JP4086717B2 - CHARGE CONTROL AGENT AND POSITIVE CHARGE TONER FOR DEVELOPING ELECTROSTATIC IMAGE - Google Patents
CHARGE CONTROL AGENT AND POSITIVE CHARGE TONER FOR DEVELOPING ELECTROSTATIC IMAGE Download PDFInfo
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- JP4086717B2 JP4086717B2 JP2003161842A JP2003161842A JP4086717B2 JP 4086717 B2 JP4086717 B2 JP 4086717B2 JP 2003161842 A JP2003161842 A JP 2003161842A JP 2003161842 A JP2003161842 A JP 2003161842A JP 4086717 B2 JP4086717 B2 JP 4086717B2
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- toner
- silicon
- charge control
- schiff base
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- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
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- 150000002689 maleic acids Chemical class 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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Images
Description
【０００１】
【発明の属する技術分野】
本発明は、ケイ素含有シッフ塩基誘導体を含む電子写真用の帯電制御剤、この帯電制御剤を含む静電荷像現像用正帯電性トナーに関するものである。
【０００２】
【従来の技術】
複写機やプリンター等に利用されている電子写真システムは、摩擦帯電させたトナーで静電潜像を現像し、記録紙上に転写して定着させて、画像や文字を複写したり印刷したりするものである。
【０００３】
トナーの帯電量が少なかったり不均一であったりすると、潜像の現像が不鮮明となってしまう。また帯電の立上がり速度が遅いと、複写や印刷の速度を速めることができない。そこで、トナーの帯電量を適切に制御したり安定化したり帯電の立上がり速度を速めたりするために、予めトナーへ、正帯電性または負帯電性の荷電制御剤が添加される。トナーにこれらの帯電特性を発現させる荷電制御剤として、シッフ塩基誘導体が知られている。例えば特許文献１及び特許文献２にシッフ塩基の金属錯体、特許文献３及び特許文献４にビスサリチルアルデヒドエチレンジイミンやビスサリチルアルデヒドトリメチレンジイミンの金属錯体、特許文献５及び特許文献６にアミノ基含有シッフ塩基が、開示されている。
【０００４】
【特許文献１】
特開昭５９−７８３６２号公報
【特許文献２】
特開昭６３−２０６７６７号公報
【特許文献３】
特開昭６１−１４７２６１号公報
【特許文献４】
特開昭６１−１４９９６７号公報
【特許文献５】
特開平５−４５９３２号公報
【特許文献６】
特開平５−２７３７８８号公報
【０００５】
プリンタや複写機の解像度向上等の高性能化に伴い、従来のトナーよりも帯電特性、その安定性、耐環境性の一層優れたトナーが求められるようになっている。そのため一層優れた帯電特性を発現させることができ、さらに簡便に効率よく製造できる荷電制御剤が望まれていた。
【０００６】
【発明が解決しようとする課題】
本発明は、前記課題を解決するためなされたもので、トナーに十分な摩擦帯電性を発現させる電子写真用の荷電制御剤、この荷電制御剤を含み、帯電特性やその経時安定性や耐環境性に優れ、帯電立上がり速度が速く、現像したトナー像の品質を優れたものにする静電荷像現像用正帯電性トナーを提供することを目的とする。
【０００７】
【課題を解決するための手段】
前記の目的を達成するためになされた本発明の荷電制御剤は、下記化学式（１）
【０００８】
【化４】
【化５】
【０００９】
このケイ素含有シッフ塩基誘導体は、前記化学式（１）のシッフ塩基に、四ハロゲン化ケイ素で例示されるケイ素付与剤を、反応させたものであることが好ましい。
【００１０】
このケイ素含有シッフ塩基誘導体は、１または２モル当量の前記シッフ塩基に、１モル当量のケイ素原子が、配位したものであると、それを含む荷電制御剤に一層優れた帯電特性を発現させる。
【００１１】
前記ケイ素含有シッフ塩基誘導体が、下記化学式（４）
【化６】
【００１２】
ケイ素含有シッフ塩基誘導体が、前記化学式（４）中ｐ＝ｑ＝１で示されるものであるとなお好ましい。
【００１３】
ケイ素含有シッフ塩基誘導体は、優れた摩擦帯電性を示し、速い帯電立上がり速度を有し、更に樹脂との高い親和性及び優れた分散性を有している。また重金属のような金属が配位した錯体でないから、安全性が高いものである。そのためこのケイ素含有シッフ塩基誘導体を含む荷電制御剤は、静電荷像現像用トナーに添加して使用され、トナーを十分に正電荷に帯電させることができる。
【００１４】
ケイ素含有シッフ塩基誘導体は、淡色であるため荷電制御剤としてカラートナーに含ませても、トナーの色相に影響しないものである。
【００１５】
本発明の静電荷像現像用正帯電性トナーは、前記の荷電制御剤を含んでいる。このトナーは、荷電制御剤０．１〜１０重量部と、トナー用樹脂１００重量部とを含んでいることが好ましい。更に着色剤を含んでいてもよい。トナーは、荷電制御剤と着色剤とが、トナー用樹脂に練り込まれ内添されたものであるとなお好ましい。
【００１６】
静電荷像現像用正帯電性トナーは、トナー用樹脂１００重量部と着色剤とを含む母粒子の表面に、荷電制御剤０．１〜１０重量部、好ましくは０．５〜５重量部を含む子粒子が付着したものであってもよい。前記母粒子が荷電制御剤を含んでいてもよい。また子粒子がトナー用樹脂を含んでいてもよい。
【００１７】
前記トナーは、帯電の立上がり速度が速く、温度や湿度が変化しても長時間優れた帯電安定性を示す。
【００１８】
本発明のトナーの荷電制御方法は、前記のトナーを摩擦することにより、正に帯電させるというものである。この方法により帯電制御しつつ帯電させたトナーで、現像されたトナー像は、明瞭であり品質が優れている。
【００１９】
【発明の実施の形態】
以下、本発明の荷電制御剤及び静電荷像現像用正帯電性トナーの実施例を詳細に説明する。
【００２０】
荷電制御剤に含まれるケイ素含有シッフ塩基誘導体は、以下のようにして合成される。先ず、始発物質であるアルデヒド誘導体ＨＯ−Ａ−ＣＨＯ及びＯＨＣ−Ｂ−ＯＨの各１当量と、ジアミン誘導体Ｈ２Ｎ−（ＣＨ２）ｎ−ＮＨ２（−Ａ−、−Ｂ−、ｎは前記に同じ）の１当量とを縮合させて前記化学式（１）で表されるシッフ塩基を合成する。
【００２１】
より具体的に、アルデヒド誘導体が３，５−ジ−ｔ−ブチルサリチルアルデヒド（５）・（７）、ジアミン誘導体がエチレンジアミン（６）である例により説明すると、下記化学反応式（ｉ）に示すように、
【化７】
【００２２】
このシッフ塩基（８）は、ケイ素含有シッフ塩基誘導体の中間体である。シッフ塩基（８）と、ケイ素付与剤であるテトラクロロシランとを、有機溶媒中で反応させると、下記化学反応式（ｉｉ）に示すように、
【化８】
【００２３】
荷電制御剤としてこのケイ素含有シッフ塩基誘導体と、トナー用樹脂と、着色剤とを混練すると、静電荷像現像用正帯電性トナーが得られる。
【００２４】
なお、ケイ素含有シッフ塩基誘導体として化合物（９）の例を示したが、前記化学式（４）で表されるケイ素含有シッフ塩基誘導体中、−Ａ−及び−Ｂ−を構成する前記式（２）のフェニレン基または前記式（３）のナフチレン基の置換基−Ｒ１〜−Ｒ４が、水素原子；水酸基；ヒドロキシアルキル基；カルボキシル基；アルコキシカルボニル基；ホルミル基；ハロゲン原子（例えば、Ｃｌ、Ｂｒ、Ｉ、Ｆ）；アルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基のような炭素数１〜１８のアルキル基）；アルコキシル基（例えばメトキシ基、エトキシ基、イソプロポキシ基のような炭素数１〜１８のアルコキシル基）；アシル基（例えばアセチル基、プロピオニル基、ブチリル基、ベンゾイル基等）；アルケニル基（例えばアリル基−ＣＨ２ＣＨ＝ＣＨ２、−Ｃ（ＣＨ３）＝ＣＨ２）；ニトロ基；シアノ基；置換基を有していてもよく、置換基を有していなくてもよいアリサイクリック基（例えばシクロプロペニル基、シクロブチル基、シクロヘキシル基、シクロヘプチル基のような炭素数３〜７のシクロアルキル基）；置換基を有していてもよく、置換基を有していなくてもよいアラルキル基（例えばベンジル基、α，α’−ジメチルベンジル基等）；Ｃｌ、Ｂｒ、Ｉ、Ｆで例示されるハロゲン原子や炭素数１〜１８のアルキル基のような置換基を有していてもよく、置換基を有していなくてもよいアリール基（例えばフェニル基、トルイル基、ナフチル基等）とするものであってもよい。フェニレン基やナフチレン基のいずれの位置であってもよい。
【００２５】
ケイ素付与剤は、テトラクロロシランのみならず他の四ハロゲン化シラン、ケイ素アルコキシドのようなケイ素化合物であってもよい。ケイ素付与剤がケイ素アルコキシドであると、得られたケイ素含有シッフ塩基誘導体は、中心ケイ素が、前記化学式（１）で示されるシッフ塩基の他に、ケイ素アルコキシド由来のアルコキシ基に結合している場合もある。
【００２６】
化学式（４）のケイ素含有シッフ塩基誘導体中、（Ｄｕ）は、シッフ塩基とケイ素原子との組成比等により、１〜３価のカチオンまたはアニオンをとり得る。１〜３価のカチオンは、例えばＨ＋；Ｎａ＋、Ｋ＋のようなアルカリ金属カチオン；アンモニウムイオン；脂肪族第１級アンモニウムイオン、脂肪族第２級アンモニウムイオン、脂肪族第３級アンモニウムイオン、第４級有機アンモニウムイオンのような有機アミン由来のカチオンである。また１〜３価のアニオンは、例えばハロゲン化物イオン；スルホン酸アニオンやカルボン酸アニオンのような有機酸アニオン；脂肪酸系アニオン；有機系アニオン；ＯＨ−、ＳＯ４ ２−、ＮＯ３ −のような無機アニオンである。
【００２７】
このようなケイ素含有シッフ塩基誘導体のより具体的な例として、誘導体例１〜２４を示す。なお、前記化合物（９）は誘導体例２である。
【００２８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
荷電制御剤は、単一または複数種のケイ素含有シッフ塩基誘導体を含むものであってもよく、幾何異性体や光学異性体の混合したケイ素含有シッフ塩基誘導体を含むものであってもよい。
【００３４】
荷電制御剤は、従来から用いられている別な荷電制御剤を、更に含んでいてもよい。このような従来の荷電制御剤として例えば、下記化学式（１０）
【００３５】
【化１４】
（式（１０）中、−Ｒ６〜−Ｒ９は、同一または異なり、置換基を有していてもよいアルキル基、または置換基を有していてもよいアラルキル基；Ｅ−は、水酸基、アミノ基、アルキル基、カルボキシル基等を置換基として有していてもよい芳香環残基（ベンゼン環またはナフタレン環の残基）；ｖ及びｗは１〜２）で示される第４級アンモニウム塩、及び下記化学式（１１）
【００３７】
【化１５】
（式（１１）中、−Ｒ１０〜−Ｒ１３は、前記化学式（１０）の−Ｒ６〜−Ｒ９に同じ；ｘ、ｙ、ｚは、ｘ＝６ｙ＋２ｚの関係を有する数）で示される第４級アンモニウムモリブデン塩が挙げられる。
【００３９】
静電荷像現像用正帯電性トナーは、前記荷電制御剤、トナー用樹脂、着色剤の他、トナーの品質を向上させるために必要に応じて適宜使用される磁性材料や流動性改質剤やオフセット防止剤を含んでいてもよい。
【００４０】
トナー用樹脂として、市販の結着樹脂例えば、スチレン樹脂、スチレン−アクリル樹脂、スチレン−ブタジエン樹脂、スチレン−マレイン酸樹脂、スチレン−ビニルメチルエーテル樹脂、スチレン−メタアクリル酸エステル共重合体、ポリエステル樹脂、ポリプロピレン樹脂のような熱可塑性樹脂；フェノール樹脂、エポキシ樹脂のような熱硬化性樹脂が挙げられる。これらの樹脂を、単独で用いてもよく、複数種ブレンドして用いてもよい。
【００４１】
このトナー用樹脂を、減法混色によるフルカラー用トナー、またはオーバーヘッドプロジェクタ（ＯＨＰ）用トナーに混合して用いるためには、トナー用樹脂が、透明性を有すること、トナー像に色調障害を生じない程度のほぼ無色であること、荷電制御剤との相溶性が良好であること、適当な熱または圧力下で流動性を有すること、微粒化が可能であることが要求される。そのようなトナー用樹脂として、スチレン樹脂、アクリル樹脂、スチレン−アクリル樹脂、スチレン−メタアクリル酸エステル共重合体、ポリエステル樹脂が挙げられる。
【００４２】
着色剤として、例えば、染料、顔料を、単独で用いてもよく、複数種配合して用いてもよい。カラー用トナーのための着色剤として、例えば、キノフタロンイエロー、ハンザイエロー、イソインドリノンイエロー、ベンジジンイエロー、ペリノンオレジン、ペリノンレッド、ペリレンマルーン、ローダミン６Ｇレーキ、キナクリドンレッド、ローズベンガル、銅フタロシアニンブルー、銅フタロシアニングリーン、ジケトピロロピロール系顔料のような有機顔料；カーボンブラック、チタンホワイト、チタンイエロー、群青、コバルトブルー、べんがら、アルミニウム粉、ブロンズのような、無機顔料や金属粉；アゾ系染料、キノフタロン系染料、アントラキノン系染料、キサンテン系染料、トリフェニルメタン系染料、フタロシアニン系染料、インドフェノール系染料、インドアニリン系染料のような、油溶性染料や分散染料；ロジン、ロジン変性フェノール、ロジン変性マレイン酸のような樹脂により変性されたトリアリールメタン系染料；高級脂肪酸や樹脂などで加工された、染料や顔料が挙げられる。カラー用トナーには、これら着色剤を、単独で配合していてもよく、複数種配合していてもよい。フルカラー用の三原色トナーの調整に好適に使用できるのは、分光特性が良好な染料や顔料である。
【００４３】
また、有彩色のモノカラー用トナーのための着色剤として、同色系の顔料と染料、例えばローダミン系の顔料と染料、キノフタロン系の顔料と染料、フタロシアニン系の顔料と染料を適宜配合してもよい。
【００４４】
磁性材料として例えば、鉄、コバルト、フェライトで例示される強磁性材料製微粉体が挙げられる。流動性改質剤として例えば、シリカ、酸化アルミニウム、酸化チタンが挙げられる。オフセット防止剤として例えば、ワックス、低分子量のオレフィンワックスが挙げられる。
【００４５】
静電荷像現像用トナーは、以下のようにして製造されることが好ましい。荷電制御剤、トナー用樹脂、着色剤、及び必要に応じ磁性材料や流動性改質剤やオフセット防止剤を、ボールミルのような混合機により十分混合した後、その混合物を加熱ロール、ニーダー、エクストルーダーのような熱混練機を用いて溶融混練する。その混練物を冷却固化させた後、その固化物を粉砕及び分級することにより、粉砕法トナー粒子である平均粒径５〜２０μｍのトナーが得られる。
【００４６】
静電荷像現像用トナーは、次のようにしても製造できる。トナー用樹脂の溶液中に、荷電制御剤、着色剤、及び必要に応じ磁性材料等を分散させた後、噴霧乾燥することにより得る方法によりトナーが得られる。
【００４７】
また、静電荷像現像用トナーは、次のようにしても製造できる。トナー用樹脂を構成する重合性単量体に、荷電制御剤、着色剤、及び必要に応じ磁性材料等を混合して乳化懸濁液とした後、重合させ、所謂重合トナーを得る懸濁重合法により、重合法トナー粒子であるトナーが得られる。
【００４８】
この懸濁重合法は例えば、単量体、荷電制御剤、着色剤、及び必要に応じ磁性材料や流動性改質剤やオフセット防止剤と重合開始剤や架橋剤や離型剤のような添加剤とを均一に溶解または分散させて、単量体組成物とした後、この単量体組成物を、分散安定剤を含有する連続層中、例えば水相中に、適当な分散機を用いて分散させながら重合反応を行わせることにより、所望の粒径を有するトナーの粒子を得るというものである。
【００４９】
このような重合性単量体として、例えばスチレン、メチルスチレンのようなスチレン誘導体；アクリル酸メチル、アクリル酸エチル、メタアクリル酸エチル、メタアクリル酸ｎ−ブチルのような（メタ）アクリル酸エステル類；アクリルロニトリル、メタクリロニトリル、アクリルアミドのようなビニル系単量体が挙げられる。
【００５０】
分散安定剤として、界面活性剤、例えばドデシルベンゼンスルホン酸ナトリウム；有機分散剤例えばポリビニルアルコール、メチルセルロース、メチルヒドロキシプロピルセルロース；無機分散剤、例えば、リン酸カルシウムやリン酸マグネシウムやリン酸アルミニウムのようなリン酸多価金属塩微粉体、炭酸カルシウムや炭酸マグネシウムのような炭酸塩微粉体、メタ珪酸カルシウム、硫酸カルシウム、硫酸バリウム、水酸化カルシウム、水酸化アルミニウムが挙げられる。
【００５１】
重合開始剤として例えば、２，２’−アゾイソブチロニトリルやアゾビスブチロニトリルのようなアゾ系またはジアゾ系重合開始剤；ベンゾイルペルオキシドのような過酸化物系重合開始剤が挙げられる。
【００５２】
また、静電荷像現像用トナーは、次のようにしても製造できる。荷電制御剤を含む前記の粉砕法トナー粒子または重合法トナー粒子を母粒子とし、この母粒子の表面に、荷電制御剤の粒子のみからなる子粒子、または荷電制御剤分散性の樹脂に１０〜９０重量％の荷電制御剤が分散した粒子からなる子粒子を、付着させることにより、トナーが得られる。
【００５３】
子粒子を母粒子表面に付着させる方法として例えば、外添方法、またはハイブリダイゼーションシステムにより子粒子を母粒子に打ち込む方法が挙げられる。
【００５４】
荷電制御剤分散性の樹脂として、例えばスチレン樹脂、スチレン−アクリル樹脂、スチレン−ブタジエン樹脂、スチレン−マレイン樹脂、スチレン−ビニルメチルエーテル樹脂、スチレン−メタアクリル酸エステル共重合体、フェノール樹脂、エポキシ樹脂、パラフィンワックス、アクリル樹脂、ポリエステル系樹脂が挙げられる。これらの樹脂を、単独で用いてもよく、複数種ブレンドして用いてもよい。
【００５５】
荷電制御剤を含んだ粉砕法トナー粒子または重合法トナー粒子を母粒子とする例について示したが、荷電制御剤を含まない粉砕法トナー粒子または重合法トナー粒子を母粒子としてもよい。
【００５６】
前記トナーを用いた２成分現像剤は、このトナーとキャリアとを混合し調製したもので、２成分磁気ブラシ現像法等により現像する際に使用される。このキャリヤとして、例えば、粒径５０〜２００μｍ程度の鉄粉、ニッケル粉、マグネタイト粉、フェライト粉、ガラスビーズ、及びこれらの表面をアクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、スチレン−メタクリル酸エステル共重合体、シリコーン樹脂、ポリアミド樹脂、またはフッ化エチレン系樹脂でコーティングしたものが挙げられる。
【００５７】
本発明のトナーを用いた１成分現像剤は、このトナーの調製の際に、例えば鉄粉、ニッケル粉、フェライト粉のような強磁性材料の微粉体を適量添加分散させたもので、接触現像法、ジャンピング現像法等により現像する際に使用される。
【００５８】
また、本発明の荷電制御剤を静電粉体塗料に含有させて、塗料中の樹脂粉体の電荷を制御したり増強したりする場合、塗料中の樹脂としては、例えば、アクリル系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂のような熱可塑性樹脂；フェノール系樹脂、エポキシ系樹脂のような熱硬化性樹脂が挙げられる。これらの樹脂を、単独で用いてもよく、複数種ブレンドして用いてもよい。
【００５９】
【実施例】
以下に、本発明を適用する荷電制御剤に含まれているケイ素含有シッフ塩基誘導体として、誘導体例２及び９を合成した例を、合成例１及び２に示す。
【００６０】
（合成例１） 誘導体例２の合成
３，５−ジ−ｔ−ブチルサリチルアルデヒド２５．０ｇ（０．１０７ｍｏｌ）をエタノール２００ｍｌに溶解し、これに、エチレンジアミン３．２１ｇ（０．０５３ｍｏｌ）がエタノール５０ｍｌに溶解している溶液を加え混合後、水浴８０℃中で２時間撹拌した。その後、反応液を室温まで放冷し、析出した結晶を吸引濾過により濾取し、少量のエタノールで洗浄後、更に水１００ｍｌで洗浄した。これを８０℃で２４時間乾燥させると、淡黄色結晶のシッフ塩基が得られた［収量：２４．５ｇ 収率：９４．０％］。
【００６１】
このシッフ塩基について、Ｍ−８０００形 ＬＣ／３ＤＱＭＳシステム（株式会社日立製作所の商品名）を用いて液体クロマトグラフ−質量分析法（ＬＣ／ＭＳ）により測定した。その結果を図１に示す。図１のとおり、実測値ｍ／ｚが４９４であり、理論値４９２．７にＨ＋が付加した理論値４９３．７とほぼ一致しているので、所望のシッフ塩基であると同定された。
【００６２】
このシッフ塩基１０．０ｇ（０．０２０３ｍｏｌ）を脱水トルエン１００ｍｌに加えて完全に溶解させた。これに、四塩化ケイ素３．４５ｇ（０．０２０３ｍｏｌ）が脱水トルエン５０ｍｌに溶解した溶液を加えた。混合後、１時間３０分加熱還流すると、結晶が析出した。放冷後、析出した結晶を吸引濾過により濾取し、脱水トルエン２００ｍｌで洗浄し、８０℃で２４時間減圧乾燥させると、淡黄色結晶のケイ素含有シッフ塩基誘導体である誘導体例２が得られた［収量：７．８４ｇ 収率：６５．５％］。誘導体例２は、原子吸光分析法での測定結果によりケイ素を含有していることが確認されたことから、ケイ素含有シッフ塩基誘導体であることが支持される。
【００６３】
（合成例２） 誘導体例９の合成
３，５−ジ−ｔ−ブチルサリチルアルデヒド２５．０ｇ（０．１０７ｍｏｌ）をエタノール２００ｍｌに溶解し、これに、トリメチレンジアミン３．９３ｇ（０．０５３ｍｏｌ）がエタノール５０ｍｌに溶解している溶液を加え混合後、水浴８０℃中で２時間撹拌した。その後、反応液を室温まで放冷し、析出した結晶を吸引濾過により濾取別し、少量のエタノールで洗浄後、更に水１００ｍｌで洗浄した。これを８０℃で２４時間乾燥させると、淡黄色結晶のシッフ塩基が得られた［収量：２３．９ｇ 収率：８９．０％］。
【００６４】
このシッフ塩基１０．０ｇ（０．０１９７ｍｏｌ）を脱水トルエン１００ｍｌに加えて完全に溶解させた。これに、四塩化ケイ素３．３５ｇ（０．０１９７ｍｏｌ）が脱水トルエン５０ｍｌに溶解した溶液を加えた。混合後、１時間３０分加熱還流すると、結晶が析出した。放冷後、析出した結晶を吸引濾過により濾取し、脱水トルエン２００ｍｌで洗浄し、８０℃で２４時間減圧乾燥させると、淡黄色結晶のケイ素含有シッフ塩基誘導体である誘導体例９が得られた［収量：８．２０ｇ 収率：６８．９％］。
【００６５】
なお、合成例１〜２の誘導体例２及び９以外の前記化学式（４）で示されるケイ素含有シッフ塩基誘導体は、同様な合成方法で、サリチルアルデヒド誘導体とジアミン誘導体を縮合反応させ、前記化学式（１）で示されるシッフ塩基とし、これをケイ素付与剤と反応させて、得られた。これらの誘導体は、合成例１と同様な測定結果によりその構造が支持された。
【００６６】
以下に、得られたケイ素含有シッフ塩基誘導体を荷電制御剤として含んでいる静電荷像現像用トナーを調製し、このトナーを用いて記録紙に画像を形成させた例について実施例１〜５に示す。また、本発明を適用外の例について比較例１〜３に示す。
【００６７】
（実施例１）
スチレン−アクリル共重合樹脂（ＣＰＲ−６００Ｂ：三井化学社製の商品名）・・・１００重量部
低重合ポリプロピレン（ビスコール５５０−Ｐ：三洋化成社製の商品名）・・・３重量部
油溶性マゼンタ色染料（オイルピンク＃３１２：オリヱント化学工業社製の商品名）・・・５重量部
誘導体例２のケイ素含有シッフ塩基誘導体である荷電制御剤・・・１重量部
【００６８】
これらを配合し高速ミキサーで均一にプレミキシングした。次いで、エクストルーダーで溶融混練し、冷却後振動ミルで粗粉砕した。得られた粗砕物を分級機付きのエアージェットミルを用いて微粉砕して、粒径１０〜２０μｍのマゼンタトナーを得た。
【００６９】
得られたトナー５重量部に対して、鉄粉キャリアであるＴＥＦＶ２００／３００（パウダーテック：日本鉄粉社製の商品名）９５重量部を混合して現像剤を調整した。
【００７０】
この現像剤をポリ瓶中に５０ｇ計量し、回転数１００ｒｐｍのボールミルにより攪拌して現像剤を帯電させ、気温２０℃、相対湿度６０％の標準条件下で経時帯電量を測定した。攪拌時間と摩擦帯電量との相関を図２に示す。
【００７１】
さらに、気温５℃で相対湿度３０％の低温低湿の条件下、及び気温３５℃で相対湿度９０％の高温高湿の各条件下で同様にして初期ブローオフ帯電量を測定し、帯電環境安定性について調べた。その測定結果を表１に示す。
【００７２】
なお、帯電量の測定は、ブローオフ帯電量測定機（ＴＢ−２００：東芝ケミカル社製の商品名）により行った。
【００７３】
有機光導電体（ＯＰＣ）ドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、カブリがなく、細線再現性が良好で、しかも分光特性に優れ、重ね合わせによる混色に適した透明性のある、鮮明なマゼンタ色の画像が得られた。
【００７４】
（実施例２）
スチレン−アクリル共重合樹脂（ＣＰＲ−６００Ｂ：三井化学社製の商品名）・・・１００重量部
ハンザ系イエロー顔料（Ｃ．Ｉ．ピグメントイエロー９７）・・・５重量部
低重合ポリプロピレン（ビスコール５５０−Ｐ：三洋化成社製の商品名）・・・３重量部
誘導体例９のケイ素含有シッフ塩基誘導体である荷電制御剤・・・１重量部
【００７５】
これらの配合物を実施例１と同様に処理して、平均粒径１３μｍのイエロートナー、及び現像剤を調製し、実施例１と同様に測定した経時帯電量、及び帯電環境安定性についての結果をそれぞれ図２及び表１に示す。
【００７６】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、カブリがなく、細線再現性、帯電安定性及び持続性が良好で、しかも分光特性に優れ、重ね合わせによる混色に適した透明性のある、鮮明なイエローの画像が得られた。
【００７７】
（実施例３）
スチレンモノマー・・・８０重量部
ｎ−ブチルメタクリレートモノマー ・・・２０重量部
ハンザ系イエロー顔料（Ｃ．Ｉ．ピグメントイエロー９７）・・・５重量部
２，２’−アゾイソブチロニトリル・・・１．８重量部
誘導体例２のケイ素含有シッフ塩基誘導体である荷電制御剤・・・１重量部
【００７８】
これらの配合物を高速ミキサーで均一にプレミキシングして重合性単量体組成物を得た。
【００７９】
一方、濃度０．１モル 第三リン酸ナトリウム水溶液１００ｍｌを蒸留水６００ｍｌにより希釈した液に、撹拌しながら濃度１．０モル／ｌの塩化カルシウム水溶液１８．７ｍｌを徐々に加え、次いで濃度２０％のドデシルベンゼンスルホン酸ナトリウム水溶液０．１５ｇを加えて分散液を調製した。
【００８０】
この分散液を前記重合性単量体組成物に加えて、ＴＫ式ホモミキサー（特殊機化工社製の商品名）により高速撹拌しながら温度６５℃に昇温し、昇温後３０分間撹拌した後、更に、８０℃に昇温し、通常の撹拌機による回転数１００ｒｐｍの撹拌に切り換え、温度８０℃のまま６時間攪拌し、モノマーを重合させた。
【００８１】
重合終了後、反応混合物を冷却して固形物を濾取し、その濾取物を濃度５重量％の塩酸水溶液中に浸漬し、分散剤に含まれているリン酸カルシウムを分解した後、その固形物を洗浄液が中性となるまで水洗し、脱水、乾燥させると、平均粒径１３μｍのイエロートナーが得られた。
【００８２】
得られたトナー５重量部に対して、鉄粉キャリアであるＴＥＦＶ２００／３００（パウダーテック：日本鉄粉社製の商品名）９５重量部を混合して現像剤を調整した。実施例１と同様に測定した経時帯電量及び帯電環境安定性を、それぞれ図２及び表１に示す。
【００８３】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、カブリがなく、細線再現性が良好で、しかも分光特性に優れ、重ね合わせによる混色に適した透明性のある、鮮明なイエローの画像が得られた。
【００８４】
（実施例４）
スチレン−アクリル共重合樹脂（ＣＰＲ−６００Ｂ：三井化学社製の商品名）・・・１００重量部
低重合ポリプロピレン（ビスコール５５０−Ｐ：三洋化成社製の商品名：）・・・３重量部
油溶性マゼンタ色染料（オイルピンク＃３１２：オリヱント化学工業社製の商品名）・・・５重量部
【００８５】
これらの配合物を高速ミキサーで均一にプレミキシングした。次いで、エクストルーダーで溶融混練し、冷却後振動ミルで粗粉砕した。得られた粗砕物を分級機付きのエアージェットミルを用いて微粉砕して、粒径１０〜２０μｍのマゼンタトナーの母粒子を得た。
【００８６】
この母粒子１０８重量部の母粒子表面に、誘導体例９のケイ素含有シッフ塩基誘導体である荷電制御剤１重量部とする子粒子を外添し、トナーを得た。
【００８７】
このトナー５重量部に、鉄粉キャリアであるＴＥＦＶ２００／３００（パウダーテック：日本鉄粉社製の商品名）９５重量部を混合して現像剤を調整した。
【００８８】
この現像剤をポリ瓶中に計量し、回転数１００ｒｐｍのボールミルで撹拌して、現像剤を帯電させ経時帯電量を測定した。実施例１と同様に測定した経時帯電量、及び帯電環境安定性についての結果をそれぞれ図２及び表１に示す。
【００８９】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、カブリがなく、細線再現性、帯電安定性及び持続性が良好で、画像の濃度低下のない良質な画像が得られた。オフセット現象も全く観測されなかった。
【００９０】
（実施例５）
スチレン−アクリル共重合樹脂（ＣＰＲ−６００Ｂ：三井化学社製の商品名）・・・１００重量部
低重合ポリプロピレン（ビスコール５５０−Ｐ：三洋化成社製の商品名）・・・３重量部
油溶性マゼンタ色染料（オイルピンク＃３１２：オリヱント化学工業社製の商品名）・・・５重量部
荷電制御剤（ＢＯＮＴＲＯＮ Ｐ−５１：オリヱント化学工業社製の商品名）・・・０．５重量部
誘導体例２のケイ素含有シッフ塩基誘導体である荷電制御剤・・・０．５重量部
【００９１】
これらの配合物を実施例１と同様に処理して、平均粒径１３μｍのマゼンタトナー、及び現像剤を調製し、実施例１と同様に測定した経時帯電量及び帯電環境安定性についての結果をそれぞれ、図２及び表１に示す。
【００９２】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、カブリがなく、細線再現性、帯電安定性及び持続性が良好で、画像の濃度低下のない良質な画像が得られた。オフセット現象も全く観測されなかった。
【００９３】
（比較例１）
実施例１で用いた荷電制御剤を下記化学式の構造を有する比較誘導体例１に変え、実施例１と同様に測定した経時帯電量及び帯電量環境安定性についての結果をそれぞれ、図２及び表１に示す。
【００９４】
【化１６】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、帯電量や帯電の安定性に問題があった。また、この現像剤を用いて繰り返し実写したところ、画像の飛び散り、乱れ、及びカブリが認められ、荷電制御剤として満足できるものではなかった。
【００９６】
（比較例２）
実施例１で用いた荷電制御剤を下記化学式の構造を有する比較誘導体例２に変え、実施例１と同様に測定した経時帯電量及び帯電環境安定性についての結果をそれぞれ、図２及び表１に示す。
【００９７】
【化１７】
ＯＰＣドラムを有する市販の複写機により、この現像剤でトナーの画像を形成したところ、帯電量や帯電の安定性に問題があった。また、この現像剤を用いて繰り返し実写したところ、画像の飛び散り、乱れ、及びカブリが認められ、荷電制御剤として満足できるものではなかった。
【００９９】
（比較例３）
実施例４で得た母粒子に、荷電制御剤の子粒子を外添することなく、母粒子をトナーとしたこと以外は、実施例４と同様にして、経時帯電量を測定した結果を図２に示す。
【０１００】
【表１】
表１、及び図２から明らかなように、実施例１〜５のトナーは、帯電特性の経時安定性や温度湿度変化に対する環境安定性に優れ、帯電立上がり速度すなわち帯電量が飽和に達するまでの速度が速く、十分に正帯電しており、現像されたトナー像は品質が優れている。一方、比較例１〜３のトナーは安定性が悪く、帯電立上がり速度が遅い上に、帯電が不充分である。
【０１０２】
本発明の荷電制御剤は、シッフ塩基をケイ素化させたケイ素含有シッフ塩基誘導体を含んでおり、この制御剤を含むトナーはトナーの帯電量に関して、従来ののシッフ塩基からなる例えば比較誘導体例１からなる従来の荷電制御剤を含むトナーよりも、（ａ）帯電の立上がりが速く、（ｂ）帯電量が飽和に達した後の安定性に優れ、（ｃ）帯電量の飽和値が高いという、優れた効果を有している。
【０１０３】
【発明の効果】
以上、詳細に説明したように本発明のケイ素含有シッフ塩基誘導体は、シッフ塩基から簡易に合成できる。ケイ素含有シッフ塩基誘導体を含む荷電制御剤は、トナーを調製する際に添加される。この荷電制御剤は、耐熱性と、微粉砕性と、トナー用樹脂に対する親和性及び分散性とが優れ、また温度や湿度の変化に対する荷電制御特性の安定性、すなわち耐環境性が優れ、荷電制御特性の経時安定性すなわち保存安定性も優れている。更に荷電制御剤は、十分にトナーを正電荷に帯電させることができる。シッフ塩基とケイ素付与剤とを適切に選択して得たケイ素含有シッフ塩基誘導体を含む荷電制御剤は、幅広く種々の有彩色のトナーや無彩色のトナーのために添加して使用される。
【０１０４】
本発明の静電荷像現像用正帯電性トナーは、ケイ素含有シッフ塩基誘導体を含んでいるため、正帯電性が優れている。また、広範な温度域での優れた定着性及び非オフセット性を有している。更に、高温高湿や温度湿度変化に対する帯電特性の安定性、帯電特性の経時的安定性、トナーを繰返し使用する場合の帯電特性の安定性が優れ、帯電の立ち上がりが速い。
【０１０５】
このトナーは、電子写真システムにおいてトナー像を現像する際に用いられ、記録紙へ高解像度の画像を綺麗に形成させることができる。
【図面の簡単な説明】
【図１】本発明を適用する荷電制御剤に含まれるケイ素含有シッフ塩基誘導体の中間体であるシッフ塩基の一例のＬＣ／ＭＳの測定結果を示す図である。
【図２】本発明を適用する静電荷像現像用正帯電性トナーの攪拌時間とその帯電量との相関を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a charge control agent for electrophotography containing a silicon-containing Schiff base derivative, and a positively chargeable toner for developing an electrostatic image containing the charge control agent.
[0002]
[Prior art]
Electrophotographic systems used in copiers and printers develop electrostatic latent images with frictionally charged toner, transfer and fix them on recording paper, and copy and print images and characters Is.
[0003]
When the charge amount of the toner is small or non-uniform, the development of the latent image becomes unclear. If the rising speed of charging is slow, the copying and printing speed cannot be increased. Therefore, a positively or negatively chargeable charge control agent is added to the toner in advance in order to appropriately control or stabilize the charge amount of the toner or to increase the rising speed of the charge. Schiff base derivatives are known as charge control agents that cause the toner to exhibit these charging characteristics. For example, Patent Documents 1 and 2 describe Schiff base metal complexes, Patent Documents 3 and 4 refer to metal complexes of bissalicylaldehyde ethylenediimine and bissalicylaldehyde trimethylenediimine, and
[0004]
[Patent Document 1]
JP 59-78362 A
[Patent Document 2]
JP-A 63-206767
[Patent Document 3]
JP 61-147261 A
[Patent Document 4]
JP-A 61-149967
[Patent Document 5]
Japanese Patent Laid-Open No. 5-45932
[Patent Document 6]
JP-A-5-273788
[0005]
Accompanying higher performance such as improved resolution of printers and copiers, there is a demand for toners that are more excellent in charging characteristics, stability, and environmental resistance than conventional toners. Therefore, there has been a demand for a charge control agent that can exhibit more excellent charging characteristics and can be easily and efficiently produced.
[0006]
[Problems to be solved by the invention]
The present invention has been made to solve the above problems, and includes a charge control agent for electrophotography that exhibits sufficient triboelectric chargeability in a toner, and the charge control agent, and includes charging characteristics, stability over time, and environmental resistance. An object of the present invention is to provide a positively chargeable toner for developing an electrostatic image that has excellent properties, has a high charge rising speed, and has an excellent quality of a developed toner image.
[0007]
[Means for Solving the Problems]
The charge control agent of the present invention made to achieve the above object has the following chemical formula (1)
[0008]
[Formula 4]
[Chemical formula 5]
[0009]
This silicon-containing Schiff base derivative is preferably obtained by reacting the Schiff base represented by the chemical formula (1) with a silicon-imparting agent exemplified by silicon tetrahalide.
[0010]
When this silicon-containing Schiff base derivative is one in which one or two molar equivalents of the Schiff base are coordinated with one molar equivalent of a silicon atom, a charge control agent containing the same develops more excellent charging characteristics. .
[0011]
The silicon-containing Schiff base derivative has the following chemical formula (4)
[Chemical 6]
[0012]
The silicon-containing Schiff base derivative is more preferably one represented by p = q = 1 in the chemical formula (4).
[0013]
The silicon-containing Schiff base derivative exhibits excellent triboelectric charging properties, has a fast charge rising speed, and has high affinity with the resin and excellent dispersibility. Further, since it is not a complex coordinated with a metal such as a heavy metal, it is highly safe. Therefore, the charge control agent containing this silicon-containing Schiff base derivative is used by adding to the toner for developing an electrostatic image, and can sufficiently charge the toner to a positive charge.
[0014]
Since the silicon-containing Schiff base derivative is light in color, even if it is included in the color toner as a charge control agent, it does not affect the hue of the toner.
[0015]
The positively chargeable toner for developing an electrostatic image of the present invention contains the above charge control agent. This toner preferably contains 0.1 to 10 parts by weight of a charge control agent and 100 parts by weight of a toner resin. Further, a colorant may be included. The toner is more preferably one in which a charge control agent and a colorant are kneaded into a toner resin and added internally.
[0016]
The positively chargeable toner for developing an electrostatic charge image has 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, of a charge control agent on the surface of a base particle containing 100 parts by weight of a toner resin and a colorant. The child particle | grains to which it contains may adhere. The mother particle may contain a charge control agent. The child particles may contain a toner resin.
[0017]
The toner has a fast charge rising speed and exhibits excellent charging stability for a long time even when the temperature and humidity change.
[0018]
The toner charge control method of the present invention is such that the toner is positively charged by friction. The developed toner image is clear and excellent in quality with the toner charged while controlling the charge by this method.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the charge control agent and the positively chargeable toner for developing an electrostatic image according to the present invention will be described in detail below.
[0020]
The silicon-containing Schiff base derivative contained in the charge control agent is synthesized as follows. First, 1 equivalent each of aldehyde derivatives HO-A-CHO and OHC-B-OH, which are starting materials, and diamine derivative H2N- (CH2)n-NH2A Schiff base represented by the chemical formula (1) is synthesized by condensing 1 equivalent of (-A-, -B-, n is the same as above).
[0021]
More specifically, an example in which the aldehyde derivative is 3,5-di-t-butylsalicylaldehyde (5) / (7) and the diamine derivative is ethylenediamine (6) is shown in the following chemical reaction formula (i). like,
[Chemical 7]
[0022]
This Schiff base (8) is an intermediate of a silicon-containing Schiff base derivative. When the Schiff base (8) is reacted with tetrachlorosilane which is a silicon imparting agent in an organic solvent, as shown in the following chemical reaction formula (ii),
[Chemical 8]
[0023]
When this silicon-containing Schiff base derivative, a toner resin, and a colorant are kneaded as a charge control agent, a positively chargeable toner for developing an electrostatic image is obtained.
[0024]
In addition, although the example of the compound (9) was shown as a silicon-containing Schiff base derivative, in the silicon-containing Schiff base derivative represented by the chemical formula (4), the formula (2) constituting -A- and -B- Or a substituent -R of the naphthylene group of the above formula (3)1~ -R4Is a hydrogen atom; hydroxyl group; hydroxyalkyl group; carboxyl group; alkoxycarbonyl group; formyl group; halogen atom (eg, Cl, Br, I, F); alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group) Alkyl group having 1 to 18 carbon atoms such as butyl group and tert-butyl group); alkoxyl group (for example, alkoxyl group having 1 to 18 carbon atoms such as methoxy group, ethoxy group and isopropoxy group); acyl group ( For example, acetyl group, propionyl group, butyryl group, benzoyl group, etc.); alkenyl group (for example, allyl group -CH2CH = CH2, -C (CH3) = CH2); Nitro group; cyano group; an alicyclic group which may or may not have a substituent (for example, a cyclopropenyl group, a cyclobutyl group, a cyclohexyl group and a cycloheptyl group) A cycloalkyl group having 3 to 7 carbon atoms); an aralkyl group which may have a substituent and may not have a substituent (for example, benzyl group, α, α′-dimethylbenzyl group, etc.); Cl , An aryl group which may have a substituent such as a halogen atom exemplified by Br, I and F or an alkyl group having 1 to 18 carbon atoms, and which may not have a substituent (for example, a phenyl group) , Toluyl group, naphthyl group, etc.). Any position of a phenylene group or a naphthylene group may be sufficient.
[0025]
The silicon imparting agent may be a silicon compound such as tetrachlorosilane, other tetrahalogenated silanes, and silicon alkoxides. When the silicon-imparting agent is a silicon alkoxide, the obtained silicon-containing Schiff base derivative has a case where the central silicon is bonded to an alkoxy group derived from silicon alkoxide in addition to the Schiff base represented by the chemical formula (1). There is also.
[0026]
In the silicon-containing Schiff base derivative of formula (4), (Du) May take 1 to 3 valent cations or anions depending on the composition ratio of the Schiff base and silicon atoms. 1-3 cation is, for example, H+; Na+, K+An alkali metal cation such as: an ammonium ion; a cation derived from an organic amine such as an aliphatic primary ammonium ion, an aliphatic secondary ammonium ion, an aliphatic tertiary ammonium ion, or a quaternary organic ammonium ion. . In addition, the 1-3 valent anions include, for example, halide ions; organic acid anions such as sulfonate anions and carboxylate anions; fatty acid anions; organic anions; OH−, SO4 2-, NO3 −Is an inorganic anion.
[0027]
Derivative examples 1 to 24 are shown as more specific examples of such silicon-containing Schiff base derivatives. The compound (9) is derivative example 2.
[0028]
[Chemical 9]
Embedded image
Embedded image
Embedded image
Embedded image
The charge control agent may contain a single or plural kinds of silicon-containing Schiff base derivatives, or may contain a silicon-containing Schiff base derivative mixed with geometric isomers and optical isomers.
[0034]
The charge control agent may further contain another charge control agent conventionally used. As such a conventional charge control agent, for example, the following chemical formula (10)
[0035]
Embedded image
(In the formula (10), -R6~ -R9Are the same or different, optionally substituted alkyl groups, or optionally substituted aralkyl groups; E- is a hydroxyl group, amino group, alkyl group, carboxyl group or the like as a substituent. A quaternary ammonium salt represented by the aromatic ring residue (residue of benzene ring or naphthalene ring); v and w are 1 to 2), and the following chemical formula (11)
[0037]
Embedded image
(In the formula (11), -R10~ -R13Is —R in the chemical formula (10)6~ -R9And x, y, z are quaternary ammonium molybdenum salts represented by the following formula: x = 6y + 2z.
[0039]
In addition to the charge control agent, the toner resin, and the colorant, the positively chargeable toner for electrostatic image development includes a magnetic material, a fluidity modifier, and the like that are appropriately used as necessary to improve the quality of the toner. An offset inhibitor may be included.
[0040]
Commercially available binder resins such as styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylate copolymer, polyester resin And thermoplastic resins such as polypropylene resins; thermosetting resins such as phenol resins and epoxy resins. These resins may be used alone or as a blend of a plurality of types.
[0041]
In order to use this toner resin mixed with subtractive color full-color toner or overhead projector (OHP) toner, the toner resin has transparency and does not cause a color tone failure in the toner image. Are almost colorless, have good compatibility with the charge control agent, have fluidity under appropriate heat or pressure, and can be atomized. Examples of such toner resins include styrene resins, acrylic resins, styrene-acrylic resins, styrene-methacrylic acid ester copolymers, and polyester resins.
[0042]
As the colorant, for example, dyes and pigments may be used alone or in combination of two or more. Examples of colorants for color toners include quinophthalone yellow, hansa yellow, isoindolinone yellow, benzidine yellow, perinone oleidine, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, rose bengal, copper phthalocyanine blue, copper phthalocyanine green Organic pigments such as diketopyrrolopyrrole pigments; carbon black, titanium white, titanium yellow, ultramarine, cobalt blue, brown, aluminum powder, bronze, inorganic pigments and metal powders; azo dyes, quinophthalone dyes Oil-soluble dyes and disperse dyes such as anthraquinone dyes, xanthene dyes, triphenylmethane dyes, phthalocyanine dyes, indophenol dyes, indoaniline dyes; , Rosin-modified phenol, triarylmethane dyes modified with a resin as rosin-modified maleic acid; was processed like in higher fatty acid and resins, dyes and pigments. In the color toner, these colorants may be blended singly or in combination. Dyes and pigments having good spectral characteristics can be suitably used for the preparation of full-color three primary color toners.
[0043]
Also, as a colorant for a chromatic monochromatic toner, the same color pigments and dyes, for example, rhodamine pigments and dyes, quinophthalone pigments and dyes, phthalocyanine pigments and dyes may be appropriately blended. Good.
[0044]
Examples of the magnetic material include fine powder made of a ferromagnetic material exemplified by iron, cobalt, and ferrite. Examples of the fluidity modifier include silica, aluminum oxide, and titanium oxide. Examples of the offset preventive agent include wax and low molecular weight olefin wax.
[0045]
The toner for developing an electrostatic image is preferably produced as follows. The charge control agent, toner resin, colorant, and magnetic materials, fluidity modifiers, and anti-offset agents, if necessary, are thoroughly mixed using a mixer such as a ball mill, and the mixture is then heated to a roll, kneader, or extensible. Melt and knead using a heat kneader such as a ruder. After the kneaded product is cooled and solidified, the solidified product is pulverized and classified to obtain toner having an average particle diameter of 5 to 20 μm, which is pulverized toner particles.
[0046]
The electrostatic image developing toner can also be produced as follows. A toner can be obtained by a method obtained by dispersing a charge control agent, a colorant, and, if necessary, a magnetic material in a toner resin solution, and then spray drying.
[0047]
The electrostatic image developing toner can also be produced as follows. The polymerizable monomer constituting the toner resin is mixed with a charge control agent, a colorant, and, if necessary, a magnetic material to obtain an emulsion suspension and then polymerized to obtain a so-called polymerized toner. By a legal method, a toner which is a polymerization method toner particle is obtained.
[0048]
This suspension polymerization method includes, for example, addition of monomers, charge control agents, colorants, and magnetic materials, fluidity modifiers, offset inhibitors, polymerization initiators, crosslinking agents, and release agents as necessary. After uniformly dissolving or dispersing the agent into a monomer composition, the monomer composition is placed in a continuous layer containing a dispersion stabilizer, for example, in an aqueous phase, using a suitable disperser. The toner particles having a desired particle diameter are obtained by carrying out the polymerization reaction while being dispersed.
[0049]
Examples of such polymerizable monomers include styrene derivatives such as styrene and methylstyrene; (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, ethyl methacrylate, and n-butyl methacrylate. A vinyl monomer such as acrylonitrile, methacrylonitrile, acrylamide;
[0050]
As a dispersion stabilizer, a surfactant such as sodium dodecylbenzenesulfonate; an organic dispersant such as polyvinyl alcohol, methylcellulose, methylhydroxypropylcellulose; an inorganic dispersant such as phosphoric acid such as calcium phosphate, magnesium phosphate, and aluminum phosphate Polyvalent metal salt fine powders, carbonate fine powders such as calcium carbonate and magnesium carbonate, calcium metasilicate, calcium sulfate, barium sulfate, calcium hydroxide, and aluminum hydroxide.
[0051]
Examples of the polymerization initiator include azo or diazo polymerization initiators such as 2,2'-azoisobutyronitrile and azobisbutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide.
[0052]
The electrostatic image developing toner can also be produced as follows. The above pulverized toner particles or polymerized toner particles containing a charge control agent are used as mother particles, and on the surface of the mother particles, child particles consisting only of charge control agent particles, or 10 to 10 charge control agent-dispersible resins. A toner is obtained by adhering child particles composed of particles in which 90% by weight of the charge control agent is dispersed.
[0053]
Examples of the method of attaching the child particles to the surface of the mother particle include an external addition method and a method of driving the child particle into the mother particle by a hybridization system.
[0054]
Examples of the charge control agent-dispersible resin include styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, phenol resin, and epoxy resin. , Paraffin wax, acrylic resin, and polyester resin. These resins may be used alone or as a blend of a plurality of types.
[0055]
Although an example in which pulverized toner particles or polymerized toner particles containing a charge control agent are used as mother particles is shown, pulverized toner particles or polymerized toner particles not containing a charge control agent may be used as mother particles.
[0056]
The two-component developer using the toner is prepared by mixing the toner and a carrier, and is used when developing by a two-component magnetic brush developing method or the like. Examples of the carrier include iron powder, nickel powder, magnetite powder, ferrite powder, glass beads having a particle size of about 50 to 200 μm, and acrylate ester copolymer, styrene-acrylate ester copolymer, styrene. -Those coated with a methacrylic acid ester copolymer, a silicone resin, a polyamide resin, or a fluorinated ethylene-based resin.
[0057]
The one-component developer using the toner of the present invention is obtained by adding and dispersing an appropriate amount of fine powder of a ferromagnetic material such as iron powder, nickel powder and ferrite powder at the time of preparation of the toner. It is used when developing by the method, jumping development method or the like.
[0058]
Further, when the electrostatic powder paint contains the charge control agent of the present invention to control or enhance the charge of the resin powder in the paint, as the resin in the paint, for example, an acrylic resin, Examples thereof include thermoplastic resins such as polyolefin resins, polyester resins, and polyamide resins; thermosetting resins such as phenol resins and epoxy resins. These resins may be used alone or as a blend of a plurality of types.
[0059]
【Example】
Examples of synthesizing derivative examples 2 and 9 as silicon-containing Schiff base derivatives contained in the charge control agent to which the present invention is applied are shown in Synthesis Examples 1 and 2.
[0060]
(Synthesis Example 1) Synthesis of Derivative Example 2
3,5-di-t-butylsalicylaldehyde 25.0 g (0.107 mol) is dissolved in 200 ml of ethanol, and a solution in which 3.21 g (0.053 mol) of ethylenediamine is dissolved in 50 ml of ethanol is added and mixed. Thereafter, the mixture was stirred in a water bath at 80 ° C. for 2 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and the precipitated crystals were collected by suction filtration, washed with a small amount of ethanol, and further washed with 100 ml of water. When this was dried at 80 ° C. for 24 hours, a Schiff base of pale yellow crystals was obtained [yield: 24.5 g, yield: 94.0%].
[0061]
About this Schiff base, it measured by the liquid chromatograph-mass spectrometry (LC / MS) using the M-8000 type LC / 3DQMS system (trade name of Hitachi, Ltd.). The result is shown in FIG. As shown in FIG. 1, the actually measured value m / z is 494, and the theoretical value 492.7 is H.+Is almost the same as the theoretical value 493.7 added, so that it was identified as the desired Schiff base.
[0062]
10.0 g (0.0203 mol) of this Schiff base was added to 100 ml of dehydrated toluene and completely dissolved. To this was added a solution in which 3.45 g (0.0203 mol) of silicon tetrachloride was dissolved in 50 ml of dehydrated toluene. After mixing, the mixture was heated to reflux for 1
[0063]
(Synthesis Example 2) Synthesis of Derivative Example 9
A solution in which 25.0 g (0.107 mol) of 3,5-di-t-butylsalicylaldehyde was dissolved in 200 ml of ethanol, and 3.93 g (0.053 mol) of trimethylenediamine was dissolved in 50 ml of ethanol was added thereto. After addition and mixing, the mixture was stirred in a water bath 80 ° C. for 2 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and the precipitated crystals were collected by suction filtration, washed with a small amount of ethanol, and further washed with 100 ml of water. When this was dried at 80 ° C. for 24 hours, a Schiff base of pale yellow crystals was obtained [yield: 23.9 g, yield: 89.0%].
[0064]
10.0 g (0.0197 mol) of this Schiff base was added to 100 ml of dehydrated toluene and completely dissolved. To this was added a solution in which 3.35 g (0.0197 mol) of silicon tetrachloride was dissolved in 50 ml of dehydrated toluene. After mixing, the mixture was heated to reflux for 1
[0065]
In addition, the silicon-containing Schiff base derivative represented by the chemical formula (4) other than the derivative examples 2 and 9 of the synthesis examples 1 and 2 is subjected to a condensation reaction of a salicylaldehyde derivative and a diamine derivative by the same synthesis method, and the chemical formula ( The Schiff base represented by 1) was obtained by reacting with a silicon-imparting agent. The structure of these derivatives was supported by the same measurement results as in Synthesis Example 1.
[0066]
Examples 1 to 5 will be described below with respect to examples in which a toner for developing an electrostatic charge image containing the obtained silicon-containing Schiff base derivative as a charge control agent was prepared and an image was formed on a recording paper using this toner. Show. Comparative examples 1 to 3 show examples where the present invention is not applied.
[0067]
Example 1
Styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals) ... 100 parts by weight
Low-polymerized polypropylene (Biscol 550-P: trade name manufactured by Sanyo Kasei) 3 parts by weight
Oil-soluble magenta dye (oil pink # 312: trade name manufactured by Orient Chemical Co., Ltd.) ... 5 parts by weight
Charge control agent which is silicon-containing Schiff base derivative of derivative example 2 ... 1 part by weight
[0068]
These were mixed and premixed uniformly with a high-speed mixer. Next, the mixture was melt-kneaded with an extruder, and after cooling, coarsely pulverized with a vibration mill. The resulting coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain a magenta toner having a particle size of 10 to 20 μm.
[0069]
To 5 parts by weight of the obtained toner, 95 parts by weight of TEFV200 / 300 (Powder Tech: trade name of Nippon Iron Powder Co., Ltd.) as an iron powder carrier was mixed to prepare a developer.
[0070]
50 g of this developer was weighed in a plastic bottle and stirred with a ball mill at a rotation speed of 100 rpm to charge the developer, and the amount of electrification with time was measured under standard conditions of an air temperature of 20 ° C. and a relative humidity of 60%. The correlation between the stirring time and the triboelectric charge amount is shown in FIG.
[0071]
In addition, the initial blow-off charge amount was measured in the same manner under conditions of low temperature and low humidity with a relative humidity of 30% at a temperature of 5 ° C, and high temperature and high humidity with a relative humidity of 90% at a temperature of 35 ° C. Investigated about. The measurement results are shown in Table 1.
[0072]
The charge amount was measured using a blow-off charge amount measuring device (TB-200: trade name manufactured by Toshiba Chemical Corporation).
[0073]
When a toner image was formed with this developer using a commercially available copying machine having an organic photoconductor (OPC) drum, there was no fogging, fine line reproducibility was excellent, and the spectral characteristics were excellent. A clear, clear, magenta image with suitable transparency was obtained.
[0074]
(Example 2)
Styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals) ... 100 parts by weight
Hansa yellow pigment (CI Pigment Yellow 97) 5 parts by weight
Low-polymerized polypropylene (Biscol 550-P: trade name manufactured by Sanyo Kasei Co., Ltd.) 3 parts by weight
Charge control agent which is silicon-containing Schiff base derivative of derivative example 9 1 part by weight
[0075]
These blends were processed in the same manner as in Example 1 to prepare yellow toner and a developer having an average particle diameter of 13 μm, and the results of the time-dependent charging amount and charging environment stability measured in the same manner as in Example 1. Are shown in FIG. 2 and Table 1, respectively.
[0076]
When a toner image was formed with this developer using a commercially available copying machine having an OPC drum, there was no fogging, fine line reproducibility, charging stability and sustainability were excellent, and the spectral characteristics were excellent. A clear, clear yellow image suitable for the above was obtained.
[0077]
(Example 3)
Styrene monomer: 80 parts by weight
n-Butyl methacrylate monomer: 20 parts by weight
Hansa yellow pigment (CI Pigment Yellow 97) 5 parts by weight
2,2'-azoisobutyronitrile ... 1.8 parts by weight
Charge control agent which is silicon-containing Schiff base derivative of derivative example 2 ... 1 part by weight
[0078]
These blends were uniformly premixed with a high-speed mixer to obtain a polymerizable monomer composition.
[0079]
On the other hand, 18.7 ml of a 1.0 mol / l aqueous solution of calcium chloride was gradually added to a solution obtained by diluting 100 ml of a 0.1 mol aqueous solution of sodium triphosphate with 600 ml of distilled water, followed by 20% concentration. A dispersion was prepared by adding 0.15 g of an aqueous sodium dodecylbenzenesulfonate solution.
[0080]
This dispersion was added to the polymerizable monomer composition, and the temperature was raised to 65 ° C. while stirring at high speed with a TK homomixer (trade name, manufactured by Tokki Kako Co., Ltd.). Thereafter, the temperature was further raised to 80 ° C., switching to stirring at a rotation speed of 100 rpm using a normal stirrer, and stirring was continued for 6 hours while maintaining the temperature at 80 ° C. to polymerize the monomer.
[0081]
After completion of the polymerization, the reaction mixture is cooled and the solid is collected by filtration. The filtered product is immersed in an aqueous hydrochloric acid solution having a concentration of 5% by weight to decompose the calcium phosphate contained in the dispersant. Was washed with water until the washing solution became neutral, dehydrated and dried to obtain a yellow toner having an average particle size of 13 μm.
[0082]
To 5 parts by weight of the obtained toner, 95 parts by weight of TEFV200 / 300 (Powder Tech: trade name of Nippon Iron Powder Co., Ltd.) as an iron powder carrier was mixed to prepare a developer. FIG. 2 and Table 1 show the time-dependent charge amount and charging environment stability measured in the same manner as in Example 1.
[0083]
When a toner image was formed with this developer using a commercially available copying machine having an OPC drum, there was no fog, good fine line reproducibility, excellent spectral characteristics, and transparency suitable for color mixing by superposition. A clear yellow image was obtained.
[0084]
Example 4
Styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals) ... 100 parts by weight
Low-polymerized polypropylene (Biscol 550-P: trade name manufactured by Sanyo Chemical Co., Ltd.) 3 parts by weight
Oil-soluble magenta dye (oil pink # 312: trade name manufactured by Orient Chemical Co., Ltd.) ... 5 parts by weight
[0085]
These formulations were uniformly premixed with a high speed mixer. Next, the mixture was melt-kneaded with an extruder, and after cooling, coarsely pulverized with a vibration mill. The obtained coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain magenta toner mother particles having a particle size of 10 to 20 μm.
[0086]
To the surface of the mother particle of 108 parts by weight of the mother particle, a child particle having 1 part by weight of the charge control agent, which is a silicon-containing Schiff base derivative of derivative example 9, was externally added to obtain a toner.
[0087]
To 5 parts by weight of this toner, 95 parts by weight of
[0088]
The developer was weighed into a plastic bottle and stirred with a ball mill with a rotation speed of 100 rpm to charge the developer and measure the amount of charge with time. FIG. 2 and Table 1 show the results of charging with time and charging environment stability measured in the same manner as in Example 1.
[0089]
When a toner image was formed with this developer using a commercial copying machine having an OPC drum, a good image without fogging, fine line reproducibility, charging stability and sustainability, and no image density reduction was obtained. Obtained. No offset phenomenon was observed at all.
[0090]
(Example 5)
Styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals) ... 100 parts by weight
Low-polymerized polypropylene (Biscol 550-P: trade name manufactured by Sanyo Kasei Co., Ltd.) 3 parts by weight
Oil-soluble magenta dye (oil pink # 312: trade name manufactured by Orient Chemical Co., Ltd.) ... 5 parts by weight
Charge control agent (BONTRON P-51: trade name manufactured by Orient Chemical Industry Co., Ltd.) 0.5 parts by weight
Charge control agent which is silicon-containing Schiff base derivative of derivative example 2 0.5 part by weight
[0091]
These blends were processed in the same manner as in Example 1 to prepare magenta toners and developers having an average particle size of 13 μm, and the results of the time-dependent charge amount and charging environment stability measured in the same manner as in Example 1 were obtained. They are shown in FIG. 2 and Table 1, respectively.
[0092]
When a toner image was formed with this developer using a commercial copying machine having an OPC drum, a good image without fogging, fine line reproducibility, charging stability and sustainability, and no image density reduction was obtained. Obtained. No offset phenomenon was observed at all.
[0093]
(Comparative Example 1)
The charge control agent used in Example 1 was changed to Comparative Derivative Example 1 having the structure of the following chemical formula, and the results of the time-dependent charge amount and charge amount environment stability measured in the same manner as in Example 1 were shown in FIG. It is shown in 1.
[0094]
Embedded image
When a toner image was formed with this developer using a commercially available copying machine having an OPC drum, there was a problem in charge amount and charging stability. Further, when this developer was repeatedly used for actual photography, the image was scattered, disturbed, and fogged, and was not satisfactory as a charge control agent.
[0096]
(Comparative Example 2)
The charge control agent used in Example 1 was changed to Comparative Derivative Example 2 having the structure of the following chemical formula, and the results of the charge over time and charging environment stability measured in the same manner as in Example 1 were shown in FIG. 2 and Table 1, respectively. Shown in
[0097]
Embedded image
When a toner image was formed with this developer using a commercially available copying machine having an OPC drum, there was a problem in charge amount and charging stability. Further, when this developer was repeatedly used for actual photography, the image was scattered, disturbed, and fogged, and was not satisfactory as a charge control agent.
[0099]
(Comparative Example 3)
The results of measuring the amount of electrification with time in the same manner as in Example 4 except that the mother particles were used as toners without adding the child particles of the charge control agent to the mother particles obtained in Example 4 are shown in FIG. It is shown in 2.
[0100]
[Table 1]
As is clear from Table 1 and FIG. 2, the toners of Examples 1 to 5 are excellent in charging characteristics over time and environmental stability against changes in temperature and humidity, and until the charge rising speed, that is, the charge amount reaches saturation. The speed is fast and it is sufficiently positively charged, and the developed toner image is excellent in quality. On the other hand, the toners of Comparative Examples 1 to 3 have poor stability, the charge rising speed is slow, and charging is insufficient.
[0102]
The charge control agent of the present invention contains a silicon-containing Schiff base derivative in which a Schiff base is siliconized, and the toner containing this control agent is composed of a conventional Schiff base, for example, with respect to the charge amount of the toner. Compared to a conventional toner containing a charge control agent comprising: (a) the rise of charge is faster, (b) the charge amount is more stable after saturation, and (c) the charge amount has a higher saturation value. , Has an excellent effect.
[0103]
【The invention's effect】
As described above in detail, the silicon-containing Schiff base derivative of the present invention can be easily synthesized from the Schiff base. A charge control agent containing a silicon-containing Schiff base derivative is added when the toner is prepared. This charge control agent has excellent heat resistance, fine grindability, affinity and dispersibility for the resin for toner, and stability of charge control characteristics with respect to changes in temperature and humidity, that is, excellent environmental resistance. The control characteristics are stable over time, that is, storage stability is also excellent. Furthermore, the charge control agent can sufficiently charge the toner to a positive charge. A charge control agent containing a silicon-containing Schiff base derivative obtained by appropriately selecting a Schiff base and a silicon-providing agent is added and used for a wide variety of chromatic and achromatic toners.
[0104]
The positively chargeable toner for developing an electrostatic charge image of the present invention contains a silicon-containing Schiff base derivative and thus has a positive chargeability. In addition, it has excellent fixing properties and non-offset properties in a wide temperature range. Furthermore, the stability of the charging characteristics with respect to high temperature and high humidity and changes in temperature and humidity, the stability over time of the charging characteristics, and the stability of the charging characteristics when the toner is used repeatedly are excellent, and the rise of charging is quick.
[0105]
This toner is used when developing a toner image in an electrophotographic system, and a high-resolution image can be clearly formed on a recording paper.
[Brief description of the drawings]
FIG. 1 is a graph showing LC / MS measurement results of an example of a Schiff base that is an intermediate of a silicon-containing Schiff base derivative contained in a charge control agent to which the present invention is applied.
FIG. 2 is a diagram showing a correlation between the stirring time of the positively chargeable toner for developing an electrostatic image to which the present invention is applied and the charge amount thereof.
Claims (8)
ｎは２または３）
で表されるシッフ塩基と、それに配位しているケイ素原子とを含有しているケイ素含有シッフ塩基誘導体が、含まれていることを特徴とする荷電制御剤。The following chemical formula (1)
n is 2 or 3)
And a silicon-containing Schiff base derivative containing a silicon base coordinated with the Schiff base.
ｐは１〜４、
ｑは１〜４、
（−Ｏ−Ｒ５）ｒは、−Ｒ５が炭素数１〜１８のアルキル基、ｒが０〜３、
ｓは２−〜２＋、
ｔは０〜２、
（Ｄｕ）は１〜３価のカチオン、または１〜３価のアニオン）
で示されるものであることを特徴とする請求項１に記載の荷電制御剤。The silicon-containing Schiff base derivative has the following chemical formula (4)
p is 1-4,
q is 1 to 4,
(—O—R 5 ) r is a group in which —R 5 is an alkyl group having 1 to 18 carbon atoms, r is 0 to 3,
s is 2- to 2+,
t is 0-2,
(D u ) is a 1 to 3 valent cation or 1 to 3 valent anion)
It is shown by these, The charge control agent of Claim 1 characterized by the above-mentioned.
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