー色現像剤、Ｃ．Ｉ．ピグメントブラック７（３．４０％）及びフタルイミドメチル銅フタロシアニン（０．６０％）を用いてブラック色現像剤を調製し、上記のマゼンタ色現像剤とともに負電荷フルカラー現像用電子写真複写機にて紙に四色フルカラー複写を行ない、鮮明なフルカラー複写画像を得た。又、ＯＨＰシートのフルカラー複写画像はスクリーンに鮮明なフルカラー映像を映した。
【００６９】
実施例５
参考例１に記載の顔料の溶融フラッシング法に従って、顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（重量比３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（重量比７０：３０）混合顔料のプレスケーキ１０７部（顔料固形分２８％）及び第三級アミノ基を有するスチレン−メタクリル系共重合樹脂７０部と加熱型ニーダーに仕込み、混合し、溶融フラッシングを行った。分離した水を排出し更に残存している水分を加熱及び蒸発しつつ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粗砕して、顔料分を３０％の濃度で含有するマゼンタ色高濃度着色組成物の粗粉を得た。
【００７０】
得られたマゼンタ色樹脂粉末１０部を脂肪族炭化水素系溶媒に可溶のメタクリルエステル系樹脂１５部とともにアイソパーＧ７５部に加えて、ガラスビーズを加えてペイントシェーカーにて２０時間振とうして分散せしめ、濃厚着色液を調製した。この濃厚溶液２００ｇを、アイソパーＧの１リットル中に加えて分散させて電子写真湿式現像剤を得た。これをフルカラー湿式電子写真複写機にて複写し、鮮明なマゼンタ色複写画像を得た。この画像は、耐光性等の諸物性に優れた堅牢性を示した。
【００７１】
又、上記と同様にして参考例１で使用した青色、黄色及び黒色顔料を用いてシアン色、イエロー色及びブラック色の湿式現像剤とし、上記で得たマゼンタ湿式現像液とともに、四色フルカラー複写を行い鮮明なフルカラー画像を得た。又、上記の四色フルカラー現像剤を使用して四色フルカラー湿式静電プロッターにて鮮明なフルカラー画像を出力させた。
【００７２】
実施例６
顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（重量比３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（７０：３０）混合顔料１０部を、エステルワックス４１部、パラフィン系ワックス４１部、スチレン−メタクリル系共重合樹脂５部及びシリカ３部をバインダーとし、分散剤として水５０部を加えて樹脂の融点又は軟化点未満の温度で常圧で混練りして分離水を除去し、残存水を蒸発させ、常法に従いポリエチレンフイルムに塗布し、マゼンタ色熱転写記録用インクフイルムとした。これをフルカラー熱転写複写機にて複写し、鮮明なマゼンタ色複写画像を得た。この画像は、耐光性等の諸物性に優れた堅牢性を示した。
【００７３】
又、ＯＨＰ用のポリエステルシートに複写すると、透明な画像が得られ、スクリーンに鮮明な画像を示した。又、上記と同様にして参考例１で使用した青色、黄色及び黒色顔料を用いてシアン色、イエロー色及びブラック色の熱転写インクフイルムとし、上記で得たマゼンタ熱転写インクフイルムとともに、四色フルカラー複写を行い、鮮明なフルカラー複写画像を得た。更に、ＯＨＰ用のポリエステルシートに複写し、スクリーンに透明なフルカラー映像を映すフルカラー画像を得た。
【００７４】
実施例７
顔料製造例６で得たジメチルキナクリドン−γ型無置換キナクリドン−β型無置換キナクリドン（重量比３５：２０：１５）固溶体顔料とジメチルキナクリドン顔料との（重量比７０：３０）混合顔料の水性プレスケーキ１７．９部（顔料固形分２８％）、スチレン−アクリレート−メタクリル酸ジエタノールアミン塩共重合体３部、エチレングリコール２２部、グリセリン８部及び水５０部の水性顔料分散液を作り、超遠心分離機で分散し得なかった顔料粗粒子を除去し、インクジェット用水性マゼンタ色インキを得た。
【００７５】
ピエゾ振動子を有するオンデマンド型のインクジェットプリンターで、上記のマゼンタ色インキを用いて画像情報をプリントし、鮮明なマゼンタ色画像を得た。又、上記と同様にして参考例１で使用した青色、黄色及び黒色顔料を用いてシアン色、イエロー色及びブラック色のインクジェットインキとし、上記で得たマゼンタ色インクジェットインキとともに、四色フルカラープリントを行い、鮮明なフルカラー複写画像を得た。
【００７６】
【発明の効果】
本発明の画像記録用着色組成物は、その顔料成分として使用されるジメチルキナクリドン−無置換キナクリドン調色顔料、即ちジメチルキナクリドン顔料とγ型、β型無置換キナクリドン顔料との混合顔料、固溶体顔料及びそれらの混合顔料はフルカラー画像記録用着色組成物のマゼンタ色顔料として非常に優れたものであり、耐光性、耐熱性、耐溶剤性、耐薬品性、耐水性等の諸堅牢性に優れ、更に高い着色力、鮮明性、冴え、透明性を有するものであるため、着色物の製造の工程においても特定の条件で安定に製造することができ、その結果、最終的にマゼンタ色の画像記録用着色組成物として使用される際にも鮮明で冴えた、透明感の高い画像を安定して記録することができるものである。
又、液体状の記録剤として使用するに際においても、長期間安定に記録することができるものである。従って、得られた画像は鮮明であるとともに顔料に関連する上記した諸堅牢性においても優れた性質を示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a recording agent for image recording such as electrophotography, electronic printing, electrostatic recording, ink jet recording and thermal transfer recording, or a high-density coloring composition used for the production thereof, and an image used for the image recording recording agent. The present invention relates to a coloring composition for recording and a production method thereof.
[0002]
More specifically, the present invention relates to a recording agent for image recording containing a pigment and a resin, which is a mixed pigment of a dimethylquinacridone pigment and an unsubstituted quinacridone pigment having excellent various fastness and a fine particle diameter as a pigment, a dimethylquinacridone pigment. For recording vivid magenta images containing a solid solution pigment of dimethylquinacridone pigment and unsubstituted quinacridone pigment or a mixed pigment of dimethylquinacridone pigment and / or unsubstituted quinacridone pigment. It is intended to provide a coloring composition and a method for producing the same.
[0003]
[Prior art]
Conventionally, as a red pigment used in a magenta recording agent used for image recording such as full-color or mono-color electrophotography, electrostatic printing, electrostatic recording, inkjet recording and thermal transfer recording, a red oil-soluble dye, Disperse dyes, thioindigo pigments, soluble azo lake pigments, insoluble azo pigments, dimethylquinacridone pigments and the like have been used.
[0004]
[Problems to be solved by the invention]
As the red pigment used in the above-described magenta image recording agent, a well-known dimethylquinacridone pigment is often used as the magenta color pigment.However, the magenta color alone is too bluish, and is often more yellow than that. A mixed and toned red pigment is used as a desired magenta color.
[0005]
However, regarding red dyes used in these, oil-soluble dyes, disperse dyes, etc. can be dissolved in a resin medium and thus have high coloring power, but light resistance, heat resistance, solvent resistance, chemical resistance, etc. Is inferior in robustness. Also, thioindigo pigments, soluble azo lake pigments, and insoluble azo pigments are superior to dyes, but are insufficient in light fastness, heat resistance and other various fastnesses. Therefore, the dyes and pigments as described above are insufficient as dyes used for magenta colors for recording agents requiring various fastnesses, and are used for magenta colors for recording agents having excellent physical properties. There is a demand for the development of pigments.
[0006]
The present inventors have solved various defects of the above-described conventional dyes for magenta color recording agents and made various studies on the development of red pigments capable of satisfying various fastnesses.As a result, a specific quinacridone-based pigment, A solid solution pigment such as an unsubstituted quinacridone pigment or a dimethylquinacridone pigment and a γ-type or β-type unsubstituted quinacridone pigment having a crystalline form having a physical property such as high robustness suitable for this use and a clear and transparent yellowish red color Color can be obtained.
[0007]
From the above findings, a mixed pigment of a dimethyl quinacridone pigment and an unsubstituted quinacridone pigment, a solid solution pigment of a dimethyl quinacridone pigment and an unsubstituted quinacridone pigment, or a dimethyl quinacridone pigment and an unsubstituted quinacridone as the pigment used in the magenta color recording agent A mixed pigment of a solid solution pigment and a dimethylquinacridone pigment and / or an unsubstituted quinacridone pigment (hereinafter collectively referred to as a dimethylquinacridone-unsubstituted quinacridone toning pigment) has an appropriate magenta hue, Excellent in various fastnesses such as solvent resistance, heat resistance, chemical resistance, etc. In addition, the sharpness of the hue is reduced by reducing the particle size compared to pigments used for conventional paints and plastic coloring applications. And it can exhibit excellent properties such as clearness, transparency, etc. Ri superior image recording recording agent and completed the present invention found that the resulting.
[0008]
[Means for Solving the Problems]
That is, the present invention relates to pigments and resinsbinderIn the coloring composition for image recording containingTheMethylquinacridone pigmentβ type and γ typeSolid solution pigments with unsubstituted quinacridone pigments and dimethylquinacridone pigments and / orgamma typeMixed face with unsubstituted quinacridone pigmentIn chargeA coloring composition for image recording and a method for producing the same.
[0009]
The coloring composition for image recording of the present invention uses dimethylquinacridone-unsubstituted quinacridone toning pigment as a pigment component, and this red pigment has light resistance, heat resistance, solvent resistance, and chemical resistance. It is excellent in various fastnesses such as water resistance and water resistance, and has higher coloring power, sharpness, sharpness, and transparency. It can be produced stably even in the process of producing colored materials by taking processing methods, etc. Also, when it is finally used as a recording agent for image recording, it is clear, clear and highly transparent image Can be stably recorded. Also, when used as a liquid recording agent, stable recording can be performed for a long period of time. Accordingly, the obtained image is excellent in hue, sharpness and transparency, and also exhibits the above-described properties of excellent fastness.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
When the present invention is described in more detail, a method for preparing a dimethylquinacridone-unsubstituted quinacridone toning pigment used in the present invention and mainly characterizing the present invention, and using the same as a coloring composition for image recording, includes: A method of directly producing a colored composition using a finely divided pigment which has been subjected to mixing and toning in a pigment production process, and a method of previously preparing a finely divided pigment by using a heat kneader such as a roll mill or an extruder, or an aqueous press of the pigment. There is a method of producing a high-concentration colorant using a heating kneader or the like for the cake, and producing a coloring composition using the high-concentration colorant.
[0011]
Specific toning pigments and high-concentration colorants containing the toning pigments include, for example, the following.
(A) A mixed pigment of a dimethylquinacridone pigment and an unsubstituted quinacridone pigment and a high-concentration colorant thereof.
(A) A mixture of finely divided pigments, each of which has been dried alone, impact-ground or ground, and a high-concentration colorant.
(B) An aqueous presscake of both pigments is mixed, dried, and then subjected to impact milling or grinding to obtain a fine powder mixed pigment and a high-concentration colorant.
(C) A high-concentration colorant produced by separately charging the aqueous presscakes of both pigments in a heating kneader or the like, and producing them by a melt flushing method or the like.
(D) A high-concentration colorant produced by mixing aqueous presscakes of both pigments and producing the same.
[0012]
(B) A solid solution pigment of a dimethylquinacridone pigment and an unsubstituted quinacridone pigment and a high-concentration colorant thereof.
(A) A fine powder pigment and a high-concentration colorant obtained by drying a solid solution of a dimethylquinacridone pigment and a γ-type unsubstituted quinacridone pigment, and then subjecting the solid solution to impact pulverization or grinding.
(B) A fine powder pigment and a high-concentration colorant obtained by drying a solid solution of a dimethyl quinacridone pigment, a γ-type unsubstituted quinacridone pigment, and a β-type unsubstituted quinacridone pigment, and then subjecting them to impact pulverization or grinding.
(C) A high-concentration colorant prepared by separately charging the aqueous presscakes of the solid solution pigments of (a) and (b) above in a heating kneader or the like, and producing the same by a melt flushing method or the like.
(D) A high-concentration colorant produced by mixing the aqueous presscakes of the solid solution pigments of (a) and (b) and producing the same.
[0013]
(C) A mixed pigment of a solid solution pigment of a dimethylquinacridone pigment and an unsubstituted quinacridone pigment, a dimethylquinacridone pigment and / or an unsubstituted quinacridone pigment, and a high-concentration colorant thereof.
(A) Toning pigments of a solid solution fine powder pigment of a dimethylquinacridone pigment and a γ-type unsubstituted quinacridone pigment, and a high-concentration colorant of a γ-type unsubstituted quinacridone fine powder pigment.
(B) Toning pigments of a solid solution of a dimethylquinacridone pigment, a γ-type unsubstituted quinacridone pigment and a solid solution of a β-type unsubstituted quinacridone pigment and a γ-type unsubstituted quinacridone fine powder pigment and a high-concentration colorant.
(C) A high-concentration colorant prepared by separately charging the aqueous presscakes of the solid solution pigments of (a) and (b) above in a heating kneader or the like, and producing the same by a melt flushing method or the like.
(D) A high-concentration colorant produced by mixing the aqueous presscakes of the solid solution pigments of (a) and (b) and producing the same.
[0014]
In the above, a solid solution pigment of a dimethyl quinacridone pigment and an unsubstituted quinacridone pigment is a solid solution by subjecting a mixed pigment of a dimethyl quinacridone pigment and an unsubstituted quinacridone pigment to a pigmentation treatment as described below to obtain a clear hue. The purpose is to improve clarity and transparency. The method for converting the mixed pigment into a solid solution is in accordance with a conventionally known method. For example, this can be achieved by blending a plurality of pigments to be a solid solution, subjecting them to an acid paste treatment or grinding step to obtain solid solution crude crystals, and treating them with an organic solvent or the like.
[0015]
The dimethylquinacridone-unsubstituted quinacridone toning pigment used in the present invention, that is, the mixed ratio of the dimethylquinacridone pigment and the unsubstituted quinacridone pigment in the mixed pigment (A), the solid solution of the dimethylquinacridone pigment and the unsubstituted quinacridone pigment The composition ratio of the two in the pigment (B) or the total ratio of the dimethyl quinacridone pigment and the unsubstituted quinacridone pigment in the mixture pigment (C) of the solid solution pigment (B) and the dimethyl quinacridone pigment and / or the unsubstituted quinacridone pigment (Weight) is determined by the hue of the desired image and is in the range of about 99: 1 to 1:99, preferably in the range of 90:10 to 30:70.
[0016]
As the unsubstituted quinacridone pigment, a γ-type unsubstituted quinacridone pigment exhibiting yellowish red and a β-type unsubstituted quinacridone pigment exhibiting purple red are used. In order to obtain a bright vivid yellowish magenta color in a solid solution pigment of a dimethylquinacridone pigment and an unsubstituted quinacridone pigment, the total ratio (weight ratio) of the dimethylquinacridone pigment and the γ-type and β-type unsubstituted quinacridone pigments is It is preferable to use a large number of yellowish γ-type unsubstituted quinacridone pigments as the unsubstituted quinacridone pigment at a ratio of about 50:50 to 20:80. The β-type unsubstituted quinacridone pigment shows a very clear color when used in a small amount, but becomes purple when used in a large amount. Therefore, it is preferable to suppress the amount to about 30% by weight or less based on the whole solid solution pigment.
[0017]
Using a relatively large amount of β-type unsubstituted quinacridone pigments, it is bright by adding a yellowish γ-type unsubstituted quinacridone pigment to a solid solution pigment of dimethyl quinacridone pigment and γ-type and β-type unsubstituted quinacridone pigment, and further adding a yellowish color. A vivid yellow magenta color can be obtained.
[0018]
The dimethylquinacridone-unsubstituted quinacridone toning pigment pigment used in the present invention is used to adjust the crystal of the pigment to bring about excellent properties such as color transparency, clarity, and clarity and physical properties of the pigment. Post-treatment such as adjusting the shape and particle size of the pigment particles to a desired range is performed according to a usual method.
[0019]
Generally, when a quinacridone pigment such as a dimethylquinacridone pigment or an unsubstituted quinacridone pigment is used for coloring a paint or a plastic, the pigment has a hiding power, easy dispersibility in a medium, weather resistance, and heat resistance. The average particle diameter of the pigment is adjusted to a large value, for example, about 500 to 700 nm in order to impart properties such as properties.
[0020]
However, when this coarse pigment is used as a colorant for an image recording agent, there is a problem that the hue lacks in transparency, sharpness, and sharpness. In particular, when used as a colorant for a full-color recording agent, it is preferable that the colorant has transparency, sharpness, and sharpness. For that purpose, the above-mentioned dimethylquinacridone-unsubstituted quinacridone toning pigment used in the present invention is dispersed by a usual dispersion method such as flushing, kneading or wet dispersion for producing a coloring composition for image recording, thereby obtaining an average particle size. It is preferable to adjust the diameter to be about 200 nm or less, preferably about 150 nm or less.
[0021]
Examples of the method for making the pigment fine particles include a method by impact pulverization and a method by attrition. As the impact crushing method, a dry milling method using a ball mill or a vibration mill is a representative method, a conventionally known crushing medium such as a steel ball or a steel rod is used, and an inorganic salt is also used as a grinding aid in combination. Is preferred. Typical examples of the grinding method include a salt milling method and a solvent salt milling method, and grinding aids such as anhydrous sodium sulfate, sodium chloride, and aluminum sulfate are used in combination. As a post-treatment of the pulverization or attrition step, the substrate is washed with a dilute acid aqueous solution and then sufficiently with water to remove metallic impurities, or sufficiently washed with water after removing water-soluble salts with water. The fine-particle pigment thus obtained has clarity, sharpness, and transparency of the hue, and also has excellent properties such as light fastness, heat resistance, solvent resistance, chemical resistance, and water resistance. showed that.
[0022]
The resin used in the present invention is a dispersion medium in a solid coloring composition, and functions as a dispersant for a pigment in a liquid coloring composition. When used as a pigment, it acts as a fixing agent for the pigment. Examples of resins used for such purposes include dry and wet developers for electrophotography, electrostatic printing, and electrostatic recording, and image recording agents such as oily and aqueous inkjet inks, thermal transfer ink ribbons and films. Any resin used may be used. In addition, conventionally known additives such as a charge controlling agent, a fluidizing agent, and the like, or a solvent and an aqueous medium as a medium are used as necessary according to each application.
[0023]
The coloring composition for image recording of the present invention can be used in various ways depending on the purpose. One of them is a high-concentration coloring composition, which contains a pigment at a high concentration, and is prepared by dispersing the pigment by sufficiently kneading it in advance, or by performing toning to facilitate the subsequent steps. It can be used in any form of solid, such as coarse particles, coarse powder, fine powder, sheet, small lumps, or paste or liquid.
[0024]
Examples of the coloring composition for image recording of the present invention include compositions used as a target image recording agent, and include so-called fine powder dry developers, liquid wet developers, electrostatic recording agents, and inkjet recording. And thermal transfer ink ribbons and films applied to substrates such as inks, films and papers.
[0025]
The content of the magenta-toned dimethylquinacridone-unsubstituted quinacridone toning pigment used in the present invention in the coloring composition containing a resin or other additives or a medium is as described above. It depends on
The content of the pigment at a high concentration is about 70% by weight to 10% by weight, preferably about 60% by weight to 20% by weight.
[0026]
The content of the pigment in the target image recording agent varies depending on the type of the recording agent. In an electrophotographic dry developer or the like, the content of the pigment is about 15% to 2% by weight, preferably 10% by weight. % To about 3% by weight, and about 1% to 20% by weight, preferably about 3% to 10% by weight for a concentrated stock solution in a wet developer for electrostatic recording, and usually 10% for a diluent. It is used by diluting it up to 30 times by volume. When used as a coloring agent for a thermal transfer ink ribbon or film, the amount is about 15% to 4% by weight, preferably about 10% to 6% by weight, and 3% to 20% by weight for an inkjet recording ink. It is preferably about 5% by weight to 10% by weight, and is used at the most preferable content depending on the purpose of use.
[0027]
As a method for producing the above-mentioned pigment high-concentration coloring composition, there are a dry heat kneading dispersion method and a wet medium dispersion method using ceramic beads, glass beads, steel balls and the like. In particular, as a method of dispersing the pigment in the resin at a high concentration, the resin is melted using a kneading and dispersing machine such as a two-roll, three-roll, heating kneader, a pressure-heating kneader, a single-screw extruder, and a twin-screw extruder. And then kneading and dispersing the pigment.
[0028]
In any of these cases, the kneading and dispersion processing is desirably performed at a temperature of 120 ° C. or lower. By performing the process under the relatively low processing temperature conditions, the particle diameter of the finely prepared pigment is kept as it is, and by performing the same in the subsequent processing step of the recording agent production, the hue of the image recording agent is reduced. It shows clarity, clarity, and transparency.
[0029]
The most preferable method for the high-concentration dispersion of the pigment is a method of flushing an aqueous paste of the pigment with a molten resin (normal pressure melting flushing method), for example, a method proposed in JP-A-2-175770. And so on. Specifically, an aqueous presscake of a pigment and a resin binder are charged into a kneader or flasher capable of steam heating without using any solvent, and kneaded at normal pressure at a temperature lower than the melting point or softening point of the resin to form an aqueous phase. Is transferred to the resin phase, the separated water is removed, and the remaining water is kneaded and evaporated. By using an aqueous press cake, the pigment particles of the press cake can be directly transferred into the resin, and the kneading and dispersing process can be performed at 100 ° C. or less while water is present. I have.
[0030]
As a high-concentration pigment dispersion step, water is added as a dispersant to the powder pigment and the resin binder, and in the same manner, at normal pressure and in the absence of a solvent, at a processing temperature of 120 ° C. or less and less than the melting point or softening point of the resin. , The pigment is transferred to the resin phase, the separated water is removed, and the remaining water is kneaded and evaporated to obtain a high-concentration dispersed coloring composition.
[0031]
In the coloring composition for image recording of the present invention, electrophotographic, electrostatic printing, dry developer and wet developer such as electrostatic recording, aqueous, oily and solid inkjet ink, thermal transfer ink ribbon and thermal transfer ink film and the like The image recording agent is obtained by using the above-mentioned dimethylquinacridone-unsubstituted quinacridone toning pigment as it is or in the form of a high-concentration coloring composition of the above-mentioned pigment, in a resin binder, a resin solution or an addition polymerizable monomer. Disperse or dilute and re-disperse in accordance with the usual method of producing each image recording agent, and in that case, if necessary, a conventionally known charge control agent, fluidizing agent, ferromagnetic material, solvent medium, aqueous medium, etc. It is manufactured by adding.
[0032]
Regarding recording agents for image recording used in electrophotography, electrostatic printing, electrostatic recording, etc., as dry recording agents, production methods such as a suspension polymerization method called a pulverization method and a polymerization method and an emulsion polymerization liquid aggregation method are used. A fine powdery dry developer produced by the method is used. The pulverization method is a production method in which a pigment, a resin binder, a charge control agent, etc. are heated and kneaded, cooled, pulverized, and classified to a predetermined particle size.The suspension polymerization method is an addition polymerization in which a pigment, a charge control agent, etc. are dispersed. Is a method in which a water-soluble monomer is converted into an O / W emulsion in which the particle diameter of droplets is controlled, and a colored fine particle polymer is formed by a suspension polymerization method. A pigment dispersion and a charge control agent are coprecipitated or adsorbed on the polymer particles by mixing a fine dispersion of the control agent, heating the obtained colored emulsion polymerization solution, and fusing and aggregating the same, and also to a predetermined particle size. This is a method of forming fine particles. Additives such as conventionally known fluidizing agents and ferromagnetic materials are further added as necessary.
[0033]
Further, as the wet recording agent, a method of dispersing a pigment with a resin binder, a dispersion stabilizer, a charge control agent, and the like using a wet medium disperser in a solvent medium, or a pigment, a resin binder, a charge control agent, or the like. Similarly, a liquid wet developer produced by a method of dispersing the colored resin fine particles together with a dispersion stabilizer or a charge control agent in a solvent medium using a wet medium disperser is used.
[0034]
Further, the coloring composition for image recording of the present invention is used as an individual color such as monochromatic or two-color, or multicolor as an image recording agent of magenta, and as a full-color recording system, cyan, yellow or even black. It goes without saying that it can be used together with a color image recording agent. Examples of these organic pigments and inorganic pigments include phthalocyanine, azo, polycondensed azo, azomethine azo, anthraquinone, perinone / perylene, indigo / thioindigo, dioxazine, isoindolinone, and pyrrolopyrrole. Conventionally used pigments such as carbon black pigments, titanium oxides, iron oxides, calcined pigments, and extender pigments.
[0035]
In particular, as a pigment used in a full-color recording agent, a phthalocyanine-based blue pigment is used as a cyan pigment, and an azo-based, polycondensed azo-based, anthraquinone-based, or isoindolinone-based yellow pigment is used as a yellow color. There are carbon black pigments, azomethine azo black pigments, and black pigments obtained by toning the pigments of each color.
[0036]
These various pigments, like the dimethylquinacridone-unsubstituted quinacridone toning pigment described above, are dispersed by a normal dispersion method such as flashing, kneading, or wet dispersion for producing a coloring composition for image recording. It is preferable to use a pigment prepared to have a particle size of about 200 nm or less, preferably about 150 nm or less.
[0037]
【Example】
Next, the present invention will be described more specifically with reference to pigment production examples and examples. It should be noted that “part” or “%” in the text is based on weight.
Pigment production example 1
A ball mill was charged with 10 parts of a crude pigment of dimethylquinacridone, 100 parts of sodium chloride, and 1 part of a high-boiling alicyclic hydrocarbon, and was ground for 10 hours. Post-treatments such as pigmentation, filtration and washing were performed to obtain a press cake. The solids content of the dimethylquinacridone pigment was 30%. The obtained press cake was dried and pulverized to obtain a dimethylquinacridone pigment. When the pigment thus produced was dispersed, the average particle diameter was about 200 nm or less, and the hue was bluish red.
[0038]
Separately, 10 parts of a crude pigment of γ-type unsubstituted quinacridone, 90 parts of anhydrous sodium sulfate and 1 part of chlorinated aliphatic hydrocarbon were charged into a ball mill, and ground for 10 hours. Post-treatments such as pigmentation, filtration and washing were performed to obtain a press cake. The solid content of the γ-type unsubstituted quinacridone pigment was 30%. The obtained press cake was dried and pulverized to obtain a γ-type unsubstituted quinacridone pigment. When the pigment thus produced was dispersed, the average particle diameter was about 200 nm or less, and the hue was yellowish red.
[0039]
Pigment production example 2
Take 70 parts by weight of the aqueous dimethylquinacridone pigment presscake obtained in Pigment Production Example 1 as a solid, mix with 30 parts of the aqueous presscake γ-type unsubstituted quinacridone pigment solid, dry and pulverize to obtain a dimethylquinacridone pigment. And a mixture pigment of γ-quinacridone pigment was obtained. The hue showed a magenta color. The average particle size when the mixture pigment was dispersed was about 200 nm or less.
[0040]
Pigment production example 3
To 50 parts of dimethylquinacridone pigment, 50 parts of crude gamma-type unsubstituted quinacridone pigment is added, and the mixture is milled to obtain a solid solution crude crystal, which is treated with an organic solvent to form a pigment, filtered, washed, dried and ground. Thus, a dimethylquinacridone-γ-quinacridone (weight ratio: 50:50) solid solution pigment was obtained. The hue was yellowish red. The average particle size when the red solid solution pigment was dispersed was about 200 nm or less.
[0041]
Pigment Production Example 4
To 35 parts of dimethylquinacridone pigment, 50 parts of crude γ-type unsubstituted quinacridone pigment and 15 parts of crude of β-type unsubstituted quinacridone pigment are added, and the mixture is ground to obtain a solid solution crude crystal. After filtration, washing and drying and pulverization, a dimethylquinacridone-γ-type quinacridone-β-type unsubstituted quinacridone (weight ratio 35:50:15) solid solution pigment was obtained. The hue was yellowish red. The average particle size when the red solid solution pigment was dispersed was about 200 nm or less.
[0042]
Pigment Production Example 5
To 35 parts of dimethylquinacridone pigment, 20 parts of crude γ-type unsubstituted quinacridone pigment and 15 parts of β-type unsubstituted quinacridone pigment are added, and the mixture is ground to obtain a solid solution crude crystal. The mixture was filtered, washed, dried and pulverized to obtain a dimethylquinacridone-γ-type unsubstituted quinacridone-β-type quinacridone (weight ratio: 35:20:15) solid solution pigment. The hue was yellowish red. The average particle size when the red solid solution pigment was dispersed was about 200 nm or less.
[0043]
Pigment Production Example 6
An aqueous presscake of a dimethylquinacridone-γ-type unsubstituted quinacridone-β-type quinacridone (weight ratio 35:20:15) solid solution pigment obtained in Pigment Production Example 5 was collected in a solid content of 70 parts and obtained in Pigment Production Example 1.TheMethylquinacridone pigment is mixed with 30 parts of solid content of an aqueous press cake, dried and pulverized to obtain a dimethylquinacridone-γ-unsubstituted quinacridone-β-quinacridone solid solution pigment;DimethylQuinacridFaceA pigment mixture was obtained. The hue showed a magenta color. The average particle size when the mixture pigment was dispersed was about 200 nm or less.
[0044]
referenceExample 1
According to the normal pressure melting flushing method for pigments proposed in JP-A-2-175770, 84 parts of a dimethylquinacridone pigment press cake (pigment solid content: 25%) obtained in Pigment Production Example 1 and a γ-type unsubstituted quinacridone pigment were prepared. 30 parts of press cake (pigment solid content: 30%) and 70 parts of styrene-methacrylic copolymer resin (softening point: about 110 ° C., glass transition point: about 56 ° C., weight average molecular weight by GPC method: about 90,000) are charged into a heating kneader. Then, steam heating was performed while mixing, and melt flushing was performed. The temperature of the kneaded resin was set to 90 to 95 ° C., flushing was continued, and water was separated. The separated water was discharged, and the remaining water was removed by evaporation while heating and kneading. Continue to knead furtherWasThereafter, the kneaded product was taken out of the kneader, cooled and crushed to obtain a coarse powder of a high-concentration magenta-colored composition containing a pigment content of 30%.
[0045]
Next, 12.3 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 8 parts of a styrene-methacrylic copolymer resin containing 3 parts of a chromium complex-based negative charge control agent were used. After cooling, the mixture was cooled, roughly crushed, finely crushed with a jet mill, and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm. Colloidal silica was added as a fluidizing agent according to a conventional method, mixed well, and then mixed with a magnetic iron powder of a carrier to obtain a magenta electrophotographic dry developer.
[0046]
This was charged in an electrophotographic copying machine for negative charge full-color development and copied on paper. The copied image exhibited a clear and clear magenta color, and exhibited fastness excellent in various physical properties such as light fastness. Further, when copied on a polyester sheet for an overhead projector (hereinafter referred to as OHP), a transparent image was exhibited, and a clear magenta color image was displayed on the OHP screen.
[0047]
Further, C.I. I. Pigment Blue 15: 3 (the pigment content in the developer is shown below: 3.5%), and C.I. I. Pigment Yellow 93 (4.4%), C.I. I. Pigment Black 7 (3.5%), using pigments that can be dispersed so that the average particle diameter of each is about 200 nm or less, is used as a cyan developer, a yellow developer, and a black developer in the same manner as described above. Then, four-color full-color copying was performed with the magenta developer obtained above to obtain a clear full-color image. Further, the image was copied onto an OHP sheet to obtain a full-color image showing a clear full-color image on an OHP screen.
[0048]
referenceExample 2
21 parts of the dimethyl quinacridone pigment obtained in Pigment Production Example 1 and 9 parts of the γ-type unsubstituted quinacridone pigmentreference70 parts of the styrene-methacrylic copolymer resin used in Example 1 and 100 parts of water were charged into a heating-type kneader, and the mixture was heated with steam and kneaded sufficiently. The temperature of the kneaded resin was set to 90 to 95 ° C. to separate water. The separated water was discharged, and the remaining water was removed by evaporation while heating and kneading. After the kneading was further continued, the kneaded product was taken out of the kneader, cooled and crushed to obtain a coarse powder of a magenta high-concentration coloring composition containing a pigment content of 30%.
[0049]
referenceIn the same manner as in Example 1, a high-concentration coloring composition containing a magenta-colored mixed pigment and a chromium complex-based negative charge control agent were kneaded with a styrene-methacrylic copolymer resin, pulverized and classified, and a magenta resin of 5 to 20 μm was obtained. A fine powder of the composition was obtained, colloidal silica was added, and mixed with magnetic iron powder to obtain a magenta electrophotographic dry developer. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color. Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen.
[0050]
or,referenceUsing the cyan, yellow and black developers used in Example 1 together with the above magenta developer, four-color full-color copying was performed on paper to obtain a clear full-color copied image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0051]
referenceExample 3
30 parts of a mixture pigment of the dimethylquinacridone pigment and the γ-type unsubstituted quinacridone pigment obtained in Pigment Production Example 2 was used.reference70 parts of the styrene-methacrylic copolymer resin used in Example 1 was sufficiently kneaded with a three-roll mill to disperse the pigment. After cooling, the mixture was crushed to obtain a coarse powder of a magenta high-concentration coloring composition containing a pigment component at a concentration of 30%.referenceAccording to the method described in Example 1, 14.7 parts of the high-concentration coloring composition thus obtained containing the mixed magenta color pigment and 3 parts of the chromium complex-based negative charge control agent are used as described above.TThe mixture was kneaded with 82.3 parts of a styrene-methacrylic copolymer resin, cooled, crushed, finely crushed and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm. The mixture was mixed with a powder to obtain a magenta electrophotographic dry developer. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color.
[0052]
Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen. or,referenceUsing the cyan, yellow and black developers used in Example 1 together with the above magenta developer, four-color full-color copying was performed on paper to obtain a clear full-color copied image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0053]
referenceExample 4
referenceAccording to the normal pressure melting flushing method of the pigment shown in Example 1, 50 parts (30% pigment solids) of the dimethylquinacridone pigment obtained in Pigment Production Example 1 and the dimethylquinacridone-γ-type quinacridone obtained in Pigment Production Example 3 (50:50) 53.6 parts (28% pigment solids) of a press cake of a solid solution pigment and 70 parts of a styrene-methacrylic copolymer resin used in Example 1 were charged into a heating kneader, mixed, and subjected to melt flushing. went. The separated water was discharged, and the remaining water was removed while heating and kneading to disperse the pigment. The kneaded product was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.
[0054]
referenceObtained above as in Example 1.TamaA high-concentration coloring composition containing a mixed color of a magenta color and a chromium complex-based negative charge control agent are kneaded with a styrene-methacrylic copolymer resin, pulverized and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm. , And colloidal silica were added and mixed with magnetic iron powder to obtain a magenta color electrophotographic dry developer. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color.
[0055]
Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen. or,referenceUsing the cyan, yellow and black developers used in Example 1 together with the above magenta developer, four-color full-color copying was performed on paper to obtain a clear full-color copied image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0056]
Example1
referenceAccording to the pigment melt-flushing method described in Example 1, 50 parts (30% pigment solids) of the dimethylquinacridone pigment obtained in Pigment Production Example 1 and dimethylquinacridone-γ-type quinacridone-β obtained in Pigment Production Example 4 were obtained. Type quinacridone (weight ratio 35:50:15) solid solution pigment press cake 53.6 parts (pigment solids 28%) and negative charge bisphenol type polyester resin (softening point about 100 ° C) are charged and mixed in a heating type kneader. Then, melt flushing was performed. The separated water was discharged, and the remaining water was removed while heating and evaporating to disperse the pigment. The kneaded product was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.
[0057]
next,referenceAccording to the method described in Example 1, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment thus obtained and 3 parts of a chromium complex-based negative charge control agent were used as described above. 3 parts, and after cooling, coarsely crushed, finely crushed and classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm, colloidal silica is added as a fluidizing agent, and mixed with magnetic iron powder, A magenta electrophotographic dry developer was used. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color.
[0058]
Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen. or,referenceUsing the cyan, yellow and black developers used in Example 1 together with the above magenta developer, four-color full-color copying was performed on paper to obtain a clear full-color copied image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0059]
Example2
referenceAccording to the pigment melt-flushing method described in Example 1, the dimethylquinacridone-γ-type unsubstituted quinacridone-β-type unsubstituted quinacridone (35:20:15) solid solution pigment obtained in Pigment Production Example 6 and the dimethylquinacridone pigment (weight) Ratio 70:30) 107.2 parts (28% pigment solids) of an aqueous presscake of the mixed pigment and 70 parts of a styrene-methacrylic copolymer resin having a tertiary amino group for positive charge were charged into a heating kneader and mixed. Then, melt flushing was performed. The separated water was discharged, and the remaining water was removed while heating and kneading to disperse the pigment. The kneaded product was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.
[0060]
referenceAccording to the method described in Example 1, 14.7 parts of the high-concentration coloring composition containing the magenta mixed pigment and 85.3 parts of the styrene-methacrylic copolymer resin used above were kneaded, cooled, crushed, and finely ground. The powder was pulverized and classified to obtain a fine powder of a magenta resin composition having a size of 5 to 20 μm. Colloidal silica was added as a fluidizing agent and mixed with magnetic iron powder to obtain a magenta electrophotographic dry developer. Copies were made on paper with a positive charge full color developing electrophotographic copier. The copied image had a clear and clear magenta color.
[0061]
Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen. Also, as abovereferenceUsing the blue, yellow, and black pigments used in Example 1 as cyan, yellow, and black developers, together with the above-described magenta developer, four-color full-color on paper using a positive-charge full-color developing electrophotographic copier. Copying was performed to obtain a clear full-color copy image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0062]
Example3
referenceThe dimethylquinacridone-γ-unsubstituted quinacridone-β-unsubstituted quinacridone (35:20:15 by weight ratio) solid solution pigment obtained in Pigment Production Example 6 and the dimethylquinacridone pigment were obtained according to the melt flushing method of the pigment shown in Example 1. (Weight ratio 70:30) of an aqueous presscake of a mixed pigment (107.2 parts (pigment solid content: 28%)) and a bisphenol-type polyester resin for negative charge (70 parts) were charged into a heating kneader, mixed, and subjected to melt flushing. Was. The separated water was discharged, and the remaining water was removed while heating and kneading to disperse the pigment. The kneaded product was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.
[0063]
Example1Obtained above in the same way asTamaA high-concentration coloring composition containing a mixed color of a zeta color and a chromium complex-based negative charge control agent are kneaded with the bisphenol type polyester resin used above, and pulverized and classified to obtain a fine powder of a magenta color resin composition of 5 to 20 μm. Then, colloidal silica was added and mixed with a magnetic iron powder of a carrier to obtain a magenta electrophotographic dry developer. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color.
[0064]
Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen. Also, as abovereferenceUsing the blue, yellow, and black pigments used in Example 1 as cyan, yellow, and black developers, together with the above-described magenta developer, four-color full-color on paper using a negative-charge full-color developing electrophotographic copier. Copying was performed to obtain a clear full-color copy image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0065]
Example4
50 parts of diethyl maleate is placed in a container, and 20 parts of a copolymer of styrene-benzyl methacrylate-2-ethylhexyl methacrylate (copolymerization molar ratio 70:20:10) is added and dissolved. 25.5 parts of a mixed pigment of the obtained dimethylquinacridone-γ type unsubstituted quinacridone-β type unsubstituted quinacridone (weight ratio 35:20:15) solid solution pigment and dimethylquinacridone pigment (weight ratio 70:30) and phthalimidomethylation 4.5 parts of dimethylquinacridone was mixed and sufficiently finely dispersed using a continuous horizontal wet bead medium dispersing machine to obtain a high-concentration magenta pigment dispersion. Similarly, 20 parts of the above styrene-methacrylic acid ester copolymer was dissolved in 50 parts of diethyl maleate, 30 parts of a chromium complex-based negative charge control agent was added and mixed, and a continuous horizontal wet bead medium dispersing machine was used. To obtain a highly concentrated monomer dispersion of the negative charge control agent.
[0066]
16.7 parts of the high concentration monomer dispersion of the magenta color pigment obtained above, 10.0 parts of the high concentration monomer dispersion of the negative charge control agent, 12.6 parts of butyl methacrylate, 60.7 parts of styrene , 1.5 parts of lauryl mercaptan and 2.0 parts of azoisobutyronitrile were added, and sufficiently stirred and mixed so as to be uniform. 200 parts of a 4% aqueous colloidal silica dispersion was prepared, and 103.5 parts of the monomer dispersion containing the pigment and the charge control agent obtained above was gradually added while stirring with a high-shear high-speed stirrer. An oil-drop type emulsion was prepared. The stirring speed and stirring time were adjusted so that the size of the oil droplets in the emulsion was about 7 to 9 μm.
[0067]
In a polymerization reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, coiled tube condenser and dropping funnel, about one third of 200 parts of the aqueous dispersion of 4% colloidal silica and 203.5 parts of the magenta emulsion obtained above. And a polymerization reaction was carried out at 75 to 80 ° C. for 2 hours. Next, the remaining about two-thirds of the emulsion was added dropwise from the dropping funnel over 3 hours, and stirring was continued for another 1 hour. Then, the temperature was raised to 85 ° C. over 30 minutes and stirred for 1 hour to complete the polymerization reaction. I let it. The produced polymer was separated by filtration, washed with an aqueous sodium hydroxide solution to remove silica, sufficiently washed with water, and dried to obtain a fine powder of a magenta polymer having an average particle size of about 8 μm. Colloidal silica was added and mixed with the magnetic iron powder of the carrier to obtain a magenta electrophotographic dry developer. Copies were made on paper with an electrophotographic copying machine for negative full-color development. The copied image had a clear and clear magenta color. Further, when copied on a polyester sheet for OHP, a transparent image was exhibited, and a clear magenta image was displayed on the screen.
[0068]
Further, C.I. I. Pigment Blue 15: 3 (hereinafter, the content of the pigment in the developer is shown as 3.40%) and phthalimidomethyl copper phthalocyanine (0.60%). I. Pigment Yellow 93 (4.25%) and phthalimidomethyl dianthraquinonyl-monophenylamino-s-triazine (0.75%), C.I. I. Pigment Black 7 (3.40%) and phthalimidomethylcopper phthalocyanine (0.60%) to prepare a black developer, and together with the above magenta developer, use a negative charge full-color electrophotographic copier to develop paper. Then, a full-color copying was performed to obtain a clear full-color copying image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0069]
Example5
referenceAccording to the melt flushing method of the pigment described in Example 1, the dimethyl quinacridone-γ-type unsubstituted quinacridone-β-type unsubstituted quinacridone (weight ratio 35:20:15) solid solution pigment obtained in Pigment Production Example 6 and the dimethylquinacridone pigment were used. (Weight ratio: 70:30) 107 parts of a mixed pigment press cake (pigment solid content: 28%) and 70 parts of a styrene-methacrylic copolymer resin having a tertiary amino group were charged into a heating kneader, mixed, and melt-flushing. Was done. The separated water was discharged, and the remaining water was removed while heating and evaporating to disperse the pigment. The kneaded product was taken out of the kneader, cooled and coarsely crushed to obtain a coarse powder of a magenta high-concentration colored composition containing a pigment content of 30%.
[0070]
10 parts of the obtained magenta resin powder is added to 75 parts of Isopar G together with 15 parts of a methacrylic ester resin soluble in an aliphatic hydrocarbon solvent, glass beads are added, and the mixture is shaken with a paint shaker for 20 hours to be dispersed. A thick colored liquid was prepared. 200 g of this concentrated solution was added and dispersed in 1 liter of Isopar G to obtain an electrophotographic wet developer. This was copied by a full-color wet electrophotographic copying machine to obtain a clear magenta color copied image. This image showed fastness excellent in various physical properties such as light fastness.
[0071]
Also, as abovereferenceUsing the blue, yellow, and black pigments used in Example 1 to form cyan, yellow, and black wet developers, together with the magenta wet developer obtained above, perform four-color full-color copying to obtain clear full-color images. Was. Using the four-color full-color developer described above, a clear full-color image was output by a four-color full-color wet electrostatic plotter.
[0072]
Example6
10 parts of a (70:30) mixed pigment of a dimethylquinacridone-γ-type unsubstituted quinacridone-β-unsubstituted quinacridone (weight ratio 35:20:15) solid solution pigment and a dimethylquinacridone pigment obtained in Pigment Production Example 6 were esterified. Using 41 parts of wax, 41 parts of paraffin wax, 5 parts of styrene-methacrylic copolymer resin and 3 parts of silica as a binder, and adding 50 parts of water as a dispersing agent, and mixing at a temperature lower than the melting point or softening point of the resin at normal pressure. The separated water was removed by kneading, the remaining water was evaporated, and applied to a polyethylene film according to a conventional method to obtain a magenta color thermal transfer recording ink film. This was copied by a full-color thermal transfer copying machine to obtain a clear magenta color copied image. This image showed fastness excellent in various physical properties such as light fastness.
[0073]
Further, when copied on a polyester sheet for OHP, a transparent image was obtained, and a clear image was shown on the screen. Also, as abovereferenceUsing the blue, yellow, and black pigments used in Example 1 to form cyan, yellow, and black thermal transfer ink films, and with the magenta thermal transfer ink film obtained above, four-color full-color copying was performed to obtain a clear full-color copied image. Got. Further, the image was copied on a polyester sheet for OHP to obtain a full-color image showing a transparent full-color image on a screen.
[0074]
Example7
Aqueous press of mixed pigment of dimethylquinacridone-γ-type unsubstituted quinacridone-β-type unsubstituted quinacridone (35:20:15 by weight) and dimethylquinacridone pigment (70:30 by weight) obtained in Pigment Production Example 6 Make an aqueous pigment dispersion of 17.9 parts of cake (28% pigment solids), 3 parts of styrene-acrylate-diethanolamine methacrylate copolymer, 22 parts of ethylene glycol, 8 parts of glycerin and 50 parts of water, and ultracentrifuge. The pigment coarse particles that could not be dispersed by the machine were removed to obtain an aqueous magenta ink for inkjet.
[0075]
Using a magenta ink, the image information was printed with an on-demand type ink jet printer having a piezo vibrator to obtain a clear magenta image. Also, as abovereferenceUsing the blue, yellow, and black pigments used in Example 1 to form cyan, yellow, and black inkjet inks, the magenta inkjet ink obtained above was used to perform four-color full-color printing to obtain a clear full-color copy image. Obtained.
[0076]
【The invention's effect】
The image-recording coloring composition of the present invention is dimethylquinacridone-unsubstituted quinacridone toning pigment used as a pigment component thereof, that is, a mixed pigment of a dimethylquinacridone pigment and a γ-type or β-type unsubstituted quinacridone pigment, a solid solution pigment, These mixed pigments are very excellent as magenta pigments of the coloring composition for full-color image recording, and are excellent in various fastnesses such as light resistance, heat resistance, solvent resistance, chemical resistance, and water resistance. Since it has high coloring power, sharpness, sharpness, and transparency, it can be stably manufactured under specific conditions even in the process of manufacturing colored products, and as a result, it is finally used for magenta image recording Even when used as a coloring composition, it is possible to stably record a clear, clear and highly transparent image.
Also, when used as a liquid recording agent, stable recording can be performed for a long period of time. Therefore, the obtained image is clear and shows excellent properties in the above-mentioned fastnesses related to the pigment.

Claims

In the image recording coloring composition containing a pigment and a resin binder, pigment comprises a solid solution pigment and dimethyl quinacridone pigments and / or γ-type unsubstituted quinacridone pigments with di quinacridone pigment and β-type and γ-type unsubstituted quinacridone pigment image recording coloring composition which is a mixture Pigments of.

The coloring composition for image recording according to claim 1, wherein the pigment has an average particle size of 200 nm or less.

The coloring composition for image recording according to claim 1, wherein the coloring composition is a solid, paste or liquid high-concentration coloring composition dispersed at a high concentration in a resin binder or a resin solution.

The image recording coloring composition according to claim 1, which is a fine powdery dry developer.

The colored composition for image recording according to claim 4, wherein the fine powdery dry developer is obtained by a pulverization method, a suspension polymerization method, or an emulsion polymerization liquid aggregation method.

The colored composition for image recording according to claim 1, which is a liquid wet developer.

The colored composition for image recording according to claim 1, which is an ink for inkjet recording.

The colored composition for image recording according to claim 1, which is a thermal transferable image recording agent applied to a substrate such as a film or paper.

A method for producing a coloring composition for image recording comprising a pigment and a resin binder, wherein the pigment is a solid solution pigment of a dimethylquinacridone pigment and a β-type or γ-type unsubstituted quinacridone pigment, a dimethylquinacridone pigment and / or a γ-type unsubstituted pigment. A mixed pigment with a quinacridone pigment, wherein an aqueous presscake of the mixed pigment is mixed with a resin binder, or water is added as a dispersant to the powder of the mixed pigment and the resin binder, and no solvent is present at normal pressure. A pigment characterized by kneading at a processing temperature of 120 ° C. or lower and a temperature lower than the melting point or softening point of the resin to transfer the pigment to the resin phase, remove separated water, and knead and evaporate residual water. A method for producing a coloring composition for high density image recording.