JP3696925B2 - Image forming method - Google Patents

Description

（ａ、ｂ：０〜４までの整数であり、且つａ＋ｂ＝４、
Ｒ１、Ｒ２：炭素数が１〜４０までの整数を有する有機基で、Ｒ１とＲ２との炭素数差が３以上、
ｍ、ｎ：０〜２５までの整数であり、ｍとｎが同時に０になることはない）
【００２７】
＜離型剤の構造式２＞

（ａ、ｂ：０〜３までの整数であり、且つ１≦ａ＋ｂ≦３、
Ｒ１、Ｒ２：炭素数が１〜４０までの整数を有する有機基で、Ｒ１とＲ２との炭素数差が３以上、
Ｒ３：水素原子、炭素数が１以上の有機基。ただし、ａ＋ｂ＝２のとき、Ｒ３のどちらか一方は、炭素数が１以上の有機基、
ｋ：１〜３までの整数、
ｍ、ｎ：０〜２５までの整数であり、ｍとｎが同時に０になることはない）
【００２８】
＜離型剤の構造式３＞

（ａ、ｂ：０〜４までの整数であり、且つａ＋ｂ＝４、ｂ≠０、
Ｒ１：炭素数が１〜４０までの整数を有する有機基、
ｍ、ｎ：０〜２５までの整数であり、ｍとｎが同時に０になることはない）
【００２９】
＜離型剤の構造式４＞

（Ｒ１、Ｒ３は炭素数６〜３２を有する有機基であり、Ｒ１とＲ３は同じものであっても、異なるものであってもよい。Ｒ２は炭素数１〜２０を有する有機基を示す）
【００３０】
＜離型剤の構造式５＞

（Ｒ１、Ｒ３：炭素数６〜３２を有する有機基であり、Ｒ１とＲ３は同じものであってもなくてもよい、
Ｒ２：−ＣＨ₂ＣＨ₂ＯＣ₆Ｈ₄ＯＣＨ₂ＣＨ₂−、
或は−(ＣＨ(ＣＨ₃)ＣＨ₂Ｏ)−Ｃ₆Ｈ₄Ｃ(ＣＨ₃)₂Ｃ₆Ｈ₄−(ＯＣＨ₂ＣＨＣＨ₃)_n−
これらの変性ビスフェノール骨格を有するもの、
或は−(ＣＨ₂ＣＨ₂)_n−であり、
ｎは１〜１０の整数を示す）
【００３１】
より具体的には、下記離型剤が挙げられるが、これに限定されるものではない。
【００３２】
離型剤１
ＣＨ₃(ＣＨ₂)₂₀ＣＯＯ(ＣＨ₂)₂₁ＣＨ₃
【００３３】
離型剤２
ＣＨ₃(ＣＨ₂)₁₆ＣＯＯ(ＣＨ₂)₂₁ＣＨ₃
【００３４】
離型剤３
ＣＨ₃(ＣＨ₂)₃₉ＣＯＯ(ＣＨ₂)₁₇ＣＨ₃
【００３５】
離型剤４
ＣＨ₃(ＣＨ₂)₂₀ＣＯＯ(ＣＨ₂)₁₇ＣＨ₃
【００３６】
離型剤５

【００３７】
離型剤６

【００３８】
離型剤７

【００３９】
離型剤８

【００４０】
離型剤９

【００４１】
離型剤１０

【００４２】
離型剤１１

【００４３】
離型剤１２

【００４４】
本発明において、上記の様な離型剤の分子量分布はＧＰＣによって、次に挙げる条件で測定される。
・装置：ＧＰＣ−１５０Ｃ（ウォーターズ社製）
・カラム：ＧＭＨ−ＨＴ３０ｃｍ２連（東ソー社製）
・温度：１３５℃
・溶媒：ｏ−ジクロロベンゼン（０．１％アイオノール添加）
・流速：１．０ｍｌ／ｍｉｎ
・試料：０．１５％の試料を０．４ｍｌ注入
以上の条件で分子量分布を測定する。又、試料の分子量算出にあたっては、単分散ポリスチレン標準試料により作成した分子量校正曲線を算出する。更に、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式で、ポリスチレン換算することによって算出される。
【００４５】
本発明で用いられる上記の様な離型剤の重量平均分子量（Ｍｗ）は、３５０以上４，０００以下、数平均分子量（Ｍｎ）は、２００以上４，０００以下であることが好ましく、より好ましくは、Ｍｗが４００以上３，５００以下、且つＭｎが２５０以上３，５００以下であることが望まれる。Ｍｗが３５０未満、Ｍｎが２００未満の場合には、トナーの耐ブロッキング性が著しく悪化して、好ましくない。又、Ｍｗが４，０００を、Ｍｎが４，０００を超える場合には、離型剤自体の結晶性が発現し、ＯＨＴ画像等の透明性が著しく悪化する為、好ましくない。
【００４６】
本発明で用いられる上記した様な離型剤の融点としては、好ましくは、３０〜１５０℃、より好ましくは５０〜９０℃の範囲である。融点が３０℃より低い場合は、トナーの耐ブロッキング性、多数枚の複写時でのスリーブ汚染抑制、感光体の汚染防止性が低下し易く、好ましくない。又、融点が１５０℃を超える場合は、粉砕法によるトナーの製法においてはバインダー樹脂との均一混合に過大のエネルギーが必要になり、他方、重合法によるトナーの製法においても、高沸点溶剤の利用や、高圧下での耐圧反応容器が必要になり装置が極めて複雑になり好ましくない。
【００４７】
又、本発明で使用することができる静電荷像現像用トナーに用いられる離型剤の溶解度パラメーター（ＳＰ）値は、原子団の化成性を利用したＦｅｄｏｒｓの方法［Ｐｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，１４（２）１４７（１９７４）］を用いて算出される。この様な方法で得られる本発明で使用される離型剤のＳＰ値は、７．６〜９．７の範囲であることが好ましい。ＳＰ値が７．６未満の値を示す離型剤は、用いるバインダー樹脂との相溶性が乏しく、結果的にバインダー樹脂中への良好な分散が得られにくく、多数枚複写時において離型剤の現像スリーブへの付着が生じ易く、トナーの帯電量が変化し易くなる為、好ましくない。更に、地カブリやトナー補給時の濃度変動等も起こし易い。本発明において、ＳＰ値が９．７を超える離型剤を用いた場合には、トナーを長期保存した際にトナー同士のブロッキングが発生し易い。更に、バインダー樹脂との相溶性がよすぎる為、定着時において定着部材とトナーの結着樹脂層間に十分な離型性層が形成しにくく、オフセット現象を起こし易い為、好ましくない。
【００４８】
本発明に使用される離型剤の溶融粘度は、ＨＡＡＫＥ社製ＶＰ−５００にて、コーンプレート型ローター（ＰＫ−１）を用い、１３５℃にて測定する方法が挙げられる。１３５℃における離型剤の溶融粘度は、好ましくは１〜３００ｃＰｓ、更に好ましくは３〜５０ｃＰｓの範囲とする。１ｃＰｓより低い溶融粘度を有する場合は、非磁性一成分現像方式で、ブレード等によりスリーブにトナー層を薄層コーティングする際、機械的なズリ力によりスリーブ汚染を招き易い。又、二成分現像方法においてもキャリアを用いてトナーを現像する際において、トナーとキャリア間のズリ力によりダメージを生じ易く、外添剤の埋没、トナー破砕が生じ易い。３００ｃＰｓを超える溶融粘度を有する場合には、重合方法を用いてトナーを製造する際、分散質の粘度が高すぎ、均一な粒径を有する微小粒径のトナーを得ることが容易でなく、粒度分布の広いトナーとなり易い。
【００４９】
又、本発明で使用する離型剤の硬度測定には、例えば、島津ダイナミック超微小硬度計（ＤＵＨ−２００）を用いる測定方法等が挙げられる。測定条件としては、ビッカース圧子を用い、０．５ｇ荷重下で、９．６７ｍｇ／秒の負荷速度にて１０μｍ変位させた後、１２秒保持させたサンプル上に付いた打痕を解析することによって、ビッカース硬度を求める。サンプルには、直径２０ｍｍφの金型を用いて予め溶融したサンプルを５ｍｍ厚の円柱状に成型して用いる。この結果得られる本発明に利用される離型剤の硬度は、好ましくは０．３〜５．０、より好ましくは０．５〜３．０の範囲とする。
【００５０】
ビッカース硬度が０．３よりも低い離型剤を含有させたトナーは、多数枚複写において複写機のクリーニング部位で破砕され易く、ドラム表面上にトナー融着を起こし易く、結果的に画像上に黒筋が発生し易い傾向にあり、好ましくない。又、画像サンプルを多重枚重ねて保存した際に裏面にトナーが転写し、所謂裏写りが発生し易く、好ましくない。ビッカース硬度が５．０を超える離型剤を含有させたトナーは、加熱定着時に用いる定着器に必要以上の加圧力を必要とする為、定着器に必要以上の強度設計が必要となり、好ましくない。通常加圧力の定着器を用いた場合には、耐オフセット性が低下し易くなり好ましくない。
【００５１】
本発明で好ましく用いられる離型剤の製造方法としては、例えば、酸化反応による合成法、カルボン酸及びその誘導体からの合成、マイケル付加反応に代表されるエステル基導入反応、カルボン酸化合物とアルコール化合物からの脱水縮合反応を利用する方法、酸ハロゲン化物とアルコール化合物からの反応、エステル交換反応等で製造される。触媒としては、エステル化反応に使う一般の酸性触媒、アルカリ性触媒、例えば、酢酸亜鉛、チタン化合物等が用いられる。又、その後、再結晶法、蒸留法等により高純度化させてもよい。
【００５２】
本発明で使用することができる静電荷像現像用トナーに用いられる結着樹脂としては、例えば、下記の樹脂が挙げられる。例えば、ポリスチレン、ポリ−ｐ−クロルスチレン、ポリビニルトルエン等のスチレン及びその置換体の単重合体；スチレン−ｐ−クロルスチレン共重合体、スチレン−ビニルトルエン共重合体、スチレン−ビニルナフタリン共重合体、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、スチレン−α−クロルメタクリル酸メチル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ビニルメチルエーテル共重合体、スチレン−ビニルエチルエーテル共重合体、スチレン−ビニルメチルケトン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−アクリロニトリル−インデン共重合体等のスチレン系共重合体；ポリ塩化ビニル、フェノール樹脂、天然樹脂変性フェノール樹脂、天然樹脂変性マレイン酸樹脂、アクリル樹脂、メタクリル樹脂、ポリ酢酸ビニル、シリコーン樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド樹脂、フラン樹脂、エポキシ樹脂、キシレン樹脂、ポリビニルブチラール、テンペン樹脂、クマロンインデン樹脂、石油系樹脂等が挙げられる。その中で特に好ましい結着樹脂としては、スチレン系共重合体、若しくはポリエステル樹脂が挙げられる。
【００５３】
スチレン系共重合体のスチレンモノマーに対するコモノマーとしては、例えば、アクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸ドデシル、アクリル酸オクチル、アクリル酸−２−エチルヘキシル、アクリル酸フェニル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸オクチル、アクリロニトリル、メタクリニトリル、アクリルアミド等の様な二重結合を有するカルボン酸若しくはその置換体；マレイン酸、マレイン酸ブチル、マレイン酸メチル、マレイン酸ジメチル等の様な二重結合を有するジカルボン酸及びその置換体；塩化ビニル、酢酸ビニル、安息香酸ビニル等の様なビニルエステル類；エチレン、プロピレン、ブチレン等の様なエチレン系オレフィン類；ビニルメチルケトン、ビニルヘキシルケトン等の様なビニルケトン類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテル等の様なビニルエーテル類；これらのビニル単量体が単独若しくは２つ以上用いられる。
【００５４】
又、本発明で使用することができる静電荷像現像用トナーに用いられる重量平均分子量Ｍｗが１００，０００≦Ｍｗ≦１，５００，０００である高分子量成分としても、上記した各種材料を使用することが出来る。
本発明で使用する結着樹脂のＴＨＦ可溶分の数平均分子量は、３，０００〜１，０００，０００であることが好ましい。又、スチレン系重合体、又はスチレン系共重合体は架橋されていてもよく、またそれらの混合樹脂でもよい。
【００５５】
結着樹脂の架橋剤としては、主として、２個以上の重合可能な二重結合を有する化合物を用いてもよい。例えば、ジビニルベンゼン、ジビニルナフタレン等の様な芳香族ジビニル化合物；エチレングリコールジアクリレート、エチレングリコールジメタクリレート、１，３−ブタジオールジメタクリレート等の様な二重結合を２個有するカルボン酸エステル；ジビニルアニリン、ジビニルエーテル、ジビニルスルフィド、ジビニルスルホン等のジビニル化合物；及び３個以上のビニル基を有する化合物；これらが単独若しくは混合物として用いられる。添加量としては、重合性単量体１００重量部に対して０．００１〜１０重量部が好ましい。
【００５６】
本発明で使用することができる静電荷像現像用トナーには、荷電制御剤を含有させてもよい。
トナーを負荷電性に制御する荷電制御剤として下記の物質が挙げられる。例えば、有機金属化合物、キレート化合物が有効であり、モノアゾ金属化合物、アセチルアセトン金属化合物、芳香族ハイドロキシカルボン酸、芳香族ダイカルボン酸系の金属化合物がある。他には、芳香族ハイドロキシカルボン酸、芳香族モノ及びポリカルボン酸及びその金属塩、無水物、エステル類、ビスフェノール等のフェノール誘導体類等がある。又、尿素誘導体、含金属サリチル酸系化合物、４級アンモニウム塩、カリックスアレーン、けい素化合物、スチレン−アクリル酸共重合体、スチレン−メタクリル酸共重合体、スチレン−アクリル−スルホン酸共重合体、ノンメタルカルボン酸系化合物等が挙げられる。
【００５７】
又、トナーを正荷電性に制御する荷電制御剤として下記の物質がある。例えば、ニグロシン及び脂肪酸金属塩等による変性物、トリブチルベンジルアンモニウム−１−ヒドロキシ−４−ナフトスルホン酸塩、テトラブチルアンモニウムテトラフルオロボレート等の４級アンモニウム塩、及びこれらの類似体であるホスホニウム塩等のオニウム塩及びこれらのレーキ顔料、トリフェニルメタン染料及びこれらのレーキ顔料（レーキ化剤としては、りんタングステン酸、りんモリブデン酸、りんタングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フェリシアン化物、フェロシアン化物等）、高級脂肪酸の金属塩；ジブチルスズオキサイド、ジオクチルスズオキサイド、ジシクロヘキシルスズオキサイド等のジオルガノスズオキサイド；ジブチルスズボレート、ジオクチルスズボレート、ジシクロヘキシルスズボレート等のジオルガノスズボレート類；これらを単独或いは２種類以上組み合わせて用いることができる。これらの中でも、ニグロシン系、４級アンモニウム塩の如き荷電制御剤が特に好ましく用いられる。
【００５８】
これらの荷電制御剤は、トナー中の樹脂成分１００重量部に対して、好ましくは０．０１〜２０重量部、更に好ましくは０．５〜１０重量部の範囲で使用するのがよい。
又、本発明で使用することができる静電荷像現像用トナーに含有される着色剤としては、例えば、黒色顔料として、カーボンブラック、アニリンブラック、アセチレンブラック等が挙げられる。
【００５９】
マゼンタ用顔料としては、赤口黄鉛、モリブデンオレンジ、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、ベンジジンオレンジＧ、カドミウムレッド、パーマネントレッド４Ｒ、ウオッチングレッドカルシウム塩、エオシンレーキ、ブリリアントカーミン３Ｂ、カーミン６Ｂ、マンガン紫、ファストバイオレットＢ、メチルバイオレットレーキ、ローダミンレーキ、アリザクンレーキ、ベンガラ、キナクリドン、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２１、２２、２３、３０、３１、３２、３７、３８、３９、４０、４１、４８、４９、５０、５１、５２、５３、５４、５５、５７、５８、６０、６３、６４、６８、８１、８３、８７、８８、８９、９０、１１２、１１４、１２２、１２３、１６３、２０２、２０６、２０７、２０９；Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．バイオレット１、２、１０、１３、１５、２３、２９、３５等が挙げられる。
【００６０】
シアン用顔料としては、Ｃ．Ｉ．ピグメントブルー２、３、１５、１６、１７、Ｃ．Ｉ．バッドブルー６、Ｃ．Ｉ．アシッドブルー４５、インダンスレンブルー、紺青、コバルトブルー、アルカリブルーレーキ、ビクリアブルーレーキ、フタロシアニンブルー、アーストスカイブルー、インダンスレンブルーＢＣ、クロムグリーン、酸化クロム、ピグメントグリーンＢ、マラカイトグリーンレーキ、ファイナルイエローグリーンＧ等が挙げられる。
【００６１】
イエロー用顔料としては、ナフトールイエロー、ハイザイエロー、黄鉛、カドミウムイエロー、ミスラルファストイエロー、ネーブルイエロー、パーマネントイエローＮＣＧ、タートラジンレーキ、Ｃ．Ｉ．ピグメントイエロー１、２、３、４、５、６、７、１０、１１、１２、１３、１４、１５、１６、１７、２３、６５、７３、８３、９７、１２０、１２７、１７４、１７６、１８０、１９１、Ｃ．Ｉ．バッドイエロー１、３、２０等が挙げられる。
これらの顔料は、定着画像の光学濃度を維持する為に必要な量が用いられるが、本発明においては、樹脂１００重量部に対し、０．１〜２０重量部、好ましくは０．２〜１０重量部の範囲で添加することが望ましい。
【００６２】
又、本発明において着色剤として使用される染料としては、例えば、以下のものが挙げられる。
マゼンタ用染料としては、Ｃ．Ｉ．ソルベントレッド１、３、８、２３、２４、２５、２７、３０、４９、８１、８２、８３、８４、１００、１０９、１２１、Ｃ．Ｉ．ディスパースレッド９、Ｃ．Ｉ．ソルベントバイオレット８、１３、１４、２１、２７、Ｃ．Ｉ．ディスパースバイオレット１、Ｃ．Ｉ．ベーシックレッド１、２、９、１２、１３、１４、１５、１７、１８、２２、２３、２４、２７、２９、３２、３４、３５、３６、３７、３８、３９、４０、Ｃ．Ｉ．ベーシックバイオレット、１、３、７、１０、１４、１５、２１、２５、２６、２７、２８、Ｃ．Ｉ．ダイレクトレッド１、４、Ｃ．Ｉ．アシッドレッド１、Ｃ．Ｉ．モーダントレッド３０等が挙げられる。
【００６３】
シアン用染料としては、Ｃ．Ｉ．ダイレクトブルー１、２、Ｃ．Ｉ．アシッドブルー９、１５、Ｃ．Ｉ．ベーシックブルー３、５、Ｃ．Ｉ．モーダントブルー７、Ｃ．Ｉ．ダイレクトグリーン６、Ｃ．Ｉ．ベーシックグリーン４、６等が挙げられる。
これらの染料は、樹脂１００重量部に対し、０．１〜２０重量部、好ましくは０．３〜１０重量部の範囲で添加することが望ましい。
【００６４】
更に、本発明で使用することができる静電荷像現像用トナーは、更に磁性材料を含有させ、磁性トナーとしても使用し得る。この場合、磁性材料は着色剤の役割を兼ねることもできる。本発明において、磁性トナー中に含まれる磁性材料としては、例えば、マグネタイト、ヘマタイト、フェライト等の酸化鉄；鉄、コバルト、ニッケルの様な金属或はこれらの金属のアルミニウム、コバルト、銅、鉛、マグネシウム、錫、亜鉛、アンチモン、ベリリウム、ビスマス、カドミウム、カルシウム、マンガン、セレン、チタン、タングステン、バナジウムの様な金属の合金及びその混合物等が挙げられる。
【００６５】
これらの強磁性体は平均粒径が２μｍ以下、０．１〜０．５μｍ程度であることが好ましい。トナー中に含有させるこれらの磁性材料の量としては、樹脂成分１００重量部に対して、約２０〜２００重量部、特に好ましくは、４０〜１５０重量部の範囲で用いることが望ましい。
又、本発明で使用される磁性体の物性としては、１０ｋＯｅ印加での磁気特性が保磁力（Ｈ_c）２０〜３００Ｏｅ、飽和磁化（σ_s）５０〜２００ｅｍｕ／ｇ、残留磁化（σ_r）２〜２０ｅｍｕ／ｇのものを使用するのが好ましい。
【００６６】
又、トナー特性付与を目的として添加する各種添加剤は、トナー中に、或いはトナーに添加したときの耐久性の点から、トナー粒子の体積平均粒径の１／５以下の粒径のものであることが好ましい。ここで、添加剤の粒径とは、電子顕微鏡におけるトナー粒子の表面観察により求めたその平均粒径を意味する。これら特性付与を目的とした添加剤としては、例えば、以下の様なものが挙げられる。
【００６７】
流動性付与剤としては、酸化けい素、酸化アルミニウム、酸化チタン等の金属酸化物、カーボンブラック、ふっ化カーボン等が挙げられる。これらは夫々、疎水化処理を行ったものを使用するのがより好ましい。
研磨剤としては、チタン酸ストロンチウム、酸化セリウム、酸化アルミニウム、酸化マグネシウム、酸化クロム等の金属酸化物、窒化けい素等の窒化物、炭化けい素等の炭化物、硫酸カルシウム、硫酸バリウム、炭酸カルシウム等の金属塩等が挙げられる。
【００６８】
又、滑剤としては、ふっ化ビニリデン、ポリテトラフルオロエチレン等のふっ素系樹脂粉末、ステアリン酸亜鉛、ステアリン酸カルシウム等の脂肪酸金属塩等が挙げられる。
荷電制御剤としては、酸化錫、酸化チタン、酸化亜鉛、酸化けい素、酸化アルミニウム等の金属酸化物、カーボンブラック等が挙げられる。
これら添加剤は、トナー粒子１００重量部に対して、０．１〜１０重量部、好ましくは０．１〜５重量部の範囲で用いられる。尚、これらの添加剤は単独で用いても、又、複数併用してもよい。
【００６９】
本発明で使用することができる静電荷像現像用トナーは、通常、一成分系現像剤及び二成分系現像剤のいずれの現像剤にも使用することが出来る。
例えば、一成分系現像剤として、磁性体をトナー中に含有せしめた磁性トナーの場合には、現像スリーブ中に内蔵せしめたマグネットを利用して、磁性トナーを搬送及び帯電せしめる方法がある。又、磁性体を含有しない非磁性トナーを用いる場合には、ブレード及びファーブラシを用い、現像スリーブにて強制的に摩擦帯電し、現像スリーブ上にトナーを付着せしめて搬送せしめる方法がある。
【００７０】
一方、一般に利用されている二成分系現像剤として用いる場合には、本発明で使用することができるトナーと共にキャリアを用い、現像剤として使用する。本発明に使用されるキャリアとしては、特に限定されるものではないが、主として、鉄、銅、亜鉛、ニッケル、コバルト、マンガン、クロム元素からなる単独及び複合フェライト状態で構成される。飽和磁化、電気抵抗を広範囲にコントロールすることができる点から、キャリア形状も重要であり、例えば、球状、扁平、不定形等を選択し、更にキャリア表面状態の微細構造、例えば、表面凹凸性をもコントロールすることが好ましい。
【００７１】
一般的には、上記の様な無機酸化物を焼成、造粒することにより、予めキャリアコア粒子を生成した後、樹脂にコーティングする方法が用いられているが、キャリアのトナーへの負荷を軽減する意味合いから、無機酸化物と樹脂を混練後、粉砕、分級して低密度分散キャリアを得る方法や、更には、直接無機酸化物とモノマーとの混練物を水系媒体中にて懸濁重合せしめ、真球状分散キャリアを得る重合キャリアを得る方法等も利用することが可能である。
上記キャリアの表面を、樹脂等で被覆する系は、特に好ましい。その方法としては、樹脂等の被覆材料を溶剤中に溶解若しくは懸濁せしめて塗布してキャリアに付着せしめる方法、単に粉体で混合する方法等、従来公知の方法がいずれも適用できる。
【００７２】
キャリア表面への固着物質としては、トナー材料により異なるが、例えば、ポリテトラフルオロエチレン、モノクロロトリフルオロエチレン重合体、ポリフッ化ビニリデン、シリコーン樹脂、ポリエステル樹脂、ジターシャリーブチルサリチル酸の金属化合物、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、ニグロシン、アミノアクリレート樹脂、塩基性染料及びそのレーキ、シリカ微粉末、アルミナ微粉末等を単独或は複数で用いるのが適当であるが、必ずしもこれに制約されない。
【００７３】
上記化合物の処理量は、一般には総量でキャリアに対して、０．１〜３０重量％、好ましくは０．５〜２０重量％の範囲であることが好ましい。
上記の様なキャリアの平均粒径は、１０〜１００μｍ、好ましくは２０〜５０μｍを有するものが好ましい。
【００７４】
キャリアの特に好ましい態様としては、フェライトであり、その表面をふっ素系樹脂とスチレン系樹脂の如き樹脂の組み合わせ、例えば、ポリフッ化ビニリデンとスチレン−メチルメタアクリレート樹脂；ポリテトラフルオロエチレンとスチレン−メチルメタアクリレート樹脂；ふっ素系共重合体とスチレン系共重合体；等を９０：１０〜２０：８０、好ましくは７０：３０〜３０：７０の比率の混合物としたもの或いはシリコーン樹脂等で、０．０１〜５重量％、好ましくは０．１〜１重量％コーティングして、上記平均粒径を有するコートフェライトキャリアであるものが挙げられる。該ふっ素系共重合体としては、フッ化ビニリデン−テトラフルオロエチレン共重合体（１０：９０〜９０：１０）が挙げられ、スチレン系共重合体としては、スチレン−アクリル酸−２−エチルヘキシル（２０：８０〜８０：２０）、スチレン−アクリル酸−２−エチルヘキシン−メタクリル酸メチル（２０〜６０：５〜３０：１０〜５０）が挙げられる。
【００７５】
上記の様なコートフェライトキャリアは、粒径分布がシャープであり、本発明で使用することができるトナーに対し好ましい摩擦帯電性が得られ、更に、電子写真特性を向上させる効果がある。
本発明におけるトナーと混合して二成分現像剤を調製する場合、その混合比率は、現像剤中のトナー濃度として、２〜１５重量％、好ましくは４〜１３重量％にすると、通常、良好な結果が得られる。トナー濃度が２重量％以下では、画像濃度が低く実用不可となり、１５重量％以上では、カブリや機内飛散を増加せしめ、現像剤の耐用寿命が短くなる為、好ましくない。
【００７６】
更に、本発明で使用するキャリアとしては、磁性特性が以下のものであることが好ましいい。即ち、磁気的に飽和させた後の１０００ Ｏｅにおける磁化の強さ（σ₁₀₀₀）は、３０〜３００ｅｍｕ／ｇであることが必要である。更に高画質化を達成するために、好ましくは１００〜２５０ｅｍｕ／ｇであることがよい。３００ｅｍｕ／ｇより大きい場合には、高画質なトナー画像が得られにくくなる。又、３０ｅｍｕ／ｇ未満であると、磁気的な拘束力も減少する為にキャリア付着を生じ易い。
【００７７】
又、キャリア形状は、丸さの度合いを示すＳＦ１が１８０以下、凹凸の度合いを示すＳＦ２が２５０以下であることが好ましい。尚、ＳＦ１、ＳＦ２の値は以下の式にて定義され、ニレコ社製のＬＵＺＥＸ IIIにて測定された。
ＳＦ１＝［（キャリアの最大長)²／面積］×（π／４）
ＳＦ２＝［（キャリアの周辺長)²／面積］×（１／４π）
【００７８】
本発明で使用することができる静電荷像現像用トナーを粉砕法で製造する場合の粉砕トナーの製造法は、先ず、結着樹脂、高分子量成分、離型剤、着色剤としての顔料又は染料、必要に応じて磁性体、荷電制御剤、その他の添加剤等をヘンシェルミキサー、ボールミル等の混合機により充分混合してから、加熱ロール、ニーダー、エクストルーダーの如き熱混練機を用いて溶融混練して樹脂類を互いに相溶せしめた中に、金属化合物、顔料、染料、磁性体を分散又は溶解せしめ、冷却固化後、粉砕及び分級を行って、本発明で使用することができるトナーを得る。
その後、更に必要に応じて、所望の添加剤をヘンシェルミキサー等の混合機により充分混合することによって外添して、本発明に係る静電荷像現像用トナーを得ることも出来る。
【００７９】
又、本発明で使用することができる静電荷像現像用トナーを直接的に重合法によって得る重合トナーは、以下の如き方法によって製造される。即ち、重合性単量体中に、高分子量成分、離型剤、着色剤、必要に応じて、荷電制御剤、重合開始剤、及びその他の添加剤を加え、ホモジナイザー又は超音波分散機等によって均一に溶解又は分散せしめた単量体系を、分散安定剤、若しくは乳化剤を含有する分散媒体中に撹拌機又はホモミキサー、ホモジナイザー等により分散せしめ、造粒する。その後は、分散安定剤の作用により、単量体系の粒子状態が維持され、且つ単量体系の粒子の沈降が防止される程度の撹拌を行えばよい。重合温度は４０℃以上、一般には５０〜９０℃の温度に設定して重合を行う。又、重合反応後半に昇温してもよく、更に、トナー定着時の臭いの原因等となる未反応の重合性単量体、副生成物等を除去する為に、反応後半、又は反応終了後に一部水系媒体を留去してもよい。反応終了後、生成したトナー粒子を洗浄し、濾別にすることにより回収し、乾燥する。懸濁重合法においては、通常、単量体系１００重量部に対して水３００〜３０００重量部を分散媒体として使用するのが好ましい。
【００８０】
トナーの粒度はコールターカウンターモデルＴＡ−II（コールターエレクトロニクス社製）における重量平均粒径が、０．１〜１２μｍ、粒度分布は重量平均径における変動係数が８〜４０％のものが好ましく、更に形状は、丸さの度合いを表すＳＦ１値が、１００＜ＳＦ１＜１５０、凹凸の度合いを表すＳＦ２値が、１００＜ＳＦ２＜２００であるものがよい。
【００８１】
又、重合法を用いて直接的にトナーを得るときに使用する重合性単量体としては、例えば、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−メトキシスチレン、ｐ−エチルスチレン等のスチレン系単量体；アクリル酸メチル、アクリル酸エチル、アクリル酸−ｎ−ブチル、アクリル酸イソブチル、アクリル酸−ｎ−プロピル、アクリル酸−ｎ−オクチル、アクリル酸ドデシル、アクリル酸−２−エチルヘキシル、アクリル酸ステアリル、アクリル酸−２−クロルエチル、アクリル酸フェニル等のアクリル酸エステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸−ｎ−プロピル、メタクリル酸−ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸−ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸−２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチル等のメタクリル酸エステル類；その他、アクリロニトリル、メタクリロニトリル、アクリルアミド等の単量体が挙げられる。これらの単量体は単独、又は混合して使用し得る。
【００８２】
又、本発明において使用する重合法トナーの単量体には、添加剤として極性基を有する重合体や共重合体を添加してもよい。この際に使用することの出来る極性重合体、及び共重合体としては、以下に挙げるものがある。例えば、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチル等の含窒素単量体の重合体；スチレン−不飽和カルボン酸エステル等との共重合体、アクリロニトリル等のニトリル系単量体；塩化ビニル等の含ハロゲン系単量体；アクリル酸、メタクリル酸等の不飽和カルボン酸；その他、不飽和二塩基酸、不飽和二塩基酸無水物、ニトロ系単量体等の重合体若しくはスチレン系単量体等との共重合体、ポリエステル、エポキシ樹脂等が挙げられる。
【００８３】
この際に使用される重合開始剤としては、例えば、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス−４−メトキシ−２，４−ジメチルバレロニトリル、アゾビスイソブチロニトリル等のアゾ系又はジアゾ系重合開始剤；ベンゾイルペルオキシド、メチルエチルケトンペルオキシド、ジイソプロピルペルオキシカーボネート、クメンヒドロペルオキシド、ｔ−ブチルヒドロペルオキシド、ジ−ｔ−ブチルペルオキシド、ジクシルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルオキシド、２，２−ビス（４，４−ｔ−ブチルペルオキシシクロヘキシル）プロパン、トリス−（ｔ−ブチルペルオキシ）トリアジン等の過酸化物系開始剤や過酸化物を側鎖に有する高分子開始剤；過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩；過酸化水素等が使用される。
【００８４】
上記の様な重合開始剤は、重合性単量体の０．５〜２０重量部の添加量が好ましく、単独又は併用してもよい。又、公知の架橋剤、連鎖移動剤を添加してもよく、好ましい添加量としては、０．００１〜１５重量部である。
【００８５】
本発明においては、乳化重合、分散重合、懸濁重合、シード重合、塩析を用いる重合法等によって重合法トナーが製造されるが、この際に用いられる分散媒には、いずれか適当な安定剤が使用される。この際の安定剤としては、例えば、無機化合物としては、りん酸三カルシウム、りん酸マグネシウム、りん酸アルミニウム、りん酸亜鉛、炭酸カルシウム、炭酸マグネシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、メタけい酸カルシウム、硫酸カルシウム、硫酸バリウム、ベントナイト、シリカ、アルミナ等が挙げられる。有機化合物としては、ポリビニルアルコール、ゼラチンメチルセルロース、メチルヒドロキシプロピルセルロース、エチルセルロース、カルボキシメチルセルロースのナトリウム塩、ポリアクリル酸及びその塩、澱粉、ポリアクリルアミド、ポリエチレンオキシド、ポリ（ハイドロオキシステアリン酸−ｇ−メタクリル酸メチル−ｅｕ−メタクリル酸）共重合体やノニオン系或はイオン系界面活性剤等が使用される。
【００８６】
又、乳化重合法を用いる場合には、アニオン系界面活性剤、カチオン系界面活性剤、両性イオン界面活性剤、及びノニオン系界面活性剤を安定剤として使用する。これらの安定剤は重合性単量体１００重量部に対して、０．２〜３０重量部を使用するのが好ましい。
これらの安定剤の中で、無機化合物を用いる場合、市販のものをそのまま用いてもよいが、細かい粒子を得る為に、分散媒中にて該無機化合物を生成させて用いてもよい。
【００８７】
又、これら安定剤の微細な分散の為に、０．００１〜０．１重量部の界面活性剤を使用してもよい。これは上記分散安定剤の所期の作用を促進するものであり、その具体例としては、ドデシルベンゼン硫酸ナトリウム、テトラデシル硫酸ナトリウム、ペンタデシル硫酸ナトリウム、オクチル硫酸ナトリウム、オレイン酸ナトリウム、ラウリル酸ナトリウム、ステアリン酸カリウム、オレイン酸カルシウム等が挙げられる。
【００８８】
又、本発明において重合法トナーに用いられる着色剤としては、着色剤の持つ重合阻害性や水相移行性に注意を払う必要があり、前記した様な着色剤を、好ましくは表面改質、例えば、重合阻害のない疎水化処理を施して使用するのが好ましい。特に、染料系やカーボンブラックは、重合阻害性を有しているものが多いので使用の際に注意を要する。染料系を表面処理する好ましい方法としては、これら染料の存在下に重合性単量体を予め重合せしめる方法が挙げられ、得られた着色重合体を単量体系に添加する。又、カーボンブラックについては、上記染料と同様の処理の他、カーボンブラックの表面官能基と反応する物質、例えば、ポリオルガノシロキサン等で処理を行ってもよい。
【００８９】
本発明において、画像記録物のトナーの定着性、耐オフセット性、混色領域の評価方法としては以下の通りである。
先ず、本発明で使用することができるトナーに対して、適当な外添剤を適量添加して現像剤を得る。得られた現像剤の未定着画像を、市販の複写機によって作製する。この際、トナーが黒トナーの場合には、オイル塗布機能のない４０ｍｍφの熱ローラー外部定着器によって、定着性及びオフセット性の評価をする。モノカラートナー又はフルカラートナーの場合には、オイル塗布機能のない４０ｍｍφの熱ローラー外部定着器の他、若干のオイルを均一に塗布した定着ローラーに塗布した（例えば、オイル量０．０２ｇ／Ａ４サイズ）４０ｍｍφの熱ローラー外部定着器を用い、定着性、耐オフセット性の評価をし、且つ透明性評価、画像評価の為の定着画像を得る。
【００９０】
尚、このときのローラー材質としては、上部、下部ともに、ふっ素系のものを使用する。又、定着条件としては、転写材がＳＫ紙（日本製紙社製）の場合には、ニップ６．５ｍｍ、プロセススピード１０５ｍｍ／ｓｅｃとし、転写材がＯＨＴシート（ＣＧ３３００／３Ｍ社製）の場合には、ニップ６．５ｍｍ、プロセススピード３５ｍｍ／ｓｅｃとし、１００〜２５０℃の温度範囲内で、５℃おきに温調をかけて行う。
【００９１】
（１）定着性
定着性は定着画像（低温オフセットした画像も含む）を５０ｇ／ｃｍ²の荷重をかけ、シルボン紙（Ｌｅｎｚ Ｃｌｅａｎｉｎｇ Ｐａｐｅｒ ”ｄａｓｐｅｒ（Ｒ）”（Ｏｚｕ Ｐａｐｅｒ Ｃｏ．，Ｌｔｄ））で擦り、擦り前後の濃度低下率が１０％未満になる温度を定着開始点とする。
【００９２】
（２）耐オフセット性
耐オフセット性は、目視でオフセットの出なくなる温度を低温オフセット始点とし、温度を上げてオフセットのでない最高温度を高温オフセット終点とする。
【００９３】
（３）光沢度
更に、グロス値は、非オフセット領域にある画像を、鏡面光沢度測定器ＰＧ−３Ｄ（日本発色工業社製）を用いて測定した。
表１、２には、低温オフセット始点（Ｔ_low）、定着最低温度Ｔ_min、Ｔ_min＋３０、高温オフセット終点（定着最高温度Ｔ_max）、最高グロス値を示す定着温度ＴＧ_max、Ｇ(Ｔ_min）、Ｇ(Ｔ_min＋３０）、Ｇ(Ｔ_max）、Ｇ(ＴＧ_max）、非オフセット領域、透過率、ヘイズの値をそれぞれ記載した。
【００９４】
【実施例】
以下、実施例に従って本発明を更に具体的に説明する。なお、本発明は実施例に限定されるものではない。
【００９５】
実施例１
イオン交換水７５０ｇに、０．１Ｍ−Ｎａ₃ＰＯ₄水溶液５００ｇを投入し、６０℃に加温した後、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、１２，０００ｒｐｍにて撹拌した。これに１．０Ｍ−ＣａＣｌ₂水溶液７５ｇを徐々に添加し、Ｃａ₃(ＰＯ₄)₂を含む水系媒体を得た。
一方、
・スチレン １７０ｇ
・ｎ−ブチルアクリレート ３０ｇ
・銅フタロシアニン顔料 １８ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ２ｇ
・離型剤（１） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝６００，０００） ２４ｇ
上記処方を６０℃に加温し、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、１０，０００ｒｐｍにて均一に溶解、分散した。これに、重合開始剤２，２´−アゾビス（２，４−ジメチルバレロニトリル）１０ｇを溶解し、重合性単量体組成物を調製した。前記、水系媒体中に上記重合性単量体組成物を投入し、６０℃、Ｎ₂雰囲気下において、ＴＫ式ホモミキサーにて１２，０００ｒｐｍで１２分間撹拌し、重合性単量体組成物を造粒した。その後、パドル撹拌翼を用いて５００ｒｐｍで撹拌しつつ、７０℃に昇温し、１５時間反応させた。重合反応終了後、冷却し、塩酸を加えリン酸カルシウムを溶解させた後、ろ過、水洗、乾燥をして、重合粒子を得た。
得られた粒子１００質量部に対して、ＢＥＴ法による比表面積が、１００ｍ²／ｇである疎水性酸化チタン微粒子１．２質量部を外添し、懸濁重合トナーを得た。なお、得られたシアントナーの重量平均粒径は６．４μｍであった。
このトナー６質量部に対し、シリコーン樹脂でコートされたフェライトキャリア９４重量部を混合し、現像剤とした。この現像剤を用いて、市販の電子写真複写機ＣＬＣ７００（キヤノン社製）にて未定着画像を出し、定着性、ＯＨＴ透明性を評価した。その結果を表１に示した。
【００９６】
実施例２
・スチレン １６９ｇ
・ｎ−ブチルアクリレート ３１ｇ
・銅フタロシアニン顔料 ２２ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ２ｇ
・離型剤（５） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝３５０，０００） ２０ｇ
上記処方で実施例１と同様の操作を行って、重合性組成物を得た後、現像剤を得る。その現像剤を用いて実施例１と同様に定着性、ＯＨＴ透明性を評価した。なお、得られたマゼンタトナーの重量平均粒径は、６．５μｍであった。その結果を表１に示した。
【００９７】
実施例３
・スチレン １７１ｇ
・ｎ−ブチルアクリレート ２９ｇ
・銅フタロシアニン顔料 ２０ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ４ｇ
・離型剤（７） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝１２０，０００） １０ｇ
上記処方で実施例１と同様の操作を行って、重合性組成物を得た後、現像剤を得る。その現像剤を用いて実施例１と同様に定着性、ＯＨＴ透明性を評価した。なお、得られたイエロートナーの重量平均粒径は、６．７μｍであった。その結果を表１に示した。
【００９８】
参考例１
・スチレン １７２ｇ
・ｎ−ブチルアクリレート ２８ｇ
・グラフト処理カーボンブラック顔料 １７ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ３ｇ
・パラフィンワックス ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝８８０，０００） ２２ｇ
上記処方で実施例１と同様の操作を行って、重合性組成物を得た後、現像剤を得る。その現像剤を用いて実施例１と同様に定着性、ＯＨＴ透明性を評価した。なお、得られたブラックトナーの重量平均粒径は、６．２μｍであった。その結果を表１に示した。
【００９９】

上記処方で実施例１と同様の操作を行って、重合性組成物を得た後、現像剤を得た。その現像剤を用いて定着性を評価した。なお、得られた磁性トナーの重量平均粒径は、６．６μｍであり、未定着画像を出す評価機としては市販の電子写真複写機ＮＰ８５８２（キヤノン社製）を採用した。その結果を表１に示した。
【０１００】

上記材料を予備混合した後、１３０℃に設定した２軸混練押し出し機によって溶融混練を行った。混練物を冷却後、粗粉砕し、ジェット気流を用いた粉砕機によって微粉砕し、更に風力分級機を用いて分級し、重量平均粒径６．７μｍのトナーを得た。このトナー１００質量部と、疎水性酸化チタン微粉末１．２質量部とを混合（外添）してトナー粒子表面に疎水性酸化チタン微粉末を有するトナーを得た。
この現像剤を用いて、市販の電子写真複写機ＮＰ−８５８２（キヤノン社製）を用いて、未定着画像を出し、実施例１と同様の評価方法で定着性を評価した。その結果を表１に示した。
【０１０１】
実施例４
・ポリエステル樹脂 １，０００ｇ
（ビスフェノールＡ系ジオール−テレフタル酸
−ドデセニルコハク酸−トリメリット酸縮合物；
モル比＝５０：４０：５：５）
・銅フタロシアニン顔料 ４０ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ２０ｇ
・離型剤（２） ５０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝４７０，０００） １５０ｇ
上記材料を混合した後、参考例３と同様にして現像剤を得て、定着性、ＯＨＴ透明性を評価した。なお、得られたシアントナーの重量平均粒径は、６．２μｍであった。その結果を表１に示した。
【０１０２】
実施例５
・スチレン １６５ｇ
・ｎ−ブチルアクリレート ３４ｇ
・銅フタロシアニン顔料 ２２ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ３ｇ
・離型剤（８） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝３５０，０００） ２０ｇ
上記処方で実施例１と同様の操作を行って、重合性組成物を得た後、現像剤を得る。その現像剤を用いて実施例１と同様に定着性、ＯＨＴ透明性を評価した。なお、得られたマゼンタトナーの重量平均粒径は、６．５μｍであった。その結果を表１に示した。
【０１０３】
実施例１と同様の方法で、キナクリドン顔料、ジスアゾイエロー顔料、グラフト処理カーボンブラック顔料にて、マゼンタ、イエロー、ブラックトナーを作り、それと実施例１のシアントナーの４色トナーにて、市販の電子写真複写機であるＣＬＣ７００（キヤノン社製）にてグラフィック調のフルカラー画像を出力したところ、光沢度の小さい、読み易く、違和感のないものが得られた。
又、このときのフルカラーＯＨＴ画像は、透明性に優れた品位の高いものであった。
【０１０４】

【０１０５】
比較例１
イオン交換水７４０ｇに、０．１Ｍ−Ｎａ₃ＰＯ₄水溶液４９０ｇを投入し、６０℃に加温した後、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、１２，０００ｒｐｍにて撹拌した。これに１．０Ｍ−ＣａＣｌ₂水溶液７７ｇを徐々に添加し、Ｃａ₃(ＰＯ₄)₂を含む水系媒体を得た。一方、
・スチレン １７０ｇ
・ｎ−ブチルアクリレート ３０ｇ
・銅フタロシアニン顔料 １７ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ２ｇ
・離型剤（１２） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝３０，０００） ３６ｇ
【０１０６】
上記処方を６０℃に加温し、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、１０，０００ｒｐｍにて均一に溶解、分散した。これに、重合開始剤２，２´−アゾビス（２，４−ジメチルバレロニトリル）１０ｇを溶解し、重合性単量体組成物を調製した。前記、水系媒体中に上記重合性単量体組成物を投入し、６０℃、Ｎ₂雰囲気下において、ＴＫ式ホモミキサーにて１２，０００ｒｐｍで１２分間撹拌し、重合性単量体組成物を造粒した。その後、パドル撹拌翼を用いて５００ｒｐｍで撹拌しつつ、７０℃に昇温し、１５時間反応させた。重合反応終了後、冷却し、塩酸を加えリン酸カルシウムを溶解させた後、ろ過、水洗、乾燥をして、重合粒子を得た。
得られた粒子１００質量部に対して、ＢＥＴ法による比表面積が、１００ｍ² ／ｇである疎水性酸化チタン微粒子１．２質量部を外添し、懸濁重合トナーを得た。なお、得られたシアントナーの重量平均粒径は６．４μｍであった。
このトナー６質量部に対し、シリコーン樹脂でコートされたフェライトキャリア９４重量部を混合し、現像剤とした。この現像剤を用いて、市販の電子写真複写機ＣＬＣ７００（キヤノン社製）にて未定着画像を出し、上記方法により、定着性、ＯＨＴ透明性を評価した。その結果を表２に示した。
【０１０７】
比較例２
・高分子量樹脂
（重量平均分子量Ｍｗ＝１，５１０，０００）３４ｇ
これ以外は、実施例４と同様にして、重量平均粒径６．７μｍのシアントナーを得て、市販の電子写真複写機ＣＬＣ７００（キヤノン社製）を用いて、未定着画像を出し、上記方法により、定着性、ＯＨＴ透明性を評価した。その結果を表２に示した。
【０１０８】
比較例３
・高分子量樹脂
（重量平均分子量Ｍｗ＝４９０，０００） １０２ｇ
これ以外は、参考例３と同様にして、重量平均粒径６．３μｍのブラックトナーを得た。評価も参考例３と同様にして行った。その結果を表２に示した。
【０１０９】
比較例４
・スチレン １７２ｇ
・ｎ−ブチルアクリレート ２８ｇ
・銅フタロシアニン顔料 ２１ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ４ｇ
・離型剤（１） ４０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝４０，０００） １ｇ
・２，２´−アゾビス（２，４
−ジメチルバレロニトリル） ６ｇ
上記のような重合性組成物を得た後、比較例１と同様にして現像剤を得て、定着性、ＯＨＴ透明性を評価した。なお、得られたマゼンタトナーの重量平均粒径は、６．５μｍであった。その結果を表２に示した。
【０１１０】

上記のような重合性組成物を得た後、比較例１と同様にして現像剤を得て、定着性を評価した。なお、得られた磁性トナーの重量平均粒径は、６．６μｍであり、未定着画像を出す評価機としては市販の電子写真複写機ＮＰ８５８２（キヤノン社製）を採用した。その結果を表２に示した。
【０１１１】

上記材料を予備混合した後、１３０℃に設定した２軸混練押し出し機によって溶融混練を行った。混練物を冷却後、粗粉砕し、ジェット気流を用いた粉砕機によって微粉砕し、更に風力分級機を用いて分級し、重量平均粒径６．７μｍのトナーを得た。このトナー１００質量部と、疎水性酸化チタン微粉末１．２質量部とを混合（外添）してトナー粒子表面に疎水性酸化チタン微粉末を有するトナーを得た。
この現像剤を用いて、市販の電子写真複写機ＮＰ−８５８２（キヤノン社製）を用いて、未定着画像を出し、定着性を評価した。その結果を表２に示した。
【０１１２】
比較例７
・ポリエステル樹脂 １，０００ｇ
（ビスフェノールＡ系ジオール−テレフタル酸
−ドデセニルコハク酸−トリメリット酸縮合物；
モル比＝５０：４０：５：５）
・銅フタロシアニン顔料 ４５ｇ
・ジ−ｔ−ブチルサリチル酸金属化合物 ２０ｇ
・離型剤（１） ５０ｇ
・高分子量樹脂
（重量平均分子量Ｍｗ＝５０，０００） １８ｇ
のような重合性組成物を混合した後、比較例６と同様にして現像剤を得て、定着性、ＯＨＴ透明性を評価した。なお、得られたシアントナーの重量平均粒径は、６．２μｍであった。その結果を表２に示した。
【０１１３】

【０１１４】
【発明の効果】
以上説明した通り、本発明によれば、グラフィック画像のようなグラフ部と文字部の混在した画像においても違和感のない画像が得られ、且つ、ＯＨＴ透明性にも優れたフルカラー画像が提供される。
更に、本発明によれば、定着ローラーに実質的にオイルを塗布することなく定着をすることも可能となった。[0001]
[Industrial application fields]
The present invention is suitable for heat fixing used in electrophotography, electrostatic recording, magnetic recording, etc.PaintingHow to record imagesTo the lawRelated.
[0002]
[Prior art]
Conventionally, as an electrophotographic method, many methods as described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748 and the like are known. However, in general, first, an electrical latent image is formed on a photosensitive member by various means using a photoconductive substance, and then the latent image is developed using toner, and if necessary, paper is used. After the toner image is transferred to a transfer material such as a toner image, the toner image is fixed by heating, pressure, heating and pressurization, solvent vapor, or the like to obtain a recorded image such as a copy. The toner remaining without being transferred onto the photosensitive member is cleaned by various methods, and the above development process is repeated.
[0003]
Further, a method for forming a general full-color image by electrophotography will be described. First, the photosensitive drum is uniformly charged by a primary charger, and image exposure is performed by laser light modulated by a magenta image signal of an original. To form an electrostatic latent image on the photosensitive drum. Next, the electrostatic latent image is developed by a magenta developing device in which magenta toner is held to form a magenta toner image. Next, the magenta toner image developed on the photosensitive drum is transferred to a transfer material conveyed by a transfer charger.
[0004]
On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a neutralizing charger, cleaned by a cleaning unit, and then charged by a primary charger again. The magenta toner A cyan toner image is formed in the same manner as in the image formation, and further, the cyan toner image is transferred to a transfer material onto which the magenta toner image is transferred. Further, the yellow color and the black color are sequentially performed in the same manner as described above, and the four color toner images are transferred to the transfer material. Finally, a transfer material having four color toner images is fixed by a fixing roller by the action of heat and pressure, thereby forming a full color image.
[0005]
In recent years, copying apparatuses such as those described above are beginning to be used not only in general-purpose copying machines for copying original documents, but also in the field of printers as computer outputs or personal copying for individuals. . Furthermore, in addition to the fields represented by such laser beam printers, the development of plain paper fax machines using basic engines is also rapidly developing.
[0006]
For this reason, smaller, lighter, faster, higher image quality, and higher reliability have been rigorously pursued, and the machine has been configured with simpler elements in various ways. . As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a better machine cannot be realized. In addition, with the recent various copying needs, demand for color copying is rapidly increasing, and in order to copy original color images more faithfully, higher image quality and higher resolution are desired. From these viewpoints, the toner used in the color image forming method needs to have good meltability and color mixing properties when heat is applied thereto, and has a low softening point and a low melt viscosity. It is preferable to use a toner having a high melt property.
That is, by using such sharp melt toner, it is possible to widen the color reproduction range of the copy and obtain a color copy faithful to the original image.
[0007]
However, in recent years, the use of such a color copying apparatus as a printer function as a computer output has been rapidly increasing in order to use a graphic image processed by a personal computer or the like for presentation. At this time, aside from outputting a pictorial image, when outputting a so-called graphic image in which a graph and characters that describe it are arranged, using a toner having a high sharp melt property as in the prior art, There is a problem in that the glossiness is too large in the character part, and the output image is difficult to see and read.
[0008]
On the other hand, there is a means of reducing the sharp melt property as the toner and considerably suppressing the glossiness of the fixed image, but in this case, the readability of the graphic image as described above is improved. This is certainly true, but pictorial images are not satisfactory in terms of gradation, brightness, and saturation. Furthermore, when using a transparency film (hereinafter abbreviated as OHT) using an overhead projector (hereinafter abbreviated as OHP), it comes from the projector due to the presence of toner particles that are not completely dissolved even after fixing. There is a problem in that irregular reflection of light increases or the projected image is reduced in transparency, brightness, and color sharpness due to factors such as insufficient color mixing. In particular, when the reflective OHP is used, this problem is further increased as compared with the case where the transmissive OHP is used.
[0009]
[Problems to be solved by the invention]
Accordingly, it is an object of the present invention to provide an image recorded matter that solves the problems of the prior art as described above. In other words, it is possible to provide an image without a sense of incongruity even in an image in which a graph portion and a character portion are mixed, such as a graphic image.PaintingHow to form an imageThe lawIt is to provide.
Another object of the present invention is that the fixing roller can be fixed well without applying a large amount of oil or without applying any oil.PaintingAn object is to provide an image recording method.
Furthermore, another object of the present invention is to obtain a high-quality full-color OHT image having excellent transparency.PaintingAn object is to provide an image recording method.
[0010]
[Means for Solving the Problems]
  The above object can be achieved by the following present invention. That is, the present invention forms a color toner image on an image carrier with a color toner containing at least a binder resin, a colorant and a release agent, and then fixes the color toner image by thermal means. In an image forming method for forming a recorded matter,
  T is the minimum temperature at which a color toner image can be fixed by thermal means._min, Maximum temperature T_maxT_minAnd T_maxThe glossiness G (T) of the image measured by fixing the color toner image on the image bearing member at a temperature T within the temperature range and entering incident light at an incident angle of 75 degrees to the surface of the image bearing member. ,
  Fixing temperature T is T_min≦ T ≦ T_minWhen in the range of +30
  [(T-T_min) / 30] + 1 ≦ G (T) ≦ [(T−T_min) / 5] +30,
  Fixing temperature T is T_min+30 <T ≦ T_minWhen within the range of +120 (however, T_min+120 is T_maxT exceeds_min+30 <T ≦ T_max),
  [(T-T_min) / 5] -4 ≦ G (T) ≦ [7 (T−T)_min) / 10] +15 and a color image recorded material is formed so as to exhibit a gloss behavior satisfying G (T) ≦ 50,
  The color toner is a toner obtained by directly producing toner particles by polymerizing a mixture containing at least a polymerizable monomer, a colorant, a release agent and a high molecular weight component,
  The release agent contained in the color toner has a weight average molecular weight of 350 to 4,000 and a number average molecular weight of 200 to 4,000.
  TheHigh molecular weight componentHas a weight average molecular weight (Mw) of 100,000 to 1,500,000.The binder resinAn image forming method comprising a high molecular weight component.
[0011]
[Action]
As a result of diligent research to solve the above-described problems of the prior art, the present inventors have found that when an image exhibits a specific glossiness behavior as described below, a graph portion and a character portion such as a graphic image are displayed. It has been found that even mixed images are provided with an uncomfortable image, are provided with a high-quality full-color OHT image with excellent transparency, and are excellent in the transportability of the transfer material. In order to obtain an image exhibiting a specific glossiness behavior, it is best to include at least 100,000 ≦ Mw ≦ 1,000,000 in the toner binder resin. And found the present invention.
[0012]
That is, when a toner image formed on an image carrier by toner containing at least a binder resin, a colorant, and a release agent is fixed on the image carrier by thermal means, thermal means are used. T is the minimum temperature at which the toner image can be fixed._min, Maximum temperature T_maxThus, when the toner image is fixed on the image carrier at a temperature T within this temperature range, the image on the image carrier surface measured by making incident light incident on the image carrier surface at an incident angle of 75 degrees is measured. When the glossiness G (T) of the recorded material exhibits a glossiness behavior satisfying the relationship of the following formula, an excellent image recorded material satisfying the above-mentioned purpose can be obtained.
First, the fixing temperature T is T_min≦ T ≦ T_minWhen it is within the range of +30, the glossiness G (T) is
[(T-T_min) / 30] + 1 ≦ G (T) ≦ [(T−T_min) / 5] +30
More preferably,
[(T-T_min) / 30] + 1 ≦ G (T) ≦ [(T−T_min) / 6] +20
It is desirable to exhibit gloss behavior in the range of
In the formula, T: temperature at which the toner image is fixed by thermal means
G (T): G (T) is the glossiness of the toner image fixed at temperature T
T_min: Minimum temperature at which toner image can be fixed by thermal means
[0013]
That is, (TT_min) Is less than 1/30 when the slope of the straight line is less than 1/30, the image glossiness at the time of fixing is too low, so high brightness and high saturation required for color images are required. The characteristics required for fine images cannot be obtained. Further, when the slope of the straight line exceeds 1/5, more preferably 1/6, the change in image glossiness with temperature is too large. For example, when an A3 portrait image is formed, before and after the fixed image. A difference in glossiness occurs at the edges, and accordingly, brightness, saturation, and the like vary greatly, resulting in an image that gives a sense of incongruity, and high image quality cannot be achieved.
[0014]
Further, the fixing temperature T is T_min+30 <T ≦ T_minWhen it is within the range of +120, the glossiness G (T) is
[(T-T_min) / 5] -4≤G (T) ≤ [7 (TT_min) / 10] +15 and G (T) ≦ 50,
More preferably,
[(T-T_min) / 3] -8 ≦ G (T) ≦ [5 (T−T)_min) / 6] and G (T) ≦ 50
It is desirable that the gloss behavior be in the range of.
[0015]
That is, (T-T_minWhen the slope of the straight line is less than 1/5, the toner cannot be completely melted when OHP is used, the transmittance is significantly reduced due to irregular reflection of light, and the mixing property is not good. Since it is sufficient, the color recognition of the projected image is extremely bad. When the slope of the straight line exceeds 7/10 or the value of G (T) exceeds 50, when an unfixed image that transfers a large amount of toner to a transfer material is fixed, The completely melted toner layer is cooled, and the volumetric shrinkage of the resin is extremely large, which causes curling of the edge portion of the fixed image, resulting in extremely high transportability of the fixed image during double-sided fixing. It deteriorates and a high-quality double-sided image cannot be obtained.
[0016]
In the present invention, the toner is constituted.Ru100,000 ≦ Mw ≦ 1, in the resin resin5By including a high molecular weight component of 00,000 in the binder resin, the above-described glossiness behavior can be obtained. The reason for this is that if the release agent in the toner composition contained during the production of the toner is present together with the specific high molecular weight component as described above, it will melt when the toner image is fixed by the heating means, Since the melted release agent enters the polymer chain in a state where the high molecular weight component that has started to melt to some extent in the binder resin is frayed, in the fixing temperature range from the fixing start point to over 30 ° C. This is because the plastic effect of the high molecular weight component occurs. Further, at this time, the molecular chain of the high molecular weight component whose plasticization has been promoted easily breaks, so that the melt viscosity of the entire binder resin of the toner also decreases. The gloss behavior is achieved even when the melt viscosity is lowered.
[0017]
[Preferred embodiment]
Next, the present invention will be described in more detail with reference to preferred embodiments.
The present inventionCan be used inThe toner for developing an electrostatic image has a weight average molecular weight Mw of at least 100,000 ≦ Mw ≦ 1,500,000 in a binder resin of a toner containing at least a binder resin, a colorant and a release agent. A certain high molecular weight component is contained. Then, using the electrostatic image developing toner, the toner image is fixed on the image carrier by thermal means to form an image recorded matter. At this time, T is the minimum temperature at which the toner image can be fixed by thermal means._min, Maximum temperature T_maxIf the toner image is fixed as an image on the image carrier at a temperature T within this temperature range, the glossiness of the image measured by making incident light incident on the surface of the image carrier at an incident angle of 75 degrees. G (T) has a certain glossiness behavior.
[0018]
The present inventionCan be used inThe high molecular weight component contained in the binder resin, which is a constituent of the electrostatic charge image developing toner, is any molecular weight component as long as the molecular weight is in the range of 100,000 ≦ Mw ≦ 1,500,000. However, more preferably, a high molecular weight component of 150,000 ≦ Mw ≦ 800,000 is desired. In particular, in the case of color toners, those having 180,000 ≦ Mw ≦ 700,000 are used. When Mw is less than 100,000, the fixing temperature T is T_min≦ T ≦ T_minIn the range of +30, G (T)> [1/5 (T−T_min)] + 30, and the gloss increases rapidly with the fixing temperature, and uniform image glossiness cannot be obtained.
[0019]
If Mw exceeds 1,500,000, T_min+30 <T ≦ T_minIn the range of +120, G (T) <[1/5 (T−T_min)]-4, resulting in a low gloss image and a high-definition image cannot be obtained.
[0020]
BookIn the present invention, the reason why the above action is obtained by incorporating a high molecular weight component of 100,000 ≦ Mw ≦ 1,500,000 in the binder resin is as described above. When the agent is present together with the high molecular weight component as described above, when the toner image is fixed by the heating means, the high molecular weight component starts to melt to some extent, and is released into the frayed polymer chain. As a result, the high molecular weight component has a plastic effect in a fixing temperature region exceeding 30 ° C. from the fixing start point. At this time, since the molecular chain of the high molecular weight component promoted by plasticization is easily cut, the melt viscosity of the entire binder resin of the toner is also lowered, which causes the above gloss behavior.
[0021]
In the present invention, the addition amount of the high molecular weight component as described above in the toner is in the range of 1 to 50 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the binder resin. When the addition amount is less than 1 part by weight, the effect until the above specific glossiness behavior is exhibited is not exhibited. When the addition amount exceeds 50 parts by weight, for example, the raw material mixture is polymerized. In the case of the polymerization method toner that directly obtains the toner, not only it takes time to dissolve the polymer in the monomer system, but also the granulation property is deteriorated, and the toner having a wide particle size distribution is produced.
[0022]
The present inventionCan be used inExamples of the release agent used in the toner for developing an electrostatic image include, for example, paraffin wax, microcrystalline wax, Fischer tropish wax, polyolefin wax, and modified products thereof (for example, oxide, grafted product, etc.) ), Higher fatty acids and metal compounds thereof, amide waxes, ester waxes and the like.
The amount of these release agents added is determined in the dry toner production method of obtaining toner particles by melting and kneading a mixture containing a binder resin, a colorant, and a wax, cooling and pulverizing, and classifying the mixture.Can be used inWhen the toner for developing an electrostatic charge image is produced, it is preferably added in an amount of 1 to 10 parts by weight, more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the binder resin.
[0023]
In contrast, in the present invention, the present invention is applied to a polymerization toner production method in which toner particles are directly produced by polymerizing a mixture containing at least a polymerizable monomer, a colorant, and a release agent.Can be used inWhen producing a toner for developing an electrostatic image, the polarity of the release agent usually used is lower than that of the binder resin as compared with the above-mentioned dry toner production method. It is easy to encapsulate a large amount of a release agent inside, and a large amount of the release agent can generally be used as compared with the dry toner production method described above, which is particularly effective for an offset prevention effect at the time of fixing.
[0024]
Further, the present invention can be achieved by a polymerization toner manufacturing method for directly obtaining toner particles.Can be used inWhen the toner for developing an electrostatic charge image is produced, the release agent is used in an amount of 5 to 40 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polymerizable monomer. desirable. When the addition amount of the release agent is less than the respective lower limit, the offset prevention effect tends to be lowered, and when the upper limit is exceeded, the anti-blocking effect is lowered, and the anti-offset effect is easily adversely affected. Sleeve fusion is likely to occur, which is not preferable. Furthermore, in the case of a polymerization method toner, a toner having a wide particle size distribution tends to be generated, which is not preferable.
[0025]
As the release agent used in the present invention, a release agent having the following structural formula is particularly preferably used from the viewpoint of fixability and transparency.
[0026]
<Structural formula 1 of release agent>

(A, b: an integer from 0 to 4, and a + b = 4,
R1, R2: an organic group having an integer of 1 to 40 carbon atoms, the difference in carbon number between R1 and R2 is 3 or more,
m and n are integers from 0 to 25, and m and n are not 0 at the same time)
[0027]
<Structural formula 2 of release agent>

(A and b are integers from 0 to 3, and 1 ≦ a + b ≦ 3,
R1, R2: an organic group having an integer of 1 to 40 carbon atoms, the difference in carbon number between R1 and R2 is 3 or more,
R3: a hydrogen atom, an organic group having 1 or more carbon atoms. However, when a + b = 2, either one of R3 is an organic group having 1 or more carbon atoms,
k: an integer from 1 to 3,
m and n are integers from 0 to 25, and m and n are not 0 at the same time)
[0028]
<Structural formula 3 of release agent>

(A, b: an integer from 0 to 4, and a + b = 4, b ≠ 0,
R1: an organic group having an integer of 1 to 40 carbon atoms,
m and n are integers from 0 to 25, and m and n are not 0 at the same time)
[0029]
<Structural formula 4 of release agent>

(R1 and R3 are organic groups having 6 to 32 carbon atoms, and R1 and R3 may be the same or different. R2 represents an organic group having 1 to 20 carbon atoms)
[0030]
<Structural formula 5 of release agent>

(R1, R3: an organic group having 6 to 32 carbon atoms, R1 and R3 may or may not be the same.
R2: -CH₂CH₂OC₆H_FourOCH₂CH₂−,
Or-(CH (CH_Three) CH₂O) -C₆H_FourC (CH_Three)₂C₆H_Four-(OCH₂CHCH_Three)_n−
Those having these modified bisphenol skeletons,
Or-(CH₂CH₂)_n−
n represents an integer of 1 to 10)
[0031]
More specifically, the following release agents may be mentioned, but are not limited thereto.
[0032]
Release agent 1
CH_Three(CH₂)₂₀COO (CH₂)_{twenty one}CH_Three
[0033]
Release agent 2
CH_Three(CH₂)₁₆COO (CH₂)_{twenty one}CH_Three
[0034]
Release agent 3
CH_Three(CH₂)₃₉COO (CH₂)₁₇CH_Three
[0035]
Release agent 4
CH_Three(CH₂)₂₀COO (CH₂)₁₇CH_Three
[0036]
Release agent 5

[0037]
Release agent 6

[0038]
Release agent 7

[0039]
Release agent 8

[0040]
Release agent 9

[0041]
Release agent 10

[0042]
Release agent 11

[0043]
Release agent 12

[0044]
In the present invention, the molecular weight distribution of the release agent as described above is measured by GPC under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: GMH-HT30cm2 series (manufactured by Tosoh Corporation)
・ Temperature: 135 ℃
Solvent: o-dichlorobenzene (0.1% ionol added)
・ Flow rate: 1.0 ml / min
・ Sample: 0.4 ml of 0.15% sample was injected
The molecular weight distribution is measured under the above conditions. Further, when calculating the molecular weight of the sample, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is calculated. Furthermore, it is calculated by converting to polystyrene using a conversion formula derived from the Mark-Houwink viscosity formula.
[0045]
The weight average molecular weight (Mw) of the release agent as used in the present invention is preferably 350 or more and 4,000 or less, and the number average molecular weight (Mn) is preferably 200 or more and 4,000 or less, more preferably. It is desirable that Mw is 400 or more and 3,500 or less and Mn is 250 or more and 3,500 or less. When Mw is less than 350 and Mn is less than 200, the blocking resistance of the toner is remarkably deteriorated, which is not preferable. On the other hand, when Mw exceeds 4,000 and Mn exceeds 4,000, the crystallinity of the release agent itself is manifested and the transparency of the OHT image and the like is remarkably deteriorated.
[0046]
The melting point of the release agent as described above used in the present invention is preferably in the range of 30 to 150 ° C, more preferably 50 to 90 ° C. When the melting point is lower than 30 ° C., the toner blocking resistance, the sleeve contamination suppression during the copying of a large number of sheets, and the anti-contamination property of the photoreceptor are liable to deteriorate, which is not preferable. If the melting point exceeds 150 ° C., excessive energy is required for uniform mixing with the binder resin in the toner manufacturing method by the pulverization method. In addition, a pressure-resistant reaction vessel under high pressure is required, and the apparatus becomes extremely complicated, which is not preferable.
[0047]
Also, the present inventionCan be used inThe solubility parameter (SP) value of the release agent used in the toner for developing an electrostatic image is determined by the method of Fedors using the chemical conversion of atomic groups [Polym. Eng. Sci. , 14 (2) 147 (1974)]. The SP value of the release agent used in the present invention obtained by such a method is preferably in the range of 7.6 to 9.7. A mold release agent having an SP value of less than 7.6 has poor compatibility with the binder resin used, and as a result, it is difficult to obtain good dispersion in the binder resin. Of the toner is likely to adhere to the developing sleeve, and the charge amount of the toner tends to change, which is not preferable. Furthermore, background fogging and density fluctuation at the time of toner replenishment are likely to occur. In the present invention, when a release agent having an SP value exceeding 9.7 is used, blocking between the toners tends to occur when the toner is stored for a long period of time. Furthermore, since the compatibility with the binder resin is too good, it is difficult to form a sufficient release layer between the fixing member and the binder resin layer of the toner at the time of fixing, and an offset phenomenon is likely to occur.
[0048]
The melt viscosity of the release agent used in the present invention may be a method of measuring at 135 ° C. using a cone plate rotor (PK-1) with VP-500 manufactured by HAAKE. The melt viscosity of the release agent at 135 ° C. is preferably in the range of 1 to 300 cPs, more preferably 3 to 50 cPs. When the melt viscosity is lower than 1 cPs, when the toner layer is thinly coated on the sleeve with a blade or the like in the non-magnetic one-component development method, the sleeve is liable to be contaminated by mechanical shearing force. Also in the two-component development method, when developing a toner using a carrier, damage is likely to occur due to a shearing force between the toner and the carrier, and external additives are easily buried and toner is crushed. In the case of having a melt viscosity exceeding 300 cPs, the polymerization methodTheWhen the toner is produced by using it, the viscosity of the dispersoid is too high, and it is not easy to obtain a toner having a fine particle size having a uniform particle size.
[0049]
Moreover, for the measurement of the hardness of the release agent used in the present invention, for example, a measuring method using a Shimadzu Dynamic Ultra Micro Hardness Tester (DUH-200) can be mentioned. As a measurement condition, by using a Vickers indenter and displacing 10 μm at a load speed of 9.67 mg / second under a load of 0.5 g, and analyzing a dent on the sample held for 12 seconds. Find Vickers hardness. As the sample, a sample previously melted using a mold having a diameter of 20 mmφ is molded into a 5 mm thick cylindrical shape and used. The hardness of the release agent used in the present invention obtained as a result of this is preferably 0.3 to 5.0, more preferably 0.5 to 3.0.
[0050]
A toner containing a release agent having a Vickers hardness of less than 0.3 is likely to be crushed at a cleaning site of a copying machine in a large number of copies, and easily causes toner fusion on the drum surface. Black stripes tend to occur, which is not preferable. Further, when multiple image samples are stored in a stacked manner, the toner is transferred to the back surface, and so-called show-through tends to occur, which is not preferable. A toner containing a release agent having a Vickers hardness of more than 5.0 requires an unnecessarily high pressure for the fixing device used for heat-fixing. . When a fixing device with a normal pressure is used, the offset resistance is liable to decrease, which is not preferable.
[0051]
Examples of the method for producing a release agent preferably used in the present invention include a synthesis method by oxidation reaction, synthesis from carboxylic acid and its derivatives, ester group introduction reaction represented by Michael addition reaction, carboxylic acid compound and alcohol compound. Produced by a method utilizing a dehydration condensation reaction from the above, a reaction from an acid halide and an alcohol compound, a transesterification reaction, or the like. As a catalyst, a general acidic catalyst used for esterification reaction, an alkaline catalyst, for example, zinc acetate, a titanium compound, etc. are used. After that, it may be highly purified by a recrystallization method, a distillation method or the like.
[0052]
The present inventionCan be used inExamples of the binder resin used in the toner for developing an electrostatic image include the following resins. For example, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, etc., and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol Resin, natural resin modified film Nord resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, tempen resin, coumarone indene resin And petroleum resins. Among them, particularly preferable binder resins include styrene copolymers or polyester resins.
[0053]
Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Carboxylic acid having a double bond such as acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or the like; maleic acid, butyl maleate, methyl maleate , Dicarboxylic acids having a double bond such as dimethyl maleate, and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; and ethylene-based olefins such as ethylene, propylene and butylene. Down like; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, such vinyl ethers and vinyl isobutyl ether; These vinyl monomers are used singly or two or more.
[0054]
Also, the present inventionCan be used inThe above-mentioned various materials can also be used as a high molecular weight component having a weight average molecular weight Mw of 100,000 ≦ Mw ≦ 1,500,000 used in the toner for developing an electrostatic image.
The number average molecular weight of the THF-soluble component of the binder resin used in the present invention is preferably 3,000 to 1,000,000. The styrene polymer or styrene copolymer may be cross-linked or a mixed resin thereof.
[0055]
As the binder for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butadiol dimethacrylate; divinyl Divinyl compounds such as aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; these may be used alone or as a mixture. As addition amount, 0.001-10 weight part is preferable with respect to 100 weight part of polymerizable monomers.
[0056]
The present inventionCan be used inThe toner for developing an electrostatic image may contain a charge control agent.
Examples of the charge control agent for controlling the toner to be negatively charged include the following substances. For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, nonmetals Examples thereof include carboxylic acid compounds.
[0057]
Further, there are the following substances as charge control agents for controlling the toner to be positively charged. For example, modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts and their lake pigments, triphenylmethane dyes and their lake pigments. ), Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; can be used in combination singly or two or more kinds. Among these, a charge control agent such as a nigrosine-type quaternary ammonium salt is particularly preferably used.
[0058]
These charge control agents are preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin component in the toner.
Also, the present inventionCan be used inExamples of the colorant contained in the electrostatic image developing toner include carbon black, aniline black, and acetylene black as black pigments.
[0059]
Magenta pigments include reddish yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3B, carmine 6B, manganese purple, Fast Violet B, Methyl Violet Lake, Rhodamine Lake, Arizakun Lake, Bengala, Quinacridone, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; I. Pigment violet 19, C.I. I. Violet 1, 2, 10, 13, 15, 23, 29, 35 etc. are mentioned.
[0060]
Examples of cyan pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bad Blue 6, C.I. I. Acid Blue 45, Indanthrene Blue, Bituminous Blue, Cobalt Blue, Alkali Blue Lake, Biclear Blue Lake, Phthalocyanine Blue, Earth Sky Blue, Indanthrene Blue BC, Chrome Green, Chrome Oxide, Pigment Green B, Malachite Green Lake, Final yellow green G etc. are mentioned.
[0061]
Examples of yellow pigments include naphthol yellow, haiza yellow, yellow lead, cadmium yellow, mythal fast yellow, navel yellow, permanent yellow NCG, tartrazine lake, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, 97, 120, 127, 174, 176, 180, 191, C.I. I. Bad yellow 1, 3, 20, etc. are mentioned.
These pigments are used in an amount necessary for maintaining the optical density of the fixed image. In the present invention, 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight per 100 parts by weight of the resin. It is desirable to add in the range of parts by weight.
[0062]
Examples of the dye used as the colorant in the present invention include the following.
Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet, 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28, C.I. I. Direct Red 1, 4, C.I. I. Acid Red 1, C.I. I. Modern tread 30 etc. are mentioned.
[0063]
Examples of cyan dyes include C.I. I. Direct Blue 1, 2, C.I. I. Acid Blue 9, 15, C.I. I. Basic Blue 3, 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic green 4, 6, etc. are mentioned.
These dyes are added in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of the resin.
[0064]
Furthermore, the present inventionCan be used inThe toner for developing an electrostatic image further contains a magnetic material and can be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant. In the present invention, examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, nickel, or aluminum, cobalt, copper, lead of these metals, Examples include alloys of metals such as magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.
[0065]
These ferromagnetic materials preferably have an average particle size of 2 μm or less and about 0.1 to 0.5 μm. The amount of these magnetic materials to be contained in the toner is desirably about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, based on 100 parts by weight of the resin component.
In addition, as a physical property of the magnetic material used in the present invention, the magnetic characteristics when 10 kOe is applied are the coercive force (H_c) 20-300 Oe, saturation magnetization (σ_s) 50 to 200 emu / g, residual magnetization (σ_r) It is preferred to use 2-20 emu / g.
[0066]
Various additives added for the purpose of imparting toner characteristics are those having a particle size of 1/5 or less of the volume average particle size of the toner particles from the viewpoint of durability in the toner or when added to the toner. Preferably there is. Here, the particle diameter of the additive means the average particle diameter obtained by observing the surface of the toner particles with an electron microscope. Examples of the additive for the purpose of imparting these characteristics include the following.
[0067]
Examples of the fluidity-imparting agent include metal oxides such as silicon oxide, aluminum oxide, and titanium oxide, carbon black, and carbon fluoride. It is more preferable to use those that have been hydrophobized.
As abrasives, metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, nitrides such as silicon nitride, carbides such as silicon carbide, calcium sulfate, barium sulfate, calcium carbonate, etc. And metal salts thereof.
[0068]
Examples of the lubricant include fluorine resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.
Examples of the charge control agent include metal oxides such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide, and carbon black.
These additives are used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination.
[0069]
The present inventionCan be used inThe toner for developing an electrostatic image can usually be used for either a one-component developer or a two-component developer.
For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as a one-component developer, there is a method of transporting and charging the magnetic toner using a magnet incorporated in the developing sleeve. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly frictionally charge the developing sleeve, and the toner adheres to the developing sleeve and is conveyed.
[0070]
On the other hand, when used as a commonly used two-component developer, the present inventionCan be used inA carrier is used together with the toner and used as a developer. Although it does not specifically limit as a carrier used for this invention, It is comprised mainly by the single and composite ferrite state which mainly consists of iron, copper, zinc, nickel, cobalt, manganese, and a chromium element. The carrier shape is also important because the saturation magnetization and electric resistance can be controlled over a wide range.For example, the spherical shape, the flat shape, and the irregular shape are selected, and the fine structure of the carrier surface state, for example, the surface irregularity Is also preferably controlled.
[0071]
In general, the carrier core particles are generated in advance by firing and granulating the inorganic oxide as described above, and then the resin is coated. However, the load on the toner of the carrier is reduced. In view of this, a method of obtaining a low-density dispersion carrier by kneading an inorganic oxide and a resin and then pulverizing and classifying the mixture, or by directly suspension-polymerizing a kneaded product of an inorganic oxide and a monomer in an aqueous medium Also, a method for obtaining a polymerized carrier for obtaining a spherical dispersion carrier can be used.
A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any of conventionally known methods such as a method of dissolving or suspending a coating material such as a resin in a solvent and applying it to a carrier and simply mixing with a powder can be applied.
[0072]
The substance to be fixed on the carrier surface varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of ditertiary butylsalicylic acid, styrene resin Acrylic resins, polyamides, polyvinyl butyral, nigrosine, aminoacrylate resins, basic dyes and their lakes, silica fine powder, alumina fine powder, etc. may be used alone or in combination, but are not necessarily limited thereto. .
[0073]
The treatment amount of the above compound is generally 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the carrier in total amount.
The average particle size of the carrier as described above is 10 to 100 μm, preferably 20 to 50 μm.
[0074]
A particularly preferable embodiment of the carrier is ferrite, and the surface thereof is a combination of a resin such as a fluorine resin and a styrene resin, for example, polyvinylidene fluoride and a styrene-methyl methacrylate resin; polytetrafluoroethylene and a styrene-methyl methacrylate. A mixture of acrylate resin; fluorine copolymer and styrene copolymer; etc. in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70, or a silicone resin, etc. A coated ferrite carrier having a mean particle diameter of about 5 to 5% by weight, preferably 0.1 to 1% by weight, may be mentioned. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based copolymer include styrene-acrylic acid-2-ethylhexyl (20 : 80-80: 20), styrene-acrylic acid-2-ethylhexine-methyl methacrylate (20-60: 5-30: 10-50).
[0075]
The coated ferrite carrier as described above has a sharp particle size distribution.Can be used inA favorable triboelectric chargeability can be obtained for the toner, and there is an effect of improving the electrophotographic characteristics.
When a two-component developer is prepared by mixing with the toner in the present invention, the mixing ratio is usually 2 to 15% by weight, preferably 4 to 13% by weight, as the toner concentration in the developer. Results are obtained. If the toner concentration is 2% by weight or less, the image density is low and unpractical, and if it is 15% by weight or more, fogging and in-machine scattering are increased and the useful life of the developer is shortened.
[0076]
Furthermore, the carrier used in the present invention preferably has the following magnetic properties. That is, the magnetization strength (σσ at 1000 Oe after magnetic saturation)₁₀₀₀) Is required to be 30 to 300 emu / g. Furthermore, in order to achieve high image quality, it is preferably 100 to 250 emu / g. When it is greater than 300 emu / g, it becomes difficult to obtain a high-quality toner image. On the other hand, if it is less than 30 emu / g, the magnetic binding force is also reduced, and carrier adhesion is likely to occur.
[0077]
The carrier shape is preferably such that SF1 indicating the degree of roundness is 180 or less and SF2 indicating the degree of unevenness is 250 or less. The values of SF1 and SF2 were defined by the following formulas, and were measured with LUZEX III manufactured by Nireco.
SF1 = [(maximum length of carrier)²/ Area] × (π / 4)
SF2 = [(carrier peripheral length)²/ Area] × (1 / 4π)
[0078]
The present inventionCan be used inIn the case of producing a toner for developing an electrostatic charge image by a pulverization method, a pulverized toner production method includes first a binder resin, a high molecular weight component, a release agent, a pigment or dye as a colorant, and a magnetic material as necessary. Charge control agents, other additives, etc. are thoroughly mixed using a mixer such as a Henschel mixer or ball mill, and then melt-kneaded using a heat kneader such as a heating roll, kneader or extruder to make the resins compatible with each other. In the caulking, a metal compound, a pigment, a dye, and a magnetic material are dispersed or dissolved, cooled and solidified, and then pulverized and classified.Can be used inGet toner.
Thereafter, the toner for developing an electrostatic charge image according to the present invention can be further externally added by sufficiently mixing a desired additive with a mixer such as a Henschel mixer, if necessary.
[0079]
Also, the present inventionCan be used inA polymerized toner obtained by directly obtaining a toner for developing an electrostatic image by a polymerization method is produced by the following method. That is, a high molecular weight component, a release agent, a colorant, and, if necessary, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer, and a homogenizer or an ultrasonic disperser is used. The monomer system uniformly dissolved or dispersed is dispersed in a dispersion medium containing a dispersion stabilizer or an emulsifier by a stirrer, a homomixer, a homogenizer or the like, and granulated. Thereafter, stirring may be performed to such an extent that the monomer-based particle state is maintained by the action of the dispersion stabilizer and the precipitation of the monomer-based particles is prevented. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing, the latter half of the reaction or the end of the reaction. A part of the aqueous medium may be distilled off later. After completion of the reaction, the produced toner particles are washed and collected by filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.
[0080]
The toner particle size is preferably 0.1 to 12 μm in weight average particle size in Coulter Counter Model TA-II (manufactured by Coulter Electronics Co., Ltd.), and the particle size distribution preferably has a coefficient of variation in weight average diameter of 8 to 40%, and more The SF1 value representing the degree of roundness is preferably 100 <SF1 <150, and the SF2 value representing the degree of unevenness is preferably 100 <SF2 <200.
[0081]
Examples of the polymerizable monomer used when directly obtaining a toner using a polymerization method include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p. -Styrene monomers such as ethyl styrene; methyl acrylate, ethyl acrylate, acrylic acid -n-butyl, acrylic acid isobutyl, acrylic acid -n-propyl, acrylic acid -n-octyl, acrylic acid dodecyl, acrylic acid Acrylic esters such as 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, -n-butyl methacrylate, methacrylic acid Isobutyl, methacrylate-n-octyl, dodecyl methacrylate, Acrylic acid 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate and the like; acrylonitrile, methacrylonitrile, and the like monomers acrylamide. These monomers can be used alone or in combination.
[0082]
Further, a polymer or copolymer having a polar group may be added as an additive to the monomer of the polymerization toner used in the present invention. Examples of polar polymers and copolymers that can be used in this case include the following. For example, polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; copolymers with styrene-unsaturated carboxylic acid esters; nitrile monomers such as acrylonitrile; vinyl chloride and the like Halogen-containing monomers; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; other polymers such as unsaturated dibasic acids, unsaturated dibasic acid anhydrides, nitro monomers, or styrene monomers And a copolymer, polyester, epoxy resin and the like.
[0083]
Examples of the polymerization initiator used in this case include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, Diisopropylperoxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl oxide, 2,2-bis (4,4-t-butylperoxy) (Cyclohexyl) propane, tris- (t- Macroinitiator having Chiruperuokishi) peroxide initiator or a peroxide such as triazine in a side chain; potassium persulfate, persulfates such as ammonium persulfate; hydrogen peroxide or the like is used.
[0084]
The polymerization initiator as described above is preferably added in an amount of 0.5 to 20 parts by weight of the polymerizable monomer, and may be used alone or in combination. Moreover, you may add a well-known crosslinking agent and a chain transfer agent, As a preferable addition amount, it is 0.001-15 weight part.
[0085]
In the present invention, a polymerization method toner is produced by a polymerization method using emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, salting out, etc., and any suitable stability may be used for the dispersion medium used in this case. Agent is used. As the stabilizer at this time, for example, as an inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Examples thereof include calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Organic compounds include polyvinyl alcohol, gelatin methylcellulose, methylhydroxypropylcellulose, ethylcellulose, carboxymethylcellulose sodium salt, polyacrylic acid and its salts, starch, polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methacrylic acid) (Methyl-eu-methacrylic acid) copolymer, nonionic or ionic surfactant and the like are used.
[0086]
In the case of using an emulsion polymerization method, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and a nonionic surfactant are used as a stabilizer. These stabilizers are preferably used in an amount of 0.2 to 30 parts by weight with respect to 100 parts by weight of the polymerizable monomer.
Among these stabilizers, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be produced in a dispersion medium.
[0087]
Further, for fine dispersion of these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This promotes the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, stearin. Examples include potassium acid and calcium oleate.
[0088]
Further, as the colorant used in the polymerization method toner in the present invention, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant, and the colorant as described above is preferably surface-modified, For example, it is preferable to use a hydrophobized treatment that does not inhibit polymerization. In particular, dyes and carbon blacks have many polymerization inhibiting properties, so care must be taken when using them. A preferable method for surface-treating the dye system includes a method in which a polymerizable monomer is previously polymerized in the presence of these dyes, and the obtained colored polymer is added to the monomer system. Carbon black may be treated with a substance that reacts with the surface functional group of carbon black, such as polyorganosiloxane, in addition to the same treatment as the above dye.
[0089]
In the present invention, the evaluation method of the toner fixability, offset resistance, and color mixture area of the recorded image is as follows.
First, the present inventionCan be used inAn appropriate amount of an appropriate external additive is added to the toner to obtain a developer. An unfixed image of the obtained developer is produced by a commercially available copying machine. At this time, when the toner is black toner, the fixing property and the offset property are evaluated by a 40 mmφ heat roller external fixing device having no oil application function. In the case of mono-color toner or full-color toner, in addition to a 40 mmφ heat roller external fixing device having no oil application function, it was applied to a fixing roller to which some oil was uniformly applied (for example, an oil amount of 0.02 g / A4 size) ) Using a 40 mmφ heat roller external fixing device, the fixing property and the offset resistance are evaluated, and a fixed image for transparency evaluation and image evaluation is obtained.
[0090]
In addition, as a roller material at this time, a fluorine-type thing is used for both the upper part and the lower part. As fixing conditions, when the transfer material is SK paper (manufactured by Nippon Paper Industries Co., Ltd.), the nip is 6.5 mm, the process speed is 105 mm / sec, and the transfer material is an OHT sheet (CG3300 / 3M company). Is performed by adjusting the temperature every 5 ° C. within a temperature range of 100 to 250 ° C. with a nip of 6.5 mm and a process speed of 35 mm / sec.
[0091]
(1) Fixability
Fixability is 50g / cm for fixed images (including low-temperature offset images)²The temperature at which the rate of density decrease before and after rubbing is less than 10% is set as the fixing start point by rubbing with Silbon paper (Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co., Ltd)).
[0092]
(2) Offset resistance
In the offset resistance, a temperature at which no offset is visually observed is set as a low temperature offset start point, and a maximum temperature without offset by increasing the temperature is set as a high temperature offset end point.
[0093]
(3) Glossiness
Further, the gloss value was measured for an image in the non-offset region using a specular gloss measuring device PG-3D (manufactured by Nippon Color Co., Ltd.).
Tables 1 and 2 show the low temperature offset starting point (T_low), Minimum fixing temperature T_min, T_min+30, high temperature offset end point (fixing maximum temperature T_max), Fixing temperature TG showing the highest gloss value_max, G (T_min), G (T_min+30), G (T_max), G (TG_max), Non-offset region, transmittance, and haze values are shown.
[0094]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to an Example.
[0095]
Example 1
To 750 g of ion-exchanged water, 0.1 M Na_ThreePO_Four500 g of the aqueous solution was added, and after heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 1.0M-CaCl₂Add 75 g of aqueous solution gradually and add Ca_Three(PO_Four)₂An aqueous medium containing was obtained.
on the other hand,
・ Styrene 170g
・ 30g of n-butyl acrylate
・ Copper phthalocyanine pigment 18g
Di-t-butyl salicylic acid metal compound 2g
-Release agent (1) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 600,000) 24 g
The above formulation was heated to 60 ° C., and uniformly dissolved and dispersed at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 10 g of polymerization initiators 2,2′-azobis (2,4-dimethylvaleronitrile) were dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition is charged into the aqueous medium, and the temperature is 60 ° C., N₂Under an atmosphere, the polymerizable monomer composition was granulated by stirring at 12,000 rpm for 12 minutes with a TK homomixer. Then, while stirring at 500 rpm using a paddle stirring blade, the temperature was raised to 70 ° C. and reacted for 15 hours. After completion of the polymerization reaction, the mixture was cooled and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, and drying to obtain polymer particles.
The specific surface area by the BET method is 100 m with respect to 100 parts by mass of the obtained particles.²Externally added 1.2 parts by mass of hydrophobic titanium oxide fine particles of / g, to obtain a suspension polymerization toner. The weight average particle size of the obtained cyan toner was 6.4 μm.
94 parts by weight of a ferrite carrier coated with a silicone resin was mixed with 6 parts by weight of the toner to obtain a developer. Using this developer, an unfixed image was produced with a commercially available electrophotographic copying machine CLC700 (manufactured by Canon Inc.), and the fixability and OHT transparency were evaluated. The results are shown in Table 1.
[0096]
Example 2
・ Styrene 169g
・ 31 g of n-butyl acrylate
・ Copper phthalocyanine pigment 22g
Di-t-butyl salicylic acid metal compound 2g
-Release agent (5) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 350,000) 20 g
The same operation as in Example 1 is performed with the above formulation to obtain a polymerizable composition, and then a developer is obtained. Using the developer, the fixability and OHT transparency were evaluated in the same manner as in Example 1. The obtained magenta toner had a weight average particle diameter of 6.5 μm. The results are shown in Table 1.
[0097]
Example 3
・ Styrene 171g
・ N-Butyl acrylate 29g
・ Copper phthalocyanine pigment 20g
・ Di-t-butylsalicylic acid metal compound 4g
-Release agent (7) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 120,000) 10 g
The same operation as in Example 1 is performed with the above formulation to obtain a polymerizable composition, and then a developer is obtained. Using the developer, the fixability and OHT transparency were evaluated in the same manner as in Example 1. The obtained yellow toner had a weight average particle diameter of 6.7 μm. The results are shown in Table 1.
[0098]
Reference example 1
・ Styrene 172g
・ N-butyl acrylate 28g
・ Grafted carbon black pigment 17g
・ Di-t-butylsalicylic acid metal compound 3g
・ 40g paraffin wax
・ High molecular weight resin
(Weight average molecular weight Mw = 880,000) 22 g
The same operation as in Example 1 is performed with the above formulation to obtain a polymerizable composition, and then a developer is obtained. Using the developer, the fixability and OHT transparency were evaluated in the same manner as in Example 1. The resulting black toner had a weight average particle size of 6.2 μm. The results are shown in Table 1.
[0099]

The same operation as in Example 1 was performed with the above formulation to obtain a polymerizable composition, and then a developer was obtained. The fixability was evaluated using the developer. The obtained magnetic toner had a weight average particle diameter of 6.6 μm, and a commercially available electrophotographic copying machine NP8582 (manufactured by Canon Inc.) was used as an evaluation machine for producing an unfixed image. The results are shown in Table 1.
[0100]

After the above materials were premixed, they were melt kneaded by a biaxial kneading extruder set at 130 ° C. The kneaded product was cooled, coarsely pulverized, finely pulverized with a pulverizer using a jet stream, and further classified with an air classifier to obtain a toner having a weight average particle diameter of 6.7 μm. 100 parts by mass of this toner and 1.2 parts by mass of hydrophobic titanium oxide fine powder were mixed (added externally) to obtain a toner having hydrophobic titanium oxide fine powder on the toner particle surface.
Using this developer, an unfixed image was produced using a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.), and the fixability was evaluated by the same evaluation method as in Example 1. The results are shown in Table 1.
[0101]
Example 4
・ Polyester resin 1,000g
(Bisphenol A diol-terephthalic acid
-Dodecenyl succinic acid-trimellitic acid condensate;
(Molar ratio = 50: 40: 5: 5)
・ Copper phthalocyanine pigment 40g
・ Di-t-butylsalicylic acid metal compound 20 g
・ Mold release agent (2) 50g
・ High molecular weight resin
(Weight average molecular weight Mw = 470,000) 150 g
After mixing the above materials, a developer was obtained in the same manner as in Reference Example 3, and the fixability and OHT transparency were evaluated. The weight average particle size of the obtained cyan toner was 6.2 μm. The results are shown in Table 1.
[0102]
Example 5
・ 165 g of styrene
・ 34g of n-butyl acrylate
・ Copper phthalocyanine pigment 22g
・ Di-t-butylsalicylic acid metal compound 3g
-Release agent (8) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 350,000) 20 g
The same operation as in Example 1 is performed with the above formulation to obtain a polymerizable composition, and then a developer is obtained. Using the developer, the fixability and OHT transparency were evaluated in the same manner as in Example 1. The obtained magenta toner had a weight average particle diameter of 6.5 μm. The results are shown in Table 1.
[0103]
In the same manner as in Example 1, magenta, yellow, and black toners were prepared from quinacridone pigment, disazo yellow pigment, and graft-treated carbon black pigment, and the four-color toner of cyan toner in Example 1 was used as a commercially available electronic toner. When a graphic full-color image was output by a photocopier CLC700 (manufactured by Canon Inc.), a glossy, easy-to-read and uncomfortable image was obtained.
The full color OHT image at this time was excellent in transparency and high in quality.
[0104]

[0105]
Comparative Example 1
To 740 g of ion-exchanged water, 0.1 M Na_ThreePO_FourAfter adding 490 g of the aqueous solution and heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 1.0M-CaCl₂77 g of aqueous solution was gradually added, and Ca_Three(PO_Four)₂An aqueous medium containing was obtained. on the other hand,
・ Styrene 170g
・ 30g of n-butyl acrylate
・ Copper phthalocyanine pigment 17g
Di-t-butyl salicylic acid metal compound 2g
-Release agent (12) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 30,000) 36 g
[0106]
The above formulation was heated to 60 ° C., and uniformly dissolved and dispersed at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 10 g of polymerization initiators 2,2′-azobis (2,4-dimethylvaleronitrile) were dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition is charged into the aqueous medium, and the temperature is 60 ° C., N₂Under an atmosphere, the polymerizable monomer composition was granulated by stirring at 12,000 rpm for 12 minutes with a TK homomixer. Then, while stirring at 500 rpm using a paddle stirring blade, the temperature was raised to 70 ° C. and reacted for 15 hours. After completion of the polymerization reaction, the mixture was cooled and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, and drying to obtain polymer particles.
The specific surface area by the BET method is 100 m with respect to 100 parts by mass of the obtained particles.² Externally added 1.2 parts by mass of hydrophobic titanium oxide fine particles of / g, to obtain a suspension polymerization toner. The weight average particle size of the obtained cyan toner was 6.4 μm.
94 parts by weight of a ferrite carrier coated with a silicone resin was mixed with 6 parts by weight of the toner to obtain a developer. Using this developer, an unfixed image was produced with a commercially available electrophotographic copying machine CLC700 (manufactured by Canon Inc.), and the fixability and OHT transparency were evaluated by the above methods. The results are shown in Table 2.
[0107]
Comparative Example 2
・ High molecular weight resin
(Weight average molecular weight Mw = 1510,000) 34 g
Except for this, a cyan toner having a weight average particle diameter of 6.7 μm was obtained in the same manner as in Example 4, and an unfixed image was obtained using a commercially available electrophotographic copying machine CLC700 (manufactured by Canon Inc.). Thus, fixability and OHT transparency were evaluated. The results are shown in Table 2.
[0108]
Comparative Example 3
・ High molecular weight resin
(Weight average molecular weight Mw = 490,000) 102 g
Other than this, a black toner having a weight average particle diameter of 6.3 μm was obtained in the same manner as in Reference Example 3. Evaluation was performed in the same manner as in Reference Example 3. The results are shown in Table 2.
[0109]
Comparative Example 4
・ Styrene 172g
・ N-butyl acrylate 28g
・ Copper phthalocyanine pigment 21g
・ Di-t-butylsalicylic acid metal compound 4g
-Release agent (1) 40g
・ High molecular weight resin
(Weight average molecular weight Mw = 40,000) 1 g
・ 2,2'-azobis (2,4
-Dimethylvaleronitrile) 6g
After obtaining the polymerizable composition as described above, a developer was obtained in the same manner as in Comparative Example 1, and the fixability and OHT transparency were evaluated. The obtained magenta toner had a weight average particle diameter of 6.5 μm. The results are shown in Table 2.
[0110]

After obtaining the polymerizable composition as described above, a developer was obtained in the same manner as in Comparative Example 1, and the fixability was evaluated. The obtained magnetic toner had a weight average particle diameter of 6.6 μm, and a commercially available electrophotographic copying machine NP8582 (manufactured by Canon Inc.) was used as an evaluation machine for producing an unfixed image. The results are shown in Table 2.
[0111]

After the above materials were premixed, they were melt kneaded by a biaxial kneading extruder set at 130 ° C. The kneaded product was cooled, coarsely pulverized, finely pulverized with a pulverizer using a jet stream, and further classified with an air classifier to obtain a toner having a weight average particle diameter of 6.7 μm. 100 parts by mass of this toner and 1.2 parts by mass of hydrophobic titanium oxide fine powder were mixed (added externally) to obtain a toner having hydrophobic titanium oxide fine powder on the toner particle surface.
Using this developer, an unfixed image was produced using a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.), and the fixability was evaluated. The results are shown in Table 2.
[0112]
Comparative Example 7
・ Polyester resin 1,000g
(Bisphenol A diol-terephthalic acid
-Dodecenyl succinic acid-trimellitic acid condensate;
(Molar ratio = 50: 40: 5: 5)
・ Copper phthalocyanine pigment 45g
・ Di-t-butylsalicylic acid metal compound 20 g
・ Release agent (1) 50g
・ High molecular weight resin
(Weight average molecular weight Mw = 50,000) 18 g
After mixing the polymerizable composition as described above, a developer was obtained in the same manner as in Comparative Example 6, and the fixability and OHT transparency were evaluated. The weight average particle size of the obtained cyan toner was 6.2 μm. The results are shown in Table 2.
[0113]

[0114]
【The invention's effect】
As described above, according to the present invention, an image having no sense of incongruity can be obtained even in an image in which a graph portion and a character portion are mixed, such as a graphic image, and a full-color image excellent in OHT transparency is provided. .
Furthermore, according to the present invention, fixing can be performed without substantially applying oil to the fixing roller.

Claims (1)

An image in which a color toner image is formed on an image carrier with a color toner containing at least a binder resin, a colorant, and a release agent, and then the color toner image is fixed by thermal means to form a color image recorded matter In the forming method,
When the minimum temperature at which the color toner image can be fixed by thermal means is T _min and the maximum temperature is T _max , the color on the image carrier at a temperature T within the temperature range between T _min and T _max. The glossiness G (T) of the image measured by fixing the toner image and making incident light incident at an incident angle of 75 degrees on the surface of the image carrier,
When the fixing temperature T is in the range of T _min ≦ T ≦ T _min +30,
[(T−T _min ) / 30] + 1 ≦ G (T) ≦ [(T−T _min ) / 5] +30
The filling,
When the fixing temperature T is in the range of T _min +30 <T ≦ T _min +120 (provided that T _min +120 exceeds T _max , T _min +30 <T ≦ T _max ),
[(T−T _min ) / 5] −4 ≦ G (T) ≦ [7 (T−T _min ) / 10] +15 and a color image so as to exhibit a gloss behavior satisfying G (T) ≦ 50 Form a record,
The color toner is a toner obtained by directly producing toner particles by polymerizing a mixture containing at least a polymerizable monomer, a colorant, a release agent and a high molecular weight component,
The release agent contained in the color toner has a weight average molecular weight of 350 to 4,000 and a number average molecular weight of 200 to 4,000.
The high molecular weight component, the weight average molecular weight (Mw) Ri der 100,000 to 1,500,000, an image forming method characterized in that the binder resin containing the high molecular weight component.