JP3670148B2 - Coloring composition for image recording and image recording agent - Google Patents
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【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あるいはその製造に使用される顔料と樹脂バインダーを含む画像記録用着色組成物及びその製造方法に関する。更に詳しくは、顔料として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及び少なくとも一種の特定の赤色顔料を含有する負帯電特性が付与された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に関するものである。
【０００２】
【従来の技術】
従来、フルカラー又はモノカラーの電子写真、電子印刷、静電印刷、インクジェット記録及び熱転写記録等の画像記録に用いられるマゼンタ色記録剤においては、赤色顔料として赤色の油溶性染料、分散性染料、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いる。
【０００３】
【発明が解決しようとする課題】
上記したマゼンタ色画像記録剤に使用される赤色顔料の中では、マゼンタ色顔料として著名なジメチルキナクリドン（２，９−ジメチルキナクリドン）顔料（Ｃ．Ｉ．ピグメントレッド １２２）が使用されていることが多い。
この顔料は単独ではマゼンタ色として青みが強過ぎ、着色濃度が不十分であるだけでなく、顔料の摩擦帯電が正帯電で、しかもかなり大きい値を示すという欠点がある。そのために、該顔料を負帯電性マゼンタ記録剤に使用すると、地汚れが発生し易い問題がある。
【０００４】
しかしながら、マゼンタ色画像記録剤に使用される赤色色素についてみると、油溶性染料、分散性染料等は樹脂媒体に溶解的に着色できるため着色力が高いが、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優れているが、耐光性、耐熱性等の諸堅牢性、鮮明性が不十分である。
従って、上記した如き染料や顔料は、諸堅牢性、鮮明性、透明性、負帯電性が要求される記録剤用のマゼンタ色用に使わ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。
【０００５】
本発明者らは、上記従来のマゼンタ色記録剤用色素の欠点を解消し、諸堅牢性、鮮明性、透明性、負帯電性を満足させ得る赤色顔料を開発すべく種々研究した結果、ジメチルキナクリドン顔料と特定の赤色顔料の少なくとも一種とを併用することにより、この用途に必要な諸堅牢性、鮮明性、透明性、負帯電性が付与された適切なマゼンタ色をもたらすことが出来ることを見出した。
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、冴え、透明性等に優れた性質を発揮させることが出来、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出し本発明を完成した。
【０００６】
【課題を解決するための手段】
即ち、本発明は、顔料及び樹脂を含む、電子写真、乾式現像剤を用いる電子印刷、静電記録、インクジェット記録及び熱転写記録から選ばれる画像記録に用いられる画像記録用着色組成物において、上記顔料としてジメチルキナクリドン顔料（１）と少なくとも一種の負帯電性又は弱正帯電性の赤色顔料（但し、キナクリドン系顔料は除く）（２）とを併用することを特徴とする画像記録用着色組成物、その製造方法及び使用方法である。
【０００７】
【発明の実施の形態】
以下に本発明を更に詳細に説明する。
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顔料（１）と負帯電性又は弱正帯電性の赤色顔料（但し、キナクリドン系顔料は除く）（２）の少なくとも一種を併用することが特徴である。この赤色顔料（２）は、更に、諸堅牢性に優れ、高い着色力、鮮明性、冴え、透明性を有するものが好ましい。
上記顔料を用いることにより、顔料を高濃度で含有する画像記録用着色組成物の製造に際しても、加工温度を１２０℃以下で行う分散加工方法を採用すること等によって高濃度着色組成物を安定に製造することが出来る。又、本発明の画像記録用着色組成物を最終的に画像記録剤として使用する際には、優れた負帯電性を有し、鮮明で冴えて、透明感の高い、地汚れのない、諸堅牢性に優れた画像を長期間安定して記録することが出来る。これらの特徴は、画像記録剤が固体状及び液体状のいずれの場合においても発現される。
【０００８】
本発明でジメチルキナクリドン顔料（１）とともに使用される赤色顔料（２）は、負帯電性もしくは弱い正帯電性の顔料であり、好ましくは、更に高い着色力、鮮明性を有する赤色顔料が使用される。好ましい赤色顔料は、ブローオフ粉体帯電量測定装置で測定した摩擦帯電量が−１００〜＋３０μｃ／ｇのものであり、例えば以下に示す顔料が挙げられる。
Ｃ．Ｉ．ピグメントレッド ５ Ｃ．Ｉ．ピグメントレッド ２３
Ｃ．Ｉ．ピグメントレッド １１２ Ｃ．Ｉ．ピグメントレッド １４４
Ｃ．Ｉ．ピグメントレッド １４６ Ｃ．Ｉ．ピグメントレッド １４７
Ｃ．Ｉ．ピグメントレッド １４９ Ｃ．Ｉ．ピグメントレッド １５０
Ｃ．Ｉ．ピグメントレッド １６６ Ｃ．Ｉ．ピグメントレッド １７０
Ｃ．Ｉ．ピグメントレッド １７６ Ｃ．Ｉ．ピグメントレッド １７７
Ｃ．Ｉ．ピグメントレッド １７８ Ｃ．Ｉ．ピグメントレッド １８５
Ｃ．Ｉ．ピグメントレッド ２０８ Ｃ．Ｉ．ピグメントレッド ２１４
Ｃ．Ｉ．ピグメントレッド ２２０ Ｃ．Ｉ．ピグメントレッド ２２１
Ｃ．Ｉ．ピグメントレッド ２３８ Ｃ．Ｉ．ピグメントレッド ２４５
Ｃ．Ｉ．ピグメントレッド ２５４
【０００９】
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顔料（１）と赤色顔料（２）とで調色顔料を調製し、それを使用して画像記録用着色組成物を製造する。これらの顔料は予め混合あるいは固溶体としたものであっても、あるいは画像記録用着色組成物を製造する工程中で混合されたものであってもよい。 画像記録用着色組成物の製造方法は特に限定されないが、例えば、顔料製造工程でジメチルキナクリドン顔料（１）と赤色顔料（２）を混合及び調色を行って得た微粉混合顔料、微粉固溶体顔料等を用いて直接画像記録剤に適した濃度で顔料を含む着色組成物を製造する方法と、該微粉混合顔料等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、あるいは混合調色した顔料（１）及び顔料（２）の混合顔料のプレスケーキ等を加熱ニーダー等を使用して高濃度に顔料を含有する着色組成物を製造する方法があるが、いずれでも構わない。
又、上記の顔料を樹脂を構成する単量体混合物中に分散させ、単量体を重合させることによって形成された重合体（樹脂）中に該顔料を含有させる方法を用いることもできる。
【００１０】
具体的な調色顔料及び該調色顔料を含む高濃度着色組成物の製造法の例として下記の如き方法が挙げられる。
（Ａ）ジメチルキナクリドン顔料（１）と赤色顔料（２）、又はこれらの混合顔料を使用する高濃度着色組成物の製造法
（ａ）各々の顔料を単独で乾燥し、衝突粉砕又は磨砕された各微粉顔料の混合物と樹脂とを加熱混練機で混練して高濃度着色組成物を得る
（ｂ）各々の顔料の水性プレスケーキを混合し、乾燥後、衝突粉砕又は磨砕された微粉混合顔料と樹脂とを加熱混練機で混練して高濃度着色組成物を得る
（ｃ）顔料（１）及び（２）の水性プレスケーキ及び樹脂を加熱ニーダー等に仕込み、溶融フラッシング法等により高濃度着色組成物を製造する
（ｄ）顔料（１）及び（２）の水性プレスケーキを予め混合し、これを用いて上記（ｃ）と同様にして高濃度着色組成物を製造する
（ｅ）顔料（１）及び顔料（２）の微粉、樹脂及び少量の水を加熱ニーダー等に仕込み、溶融フラッシング法等により高濃度着色組成物を製造する
（ｆ）上記（ａ）又は（ｂ）の微粉混合顔料、樹脂及び少量の水を加熱ニーダー等に仕込み、溶融フラッシング法等により高濃度着色組成物を製造する
【００１１】
（Ｂ）ジメチルキナクリドン顔料（１）と赤色顔料（２）との固溶体顔料を用いる高濃度着色組成物の製造方法
（ａ）ジメチルキナクリドン顔料（１）と赤色顔料（２）との固溶体を乾燥し、衝突粉砕又は磨砕された微粉固溶体顔料と樹脂とを加熱混練機で混練して高濃度着色組成物を得る
（ｂ）上記（ａ）の固溶体顔料の水性プレスケーキと樹脂を加熱ニーダー等に仕込み、溶融フラッシング法等により高濃度着色組成物を製造する
（ｃ）（ａ）の微粉固溶体顔料、樹脂及び少量の水を加熱ニーダー等に仕込み、溶融フラッシング法等により高濃度着色組成物を製造する
【００１２】
上記（Ｂ）において、ジメチルキナクリドン顔料（１）と赤色顔料（２）との固溶体顔料とは、これらの混合顔料を下記のような顔料化処理をすることにより固溶体の状態にしたものであり、固溶体とすることで色相の鮮明性、冴え、透明性、負帯電性を向上させることが出来る。
混合顔料を固溶体にする方法は、従来公知の方法を用いることが出来、特に制限されない。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、これを有機溶剤等で処理することによって固溶体顔料が得られる。
【００１３】
本発明で使用されるジメチルキナクリドン顔料（１）と赤色顔料（２）との調色顔料、即ち、両顔料の使用割合は、希望する画像の色相によって適宜決められるものであり、特に限定されないが、通常、該顔料（１）対該顔料（２）は９９：１〜１：９９（重量比）の範囲であり、好ましくは９５：５〜３０：７０の範囲である。
【００１４】
本発明の画像記録用組成物を使用して画像の色の透明性、冴え、鮮明性、負帯電性等の性質や物性をより優れたものとするために、本発明に使用するジメチルキナクリドン顔料（１）と赤色顔料（２）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を従来公知の方法に準じて施すことが出来る。
一般ににジメチルキナクリドン顔料や赤色顔料が塗料あるいはプラスチックなど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、凡そ５００〜７００ｎｍの大きさに調整されている。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、冴え及び鮮明性を低下させるという問題がある。
【００１５】
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しい。
そのために、本発明で使用されるジメチルキナクリドン顔料（１）と赤色顔料（２）との調色顔料は、画像記録用着色組成物を製造するフラッシング、加熱混練あるいは湿式分散等の通常の分散方法で樹脂中に重量平均粒子径が２００ｎｍ以下、好ましくは１５０ｎｍ以下になるように分散させることが好ましい。
従って、該組成物の製造に際しては、これらの顔料は上記の分散粒子径となるように予め微粒子化されたものを使用することが好ましい。
【００１６】
顔料を微粒子化する方法は特に限定されず、従来公知の方法を用いることが出来る。例えば、顔料を酸ペースト処理する方法や、衝突粉砕や磨砕により微細化する方法等が挙げられる。衝突粉砕法にはボールミルや振動ミルを用いるドライミリング法があり、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、必要により、無機塩が磨砕助剤として使用される。磨砕法にはソルトミリング法やソルベントソルトミリング法があり、磨砕助剤として無水芒硝、塩化ナトリウム、硫酸アルミニウム等の無機塩が使用される。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、負帯電性に優れた性質を示す。
【００１７】
本発明の画像記録用着色組成物を製造するために使用される熱可塑性重合体樹脂やワックス類等の樹脂は、固体の形態で使用される該組成物にあっては分散媒体であり、液体の状態で使用される該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る。又、実際に記録剤として使用されるときに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、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ィルム等の画像記録剤に従来から使用されている樹脂はいずれも使用することができ、特に限定されない。又、上記の各々の用途に合わせて、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、あるいは媒体として溶剤、水系媒体等を使用することが出来る。
【００１８】
本発明の画像記録用着色組成物は、その使用目的の画像記録剤に適した顔料濃度となるように初めから製造されたものでも、高濃度に顔料を含む高濃度着色組成物として製造されたもののいずれでもよい。
高濃度着色組成物は、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、後の画像記録剤製造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、ペースト状又は液状の任意の形態で使用される。該組成物中の顔料の含有量は、通常１０〜７０重量％程度であり、好ましくは２０〜６０重量％程度である。
【００１９】
本発明の画像記録用着色組成物には、それぞれの使用目的に応じて従来から使用されている各種添加剤や溶剤等が添加され、目的の画像記録剤として使用される。画像記録剤としては、例えば、いわゆる微細粉体状乾式現像剤、静電記録剤、インクジェット記録用インキ、フィルム、紙等の基材に塗布された熱転写インクリボン及びフィルム等が挙げられる。
【００２０】
本発明の画像記録用着色組成物（使用目的の画像記録剤に適した濃度の顔料を含む）中の顔料の含有量は、該組成物の使用目的によって異なり、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顔料（１）と赤色顔料（２）との調色顔料、樹脂やその他添加剤あるいは媒体を含む全着色組成物中における顔料の含有量は、通常２〜２０重量％程度である。電子写真用乾式記録剤等として使用する場合には、顔料の含有量２〜１５重量％程度、好ましくは３〜１０重量％程度である。又、熱転写インクリボン、フイルムの着色剤として使用される場合には、４〜１５重量％程度、好ましくは６〜１０重量％程度であり、インクジェット記録用インクとして使用される場合には３〜２０重量％程度、好ましくは５〜１０重量％程度であり、各々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。
【００２１】
前記した顔料の高濃度着色組成物の製造方法としては、例えば、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させる方法としては、通常、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させる方法が用いられる。これらのいずれの方法においても、混練分散加工は１２０℃以下の温度でなされることが望ましい。この比較的低温の加工温度条件で混練分散を行うことによって、予め微細に調整された顔料の粒子径が該組成物中にそのまま保たれ、引き続き行われる記録剤製造の加工工程を同様に１２０℃以下の温度条件で行うことにより、色相の鮮明性、冴え、透明性が発現される画像記録剤が得られる。
【００２２】
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を蒸気加熱の出来るニーダー又はフラッシヤーに仕込み、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出来、又、混練分散加工温度も水が存在する間は１００℃以下で進めることが出来るという特徴を有している。
又、好ましい他の高濃度顔料分散方法としては、粉末顔料、樹脂バインダーに分散剤として水を加えて、上記の方法と同様にして常圧で溶剤不存在下、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着色組成物を得ることができる。
【００２３】
本発明の画像記録用着色組成物を使用して製造される、電子写真、静電印刷、静電記録等の乾式現像剤、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、熱転写インクフィルム等の画像記録剤は、ジメチルキナクリドン顔料（１）と赤色顔料（２）との調色顔料を最初から各用途に適した顔料濃度となるように形成した該組成物をそのまま使用して、あるいは前記した顔料を高濃度に分散させた高濃度着色組成物を、樹脂バインダー、樹脂溶液あるいは付加重合性単量体中に分散あるいは希釈再分散し、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。
【００２４】
例えば、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荷電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、凝集させる事により重合体粒子に顔料や帯電制御剤を共沈或いは吸着させると共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、強磁性剤等の材料が添加される。
【００２５】
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、イエロー色あるいは更にブラック色の画像記録剤とセットで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が挙げられる。
【００２６】
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が、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各々の黄色顔料が、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れぞれの代表的のものとして挙げられる。
これらの各種の顔料も本発明で使用するジメチルキナクリドン顔料（１）と赤色顔料（２）との調色顔料と同様に、画像記録用着色組成物を製造するフラッシング、加熱混練あるいは湿式分散等の通常の分散方法で樹脂中に分散させることによって平均粒子径が凡そ２００ｎｍ以下、好ましくは凡そ１５０ｎｍ以下になる様に粒径が調整された顔料を使用することが好ましい。
【００２７】
【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。文中、部または％とあるのは重量基準である。
以下の例における顔料自体の平均粒子径及び組成物中の顔料の平均粒子径は、下記の方法で測定した重量平均粒子径である。
（１）顔料自体の平均粒子径の測定方法
顔料０．５ｇと分散剤０．７ｇとをフーバー式マーラーで荷重１５０ポンド、練り回数３００回の条件で分散させ、測定装置に規定されている濃度まで水で希釈した後、超音波を１分間作用させて調製した試験液をコールターサブミクロン粒子アナライザー（コールター社製ＭＯＤＥＬ Ｎ−４）で測定する。
（２）組成物中の顔料の平均粒径の測定法
着色組成物０．１ｇをキシレン１０ｃｃに溶解させ、測定装置に規定されている濃度までキシレンで希釈した後、超音波を１分間作用させて調製した試験液をコールターサブミクロン粒子アナライザー（コールター社製ＭＯＤＥＬ Ｎ−４）で測定する。
【００２８】
顔料製造例１
２，９−ジメチルキナクリドン顔料（Ｃ．Ｉ．ピグメントレッド １２２）の粗顔料１０部、塩化ナトリウム１００部、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。続いて顔料化、濾過、洗浄等の後処理を行って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、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上記顔料の平均粒子径は、２００ｎｍ以下であり、色相は青味みの赤色を示した。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量をブローオフ粉体帯電量測定装置（東芝ケミカル社製 ＴＢ−２００型）（以下も同様）で測定したところ＋５６．６μｃ／ｇであった。
【００２９】
一方、４，４′−ジアミノ−１，１′−ジアントラキノニル顔料（Ｃ．Ｉ．ピグメントレッド １７７）の粗顔料１０部、無水芒硝９０部、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。続いて、顔料化、濾過、洗浄等の後処理を行ってプレスケーキを得た。ジアントラキノニル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、粉砕してジアントラキノニル顔料を得た。
このようにして製造された上記顔料平均粒子径は２００ｎｍ以下であり、色相は赤色を示した。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ−３６．９μｃ／ｇであった。
【００３０】
次に、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８部とジアントラキノニル顔料の水性プレスケーキの固形分２部とを混合し、乾燥、粉砕してジメチルキナクリドン顔料及びジアントラキノニル顔料の混合物顔料を得た。このものは色相はマゼンタ色を示した。混合物顔料の平均粒子径は２００ｎｍ以下であった。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ＋１１．５μｃ／ｇであった。
【００３１】
顔料製造例２
顔料製造例１に示した方法により、２，９−ジメチルキナクリドン顔料の粗顔料７部に４，４′−ジアミノ−１，１′−ジアントラキノニル顔料の粗顔料３部を加えて磨砕して固溶体顔料を得、有機溶剤処理による顔料化を行い、続いて濾過、洗浄後、乾燥、粉砕してジメチルキナクリドン顔料／ジアントラキノニル顔料の固溶体顔料（７／３（重量比））を得た。色相はマゼンタ色を示した。製造された固溶体顔料の平均粒子径は２００ｎｍ以下であった。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ＋１４．５μｃ／ｇであった。
【００３２】
顔料製造例３
顔料製造例１に示した方法により、２，９−ジメチルキナクリドン顔料の粗顔料５部にジクロルキナクリドン顔料（Ｃ．Ｉ．ピグメントレッド ２０９）の粗顔料２部、γ型無置換キナクリドン顔料（Ｃ．Ｉ．ピグメントバイオレッド １９）顔料３部を加えて磨砕して固溶体顔料を得、有機溶剤処理による顔料化を行い、続いて濾過、洗浄後、乾燥、粉砕してジメチルキナクリドン顔料／ジクロルキナクリドン顔料／無置換キナクリドン顔料の固溶体顔料（５／２／３（重量比））を得た。色相はマゼンタ色を示した。製造された固溶体顔料の平均粒子径は２００ｎｍ以下であった。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ＋２０．９μｃ／ｇであった。
【００３３】
顔料製造例４
２，９−ジメチルキナクリドン顔料の粗顔料９部とジケトピロロピロール顔料（Ｃ．Ｉ．ピグメントレッド ２５４）の粗顔料１部を１００部の９８％硫酸に溶解させ、この溶液を５００部の冷水中に注入して固溶体顔料として析出させた。濾過、洗浄（中和）後、有機溶剤処理による顔料化を行い、濾過、洗浄、乾燥、粉砕してジメチルキナクリドン顔料／ジケトピロロピロール顔料の固溶体顔料（９／１（重量比））を得た。色相はマゼンタ色を示した。製造された固溶体顔料の平均粒子径は２００ｎｍ以下であった。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ＋１２．６μｃ／ｇであった。
【００３４】
顔料製造例５
顔料製造例１に示した方法により、２，９−ジメチルキナクリドン顔料の粗顔料５部にＣ．Ｉ．ピグメントレッド５の粗顔料５部を加えて磨砕して固溶体顔料を得て、有機溶剤処理による顔料化を行い、続いて濾過、洗浄後、乾燥、粉砕してジメチルキナクリドン／Ｃ．Ｉ．ピグメントレッド５顔料の固溶体顔料（５／５）（重量比）を得た。色相はマゼンタ色を示した。製造された固溶体顔料を分散させたときの平均粒子径は２００ｎｍ以下であった。
この顔料５部に磁性鉄粉１００部を混合して摩擦帯電量を測定したところ＋１３．５μｃ／ｇであった。
【００３５】
実施例１
特開平２- １７５７７０号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９６部（顔料固形分２５％）及びジアントラキノニル顔料のプレスケーキ２０部（顔料固形分３０％）、及びスチレン／メタリル系共重合樹脂（軟化点１１０℃、ガラス転移点約５６℃、ＧＰＣ法重量平均分子量約５万）７０部と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℃にしてフラッシングを続け、水分を分離した。分離水を排出し、更に残存す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、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００３６】
次に、この様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、粉砕後、ジェツトミルで微粉砕し、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。続いて、常法に従い上記微粉末に流動化剤としてコロイダルシリカを添加して十分に混合した後、キャリアの磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
【００３７】
これを負電荷フルカラー現像用電子写真複写機に仕込んで紙に複写したところ、複写画像は鮮明で冴えた地汚れのないマゼンタ色を呈し、耐光性等の諸物性に優れた堅牢性を示した。また、オーバーヘッドプロジェクター（以下ＯＨＰと略す）用のポリエステルシートに複写すると、透明な画像を示し、ＯＨＰスクリーンに鮮明なマゼンタ色の映像を示した。
【００３８】
また、シアン色顔料としてＣ．Ｉ．ピグメントブルー １５：３（現像剤中の顔料含有率：３．５％）、イエロー色顔料としてＣ．Ｉ．ピグメントイエロー９３（顔料含有率：４．４％）、ブラック色顔料として Ｃ．Ｉ．ピグメントブラック ７（顔料含有率：３．５％）のそれぞれ平均粒子径が２００ｎｍ以下になるように分散できる顔料を用いて、上記と同様にして各々シアン色現像剤、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共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。また、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。
【００３９】
実施例２
顔料製造例１で得たジメチルキナクリドン顔料２１部及びジアントラキノニル顔料９部と、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部と水１００部を加熱型ニーダーに仕込み、常圧で混合しつつ蒸気加熱を行い、十分混練を行った。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、更に残存す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、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００４０】
次に、実施例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上記のスチレン／メタクリル系共重合樹脂と混練し、冷却、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、磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
これを用いて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ところ、複写画像は鮮明で冴えた地汚れのない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、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に使用して紙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。また、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。
【００４１】
実施例３
顔料製造例１で得たジメチルキナクリドン顔料／ジアントラキノニル顔料（８／２（重量比））の混合顔料３０部を、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部と三本ロールにて十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の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
次に、実施例１と同様にして、得られ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、冷却粉砕後、微粉砕、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、磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
【００４２】
これを用いて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ところ、複写画像は鮮明で冴えた地汚れのないマゼンタ色を呈した。また、ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
さらに、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に使用して紙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。また、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。
【００４３】
実施例４
実施例１の溶融フラッシング法に従って、顔料製造例２で得た固溶体顔料のプレスケーキ１０７．２部（固形分２８％）及び負帯電用ビスフェノール型ポリエステル樹脂（軟化点約１００℃）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。分離水を排出し、更に残存する水分を加熱混練しつつ蒸発させ除去した。更に混練を続けて顔料を分散させた後ニーダーから混練物を取り出し、冷却、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００４４】
次に、実施例１の方法に従って、この様にして得たマゼンタ色固溶体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部と上記で使用したビスフェノール型ポリエステル樹脂８２．５部とを混練し、冷却後粗砕、微粉砕、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て十分混合した後、キャリアの磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
これを用いて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ところ、複写画像は鮮明で冴えた地汚れのないマゼンタ色を呈した。ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に使用して紙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。また、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。
【００４５】
参考例１
実施例１の溶融フラッシング法に従って、顔料製造例３で得た固溶体顔料のプレスケーキ１００．０部（固形分３０％）及び負帯電用ビスフェノール型ポリエステル樹脂（軟化点約１００℃）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。分離水を排出し、更に残存する水分を加熱混練しつつ蒸発させ除去した。更に混練を続けて顔料を分散させた後ニーダーから混練物を取り出し、冷却、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００４６】
次に、実施例１の方法に従って、この様にして得たマゼンタ色固溶体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部及び上記で使用した負電荷用ビスフェノール型ポリエステル樹脂８２．５部とを混練し、冷却後粗砕、微粉砕、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て十分混合した後キャリアの、磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
これを用いて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地汚れのないマゼンタ色を呈した。ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に使用して紙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。また、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。
【００４７】
実施例５
実施例１の溶融フラッシング法に従って、顔料製造例４で得た固溶体顔料のプレスケーキ１１１．１部（固形分２７％）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℃）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。分離水を排出し、更に残存する水分を加熱混練しつつ蒸発させ除去した。更に混練を続けて顔料を分散させた後ニーダーから混練物を取り出し、冷却、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００４８】
次に、実施例１の方法に従って、この様にして得たマゼンタ色固溶体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負電荷用ビスフェノール型ポリエステル樹脂８２．５部と混練し、冷却後粗砕、微粉砕、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て十分混合した後、キャリアの磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
これを使用して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地汚れのないマゼンタ色を呈した。ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に紙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。また、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。
【００４９】
実施例６
実施例１の溶融フラッシング法に従って、顔料製造例５で得た固溶体顔料のプレスケーキ１０７．２部（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℃）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。分離水を排出し、更に残存する水分を加熱混練しつつ蒸発させ除去した。更に混練を続けて顔料を分散させた後ニーダーから混練物を取り出し、冷却、粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００５０】
次に、実施例１の方法に従って、この様にして得たマゼンタ色固溶体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負電荷ビスフェノール型ポリエステル樹脂８２．５部と混練し、冷却後粗砕、微粉砕、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て十分混合した後、キャリアの磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
これを用いて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地汚れのないマゼンタ色を呈した。ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、実施例１で使用したシアン色、イエロー色、ブラック色の現像剤を上記のマゼンタ色現像剤と共に紙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。また、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】
実施例７
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（７／２／１（重量比））共重合体２０部を加えて溶解させ、そこに顔料製造例２で得たジメチルキナクリドン顔料／ジアントラキノニル顔料（７／３（重量比））の固溶体顔料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顔料４．５部を加えて混合し、連続式横型湿式ビーズ媒体分散機を用いて十分に微細に分散させ、マゼンタ色顔料高濃度単量体分散液を得た。分散液中の顔料の平均粒子径は２００ｎｍ以下であった。
【００５２】
同様にしてマレイン酸ジエチル５０部に実施例１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、クロム錯塩系負帯電制御剤３０部を加え、混合し、連続式横型湿式ビーズ媒体分散機を用いて微細に分散させ、負帯電制御剤の高濃度単量体分散液を得た。
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ルロニトリル２．０部を容器に添加し、均一になるように十分に攪拌混合した。４％コロイダルシリカ水分散液２００部に、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整した。エマルジョンの油滴の大きさがおよそ７〜９μｍ程度になるように攪拌速度及び攪拌時間を調整した。
【００５３】
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漏斗の付いた重合反応装置に、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の凡そ３分の１を仕込み、７５〜８０℃にて２時間重合反応を行った。次いで残りの凡そ３分の２のエマルジョンを滴下漏斗より３時間かけて滴下し更に１時間攪拌した後、３０分かけて８５℃に昇温し１時間攪拌して重合反応を完結した。
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、十分に水洗した後乾燥して平均粒子径凡そ８μｍのマゼンタ色重合体の微粉末を得た。続いて流動化剤としてコロイダルシリカを添加し、磁性鉄粉と混合してマゼンタ色電子写真乾式現像剤とした。
【００５４】
これを用いて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、鮮明で冴えた地汚れのないマゼンタ色を呈した。また、ＯＨＰ用のポリエステルシートに複写すると、透明な画像を示し、スクリーンに鮮明なマゼンタ色の映像を示した。
また、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含有率を示す：３．４％）、及びフタルイミドメチル銅フタロシアニン顔料（０．６％）を用いてシアン色現像剤を、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−トリアジン顔料（０．７５％）を用いてイエロー色現像剤を、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顔料（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共に使用して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い、鮮明なフルカラー画像を得た。また、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。
【００５５】
参考例２
実施例１の溶融フラッシング法に従って、顔料製造例３で得たジメチルキナクリドン顔料／ジクロルキナクリドン顔料／無置換キナクリドン顔料（５／２／３（重量比））固溶体顔料のプレスケーキ１０７．２部（固形分２８％）及び実施例１のスチレン／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。分離水を排出し、更に残存する水分を加熱混練しつつ蒸発させ除去し、顔料を分散させた。ニーダーから混練物を取り出し、冷却後粉砕して顔料分を３０％の濃度で含有するマゼンタ色の高濃度着色組成物の粗粉を得た。粗粉中の顔料の平均粒径は２００ｎｍ以下であった。
【００５６】
次に、この様にして得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部と共に７５部のアイソパーＧに加えて、ガラスビーズを加えてペイントコンディショナーにて２０時間振とう分散して濃高着色液を調整した。濃高液中の顔料の平均粒径は２００ｎｍ以下であった。
この濃厚液２００部を１リットルのアイソパーＧ中に加えて分散させて電子写真湿式現像剤を得た。
これを用いて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。
また、上記と同様にして実施例１で使用したシアン色顔料、イエロー色顔料、ブラック色顔料を用いて各々シアン色、イエロー色、ブラック色の湿式現像剤とし、上記で得たマゼンタ色湿式現像剤と共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。また、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。
【００５７】
実施例８
実施例２と同様にして、エステルワックス４１部、パラフィン系ワックス４１部、実施例１のスチレン／メタクリル系共重合樹脂５部、シリカ３部をバインダーとし、顔料製造例２で得た固溶体顔料１０部、分散剤として水５０部をニーダーに加えて樹脂の融点又は軟化点未満の温度で常圧で混練して分離水を除去し、残存水を蒸発させた。
【００５８】
得られた着色組成物を、常法に従ってポリエチレンフィルムに塗布し、マゼンタ色熱転写記録用インクフィルムとした。これを用いて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。また、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。
また、上記と同様にして、実施例１で使用したシアン色顔料、イエロー色顔料、ブラック色顔料を用いて各々シアン色、イエロー色、ブラック色の熱転写用記録用インクフィルムとし、上記で得たマゼンタ色熱転写記録剤と共に使用して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。更に、ＯＨＰ用ポリエステルシートに複写すると、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。
【００５９】
参考例３
顔料製造例３で得た固溶体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／メタクリレート共重合体３部、エチレングリコール２２部、グリセリン８部、及び水５０部からなる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。
このインキを用いて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画像情報をプリントし、鮮明なマゼンタ色画像を得た。
また、実施例１で使用したシアン色、イエロー色、ブラック色顔料を用いて各々シアン色、イエロー色、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共に四色フルカラープリントを行い、鮮明なフルカラー画像を得た。
【００６０】
【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２，９−ジメチルキナクリドンと負帯電性もしくは弱い正帯電性の１種或いは２種の赤色調色顔料（但し、キナクリドン系顔料は除く）、即ち２，９−ジメチルキナクリドン顔料と負帯電性もしくは弱い正帯電性の１種或いは２種の赤色顔料（但し、キナクリドン系顔料は除く）との混合顔料或いは固溶体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、負帯電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、鮮明性で冴えた、地汚れのない、透明感の高い画像を安定して記録することが出来るものである。
また、液状の記録剤として使用される際においても、長時間安定に記録することが出来るものである。従って、得られた画像は鮮明であると共に、顔料に関する上記した諸堅牢性においても優れた性質を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording agent in image recording such as electrophotography, electronic printing, electrostatic recording, ink jet recording, and thermal transfer recording, or a coloring composition for image recording containing a pigment and a resin binder used in the production thereof, and a method for producing the same. More specifically, a clear magenta color image-recording composition having negative charging characteristics and containing a dimethylquinacridone pigment having various fastnesses and fine particle diameters and at least one specific red pigment as a pigment, and its It relates to a manufacturing method.
[0002]
[Prior art]
Conventionally, in magenta color recording agents used for image recording such as full-color or mono-color electrophotography, electronic printing, electrostatic printing, ink jet recording, and thermal transfer recording, red oil-soluble dyes, disperse dyes, thioindigos are used as red pigments. Pigments, soluble azo lake pigments, insoluble azo pigments, dimethylquinacridone pigments and the like are used.
[0003]
[Problems to be solved by the invention]
Among the red pigments used in the above-described magenta color image recording agent, dimethylquinacridone (2,9-dimethylquinacridone) pigment (CI Pigment Red 122), which is famous as a magenta color pigment, is used. Many.
This pigment alone has a disadvantage that not only the magenta color is too bluish and the coloring density is insufficient, but also the triboelectric charge of the pigment is positively charged and exhibits a considerably large value. For this reason, when the pigment is used in a negatively chargeable magenta recording agent, there is a problem that background staining is likely to occur.
[0004]
However, regarding red pigments used in magenta color image recording agents, oil-soluble dyes, dispersible dyes, etc. can be colored dissolvably in resin media, so they have high coloring power, but they are light resistant, heat resistant, and solvent resistant. There is a disadvantage that it is inferior in various fastnesses such as chemical resistance. Further, thioindigo pigments, soluble azo lake pigments, and insoluble azo pigments are also superior to dyes, but they are insufficient in fastness such as light resistance and heat resistance and sharpness.
Therefore, the dyes and pigments as described above are insufficient as dyes used for magenta colors for recording agents that require various fastness properties, sharpness, transparency, and negative chargeability, and have excellent physical properties. There is a demand for the development of pigments used in magenta colors for recording agents.
[0005]
As a result of various researches to develop a red pigment that can solve the above-mentioned conventional dyes for magenta color recording agents and satisfy various fastness, sharpness, transparency, and negative chargeability, By using a quinacridone pigment and at least one of the specific red pigments together, it is possible to provide an appropriate magenta color with the various fastnesses, sharpness, transparency, and negative charge required for this application. I found it.
Furthermore, by reducing the particle size compared to pigments used for conventional paints and plastic coloring, it is possible to exhibit properties that are excellent in hue clarity, texture, transparency, etc. The present invention has been completed by finding that an excellent recording agent for image recording can be obtained by using it as a colorant.
[0006]
[Means for Solving the Problems]
That is, the present invention relates to an electrophotography comprising a pigment and a resin,Use dry developerSelected from electronic printing, electrostatic recording, inkjet recording, and thermal transfer recordingUsed for image recordingIn the coloring composition for image recording,the aboveA dimethylquinacridone pigment (1) and at least one negatively or weakly positively charged red pigment (excluding a quinacridone pigment) (2) are used in combination as a pigment. , Its manufacturing method and method of use.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
The colored composition for image recording of the present invention comprises a dimethylquinacridone pigment (1) as a pigment component and a negatively or weakly positively charged red pigment (provided that, KiIt is characterized in that at least one of (2) is used in combination, excluding nacridon pigments. The red pigment (2) is preferably excellent in various fastness properties and has high coloring power, sharpness, texture and transparency.
By using the above-mentioned pigment, even when producing a colored composition for image recording containing a pigment at a high concentration, the high-concentration colored composition can be stably produced by adopting a dispersion processing method in which a processing temperature is 120 ° C. or lower. Can be manufactured. Further, when the color composition for image recording of the present invention is finally used as an image recording agent, it has excellent negative chargeability, is clear and has a high transparency, and is free from background stains. An image having excellent fastness can be stably recorded for a long time. These characteristics are manifested when the image recording agent is either solid or liquid.
[0008]
The red pigment (2) used together with the dimethylquinacridone pigment (1) in the present invention is a negatively charged or weakly positively charged pigment, and preferably a red pigment having higher coloring power and sharpness is used. The Preferred red pigments are those having a triboelectric charge amount of −100 to +30 μc / g as measured with a blow-off powder charge amount measuring device, and examples thereof include the following pigments.
C. I. Pigment Red 5 C.I. I. Pigment Red 23
C. I. Pigment Red 112 C.I. I. Pigment Red 144
C. I. Pigment red 146 C.I. I. Pigment Red 147
C. I. Pigment red 149 C.I. I. Pigment Red 150
C. I. Pigment red 166 C.I. I. Pigment Red 170
C. I. Pigment red 176 C.I. I. Pigment Red 177
C. I. Pigment red 178 C.I. I. Pigment Red 185
C. I. Pigment Red 208 C. I. Pigment Red 214
C. I. Pigment red 220 C.I. I. Pigment Red 221
C. I. Pigment red 238 C.I. I. Pigment Red 245
C. I. Pigment Red 254
[0009]
A toning pigment is prepared from the dimethylquinacridone pigment (1) and the red pigment (2), which are mainly used in the present invention and characterizes the present invention, and is used to produce a coloring composition for image recording. These pigments may be premixed or made into a solid solution, or may be mixed in the process for producing the color composition for image recording. The method for producing the coloring composition for image recording is not particularly limited. For example, the fine powder mixed pigment and the fine powder solid solution pigment obtained by mixing and toning the dimethylquinacridone pigment (1) and the red pigment (2) in the pigment production process. A method for producing a coloring composition containing a pigment at a concentration suitable for an image recording agent directly using a etc., and using a heated kneader such as a roll mill or an extruder, or mixing and toning the fine powder mixed pigment, etc. There is a method of producing a colored composition containing a pigment at a high concentration using a heated kneader or the like using a press cake of a mixed pigment of the pigment (1) and the pigment (2), or the like.
Alternatively, a method may be used in which the pigment is contained in a polymer (resin) formed by dispersing the pigment in a monomer mixture constituting the resin and polymerizing the monomer.
[0010]
Specific examples of the toning pigment and a method for producing a highly concentrated colored composition containing the toning pigment include the following methods.
(A) Method for producing a highly concentrated colored composition using dimethylquinacridone pigment (1) and red pigment (2), or a mixed pigment thereof
(A) Each pigment is dried alone, and a mixture of finely divided pigments collided or ground and a resin are kneaded with a heating kneader to obtain a highly concentrated colored composition.
(B) After mixing the aqueous press cakes of the respective pigments, drying, kneading the finely powdered mixed pigment and resin, which have been impact pulverized or ground, with a heating kneader to obtain a highly concentrated colored composition.
(C) The aqueous press cake and the resin of pigments (1) and (2) are charged into a heating kneader or the like, and a high-concentration colored composition is produced by a melt flushing method or the like.
(D) The aqueous press cakes of the pigments (1) and (2) are mixed in advance, and a high-concentration colored composition is produced in the same manner as in the above (c) using this.
(E) Fine powder of pigment (1) and pigment (2), resin and a small amount of water are charged into a heating kneader and the like, and a high-concentration colored composition is produced by a melt flushing method or the like.
(F) The fine powder mixed pigment of (a) or (b), resin and a small amount of water are charged into a heating kneader and the like, and a high-concentration colored composition is produced by a melt flushing method or the like.
[0011]
(B) Method for producing high-concentration colored composition using solid solution pigment of dimethylquinacridone pigment (1) and red pigment (2)
(A) The solid solution of the dimethylquinacridone pigment (1) and the red pigment (2) is dried, and the finely divided solid solution pigment and the resin that have been impact-pulverized or ground are kneaded with a heating kneader to obtain a high-concentration colored composition.
(B) An aqueous press cake of the solid solution pigment (a) and a resin are charged into a heating kneader or the like, and a high-concentration colored composition is produced by a melt flushing method or the like.
(C) The fine powder solid solution pigment of (a), resin and a small amount of water are charged into a heating kneader and the like, and a high-concentration colored composition is produced by a melt flushing method or the like.
[0012]
In the above (B), the solid solution pigment of the dimethylquinacridone pigment (1) and the red pigment (2) is obtained by subjecting these mixed pigments to a solid solution state by the following pigmentation treatment. By using a solid solution, it is possible to improve the vividness, hue, transparency and negative chargeability of the hue.
The method of making the mixed pigment into a solid solution can be a conventionally known method and is not particularly limited. For example, a plurality of pigments to be formed into a solid solution are blended, a solid solution crude crystal is obtained through an acid paste treatment or grinding step, and this is treated with an organic solvent or the like to obtain a solid solution pigment.
[0013]
The toning pigment of the dimethylquinacridone pigment (1) and the red pigment (2) used in the present invention, that is, the usage ratio of both pigments is appropriately determined according to the hue of the desired image, and is not particularly limited. Usually, the pigment (1) to the pigment (2) are in the range of 99: 1 to 1:99 (weight ratio), preferably in the range of 95: 5 to 30:70.
[0014]
The dimethylquinacridone pigment used in the present invention in order to further improve the properties and physical properties such as transparency, color, clarity, and negative chargeability of the image color by using the image recording composition of the present invention. The post-treatment such as adjusting the pigment crystals and adjusting the shape and particle diameter of the pigment particles to a desired range can be applied to (1) and the red pigment (2) according to a conventionally known method.
In general, when dimethylquinacridone pigments or red pigments are used for coloring applications such as paints or plastics, the pigments have properties such as hiding power, ease of dispersion in media, weather resistance, and heat resistance. Therefore, the average particle diameter of the pigment is large, for example, adjusted to a size of about 500 to 700 nm. However, when this coarse pigment is used as a colorant for an image recording agent, there is a problem in that the transparency, tone and sharpness of the hue are lowered.
[0015]
In particular, when used as a colorant for a full-color recording agent, it is preferable that the hue has transparency, contrast, and clarity.
Therefore, the toning pigment of dimethylquinacridone pigment (1) and red pigment (2) used in the present invention is a conventional dispersion method such as flushing, heat kneading or wet dispersion for producing a colored composition for image recording. In the resin, it is preferable to disperse the resin so that the weight average particle diameter is 200 nm or less, preferably 150 nm or less.
Accordingly, in the production of the composition, it is preferable to use those pigments that have been finely divided in advance so as to have the above-mentioned dispersed particle size.
[0016]
The method for making the pigment fine particles is not particularly limited, and a conventionally known method can be used. For example, a method of treating the pigment with an acid paste, a method of making the pigment fine by collision grinding or grinding, and the like can be mentioned. The collision pulverization method includes a dry milling method using a ball mill or a vibration mill. A pulverization medium such as a steel ball or a steel rod is used, and an inorganic salt is used as a grinding aid if necessary. The grinding method includes a salt milling method and a solvent salt milling method, and an inorganic salt such as anhydrous sodium sulfate, sodium chloride, and aluminum sulfate is used as a grinding aid. The fine pigments thus obtained have a clear hue, a clear appearance and transparency, and also have various fastnesses such as light resistance, heat resistance, solvent resistance, chemical resistance, water resistance, and negative chargeability. Excellent properties.
[0017]
Resins such as thermoplastic polymer resins and waxes used for producing the colored composition for image recording of the present invention are dispersion media in the composition used in a solid form, and are liquids. In the composition used in this state, it functions as a pigment dispersant. Further, when actually used as a recording agent, it acts as a pigment fixing agent.
Resins used for such purposes include dry development such as electrophotography, electrostatic printing, electrostatic recording, etc.Agent,Any of the resins conventionally used for image recording agents such as oil-based and water-based inkjet inks, thermal transfer ink ribbons, and films can be used and is not particularly limited. Further, conventionally known additives such as a charge control agent, a fluidizing agent, or a solvent, an aqueous medium, or the like can be used as necessary according to each of the above applications.
[0018]
The coloring composition for image recording of the present invention was manufactured as a high-concentration coloring composition containing a pigment at a high concentration even if it was manufactured from the beginning so as to have a pigment concentration suitable for the intended image recording agent. Any of those can be used.
The high-concentration coloring composition contains a pigment at a high concentration, and is intended to facilitate the subsequent image recording agent production process by dispersing the pigment by sufficiently kneading in advance and performing color matching. It is used in any form of solid, paste, or liquid such as coarse particles, coarse powder, fine powder, sheet form, or small lump form. The content of the pigment in the composition is usually about 10 to 70% by weight, preferably about 20 to 60% by weight.
[0019]
Various additives, solvents, and the like that have been conventionally used are added to the coloring composition for image recording of the present invention depending on the purpose of use, and used as a target image recording agent. As the image recording agent, for example, a so-called fine powder dry developer, StaticElectric recording agent, ink for inkjet recording, film, paper, etc.MaterialAnd a thermal transfer ink ribbon and film applied to the film.
[0020]
The content of the pigment in the coloring composition for image recording of the present invention (including a pigment having a concentration suitable for the intended image recording agent) varies depending on the purpose of use of the composition, and the magenta color used in the present invention. The content of the pigment in the total coloring composition including the toning pigment of the dimethylquinacridone pigment (1) and the red pigment (2) toned in color, resin, other additives or medium is usually 2 to 20% by weight. Degree. When used as a dry recording agent for electrophotography, the pigment content is about 2 to 15% by weight, preferably about 3 to 10% by weight.is there. Further, when used as a colorant for a thermal transfer ink ribbon or film, it is about 4 to 15% by weight, preferably about 6 to 10% by weight, and 3 to 20 when used as an ink for ink jet recording. It is about 5% by weight, preferably about 5 to 10% by weight, and is used at the most preferable content depending on the purpose of use.
[0021]
As a method for producing the above-described pigment high-concentration coloring composition, there are, for example, 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, usually, a kneading and dispersing machine such as a two-roll, three-roll, heating kneader, pressure heating kneader, single screw extruder, twin screw extruder is used. A method of melting the resin and kneading and dispersing the pigment is used. In any of these methods, the kneading and dispersing process is desirably performed at a temperature of 120 ° C. or lower. By kneading and dispersing under this relatively low processing temperature condition, the particle diameter of the pigment finely adjusted in advance is maintained as it is in the composition, and the subsequent processing step of recording agent production is similarly performed at 120 ° C. By carrying out under the following temperature conditions, an image recording agent exhibiting the clearness, hue and transparency of the hue can be obtained.
[0022]
The most preferable method as a high concentration dispersion method of the pigment is a method of flushing with a resin in which an aqueous pigment paste is melted (normal pressure melt flushing method), for example, a method proposed in Japanese Patent Laid-Open No. 2-175770. .
Specifically, without using any solvent, an aqueous press cake of pigment and a resin binder are charged into a kneader or flasher that can be heated by steam, and kneaded at normal pressure at a temperature below the melting point or softening point of the resin. In this method, the pigment 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 transferred into the resin as they are, and the kneading and dispersing temperature can be advanced at 100 ° C. or lower while water is present. ing.
As another preferable high concentration pigment dispersion method, water is added as a dispersant to the powder pigment and the resin binder, and the processing temperature is 120 ° C. or less in the absence of a solvent at normal pressure in the same manner as the above method. A highly concentrated colored composition can also be obtained by a method in which the pigment is transferred to the resin phase by kneading at a temperature lower than the melting point or softening point of the resin, the separated water is removed, and the remaining water is kneaded and evaporated.
[0023]
Dry development such as electrophotography, electrostatic printing, electrostatic recording, etc. produced using the coloring composition for image recording of the present inventionAgent,For image recording agents such as water-based, oil-based and solid ink-jet inks, thermal transfer ink ribbons, thermal transfer ink films, and the like, the toning pigments of dimethylquinacridone pigment (1) and red pigment (2) have pigment concentrations suitable for each application from the beginning. The composition thus formed is used as it is, or a high-concentration colored composition in which the above-mentioned pigment is dispersed at a high concentration is dispersed or diluted in a resin binder, a resin solution or an addition polymerizable monomer. Dispersed and manufactured in accordance with a conventional method for manufacturing each image recording agent, adding a conventionally known charge control agent, fluidizing agent, ferromagnetic material, solvent medium, aqueous medium, etc. as necessary. .
[0024]
For example, recording agents for image recording used for electrophotography, electrostatic printing, electrostatic recording, etc. are described. As dry recording agents, suspension polymerization method called emulsion method and polymerization method, emulsion polymerization liquid aggregation method, etc. A fine powdery dry developer produced by the production 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, and the suspension polymerization method is an addition polymerization in which the pigment, charge control agent, etc. are dispersed. This is a method in which an O / W emulsion having a controlled droplet size is used and a colored fine particle polymer is formed by a suspension polymerization method. A fine dispersion of the control agent is mixed, and the resulting colored emulsion polymerization liquid is heated, fused, and agglomerated to co-precipitate or adsorb the pigment and the charge control agent on the polymer particles and atomize to a predetermined particle size. It is a method to do. In addition, materials such as conventionally known fluidizing agents and ferromagnetic agents are added as necessary..
[0025]
The color composition for image recording of the present invention is used as a magenta image recording agent in individual colors such as monochromatic to bicolor and multicolor, and as a full color recording system, cyan, yellow or even black. Of course, it can be used together with other image recording agents.
Examples of these organic pigments and inorganic pigments include phthalocyanine, azo, polycondensed azo, azomethine azo, anthraquinone, perinone / perylene, indigo / thioindigo, dioxazine, isoindolinone, pyrrolopyrrole. Conventional pigments such as carbon pigments, carbon black pigments, titanium oxides, iron oxides, calcined pigments, extender pigments and the like can be mentioned.
[0026]
In particular, as a pigment used in a full color recording agent, a phthalocyanine blue pigment as a cyan pigment, and an azo, polycondensed azo, anthraquinone, and isoindolinone yellow pigment as a yellow color, Representative examples of the black color include carbon black pigments, azomethine azo black pigments, and black pigments obtained by toning each color pigment.
These various pigments, like the toning pigments of the dimethylquinacridone pigment (1) and the red pigment (2) used in the present invention, can be used for flashing, heat kneading, wet dispersion, etc. for producing a colored composition for image recording. It is preferable to use a pigment having a particle size adjusted so that the average particle size is about 200 nm or less, preferably about 150 nm or less by dispersing in the resin by a normal dispersion method.
[0027]
【Example】
Next, the present invention will be described more specifically with reference to pigment production examples and examples. In the text, parts or percentages are based on weight.
The average particle diameter of the pigment itself and the average particle diameter of the pigment in the composition in the following examples are weight average particle diameters measured by the following method.
(1) Measuring method of average particle diameter of pigment itself
0.5 g of pigment and 0.7 g of dispersant are dispersed with a Hoover-type Mahler under a load of 150 pounds and a kneading frequency of 300 times, diluted with water to the concentration specified in the measuring apparatus, and then subjected to ultrasonic waves for 1 minute. The test solution prepared by the action is measured by a Coulter submicron particle analyzer (MODEL N-4 manufactured by Coulter).
(2) Method for measuring the average particle size of the pigment in the composition
After dissolving 0.1 g of the coloring composition in 10 cc of xylene and diluting with xylene to the concentration specified in the measuring device, the test solution prepared by applying ultrasonic waves for 1 minute was used as a Coulter submicron particle analyzer (manufactured by Coulter Co., Ltd.). Measure with MODEL N-4).
[0028]
Pigment production example 1
A ball mill was charged with 10 parts of a crude pigment of 2,9-dimethylquinacridone pigment (CI Pigment Red 122), 100 parts of sodium chloride and 1 part of a high-boiling alicyclic hydrocarbon, and milled for 10 hours. Subsequently, post-treatments such as pigmentation, filtration, and washing were performed to obtain a press cake. The solid content as the dimethylquinacridone pigment was 30%. The obtained press cake was dried and pulverized to obtain a dimethylquinacridone pigment.
The average particle diameter of the pigment thus produced was 200 nm or less, and the hue showed bluish red.
When 5 parts of this pigment were mixed with 100 parts of magnetic iron powder, the triboelectric charge amount was measured with a blow-off powder charge amount measuring device (TB-200 type manufactured by Toshiba Chemical Co., Ltd.) (the same applies hereinafter), and it was +56.6 μc / g. there were.
[0029]
On the other hand, a ball mill is charged with 10 parts of a crude pigment of 4,4'-diamino-1,1'-dianthraquinonyl pigment (CI Pigment Red 177), 90 parts of anhydrous sodium sulfate, and 1 part of chlorinated aliphatic hydrocarbon. And milled for 10 hours. Subsequently, post-treatments such as pigmentation, filtration, and washing were performed to obtain a press cake. The solid content as a dianthraquinonyl pigment was 30%. The obtained press cake was dried and pulverized to obtain a dianthraquinonyl pigment.
The average particle diameter of the pigment thus produced was 200 nm or less, and the hue was red.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge was measured, it was -36.9 μc / g.
[0030]
Next, 8 parts solid content of an aqueous press cake of dimethylquinacridone pigment and 2 parts solid content of an aqueous press cake of dianthraquinonyl pigment are mixed, dried and pulverized to obtain a mixture pigment of dimethylquinacridone pigment and diantraquinonyl pigment Got. This showed a magenta hue. The average particle size of the mixture pigment was 200 nm or less.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge was measured, it was +11.5 μc / g.
[0031]
Pigment production example 2
According to the method shown in Pigment Production Example 1, 3 parts of 4,4'-diamino-1,1'-dianthraquinonyl pigment is added to 7 parts of 2,9-dimethylquinacridone pigment and then ground. Thus, a solid solution pigment was obtained, converted into a pigment by treatment with an organic solvent, then filtered, washed, dried and pulverized to obtain a solid solution pigment (7/3 (weight ratio)) of dimethylquinacridone pigment / dianthraquinonyl pigment. . The hue showed a magenta color. The average particle diameter of the produced solid solution pigment was 200 nm or less.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge was measured, it was +14.5 μc / g.
[0032]
Pigment production example 3
According to the method shown in Pigment Production Example 1, 2 parts of a crude pigment of 2,9-dimethylquinacridone pigment, 2 parts of a crude pigment of dichloroquinacridone pigment (CI Pigment Red 209), and γ-type unsubstituted quinacridone pigment (C I. Pigment Bio Red 19) Add 3 parts of pigment and grind to obtain solid solution pigment, pigmentize by organic solvent treatment, then filter, wash, dry and grind to dimethylquinacridone pigment / dichloro A solid solution pigment (5/2/3 (weight ratio)) of quinacridone pigment / unsubstituted quinacridone pigment was obtained. The hue showed a magenta color. The average particle diameter of the produced solid solution pigment was 200 nm or less.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge amount was measured, it was +20.9 μc / g.
[0033]
Pigment production example 4
9 parts of a crude pigment of 2,9-dimethylquinacridone pigment and 1 part of a crude pigment of diketopyrrolopyrrole pigment (CI Pigment Red 254) are dissolved in 100 parts of 98% sulfuric acid, and this solution is added with 500 parts of cold water. It was poured into and precipitated as a solid solution pigment. Filtration, washing (neutralization), pigmentation by organic solvent treatment, filtration, washing, drying, and grinding to obtain a solid solution pigment (9/1 (weight ratio)) of dimethylquinacridone pigment / diketopyrrolopyrrole pigment It was. The hue showed a magenta color. The average particle diameter of the produced solid solution pigment was 200 nm or less.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge amount was measured, it was +12.6 μc / g.
[0034]
Pigment production example 5
By the method shown in Pigment Production Example 1, 5 parts of a crude pigment of 2,9-dimethylquinacridone pigment was added to C.I. I. Pigment Red 5 crude pigment (5 parts) was added and ground to obtain a solid solution pigment, which was then pigmented by treatment with an organic solvent, followed by filtration, washing, drying and grinding, and dimethylquinacridone / C.I. I. Pigment Red 5 pigment solid solution pigment (5/5) (weight ratio) was obtained. The hue showed a magenta color. The average particle diameter when the produced solid solution pigment was dispersed was 200 nm or less.
When 100 parts of magnetic iron powder was mixed with 5 parts of this pigment and the triboelectric charge was measured, it was +13.5 μc / g.
[0035]
Example 1
According to the normal pressure melt flushing method of the pigment proposed in JP-A-2-175770, 96 parts of a dimethylquinacridone pigment presscake (pigment solid content 25%) obtained in Pigment Production Example 1 and a press cake 20 of a dianthraquinonyl pigment were obtained. 70 parts by weight (solid content of pigment 30%) and 70 parts of styrene / methallyl copolymer resin (softening point 110 ° C., glass transition point about 56 ° C., GPC weight average molecular weight about 50,000) are charged into a heating kneader and mixed. Then, steam heating was performed, and melt flushing was performed. Flushing was continued at a temperature of the kneaded resin of 90 to 95 ° C. to separate moisture. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. After further kneading, the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a high-density coloring composition of magenta color containing a pigment content of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0036]
Next, 82.3 parts of a styrene / methacrylic copolymer resin using 14.7 parts of the high-concentration coloring composition containing the magenta color mixed pigment thus obtained and 3 parts of a chromium complex-based negative charge control agent as described above. The mixture was kneaded according to a conventional method, cooled, pulverized, finely pulverized with a jet mill, and further classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm. Subsequently, colloidal silica as a fluidizing agent was added to the fine powder according to a conventional method and mixed well, and then mixed with the carrier magnetic iron powder to obtain a magenta electrophotographic dry developer.
[0037]
When this was loaded into an electrophotographic copying machine for negative charge full color development and copied on paper, the copied image showed a clear, fuzzy magenta color, and showed excellent fastness with various physical properties such as light resistance. . Further, when copied on a polyester sheet for an overhead projector (hereinafter abbreviated as OHP), a transparent image was shown, and a clear magenta image was shown on the OHP screen.
[0038]
In addition, C.I. I. Pigment Blue 15: 3 (pigment content in developer: 3.5%), C.I. I. Pigment Yellow 93 (pigment content: 4.4%), C.I. I. Pigment Black 7 (pigment content: 3.5%), each of which can be dispersed so that the average particle diameter is 200 nm or less, is treated in the same manner as described above, and each of cyan developer, yellow developer, and black color As a developer, four-color full-color copying was performed together with the magenta developer obtained above to obtain a clear full-color image. In addition, a full-color image in which a clear full-color image was projected on the OHP screen was obtained.
[0039]
Example 2
In a heating kneader, 21 parts of the dimethylquinacridone pigment and 9 parts of dianthraquinonyl pigment obtained in Pigment Production Example 1, 70 parts of the styrene / methacrylic copolymer resin used in Example 1 and 100 parts of water were charged at normal pressure. Steam mixing was performed while mixing, and kneading was sufficiently performed. The temperature of the kneaded resin was set to 90 to 95 ° C. to separate moisture. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. After further kneading, the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta colored high-concentration colored composition containing a pigment content of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0040]
Next, in the same manner as in Example 1, a high-concentration coloring composition containing a magenta mixed pigment and a chromium complex salt negative charge control agent were kneaded with the styrene / methacrylic copolymer resin, cooled and classified, and A fine powder of a 20 m magenta resin composition was obtained, colloidal silica was added, and mixed with magnetic iron powder to obtain a magenta electrophotographic dry developer.
When this was used for copying on paper with a negative charge full color developing electrophotographic copying machine, the copied image had a clear and fuzzy magenta color. In addition, when copied on a polyester sheet for OHP, a transparent image was displayed and a clear magenta image was displayed on the screen.
In addition, using the cyan, yellow, and black developers used in Example 1 together with the magenta developer described above, four-color full-color copying was performed on paper to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0041]
Example 3
30 parts of a mixed pigment of dimethylquinacridone pigment / dianthraquinonyl pigment (8/2 (weight ratio)) obtained in Pigment Production Example 1 and 70 parts of styrene / methacrylic copolymer resin used in Example 1 and a three-roll Was sufficiently kneaded to disperse the pigment. After cooling, the mixture was coarsely crushed to obtain a coarse powder of a magenta colored high-concentration colored composition containing a pigment content at a concentration of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
Next, in the same manner as in Example 1, a styrene / methacrylic copolymer using 14.7 parts of the resulting highly concentrated colored composition containing the magenta mixed pigment and 3 parts of a chromium complex salt negative charge control agent as described above. Kneaded with 82.3 parts of resin, cooled and pulverized, finely pulverized and classified to obtain a fine powder of magenta resin composition of 5 to 20 μm, added colloidal silica, mixed with magnetic iron powder, and magenta A photographic dry developer was obtained.
[0042]
When this was used for copying on paper with a negative charge full color developing electrophotographic copying machine, the copied image had a clear and fuzzy magenta color. In addition, when copied on a polyester sheet for OHP, a transparent image was displayed and a clear magenta image was displayed on the screen.
Furthermore, using the cyan, yellow and black developers used in Example 1 together with the magenta developer described above, four-color full-color copying was performed on paper to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0043]
Example 4
According to the melt flushing method of Example 1, 107.2 parts (solid content 28%) of the solid solution pigment obtained in Pigment Production Example 2 and 70 parts of a negatively charged bisphenol-type polyester resin (softening point of about 100 ° C.) The mixture was charged into a heating kneader, mixed, and melted and flushed. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. Further, kneading was continued to disperse the pigment, and then the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta high-concentration colored composition containing the pigment content at a concentration of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0044]
Next, according to the method of Example 1, 14.7 parts of a high-concentration colored composition containing the magenta solid solution pigment thus obtained and 3 parts of a chromium complex-based negative charge control agent and the bisphenol-type polyester resin used above 82.5 parts is kneaded, and after cooling, coarsely pulverized, finely pulverized, classified to obtain a fine powder of a magenta resin composition of 5 to 20 μm, and after adding colloidal silica as a fluidizing agent and sufficiently mixing, A magenta electrophotographic dry developer was prepared by mixing with the magnetic iron powder of the carrier.
When this was used for copying on paper with a negative charge full color developing electrophotographic copying machine, the copied image had a clear and fuzzy magenta color. When copied on a polyester sheet for OHP, a transparent image was shown and a clear magenta image was shown on the screen.
In addition, using the cyan, yellow, and black developers used in Example 1 together with the magenta developer described above, four-color full-color copying was performed on paper to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0045]
referenceExample1
According to the melt flushing method of Example 1, 100.0 parts (solid content 30%) of the solid solution pigment obtained in Pigment Production Example 3 and 70 parts of a negatively charged bisphenol-type polyester resin (softening point of about 100 ° C.) The mixture was charged into a heating kneader, mixed, and melted and flushed. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. Further, kneading was continued to disperse the pigment, and then the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta high-concentration colored composition containing the pigment content at a concentration of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0046]
Next, according to the method of Example 1, 14.7 parts of a high-concentration colored composition containing the magenta solid solution pigment thus obtained, 3 parts of a chromium complex negative charge control agent, and the bisphenol for negative charge used above 82.5 parts of a polyester resin, kneaded, cooled, coarsely pulverized, finely pulverized and classified to obtain a fine powder of 5-20 μm magenta resin composition, and colloidal silica was added as a fluidizing agent and mixed well After that, the carrier was mixed with magnetic iron powder to obtain a magenta electrophotographic dry developer.
Using this, it was copied on paper by an electrophotographic copying machine for negative charge full color development. The copied image had a clear and fuzzy magenta color. When copied on a polyester sheet for OHP, a transparent image was shown and a clear magenta image was shown on the screen.
In addition, using the cyan, yellow, and black developers used in Example 1 together with the magenta developer described above, four-color full-color copying was performed on paper to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0047]
Example5
According to the melt flushing method of Example 1, 111.1 parts (solid content 27%) of the solid solution pigment obtained in Pigment Production Example 4 and 70 parts of bisphenol-type polyester resin for negative charge (softening point of about 100 ° C.) The mixture was charged into a heating kneader, mixed, and melted and flushed. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. Further, kneading was continued to disperse the pigment, and then the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta high-concentration colored composition containing the pigment content at a concentration of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0048]
Next, in accordance with the method of Example 1, negatively charged bisphenol using 14.7 parts of the high-concentration colored composition containing the magenta solid solution pigment thus obtained and 3 parts of the chromium complex-based negative charge control agent was used above. Kneaded with 82.5 parts of type polyester resin, and after cooling, coarsely pulverized, finely pulverized and classified to obtain a fine powder of 5-20 μm magenta resin composition, and added with colloidal silica as a fluidizing agent and mixed well. Thereafter, it was mixed with carrier magnetic iron powder to obtain a magenta electrophotographic dry developer.
Using this, it was copied on paper with an electrophotographic copying machine for negative charge full color development. The copied image had a clear and fuzzy magenta color. When copied on a polyester sheet for OHP, a transparent image was shown and a clear magenta image was shown on the screen.
In addition, the cyan, yellow and black developers used in Example 1 were four-color full-color copied on paper together with the magenta developer described above to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0049]
Example6
According to the melt flushing method of Example 1, 107.2 parts (solid content 28%) of the solid solution pigment obtained in Pigment Production Example 5 and 70 parts of bisphenol-type polyester resin for negative charge (softening point of about 100 ° C.) The mixture was charged into a heating kneader, mixed, and melted and flushed. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading. Further, kneading was continued to disperse the pigment, and then the kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta high-concentration colored composition containing the pigment content at a concentration of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0050]
Next, according to the method of Example 1, a negatively charged bisphenol type using 14.7 parts of the high-concentration colored composition containing the magenta solid solution pigment thus obtained and 3 parts of a chromium complex negative charge control agent as described above. After kneading with 82.5 parts of polyester resin, after cooling, coarsely pulverized, finely pulverized and classified to obtain a fine powder of magenta resin composition of 5 to 20 μm, and after adding colloidal silica as a fluidizing agent and sufficiently mixing A magenta electrophotographic dry developer was prepared by mixing with the magnetic iron powder of the carrier.
This was used for copying on paper with an electrophotographic copying machine for full color development. The copied image had a clear and fuzzy magenta color. When copied on a polyester sheet for OHP, a transparent image was shown and a clear magenta image was shown on the screen.
In addition, the cyan, yellow and black developers used in Example 1 were four-color full-color copied on paper together with the magenta developer described above to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0051]
Example7
Take 50 parts of diethyl maleate in a container, add 20 parts of a styrene / benzyl methacrylate / 2-ethylhexyl methacrylate (7/2/1 (weight ratio)) copolymer and dissolve it in Pigment Production Example 2. 25.5 parts of a solid solution pigment of the obtained dimethylquinacridone pigment / dianthraquinonyl pigment (7/3 (weight ratio)) and 4.5 parts of phthalimidomethylated dimethylquinacridone pigment were added and mixed to obtain a continuous horizontal wet bead medium dispersion. Was sufficiently finely dispersed using a machine to obtain a magenta color pigment high-concentration monomer dispersion. The average particle size of the pigment in the dispersion was 200 nm or less.
[0052]
Similarly, 20 parts of the styrene / methacrylic acid ester copolymer of Example 1 is dissolved in 50 parts of diethyl maleate, and 30 parts of a chromium complex salt-based negative charge control agent is added and mixed. Was dispersed finely to obtain a high concentration monomer dispersion of a negative charge control agent.
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 Part, 1.5 parts of lauryl mercaptan and 2.0 parts of azoisobutylronitrile were added to the container and sufficiently stirred and mixed so as to be uniform. To 200 parts of 4% colloidal silica aqueous dispersion, 103.5 parts of the monomer dispersion containing the pigment and the charge control agent obtained above was stirred while being stirred with a high shear force high-speed stirrer, and an oil-in-water type The 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.
[0053]
A polymerization reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, serpentine condenser and dropping funnel was charged with 200 parts of a 4% colloidal silica aqueous dispersion and about one third of the magenta emulsion obtained above, 75 The polymerization reaction was performed at ˜80 ° C. for 2 hours. Next, the remaining two-thirds of the emulsion was dropped from the dropping funnel over 3 hours and stirred for another 1 hour, then heated to 85 ° C. over 30 minutes and stirred for 1 hour to complete the polymerization reaction.
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. Subsequently, colloidal silica was added as a fluidizing agent and mixed with magnetic iron powder to obtain a magenta electrophotographic dry developer.
[0054]
Using this, a copied image copied on paper with an electrophotographic copying machine for negative charge full color development exhibited a magenta color that was clear and free of background stains. In addition, when copied on a polyester sheet for OHP, a transparent image was displayed and a clear magenta image was displayed on the screen.
In the same manner as described above, C.I. I. Pigment Blue 15: 3 (hereinafter referred to as pigment content in the developer: 3.4%) and phthalimidomethyl copper phthalocyanine pigment (0.6%) were used to prepare a cyan developer, C.I. I. Pigment Yellow 93 (4.25%) and phthalimidomethyldianthraquinonyl-monophenylamino-s-triazine pigment (0.75%) were used to produce a yellow color developer. I. A black developer was prepared using Pigment Black 7 (3.40%) and phthalimidomethyl copper phthalocyanine pigment (0.60%) and used with the magenta developer described above for electrophotographic copying for negative charge full color development. A four-color full-color copy was made on paper with a machine to obtain a clear full-color image. The full-color copy image of the OHP sheet displayed a clear full-color image on the screen.
[0055]
referenceExample2
According to the melt flushing method of Example 1, 107.2 parts of a press cake of a dimethylquinacridone pigment / dichloroquinacridone pigment / unsubstituted quinacridone pigment (5/2/3 (weight ratio)) solid solution pigment obtained in Pigment Production Example 3 ( The solid content was 28%) and 70 parts of the styrene / methacrylic copolymer resin of Example 1 were charged into a heating kneader, mixed and melted and flushed. The separated water was discharged, and the remaining water was evaporated and removed while heating and kneading to disperse the pigment. The kneaded product was taken out from the kneader, cooled and pulverized to obtain a coarse powder of a magenta colored high-concentration colored composition containing a pigment content of 30%. The average particle size of the pigment in the coarse powder was 200 nm or less.
[0056]
Next, 10 parts of the magenta resin powder thus obtained is added to 75 parts of Isopar G together with 15 parts of a methacrylic ester resin soluble in an aliphatic hydrocarbon solvent, and glass beads are added to form a paint conditioner. The mixture was shaken and dispersed for 20 hours to prepare a concentrated and highly colored liquid. The average particle size of the pigment in the concentrated liquid was 200 nm or less.
200 parts of this concentrated liquid was added and dispersed in 1 liter of Isopar G to obtain an electrophotographic wet developer.
This was used for copying with a full-color wet electrophotographic copying machine to obtain a clear magenta color copying image. This image showed fastness excellent in various physical properties such as light resistance.
In the same manner as described above, the cyan, yellow, and black pigments used in Example 1 were used as the cyan, yellow, and black wet developers, respectively, and the magenta wet development obtained above. A four-color full-color copy was made together with the agent to obtain a clear full-color image. A clear full-color image was output using a four-color full-color wet electrostatic plotter using the four-color full-color developer.
[0057]
Example8
In the same manner as in Example 2, 41 parts of ester wax, 41 parts of paraffin wax, 5 parts of the styrene / methacrylic copolymer resin of Example 1 and 3 parts of silica were used as binders, and the solid solution pigment 10 obtained in Pigment Production Example 2 was used. And 50 parts of water as a dispersant were added to a kneader and kneaded at normal pressure at a temperature below the melting point or softening point of the resin to remove the separated water, and the remaining water was evaporated.
[0058]
The obtained colored composition was applied to a polyethylene film according to a conventional method to obtain a magenta thermal transfer recording ink film. This was used for copying with a full color thermal transfer copying machine to obtain a clear magenta color copy image. This image showed fastness excellent in various physical properties such as light resistance. Further, when copied on a polyester sheet for OHP, a transparent image was obtained, and a clear image was shown on the screen.
In the same manner as described above, cyan, yellow, and black color inks for thermal transfer were prepared using the cyan, yellow, and black pigments used in Example 1, respectively, and the magenta obtained above. Using with a color heat transfer recording agent, four-color full-color copying was performed to obtain a clear full-color image. Furthermore, when copied on a polyester sheet for OHP, a full color image showing a transparent full color image on the screen was obtained.
[0059]
referenceExample3
From 17.9 parts of an aqueous press cake of the solid solution pigment obtained in Pigment Production Example 3 (pigment solid content 28%), 3 parts of a styrene / acrylate / methacrylate copolymer, 22 parts of ethylene glycol, 8 parts of glycerin, and 50 parts of water NaWaterAn aqueous pigment magenta ink was prepared by removing a pigment coarse particle that could not be dispersed with an ultracentrifuge.
Using this ink, image information was printed by an on-demand type ink jet printer having a piezoelectric vibrator, and a clear magenta color image was obtained.
In addition, cyan, yellow, and black pigments used in Example 1 were used as inkjet inks of cyan, yellow, and black, respectively, and four-color full-color printing was performed together with the magenta inkjet ink obtained above. A clear full-color image was obtained.
[0060]
【The invention's effect】
The coloring composition for image recording of the present invention comprises 2,9-dimethylquinacridone used as a pigment component thereof, and one or two red toning pigments of negative chargeability or weak positive chargeability (provided that, Ki2) 9-dimethylquinacridone pigment and one or two red pigments that are negatively charged or weakly positively charged (except for nacridone pigments), KiMixed pigments or solid solution pigments (excluding nacridone pigments) are excellent as magenta color pigments for coloring compositions for full-color image recording, and are light resistant, heat resistant, solvent resistant, chemical resistant, water resistant It has excellent fastness such as high coloring power, sharpness, clearness, transparency, and negative chargeability, so it can be manufactured stably under specific conditions in the manufacturing process of colored products. As a result, even when finally used as a magenta color image recording coloring composition, it is possible to stably record a clear and clear image having no background stain and high transparency. It is.
Further, even when used as a liquid recording agent, recording can be performed stably for a long time. Therefore, the obtained image is clear and exhibits excellent properties in the above-mentioned fastnesses related to the pigment.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35635098A JP3670148B2 (en) | 1998-12-15 | 1998-12-15 | Coloring composition for image recording and image recording agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35635098A JP3670148B2 (en) | 1998-12-15 | 1998-12-15 | Coloring composition for image recording and image recording agent |
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| JP2000181144A JP2000181144A (en) | 2000-06-30 |
| JP3670148B2 true JP3670148B2 (en) | 2005-07-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009093721A1 (en) | 2008-01-22 | 2009-07-30 | Ricoh Company, Ltd. | Magenta recording ink composition, inkjet recording method, and ink recorded matter |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4387613B2 (en) | 2000-07-10 | 2009-12-16 | キヤノン株式会社 | Magenta toner |
| JP2007270154A (en) * | 2002-02-19 | 2007-10-18 | Seiko Epson Corp | Ink composition, ink set, and recording method |
| JP3927998B2 (en) | 2002-09-06 | 2007-06-13 | 日本ゼオン株式会社 | Magenta toner |
| DE102008025006A1 (en) * | 2008-05-24 | 2009-11-26 | Lanxess Deutschland Gmbh | Fluorine-containing quinacridones in color filters for LCD |
| WO2012176255A1 (en) * | 2011-06-20 | 2012-12-27 | Dic株式会社 | Aqueous pigment dispersion for use in water-based ink for inkjet recording, water-based ink for inkjet recording, and water-based ink set |
| WO2014156569A1 (en) * | 2013-03-29 | 2014-10-02 | 日本化薬株式会社 | Ink composition, ink set, ink jet recording method, and colored body |
| JP6354266B2 (en) * | 2014-03-31 | 2018-07-11 | 大日本印刷株式会社 | Thermal transfer sheet, magenta color material layer coating solution, thermal transfer sheet manufacturing method, image forming method |
| JP6085357B1 (en) * | 2015-12-11 | 2017-02-22 | 大日精化工業株式会社 | Method for producing aqueous colorant |
| JP7144231B2 (en) * | 2018-08-06 | 2022-09-29 | 花王株式会社 | Aqueous pigment dispersion |
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1998
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009093721A1 (en) | 2008-01-22 | 2009-07-30 | Ricoh Company, Ltd. | Magenta recording ink composition, inkjet recording method, and ink recorded matter |
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