JP4227268B2 - Dry toner - Google Patents

Description

【００４９】
本発明において、結着樹脂はカルボキシル基含有ビニル樹脂とグリシジル基含有ビニル樹脂が反応した樹脂を含有する。この両者を反応させる場合、この反応は結着樹脂製造時あるいはトナー製造時のいずれで行われても良い。
【００５０】
本発明の特徴とするカルボキシル基含有ビニル樹脂を得るためには、高分子量成分の酸価は高く、低分子量成分の酸価は低くする設計が好ましい。これは、高分子量成分に選択的に反応を起こさせ、低温定着性に影響を与えず、耐オフセット性を向上させるためである。
【００５１】
本発明のカルボキシル基含有ビニル樹脂を得るためには、高分子量成分，低分子量成分共にビニル系重合体のモノマーとして以下のものを用いることができる。
【００５２】
例えば、マレイン酸、シトラコン酸、ジメチルマレイン酸、イタコン酸、アルケニルコハク酸、及びこれらの無水物；フマル酸、メタコン酸、ジメチルフマル酸；などの不飽和二塩基酸、無水物モノマー。更に上記不飽和二塩基酸のモノエステル。また、アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸及びこれらの無水物；上記α，β−不飽和酸間の無水物及び、低級脂肪酸との無水物；などのα，β−不飽和酸、これらの無水物モノマー。アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸及びこれらの無水物、モノエステル。これらの中でも、マレイン酸、マレイン酸ハーフエステル、マレイン酸無水物が本発明の結着樹脂を得るモノマーとして特に好ましく用いられる。
【００５３】
更にビニル重合体のコモノマーとしては、次のようなものが挙げられる。
【００５４】
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−フェニルスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン等のスチレン及びその誘導体；エチレン、プロピレン、ブチレン、イソブチレンなどのエチレン不飽和モノオレフィン類；ブタジエン等の不飽和ポリエン類；塩化ビニル、塩化ビニリデン、臭化ビニル、沸化ビニルなどのハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルなどのビニルエステル類；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などのα−メチル脂肪族モノカルボン酸エステル類；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などのアクリル酸エステル類；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などのビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンなどのビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンなどのＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドなどのアクリル酸もしくはメタクリル酸誘導体；前述のα，β−不飽和酸のエステル、二塩基酸のジエステル類；のビニル系モノマが単独もしくは２つ以上で用いられる。
【００５５】
これらの中でも、スチレン系共重合体、スチレン−アクリル系共重合体となるようなモノマーの組み合わせが好ましい。
【００５６】
スチレン系共重合体が好ましい理由としては、スチレン系共重合体のポリマー鎖のところどころに存在するカルボキシル基が効果的にグリシジル基含有ビニル樹脂中のグリシジル基と相互作用し、離型剤，磁性体等の原料との分散性を向上させるためである。
【００５７】
また架橋性モノマーとしては、主として２個以上の重合可能な二重結合を有するモノマーが用いられる。
【００５８】
本発明に用いられる結着樹脂は、必要に応じて以下に例示する様な架橋性モノマーで架橋された重合体であってもよい。
【００５９】
芳香族ジビニル化合物、例えば、ジビニルベンゼン、ジビニルナフタレン等；アルキル鎖で結ばれたジアクリレート化合物類、例えば、エチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたもの；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたもの；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類、例えば、ポリオキシエチレン（２）−２，２−ビス（４−ヒドロキジフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキジフェニル）プロパンジアクリレート及び、以上の化合物のアクリレートをメタアクリレートに代えたもの；更には、ポリエステル型ジアクリレート化合物類、例えば、商品名ＭＡＮＤＡ（日本化薬）が挙げられる。多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタアクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテート；等が挙げられる。
【００６０】
これらの架橋剤は、他のモノマー成分１００質量部に対して、０．０１〜５質量部程度（更に好ましくは０．０３〜３質量部程度）用いることが好ましい。
【００６１】
本発明の樹脂を製造する時の開始剤、溶剤の種類及び反応条件の選択は本発明の目的とする樹脂を得る為に重要な要素である。開始剤としては、例えはベンゾイルパーオキシド、１，１−ジ（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ジ（ｔ−ブチルパーオキシ）バレレート、ジクミルパーオキシド、α，α’−ビス（ｔ−ブチルパーオキシジイソプロピル）ベンゼン、ｔ−ブチルパーオキシクメン、ジ−ｔ−ブチルパーオキシド等の有機過酸化物；アゾビスイソブチロニトリル、ジアゾアミノアゾベンゼン等のアゾ及びジアゾ化合物などが利用できる。
【００６２】
本発明に係るカルボキシル基含有ビニル樹脂の低分子量成分重合体を合成する方法としては、公知の方法を用いることができる。しかしながら塊状重合法では、高温で重合させて停止反応速度を速めることで低分子量の重合体を得ることができるが、反応をコントロールしにくいという問題点がある。その点、溶液重合法では溶媒によるラジカルの連鎖移動の差を利用して、また、開始剤量や反応温度を調整することで低分子量重合体を温和な条件で得ることができるため、低分子量成分を得るには好ましい。
【００６３】
溶液重合で用いる溶媒として、キシレン，トルエン，クメン，酢酸セロソルブ，イソプロピルアルコール又はベンゼンが用いられる。スチレンモノマーを使用する場合、キシレン，トルエン又はクメンが好ましい。重合するポリマーによって溶媒は適宜選択される。反応温度としては、使用する溶媒，重合開始剤，重合するポリマーによって異なるが、通常７０〜２３０℃で行うのが良い。溶液重合においては、溶媒１００質量部に対してモノマー３０〜４００質量部で行うのが好ましい。さらに重合終了時に溶液中で他の重合体を混合することも好ましく、数種の重合体を混合できる。
【００６４】
また、高分子量成分重合体を合成する方法としては、塊状重合法，溶液重合法，乳化重合法や懸濁重合法が挙げられる。このうち、乳化重合法は、水にほとんど不溶の単量体（モノマー）を乳化剤で小さい粒子として水相中に分散させ、水溶性の重合開始剤を用いて重合を行う方法である。この方法では反応熱の調節が容易であり、重合の行われる相（重合体と単量体からなる油相）と水相とが別であるから停止反応速度が小さく、その結果重合速度が大きく、高重合度のものが得られる。更に、重合プロセスが比較的簡単であること、及び重合生成物が微細粒子であるために、トナーの製造において着色剤及び荷電制御剤等の添加物との混合が容易であること等の理由から、トナー用バインダー樹脂の製造方法として有利な点がある。
【００６５】
しかし、添加した乳化剤のため重合体が不純になり易く、重合体を取り出すのには塩析などの操作が必要で、この不便をさけるためには懸濁重合法が好都合である。
【００６６】
しかし、本発明のカルボキシル基含有ビニル樹脂中の高分子量成分重合体を合成する方法として最も好ましい方法は溶液重合法である。これは、溶液重合法が温和な条件で行えるため、架橋に必要なカルボキシル基を高分子量成分に架橋点間距離をコントロールしながら導入することができるためである。
【００６７】
また、溶液重合法で合成した高分子成分重合体は低分子量成分重合体と混合した際にも良好な相溶性を示す。その結果、これが現像性のさらなる向上に効果をもたらすことが示されており、そのようなことからも溶液重合法による合成が好ましい。
【００６８】
グリシジル基含有ビニル樹脂を構成するグリシジル基ユニットを有するモノマーとしては、ビニル基とエポキシ基を有する化合物であれば良く、例えば、グリシジルアルコールと不飽和カルボン酸のエステル、不飽和グリシジルエーテルなどである。例えば、アクリル酸グリシジル、メタクリル酸グリシジル、アクリル酸β−メチルグリシジル、メタクリル酸β−メチルグリシジル、アリルグリシジルエーテル、アリルβ−メチルグリシジルエーテル等が挙げられる。
【００６９】
特に、下記一般式で表わされるグリシジルモノマーが好ましく用いられる。
【００７０】
【化５】

（式中、Ｒ^’ ₁，Ｒ^’ ₂及びＲ^’ ₃は、水素、アルキル基、アリール基、アラルキル基、カルボキシル基及びアルコキシカルボニル基を示す。）
【００７１】
このようなグリシジル基ユニットを有するモノマーは単独あるいは混合して、ビニル系モノマーと公知の重合方法により共重合させることにより該グリシジル基含有ビニル樹脂を得ることができる。
【００７２】
グリシジル基含有ビニル樹脂は、重量平均分子量（Ｍｗ）が、好ましくは５，０００乃至３０，０００、より好ましくは６，０００乃至２０，０００、更に好ましくは７，０００乃至１５，０００であることが良い。Ｍｗが５，０００未満の場合、結着樹脂中の架橋反応において分子量が増大しても混練工程においての分子鎖切断が多く、耐オフセット性への効果が少なくなる場合がある。Ｍｗが３０，０００を超える場合には、定着性に影響を及ぼすようになる場合がある。
【００７３】
また、グリシジル基含有ビニル樹脂は、エポキシ価が０．１乃至１．０ｅｑ／ｋｇのものが好ましい。０．１ｅｑ／ｋｇ未満の場合、架橋反応が起こりにくく、高分子量成分やＴＨＦ不溶分の生成量が少なく、耐オフセット性への効果が減少する。１．０ｅｑ／ｋｇを超える場合、架橋反応は起こりやすくなる反面、混練工程においての分子鎖切断が多く、耐オフセット性への効果が減少する。
【００７４】
グリシジル基含有ビニル樹脂のエポキシ価は、以下の方法により求める。
【００７５】
＜エポキシ価の測定＞
基本操作はＪＩＳ Ｋ−７２３６に準ずる。
（１）試料を０．５〜２．０（ｇ）を精秤し、結着樹脂の重さをＷ（ｇ）とする。
（２）３００（ｍｌ）のビーカーに試料を入れ、クロロホルム１０ｍｌ及び酢酸２０ｍｌに溶解する。
（３）この溶液に、臭化テトラエチルアンモニウム酢酸溶液１０ｍｌを加える。
（４）０．１ｍｏｌ／ｌの過塩素酸酢酸溶液を用いて、電位差滴定装置を用いて滴定する。（例えば、京都電子株式会社製の電位差滴定装置ＡＴ−４００（ｗｉｎ ｗｏｒｋｓｔａｔｉｏｎ）とＡＢＰ−４１０電動ビュレットを用い、の自動滴定が利用できる。）
（５）この時の過塩素酸酢酸溶液の使用量をＳ（ｍｌ）とし、同時にブランクを測定し、この時の過塩素酸酢酸溶液の使用量をＢ（ｍｌ）とする。
（６）次式によりエポキシ価を計算する。ｆは過塩素酸酢酸溶液のファクターである。
【００７６】
エポキシ価（ｅｑ／ｋｇ）＝０．１×ｆ×（Ｓ−Ｂ）／Ｗ
【００７７】
カルボキシル基含有モノマー及びグリシジル基含有モノマーと共重合させるビニルモノマーは以下のものが挙げられる。
【００７８】
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−フェニルスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン及びｐ−ｎ−ドデシルスチレンの如きスチレン誘導体；エチレン、プロピレン、ブチレン及びイソブチレンの如きエチレン不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、塩化ビニリデン、臭化ビニル、沸化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；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の如きα−メチレン脂肪族モノカルボン酸エステル類；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の如きアクリル酸エステル類；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の如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸誘導体もしくはメタクリル酸誘導体；前述のα，β−不飽和酸のエステル、二塩基酸のジエステル類；のビニル系モノマーが単独もしくは２つ以上で用いられる。
【００７９】
これらの中でもスチレン系共重合体及びスチレン−アクリル系共重合体となるようなモノマーの組み合わせが好ましい。
【００８０】
本発明に用いられる磁性体としては、マグネタイト，マグヘマイト，フェライト等の酸化鉄；鉄，コバルト，ニッケルのような金属あるいはこれらの金属とアルミニウム，コバルト，銅，鉛，マグネシウム，マンガン，セレン，チタン，タングステン，バナジウムのような金属の合金及びその混合物が用いられ、その磁性体表面あるいは内部に非鉄元素を含有するものが好ましい。
【００８１】
本発明に用いられる磁性体は、異種元素を含有するマグネタイト，マグヘマイト，フェライト等の磁性酸化鉄及びその混合物が好ましく用いられる。
【００８２】
中でもリチウム，ベリリウム，ボロン，マグネシウム，アルミニウム，シリコン，リン，ゲルマニウム，チタン，ジルコニウム，錫，鉛，亜鉛，カルシウム，バリウム，スカンジウム，バナジウム，クロム，マンガン，コバルト，銅，ニッケル，ガリウム，カドミウム，インジウム，銀，パラジウム，金，水銀，白金，タングステン，モリブデン，ニオブ，オスミウム，ストロンチウム，イットリウム，テクネチウム，ルテニウム，ロジウム，ビスマスから選ばれる少なくとも一つ以上の元素を含有する磁性酸化鉄であることが好ましい。特にリチウム，ベリリウム，ボロン，マグネシウム，アルミニウム，シリコン，リン，ゲルマニウム，ジルコニウム，錫，第４周期の遷移金属元素が好ましい元素である。これらの元素は酸化鉄結晶格子の中に取り込まれても良いし、酸化物として酸化鉄中に取り込まれても良いし、表面に酸化物あるいは水酸化物として存在しても良い。また、酸化物として含有されているのが好ましい形態である。
【００８３】
これらの元素を有する磁性体は結着樹脂に対し馴染みが良く、非常に分散性が良い。
【００８４】
また、これらの磁性体は粒度分布が揃い、その結着樹脂への分散性とあいまって、トナーの帯電性を安定化することができる。また近年はトナー粒径の小径化が進んでおり、重量平均粒径１０μｍ以下のような場合でも、帯電均一性が促進され、トナーの凝集性も軽減され、画像濃度の向上やカブリの改善等現像性が向上する。特に重量平均粒径６．０μｍ以下のトナーにおいてはその効果は顕著であり、きわめて高精細な画像が得られる。重量平均粒径は２．５μｍ以上である方が十分な画像濃度が得られて好ましい。
【００８５】
これらの異種元素の含有率は磁性酸化鉄の鉄元素を基準として０．０５〜１０質量％であることが好ましい。更に好ましくは０．１〜７質量％であり、特に好ましくは０．２〜５質量％、更には０．３〜４質量％である。０．０５質量％より少ないと、これら元素の含有効果が得られなく、良好な分散性や帯電均一性が得られなくなる。また、１０質量％より多くなると、電荷の放出が多くなり帯電不足を生じ、画像濃度が低くなったり、カブリが増加することがある。
【００８６】
また、これら異種元素の含有分布において、磁性体の表面に近い方に多く存在しているものが好ましい。例えば、酸化鉄の鉄元素溶解率が２０質量％までに存在する異種元素の含有量Ｂと該磁性酸化鉄の異種元素の全含有量Ａとの比（Ｂ／Ａ）×１００が４０％以上であることが好ましい。さらには４０〜８０％が好ましく、６０〜８０％が特に好ましい。表面存在量を多くすることにより分散効果や電気的拡散効果を、より向上させることが出来る。また、トナー中に含有される量としては樹脂成分１００質量部に対して、２０〜２００質量部、特に好ましくは樹脂成分１００質量部に対して４０〜１５０質量部が良い。
【００８７】
さらに、本発明で使用される磁性酸化鉄の球形度（Ψ）が０．８以上であることが好ましい。球形度（Ψ）が０．８より小さい場合には磁性酸化鉄の個々の粒子が、面と面で接触する形となり、粒径０．１〜１．０μｍ付近の小さな磁性酸化鉄粒子では機械的せん断力をもってしても容易に磁性酸化鉄同士を引き離すことができず、そのためトナー中への磁性酸化鉄の分散が十分に行えない場合がある。
【００８８】
また、場合により、本発明のトナーに用いる磁性酸化鉄は、シリル化剤、シランカップリング剤、チタンカップリング剤、チタネート、アミノシラン等で処理しても良い。
【００８９】
本発明の磁性酸化鉄中の元素量は、蛍光Ｘ線分析装置 ＳＹＳＴＥＭ３０８０（理学電機工業（株）社製）を使用し、ＪＩＳ Ｋ０１１９蛍光Ｘ線分析通則に従って、蛍光Ｘ線分析を行うことにより測定した。元素分布については、塩酸溶解しながらの元素量をプラズマ発光分光（ＩＣＰ）により測定定量し、各元素の全溶時の濃度に対する各溶解時の各元素濃度からその溶解率を求めた。
【００９０】
磁性酸化鉄の球形度（Ψ）は、電子顕微鏡（日立製作所Ｈ−７００Ｈ）でコロジオン膜銅メッシュに処理した磁性酸化鉄の試料を用いて、加電圧１００ｋＶにて、１０，０００倍で撮影し、焼きつけ倍率３倍として、最終倍率３０，０００倍とする。これによって、形状の観察を行い、各粒子の最大長（μｍ）及び最小長（μｍ）を計測しランダムに１００個を選び出し次式に従って計算し次いで計算値を平均したものである。
【００９１】
球形度＝磁性酸化鉄の最小長（μｍ）／磁性酸化鉄の最大長（μｍ）
【００９２】
トナーに使用し得るその他の着色剤としては、任意の適当な顔料または染料が挙げられる。
【００９３】
例えば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，ナフトールイエロー，ハンザイエロー，ローダミンレーキ，アリザリンレーキ，ベンガラ，フタロシアニンブルー，インダンスレンブルー等が挙げられる。これらは定着画像の光学濃度を維持するのに充分な量が用いられる。樹脂１００質量部に対し０．１〜２０質量部、好ましくは１〜１０質量部の顔料を使用することが好ましい。同様の目的で、さらに染料が用いられる。例えばアゾ系染料、アントラキノン系染料、キサンテン系染料、メチン系染料があり、樹脂１００質量部に対し０．１〜２０質量部、好ましくは０．３〜１０質量部の染料を使用することが好ましい。
【００９４】
本発明に用いられる離型剤としてのワックスには次のようなものがある。例えば、低分子量ポリエチレン、低分子量ポリプロピレン、ポリオレフィン共重合物、ポリオレフィンワックス、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックスの如き脂肪族炭化水素系ワックス；酸化ポリエチレンワックスの如き脂肪族炭化水素系ワックスの酸化物；または、それらのブロック共重合物；キャンデリラワックス、カルナバワックス、木ろう、ホホバろうの如き植物系ワックス；みつろう、ラノリン、鯨ろうの如き動物系ワックス；オゾケライト、セレシン、ペトロラクタムの如き鉱物系ワックス；モンタン酸エステルワックス、カスターワックスの如き脂肪酸エステルを主成分とするワックス類；脱酸カルナバワックスの如き脂肪酸エステルを一部又は全部脱酸化したものが挙げられる。さらに、パルミチン酸、ステアリン酸、モンタン酸、あるいは更に長鎖のアルキル基を有する長鎖アルキルカルボン酸の如き飽和直鎖；ブラシジン酸、エレオステアリン酸、バリナリン酸の如き不飽和脂肪酸；ステアリルアルコール、エイコシルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコール、あるいは更に長鎖のアルキル基を有する長鎖アルキルアルコールの如き飽和アルコール；ソルビトールの如き多価アルコール；リノール酸アミド、オレイン酸アミド、ラウリン酸アミドの如き脂肪族アミド；メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドの如き飽和脂肪酸ビスアミド；エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’−ジオレイルアジピン酸アミド、Ｎ，Ｎ’−ジオレイルセバシン酸アミドの如き不飽和脂肪酸アミド類；ｍ−キシレンビスステアリン酸アミド、Ｎ，Ｎ’−ジステアリルイソフタル酸アミドの如き芳香族系ビスアミド；ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムの如き脂肪酸金属塩（一般に金属石けんといわれているもの）；脂肪族炭化水素系ワックスにスチレンやアクリル酸の如きビニル系モノマーを用いてグラフト化させたワックス；ベヘニン酸モノグリセリドの如き脂肪酸と多価アルコールの部分エステル化物；植物性油脂を水素添加することによって得られるヒドロキシル基を有するメチルエステル化合物が挙げられる。
【００９５】
好ましく用いられるワックスとしては、オレフィンを高圧下でラジカル重合したポリオレフィン；高分子量ポリオレフィン重合時に得られる低分子量副生成物を精製したポリオレフィン；低圧下でチーグラー触媒、メタロセン触媒の如き触媒を用いて重合したポリオレフィン；放射線、電磁波又は光を利用して重合したポリオレフィン；高分子ポリオレフィンを熱分解して得られる低分子量ポリオレフィン；パラフィンワックス、マイクロクリスタリンワックス、フィッシャートロプシュワックス；ジンドール法、ヒドロコール法、アーゲ法等により合成される合成炭化水素ワックス；炭素数１個の化合物をモノマーとする合成ワックス、水酸基又はカルボキシル基の如き官能基を有する炭化水素系ワックス；炭化水素系ワックスと官能基を有するワックスとの混合物；これらのワックスを母体としてスチレン、マレイン酸エステル、アクリレート、メタクリレート、無水マレイン酸の如きビニルモノマーをグラフト変性したワックスが挙げられる。
【００９６】
また、これらのワックスをプレス発汗法、溶剤法、再結晶法、真空蒸留法、超臨界ガス抽出法又は融液晶法を用いて分子量分布をシャープにしたものや、低分子量固形脂肪酸、低分子量固形アルコール、低分子量固形化合物、その他の不純物を除去したものも好ましく用いられる。
【００９７】
本発明に使用するワックスは、定着性と耐オフセット性のバランスを取るために融点が６５〜１６０℃であることが好ましく、更には６５〜１３０℃であることが好ましく、特には７０℃〜１２０℃であることが好ましい。６５℃未満では耐ブロッキング性が低下し、１６０℃を超えると耐オフセット効果が発現し難くなる。
【００９８】
本発明のトナーにおいては、これらのワックス総含有量は、結着樹脂１００質量部に対し、０．２〜２０質量部で用いられ、好ましくは０．５〜１０質量部で用いるのが効果的である。また、悪影響を与えない限り他のワックス類と併用しても構わない。
【００９９】
本発明においてワックスの融点は、ＤＳＣにおいて測定されるワックスの吸熱ピークの最大ピークのピークトップの温度をもってワックスの融点とする。
本発明において、ワックス又はトナーの示差走査熱量計によるＤＳＣ測定では、高精度の内熱式入力補償型の示差走査熱量計で測定することが好ましい。例えば、パーキンエルマー社製のＤＳＣ−７が利用できる。
【０１００】
測定方法は、ＡＳＴＭ Ｄ３４１８−８２に準じて行う。本発明に用いられるＤＳＣ曲線は、１回昇温させ前履歴を取った後、温度測定１０℃／ｍｉｎ、温度０〜２００℃の範囲で降温させた後、昇温させた時に測定されるＤＳＣ曲線を用いる。
【０１０１】
本発明のトナーには、添加し得る着色材料として、従来公知のカーボンブラック、銅フタロシアニンの如き顔料または染料などが使用できる。
【０１０２】
本発明のトナーは、荷電制御剤を添加して負帯電性トナーとして使用することが好ましい。
【０１０３】
負荷電制御剤の具体例としては、特公昭４１−２０１５３号公報、特公昭４２−２７５９６号公報，特公昭４４−６３９７号公報，特公昭４５−２６４７８号公報などに記載されているモノアゾ染料の金属錯体、さらには特開昭５０−１３３８３８号公報に記載されているニトロフミン酸及びその塩或いはＣ．Ｉ．１４６４５などの染顔料、特公昭５５−４２７５２号公報，特公昭５８−４１５０８号公報，特公昭５８−７３８４号公報，特公昭５９−７３８５号公報などに記載されているサリチル酸、ナフトエ酸、ダイカルボン酸のＺｎ，Ａｌ，Ｃｏ，Ｃｒ，Ｆｅ，Ｚｒ等の金属錯体、スルホン化した銅フタロシアニン顔料、ニトロ基，ハロゲンを導入したスチレンオリゴマー，塩素化パラフィン等を挙げることができる。特に分散性に優れ、画像濃度の安定性やカブリの低減に効果のある、一般式（Ｉ）で表されるアゾ系金属錯体や一般式（ＩＩ）で表される塩基性有機酸金属錯体が好ましい。
【０１０４】
【化６】

【０１０５】
【化７】

【０１０６】
そのうち上記式（Ｉ）で表されるアゾ系金属錯体がより好ましく、とりわけ、中心金属がＦｅである下記式（ＩＩＩ）あるいは（ＩＶ）で表されるアゾ系鉄錯体が最も好ましい。
【０１０７】
【化８】

【０１０８】
【化９】

【０１０９】
次に、上記式（ＩＩＩ）で示されるアゾ系鉄錯体の具体例を下記に示す。
【０１１０】
【化１０】

【０１１１】
【化１１】

【０１１２】
【化１２】

【０１１３】
また、上記式（Ｉ），（ＩＩ），（ＩＶ）で示される荷電制御剤の具体例を以下に示す。
【０１１４】
【化１３】

【０１１５】
【化１４】

【０１１６】
【化１５】

【０１１７】
これらの金属錯化合物は、単独でも或いは２種以上組み合わせて用いることが可能である。
【０１１８】
これらの帯電制御剤の使用量は、トナーの帯電量の点から結着樹脂１００質量部あたり０．１〜５．０質量部が好ましい。
【０１１９】
一方、トナーを正荷電性に制御するものとして下記物質がある。
【０１２０】
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−ナフトスルフォン酸塩、テトラブチルアンモニウムテトラフルオロボレートなどの四級アンモニウム塩、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、フェロシアン化物など）、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など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などのジオルガノスズボレート類；これらを単独で或いは２種類以上組合せて用いることができる。
【０１２１】
また、本発明のトナーには、無機微粉体または疎水性無機微粉体が混合されることが好ましい。例えば、シリカ微粉末を添加して用いることが好ましい。
【０１２２】
本発明に用いられるシリカ微粉体は、ケイ素ハロゲン化合物の蒸気相酸化により生成されたいわゆる乾式法またはヒュームドシリカと称される乾式シリカ及び水ガラス等から製造されるいわゆる湿式シリカの両方が使用可能であるが、表面及び内部にあるシラノール基が少なく、製造残渣のない乾式シリカの方が好ましい。
【０１２３】
さらに本発明に用いるシリカ微粉体は疎水化処理されているものが好ましい。疎水化処理するには、シリカ微粉体と反応あるいは物理吸着する有機ケイ素化合物などで化学的に処理することによって付与される。好ましい方法としては、ケイ素ハロゲン化合物の蒸気相酸化により生成された乾式シリカ微粉体をシランカップリング剤で処理した後、あるいはシランカップリング剤で処理すると同時にシリコーンオイルの如き有機ケイ素化合物で処理する方法が挙げられる。
【０１２４】
疎水化処理に使用されるシランカップリング剤としては、例えばヘキサメチルジシラザン、トリメチルシラン、トリメチルクロルシラン、トリメチルエトキシシラン、ジメチルジクロルシラン、メチルトリクロルシラン、アリルジメチルクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、β−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、トリオルガノシランメルカプタン、トリメチルシリルメルカプタン、トリオルガノシリルアクリレート、ビニルジメチルアセトキシシラン、ジメチルエトキシシラン、ジメチルジメトキシシラン、ジフェニルジエトキシシラン、ヘキサメチルジシロキサン、１，３−ジビニルテトラメチルジシロキサン、１，３−ジフェニルテトラメチルジシロキサンが挙げられる。
【０１２５】
有機ケイ素化合物としては、シリコーンオイルが挙げられる。好ましいシリコーンオイルとしては、２５℃における粘度がおよそ３×１０^-5〜１×１０^-3ｍ²／ｓのものが用いられ、例えばジメチルシリコーンオイル、メチルフェニルシリコーンオイル、α−メチルスチレン変性シリコーンオイル、クロルフェニルシリコーンオイル、フッ素変性シリコーンオイル等が好ましい。
【０１２６】
シリコーンオイル処理の方法は例えばシランカップリング剤で処理されたシリカ微粉体とシリコーンオイルとをヘンシェルミキサー等の混合機を用いて直接混合しても良いし、べースとなるシリカへシリコーンオイルを噴射する方法によっても良い。あるいは適当な溶剤にシリコーンオイルを溶解あるいは分散せしめた後、べースのシリカ微粉体とを混合し、溶剤を除去して作製しても良い。
【０１２７】
本発明中のトナーには、必要に応じてシリカ微粉体以外の外部添加剤を添加してもよい。
【０１２８】
例えば帯電補助剤、導電性付与剤、流動性付与剤、ケーキング防止剤、熱ロール定着時の離型剤、滑剤、研磨剤等の働きをする樹脂微粒子や無機微粒子である。
【０１２９】
例えばテフロン，ステアリン酸亜鉛，ポリ弗化ビニリデンの如き滑剤、中でもポリ弗化ビニリデンが好ましい。或いは酸化セリウム，炭化ケイ素，チタン酸ストロンチウム等の研磨剤、中でもチタン酸ストロンチウムが好ましい。或いは例えば酸化チタン，酸化アルミニウム等の流動性付与剤、中でも特に疎水性のものが好ましい。ケーキング防止剤、或いは例えばカーボンブラック，酸化亜鉛，酸化アンチモン，酸化スズ等の導電性付与剤、また逆極性の白色微粒子及び黒色微粒子を現像性向上剤として少量用いることもできる。
【０１３０】
トナーと混合される無機微粉体または疎水性無機微粉体は、トナー１００質量部に対して０．１〜５質量部（好ましくは０．１〜３質量部）使用するのが良い。
【０１３１】
本発明に係るトナーを作製するには、上述したようなトナー構成材料をボールミルその他の混合機により十分混合した後、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よく混練し、冷却固化後、機械的な粉砕・分級によってトナーを得る方法が好ましく、他にはあるいは結着樹脂を構成すべき単量体に所定の材料を混合して乳化懸濁液とした後に、重合させてトナーを得る重合トナー製造法、あるいはコア材，シェル材から成るいわゆるマイクロカプセルトナーにおいてコア材あるいはシェル材、あるいはこれらの両方に所定の材料を含有させる方法、結着樹脂中溶液中に構成材料を分散した後、噴霧乾燥によりトナーを得る方法等が応用出来る。さらに必要に応じ所望の添加剤をヘンシェルミキサー等の混合機により十分混合し、本発明に係るトナーを製造することができる。
【０１３２】
例えば混合機としては、ヘンシェルミキサー（三井鉱山社製）；スーパーミキサー（カワタ社製）；リボコーン（大川原製作所社製）；ナウターミキサー、タービュライザー、サイクロミックス（ホソカワミクロン社製）；スパイラルピンミキサー（太平洋機工社製）；レーディゲミキサー（マツボー社製）が挙げられ、混練機としては、ＫＲＣニーダー（栗本鉄工所社製）；ブス・コ・ニーダー（Ｂｕｓｓ社製）；ＴＥＭ型押し出し機（東芝機械社製）；ＴＥＸ二軸混練機（日本製鋼所社製）；ＰＣＭ混練機（池貝鉄工所社製）；三本ロールミル、ミキシングロールミル、ニーダー（井上製作所社製）；ニーデックス（三井鉱山社製）；ＭＳ式加圧ニーダー、ニダールーダー（森山製作所社製）；バンバリーミキサー（神戸製鋼所社製）が挙げられる。粉砕機としては、カウンタージェットミル、ミクロンジェット、イノマイザ（ホソカワミクロン社製）；ＩＤＳ型ミル、ＰＪＭジェット粉砕機（日本ニューマチック工業社製）；クロスジェットミル（栗本鉄工所社製）；ウルマックス（日曹エンジニアリング社製）；ＳＫジェット・オー・ミル（セイシン企業社製）；クリプトロン（川崎重工業社製）；ターボミル（ターボ工業社製）が挙げられる。分級機としては、クラッシール、マイクロンクラッシファイアー、スペディッククラッシファイアー（セイシン企業社製）；ターボクラッシファイアー（日新エンジニアリング社製）；ミクロンセパレータ、ターボフレックス（ＡＴＰ）、ＴＳＰセパレータ（ホソカワミクロン社製）；エルボージェット（日鉄鉱業社製）、ディスパージョンセパレータ（日本ニューマチック工業社製）；ＹＭマイクロカット（安川商事社製）が挙げられる。粗粒などをふるい分けるために用いられる篩い装置としては、ウルトラソニック（晃栄産業社製）；レゾナシーブ、ジャイロシフター（徳寿工作所杜）；バイブラソニックシステム（ダルトン社製）；ソニクリーン（新東工業社製）；ターボスクリーナー（ターボ工業社製）；ミクロシフター（槙野産業社製）；円形振動篩い等が挙げられる。
【０１３３】
【実施例】
以上本発明の基本的な構成と特色について述べたが、以下実施例にもとづいて具体的に本発明について説明する。しかしながら、これによって本発明の実施の態様がなんら限定されるものではない。実施例中の部数は質量部である。
【０１３４】
＜低分子量成分（Ｂ−１）の製造例＞
四つ口フラスコ内にキシレン３００部を投入し、撹拌しながら容器内を充分に窒素で置換した後、昇温して還流させる。
【０１３５】
この還流下で、スチレン７５部，アクリル酸−ｎ−ブチル２５部及びジ−ｔｅｒｔ−ブチルパーオキサイド（開始剤１）２部の混合液を４時間かけて滴下した後、２時間保持し重合を完了し、低分子量重合体溶液（Ｂ−１）を得た。
【０１３６】
＜低分子量成分（Ｂ−２）の製造例＞
スチレン８０部，アクリル酸−ｎ−ブチル２０部，開始剤１を２．５部用いて低分子量成分Ｂ−１の製造例と同様に重合を行い、低分子量重合体溶液Ｂ−２を得た。
【０１３７】
＜低分子量成分（Ｂ−３）の製造例＞
スチレン７８部，アクリル酸−ｎ−ブチル２２部，開始剤１を２部用いて低分子量成分Ｂ−１の製造例と同様に重合を行い、低分子量重合体溶液Ｂ−３を得た。
【０１３８】
＜低分子量成分（Ｂ−４）の製造例＞
スチレン６０部，アクリル酸−ｎ−ブチル４０部，開始剤１を１．５部用いて低分子量成分Ｂ−１の製造例と同様に重合を行い、低分子量重合体溶液Ｂ−４を得た。
【０１３９】
＜低分子量成分（Ｂ−５）の製造例＞
スチレン７５部，アクリル酸−ｎ−ブチル２０部，マレイン酸モノブチル５部，開始剤１を２．５部用いて低分子量成分Ｂ−１の製造例と同様に重合を行い、低分子量重合体溶液Ｂ−５を得た。
【０１４０】
＜低分子量成分（Ｂ−６）の製造例＞
スチレン８０部，アクリル酸−ｎ−ブチル２０部，開始剤１を２部用いて低分子量成分Ｂ−１の製造例と同様に重合を行い、低分子量重合体溶液Ｂ−６を得た。
【０１４１】
＜高分子量成分（Ａ−１）の製造例＞
四つ口フラスコ内にキシレン３００部を投入し、撹拌しながら容器内を充分に窒素で置換した後、昇温して還流させる。
【０１４２】
この還流下で、スチレン７０部，アクリル酸−ｎ−ブチル２５部，マレイン酸モノブチル５部及び２，２−ビス（４，４−ジ−ｔｅｒｔ−ブチルパーオキシシクロヘキシル）プロパン（開始剤２；半減期１０時間温度：９２℃）１部の混合液を４時間かけて滴下した後、２時間保持し重合を完了し、高分子量成分（Ａ−１）溶液を得た。
【０１４３】
＜高分子量成分（Ａ−２）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン７０部，アクリル酸−ｎ−ブチル２７部，マレイン酸モノブチル３部及び開始剤２を１部用いて、高分子量成分（Ａ−２）溶液を得た。
【０１４４】
＜高分子量成分（Ａ−３）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン７２部，アクリル酸−ｎ−ブチル２３部，アクリル酸５部及び開始剤２を１部用いて、高分子量成分（Ａ−３）溶液を得た。
【０１４５】
＜高分子量成分（Ａ−４）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン７０部，アクリル酸−ｎ−ブチル２７部，メタクリル酸３部及び開始剤２を１部用いて、高分子量成分（Ａ−４）溶液を得た。
【０１４６】
＜高分子量成分（Ａ−５）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン７５部，アクリル酸−ｎ−ブチル２５部及び開始剤２を１部用いて、高分子量成分（Ａ−５）溶液を得た。
【０１４７】
＜高分子量成分（Ａ−６）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン６５部，アクリル酸−ｎ−ブチル２５部，マレイン酸モノブチル１０部及び開始剤２を１部用いて、高分子量成分（Ａ−６）溶液を得た。
【０１４９】
＜高分子量成分（Ａ−８）の製造例＞
四つ口フラスコ内に、脱気水１８０部とポリビニルアルコールの２質量％水溶液２０部を投入した後、スチレン７０部，アクリル酸−ｎ−ブチル２５部，マレイン酸モノブチル５部，ジビニルベンゼン０．００５部及び開始剤２を０．１部で混合した混合液を加え、撹拌し懸濁液とした。
【０１５０】
フラスコ内を充分に窒素で置換した後、８５℃まで昇温して、重合を開始した。同温度に２４時間保持した後、ベンゾイルパーオキサイド（半減期１０時間温度：７２℃）０．１部を追加した。さらに１２時間保持して重合を完了した。その後、該高分子量重合体を濾別し、水洗，乾燥し高分子量成分（Ａ−８）を得た。
【０１５１】
＜高分子量成分（Ａ−９）の製造例＞
高分子量成分（Ａ−８）の製造例と同様に、スチレン７０部，アクリル酸−ｎ−ブチル２６部，マレイン酸モノブチル４部，ジビニルベンゼン０．００５部及び開始剤２を１部用いて、高分子量成分（Ａ−９）を得た。
【０１５２】
＜カルボキシル基含有ビニル樹脂（Ｃ−１）の製造＞
四つ口フラスコ内に、上記低分子量成分（Ｂ−１）のキシレン溶液２００部（低分子量成分５０部相当）を投入し、昇温して還流下で撹拌する。一方、別容器に上記高分子量成分（Ａ−１）溶液２００部（高分子量成分５０部相当）を投入し、還流させる。上記低分子量成分（Ｂ−１）溶液と高分子量成分（Ａ−１）溶液を還流下で混合した後、有機溶剤を留去し、得られた樹脂を冷却、固化後粉砕してカルボキシル基含有ビニル樹脂（Ｃ−１）を得た。その分子量分布，酸価等の結果を表１に示す。
【０１５３】
＜カルボキシル基含有ビニル樹脂（Ｃ−２〜１０）の製造例＞
高分子量成分溶液及び高分子量成分重合体（Ａ−２〜９）と低分子量成分溶液（Ｂ−２〜６）を表１に示すように組み合せ、カルボキシル基含有ビニル樹脂（Ｃ−１）の製造例と同様にして、カルボキシル基含有ビニル樹脂（Ｃ−２〜１０）を得た。その分子量分布，酸価等の結果を表１に示す。
【０１５４】
＜カルボキシル基含有ビニル樹脂（Ｃ−１１）の製造例＞
高分子量成分（Ａ−１）の製造例と同様にスチレン７０部，アクリル酸−ｎ−ブチル２０部，マレイン酸モノブチル１０部，ジビニルベンゼン０．００５部及び開始剤１を１部用いて、分子量分布におけるピークが一つのカルボキシル基含有ビニル樹脂（Ｃ−１１）を得た。その分子量分布，酸価等の結果を表１に示す。
【０１５５】
＜グリシジル基含有ビニル樹脂（Ｄ−１）の製造例＞
四つ口フラスコ内にキシレン３００部を投入し、撹拌しながら容器内を充分に窒素で置換した後、昇温して還流させる。
【０１５６】
この還流下で、スチレン７５部，アクリル酸−ｎ−ブチル１８部，メタクリル酸グリシジル７部及びジ−ｔｅｒｔ−ブチルパーオキサイド２部の混合液を４時間かけて滴下した後、２時間保持し重合を完了し、減圧下で溶媒を蒸留留去した。この様にしてグリシジル基含有ビニル樹脂（Ｄ−１）を得た。
【０１５７】
＜グリシジル基含有ビニル樹脂（Ｄ−２）の製造例＞
グリシジル基含有ビニル樹脂（Ｄ−１）の製造例と同様にスチレン７５部，アクリル酸−ｎ−ブチル２１部，メタクリル酸グリシジル４部及び開始剤１を３部用いて、グリシジル基含有ビニル樹脂（Ｄ−２）を得た。その分子量分布，エポキシ価の結果を表２に示す。
【０１５８】
＜グリシジル基含有ビニル樹脂（Ｄ−３）の製造例＞
グリシジル基含有ビニル樹脂（Ｄ−１）の製造例と同様にスチレン７５部，アクリル酸−ｎ−ブチル１８部，メタクリル酸グリシジル７部及び開始剤１を１．５部用いて、グリシジル基含有ビニル樹脂（Ｄ−３）を得た。その分子量分布，エポキシ価の結果を表２に示す。
【０１５９】
＜グリシジル基含有ビニル樹脂（Ｄ−４）の製造例＞
グリシジル基含有ビニル樹脂（Ｄ−１）の製造例と同様にスチレン７５部，アクリル酸−ｎ−ブチル２０部，メタクリル酸グリシジル５部及び開始剤１を０．５部用いて、グリシジル基含有ビニル樹脂（Ｄ−４）を得た。その分子量分布，エポキシ価の結果を表２に示す。
【０１６０】
＜グリシジル基含有ビニル樹脂（Ｄ−５）の製造例＞
グリシジル基含有ビニル樹脂（Ｄ−１）の製造例と同様にスチレン７０部，アクリル酸−ｎ−ブチル１５部，メタクリル酸グリシジル１５部及び開始剤１を２部用いて、グリシジル基含有ビニル樹脂（Ｄ−５）を得た。その分子量分布，エポキシ価の結果を表２に示す。
【０１６１】
＜ワックス＞
実施例で用いるワックスは表３に示す通りのものである。
【０１６２】
＜磁性酸化鉄粒子の製造例＞
磁性酸化鉄粒子は、マグネタイト生成時に内部に存在する元素の塩を添加しｐＨを調整しながらマグネタイト粒子を生成させ、表４に示す磁性酸化鉄粒子１〜５を得た。磁性酸化鉄粒子１，３は珪酸塩を、磁性酸化鉄粒子２は燐酸塩を、磁性酸化鉄粒子４はマグネシウム塩を添加してマグネタイト粒子を生成した。特に塩を添加せずにマグネタイト粒子を生成させ、その後ジルコニウム塩を添加してｐＨ調整しマグネタイト粒子表面にジルコニアを析出させて磁性酸化鉄粒子５を得た。
【０１６３】
［実施例１］
製造例Ｃ−１で得られたカルボキシ基含有ビニル樹脂９３部及び製造例Ｄ−３で得られたグリシジル基含有ビニル樹脂７部（グリシジル基配合比で２．５ｍｏｌに相当）を、ヘンシェルミキサーにて混合後、二軸混練押出機にて１８０℃で混練し、冷却粉砕し、結着樹脂１を得た。
【０１６４】
・上記結着樹脂１ １００部
・磁性酸化鉄粒子１ ９０部
・ワックスｅ ４部
・アゾ系鉄錯体化合物Ａ ２部
【０１６５】
上記材料をヘンシェルミキサーで前混合した後、１３０℃に設定した二軸混練押出機によって溶融混練した。
【０１６６】
得られた混練物を冷却し、カッターミルで粗粉砕した後、ジェット気流を用いた微粉砕機で粉砕し、得られた微粉砕粉末をコアンダ効果を利用した多分割分級機を用いて分級し、重量平均粒径６．５μｍのトナー粒子を得た。トナー粒子１００部に対し、ヘキサメチルジシラザン１５質量％とジメチルシリコーン１５質量％で疎水化処理したメタノールウェッタビリティ８０％，ＢＥＴ比表面積１２０ｍ²／ｇの疎水性シリカ微粉体１．２部とチタン酸ストロンチウム１．０部とを外添混合して負帯電性トナーＮｏ．１を調製した。
【０１６７】
トナー内添処方及び物性値を表５に記す。
【０１６８】
このトナーＮｏ．１を、市販のＬＢＰプリンター（ＬＢＰ−９３０，キヤノン社製）を１．５倍のプリントスピードに改造し、１５℃，１０％ＲＨの環境と３０℃，８０％ＲＨの環境で１万５千枚のプリント試験を行った。さらに、熱ロール定着器が用いられているこのＬＢＰ−９３０の定着器を外部へ取り出し、プリンター外でも動作し、定着ローラー温度を任意に設定可能にし、プロセススピードを２３５ｍｍ／ｓｅｃとなるように改造した外部定着器を用い、定着性と耐オフセット性の評価を行った。また、フィルムを介して記録材を加熱体に密着させる加圧部材からなる定着装置を使用している市販のＬＢＰプリンター（ＬＢＰ−４３０，キヤノン社製）の定着器を外部へ取り出し、プリンター外でも動作し、定着フィルム温度を任意に設定可能にし、プロセススピードを１４０ｍｍ／ｓｅｃとなるように改造した外部定着器を用い、定着性，耐オフセット性の評価を行った。その評価結果を表６乃至８に示す。
【０１６９】
「定着性」は、ベタ黒とハーフトーンの２種類の画像を１５０℃に温調した定着器に通し、５０ｇ／ｃｍ²の荷重をかけ、シルボン紙によりその定着画像を摺擦し、摺擦前後での画像濃度の低下率（％）で評価した。また、「テープはがしによる定着性」については、ベタ黒の画像を１８０℃に温調した定着器に通し、その定着画像上にポリエステルテープを貼り、その上から同様に５０ｇ／ｃｍ²の荷重をかけ、シルボン紙により摺擦し、その後テープを剥がし、テープを剥がす前後の画像濃度の低下率（％）で評価した。「折り曲げ定着性」については、まず、ベタ黒の画像を１７０℃に温調した定着器に通す。そして、その定着画像を縦方向に折り曲げて一定の圧力をかけるために、温調のかかっていない室温状態の定着器に通す。次に、定着画像を一度開き横方向に折り曲げて同様に温調のかかっていない定着器に通す。そして定着画像上の縦と横の折り目の交差した部分に５０ｇ／ｃｍ²の荷重をかけ、シルボン紙により摺擦し、摺擦前後での画像濃度の低下率（％）で評価した。
【０１７０】
（評価基準）
○：１０％未満
△：１０％以上、２０％未満
×：２０％以上
【０１７１】
「耐オフセット性」は、画像面積率約５％のサンプル画像をプリントアウトし、３０００枚後の画像上の汚れの程度により評価した。
【０１７２】
（評価基準）
○：良好
△：わずかに汚れる程度
×：画像に影響する汚れ発生
【０１７３】
「画像濃度」はマクベス濃度計（マクベス社製）でＳＰＩフィルターを使用して、反射濃度測定を行い、５ｍｍ角の画像を測定した。「カブリ」は反射濃度計（リフレクトメーターモデルＴＣ−６ＤＳ 東京電色社製）を用いて行い、画像形成後の白地部反射濃度最悪値をＤｓ，画像形成前の転写材の反射平均濃度をＤｒとし、Ｄｓ−Ｄｒをカブリ量としてカブリの評価を行った。数値の少ない方がカブリ抑制が良い。「画質」の評価としては、孤立ドット１００個画像形成し、１００個のうち何ドット表すことができたかによって評価する。ドット再現数が多い方が高画質といえるものである。
【０１７４】
これらの評価を、初期、１５０００枚時、機外に一日放置した後に行った。
【０１７５】
［実施例２〜８、参考例１及び２］
表５に記載の処方で実施例１と同様にトナーＮｏ．２〜１０を作製した。但し、トナーＮｏ．４については、カルボキシル基含有ビニル樹脂とグリシジル基含有ビニル樹脂をあらかじめ混練することはせず、他の原材料と同時に前混合を行い１５０℃で混練を行った。このようにして得られた物性値を表５に示し、同様の試験をした結果を表６乃至８に示す。
【０１７６】
［比較例１〜７］
表５に記載の処方で、実施例１と同様にトナーＮｏ．１１〜１５を作製し、同様の試験をした結果を表６乃至８に示す。
【０１７７】
【表１】

【０１７８】
【表２】

【０１７９】
【表３】

【０１８０】
【表４】

【０１８１】
【表５】

【０１８２】
【化１６】

【０１８３】
【化１７】

【０１８４】
【化１８】

【０１８５】
【表６】

【０１８６】
【表７】

【０１８７】
【表８】

【０１８８】
【発明の効果】
本発明によれば、上記構成の結着樹脂を有しているトナーによって、定着器の構成に関わらず、低温定着が可能であり、耐オフセット性に優れ、経時あるいは放置において画像欠陥が生じず、低湿下で使用しても、高湿下で使用しても高い画像品質を安定して得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotography, an image forming method for developing an electrostatic image, and a dry toner used in a toner jet.
[0002]
[Prior art]
Conventionally, as an electrophotographic method, many methods are known as described in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, and the like. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed with toner to form a visible image, and if necessary, paper is used. After transferring the toner to a transfer material such as heat, the toner image is fixed on the transfer material by heat, pressure, etc. to obtain a copy, and the toner remaining on the photosensitive member without being transferred can be obtained by various methods. And the above process is repeated.
[0003]
In recent years, such a copying apparatus has been strictly pursued to be smaller, lighter, faster, and more reliable. In addition, it is not only used as a general-purpose copying machine for copying original documents, but also used for copying high-definition images such as digital printers or graphic designs as computer output. Therefore, higher definition and higher image quality are demanded, and as a result, the performance required for toner has become higher.
[0004]
Incidentally, fixing performance is the most important performance required for toners in digital printers and high-definition image copying.
[0005]
Various methods and apparatuses have been developed for the fixing process, but the most common method at present is a pressure heating method using a heat roller.
[0006]
The pressure heating method using a heating roller performs fixing by allowing the toner image surface of a fixing sheet to pass through the surface of a heat roller formed with a material having releasability with respect to the toner while being in contact with pressure. It is. In this method, since the surface of the heat roller and the toner image of the fixing sheet are in contact with each other under pressure, the thermal efficiency when fusing the toner image on the fixing sheet is extremely good, and the fixing is performed quickly. This is very effective in a high-speed electrophotographic copying machine. However, in the above method, since the surface of the heat roller and the toner image are in contact in a molten state under pressure, a part of the toner image may adhere to and transfer to the surface of the fixing roller, and the next fixing sheet may be soiled ( Offset phenomenon). Preventing toner from adhering to the surface of the heat fixing roller is one of the essential conditions for the heat roller fixing method.
[0007]
Recently, in place of a heat roller, a fixing device composed of a pressure member that is opposed to a heating member and is in contact with the heating member through a film has been put into practical use, which is advantageous in terms of heat efficiency. However, since the toner surface is melted, the offset phenomenon is more likely to occur, and it is more necessary to prevent this phenomenon.
[0008]
Also, in the fixing process, in order to realize a fixing method with a short wait time and low power consumption, the toner is required to have a design that can realize lower temperature fixing.
[0009]
As one of the proposals for preventing offset, many proposals have been made for a system to which a crosslinking agent is added.
[0010]
Japanese Patent Publication No. 51-23354 proposes a toner comprising a vinyl polymer that has been appropriately crosslinked by adding a crosslinking agent and a molecular weight modifier. Japanese Patent Publication No. 55-6805 discloses a molecular weight distribution such that the ratio of the weight average molecular weight to the number average molecular weight is 3.5 to 4.0 with α, β unsaturated ethylenic monomer as a constituent unit. Toners with a wide range have been proposed.
[0011]
Certainly, these toners can be fixed between the lower fixing temperature (the lowest temperature at which fixing is possible) and the offset temperature (the temperature at which offset begins to occur) compared to toners made from a single resin with a narrow molecular weight distribution. Although the temperature range is widened, it is difficult to sufficiently lower the fixing temperature when sufficient offset prevention performance is imparted. On the other hand, when emphasizing the low-temperature fixability, there is a problem that the offset prevention performance becomes insufficient.
[0012]
JP-A-57-208559 discloses a toner obtained by crosslinking a polyester resin, which is essentially superior to a vinyl resin in terms of low-temperature fixability, and adding an offset preventive agent. Proposed in the gazette. This toner is excellent in both low-temperature fixing property and offset prevention property, but has a problem in terms of toner productivity (grindability).
[0013]
Furthermore, in Japanese Patent Laid-Open No. 56-116043, a resin obtained by polymerizing a vinyl monomer in the presence of a reactive polyester resin and polymerizing the polymer through a crosslinking reaction, an addition reaction, and a grafting reaction in the process of polymerization. The toner used has been proposed.
[0014]
Such a crosslinked vinyl polymer or a toner containing a gel content in the toner certainly improves the anti-offset property. However, when this crosslinked vinyl polymer is used as a toner raw material for inclusion in the toner, the internal friction in the polymer becomes very large at the time of melt kneading at the time of toner production, and a large shearing force is applied to the polymer. . For this reason, in many cases, the molecular chain is broken, resulting in a decrease in melt viscosity and adversely affecting the offset resistance.
[0015]
In order to solve this problem, JP-A-55-90509, JP-A-57-178249, JP-A-57-178250 and JP-A-60-4946 disclose a resin having a carboxylic acid. And a metal compound are used as a raw material for the toner, and are subjected to a heat reaction at the time of melt kneading to form a crosslinked polymer, which is contained in the toner.
[0016]
In JP-A-63-214760, JP-A-63-217362 and JP-A-63-217363, a vinyl resin having a vinyl polymer and a specific half-ester compound as essential constituent units is disclosed. It has been proposed that a polyvalent metal compound is allowed to react with each other for crosslinking.
[0017]
In JP-A-63-214760, JP-A-63-217362 and JP-A-63-217363, a molecular weight distribution divided into two groups of low molecular weight and high molecular weight is formed and contained on the low molecular weight side. It has been proposed to react a carboxyl group of a specific half-ester compound that has been allowed to react with a polyvalent metal ion.
[0018]
However, even when any cross-linking agent is used, it is still insufficient to satisfy both the offset resistance and the low-temperature fixability and needs to be improved.
[0019]
JP-A-6-11890, JP-A-6-222612, JP-A-9-319140, JP-A-10-87837, and JP-A-10-90943 disclose a carboxyl group-containing resin and glycidyl. In binder resins containing group-containing resins, it has been proposed to control the molecular weight distribution, acid value, and the amount of each resin present, and greatly improve the balance of fixability, offset resistance and blocking resistance. Yes.
[0020]
Although these proposals show the effect of improving the anti-offset and blocking resistance, the developability is still inadequate, and the machine that has realized the high-speed copying system and the low-power-consumption fixing method that have been required in recent years. Is still insufficient. That is, when the copying speed is further increased, the time for the recording material to pass through the fixing device is shortened even if the heating temperature and the applied pressure at the time of fixing are the same as those in the past. That is, the total heat amount (work amount) applied to the recording material is decreasing, and further improvement of the fixing property is indispensable for the toner.
[0021]
[Problems to be solved by the invention]
An object of the present invention is to provide a dry toner that solves the above problems.
[0022]
The object of the present invention is that low-temperature fixing is possible regardless of the configuration of the fixing device, excellent offset resistance, and high image quality can be stably obtained even when used under high and low humidity. It is an object of the present invention to provide a dry toner that does not cause image defects.
[0023]
[Means for Solving the Problems]
  The present invention relates to a dry toner having at least a binder resin, a colorant, a charge control agent, and a release agent.
  The binder resin, MosquitoRubixyl group-containing vinyl resin and glycidyl group-containing vinyl resinIt is a reaction,
  The carboxyl group-containing vinyl resinBefore the reaction with the glycidyl group-containing vinyl resin,Acid valueBut0.1-1 mg KOH / g,The carboxyl group is generated from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride;
  In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the toner, the toner has at least one peak at a molecular weight of 4,000 to 30,000, and further has a molecular weight of 100,000 to 500,000 has at least one peak or shoulder, and the peak area with a molecular weight of 100,000 or more is a ratio of 5 to 40% with respect to the total peak area,
  The present invention relates to a dry toner characterized in that the binder resin component in the toner contains 5 to 50% by mass of THF insoluble matter.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors include (1) a carboxyl group-containing vinyl resin and a glycidyl group-containing vinyl resin as a binder resin, and the acid value of the carboxyl group-containing vinyl resin is 0.1 to 1 mgKOH / g, 2 In the molecular weight distribution measured by GPC, it has at least one peak at a molecular weight of 4,000 to 30,000, further has at least one peak or shoulder at a molecular weight of 100,000 to 500,000, and has a molecular weight of 100 And a toner having a binder resin containing 5 to 50% by mass of THF insolubles in the structure of the fixing unit. Regardless, low-temperature fixing is possible, excellent offset resistance, and high image quality can be stably obtained even when used under high and low humidity. Was found that no image defects.
[0025]
In the binder resin in the present invention, the glycidyl group in the glycidyl group-containing vinyl resin component undergoes a ring-opening addition reaction with the carboxyl group in the binder resin to form a crosslinked structure. This crosslinked structure improves the offset resistance. However, not only those effects, but also low-temperature fixing is possible regardless of the configuration of the fixing device, and high image quality can be stably obtained even when used under high and low humidity, and image defects are eliminated over time. A dry toner that does not occur was obtained.
[0026]
This is because the acid value of the carboxyl group-containing vinyl resin is designed to be 0.1 to 1 mgKOH / g, so that the distance between the crosslinking points of the binder resin is increased, and the glycidyl group and the carboxyl group are effective in offset resistance. This is because the cross-linked structure can be controlled to such an extent that the low-temperature fixability is not affected. In addition, it has a branched structure instead of a cross-linked structure, and its entanglement results in a flexible but sticky polymer state, and the fixed image becomes strong against bending. Furthermore, it becomes possible to achieve both high fixing performance and offset resistance. In general, when the anti-offset property is improved, there is no effect on the fixing property of the solid part, but the fixing property of the halftone, the dot part, and the line part becomes inferior. Offset resistance can be improved with excellent fixing properties.
[0027]
Further, by blending the glycidyl group-containing vinyl resin with the carboxyl group-containing vinyl resin at a ratio of 1 to 4 moles as the glycidyl group, the residual glycidyl group-containing vinyl resin component and the residual glycidyl group that do not have a crosslinked structure are fixed. It can work effectively as a resin component or a resin functional group for improving the resistance. Furthermore, the contact property with the transfer material becomes strong, and not only the rubbing but also the fixing property to the tape peeling is improved.
[0028]
Also, it is caused by good compatibility between the residual glycidyl group in the binder resin and raw materials such as a release agent, a magnetic substance, a pigment, and a charge control agent, or a branched structure or a crosslinked structure obtained as described above. Although it is mild at the time of melt kneading at the time of toner particle production, the kneading share with a heavy load further improves the dispersibility of the raw materials such as the release agent, magnetic substance, pigment, and charge control agent in the toner particles. It is thought that it was because it was possible.
[0029]
That is, the acid value of the carboxyl group-containing vinyl resin is 0.1 to 1 mg KOH / g, and preferably the glycidyl group-containing vinyl resin is contained in the binder resin at a ratio of 1 to 4 mol as the glycidyl group. By blending, it can be said that uniform charge and durable stability of charge were obtained.
[0030]
The glycidyl group-containing vinyl resin of the present invention is blended with a glycidyl group-containing vinyl resin at a ratio of 1 to 4 moles, preferably 1.5 to 3 moles as glycidyl groups per mole of carboxyl groups in the carboxyl group-containing vinyl resin. It is good to have.
[0031]
When the glycidyl group is less than 1 mol, the number of glycidyl groups in the binder resin is less than that of the carboxyl group, so the number of crosslinking points is reduced, and even when a glycidyl group-containing vinyl resin is blended in the binder resin, sufficient offset resistance is achieved. It becomes difficult to form a cross-linked structure that is effective. Furthermore, since it becomes impossible to apply a kneading share at the time of melt kneading at the time of toner particle production caused by the crosslinked structure, the dispersibility of the raw material such as the release agent, the magnetic material, and the charge control agent in the toner particle deteriorates, and the development Affects the sex. Furthermore, since residual carboxyl groups are present in the binder resin, the carboxyl groups cause the effect of uniform charge and durability of charge stability. On the other hand, if it exceeds 4 moles, the reaction between the carboxyl group and glycidyl group in the binder resin can provide a crosslinked structure that is only effective in offset resistance, but residual glycidyl that has not formed a crosslinked structure. Since the group-containing vinyl resin is excessively present, as a result, low molecular weight components and residual glycidyl groups in the binder resin increase more than necessary, and toner adheres to the developer carrier and develops. May be affected.
[0032]
In other words, the combination of the acid value of the carboxyl group-containing vinyl resin and the content of the glycidyl group-containing vinyl resin in the binder resin described above not only improves low-temperature fixability and offset resistance, but also developability. A good toner can be obtained.
[0033]
Further, when the acid value is larger than 1 mg KOH / g, the distance between the crosslinking points of the binder resin main chain is shortened, and when the glycidyl group-containing vinyl resin is blended in the binder resin, the crosslinking structure component is progressed with the progress of the crosslinking reaction. High molecular weight component with a large amount or THF insoluble matter increases. As a result, the balance between the low temperature fixing property and the offset resistance and the resistance to bending are affected. Moreover, the method of applying the share in the kneading process is abrupt, and the effect for improving the material dispersibility is reduced. That is, when the acid value is larger than 1 mgKOH / g, it becomes difficult to control the reaction to a crosslinked branched structure that does not affect low-temperature fixability and offset resistance. When the acid value is less than 0.1 mg KOH / g, the distance between the cross-linking points is too wide. Therefore, even when the glycidyl group-containing vinyl resin is blended in the binder resin, the cross-linked structure has a sufficient effect on offset resistance. Cannot be formed. Furthermore, since it becomes impossible to apply a kneading share at the time of melt kneading at the time of toner particle production caused by the crosslinked structure, the dispersibility of the raw material such as the release agent, the magnetic material, and the charge control agent in the toner particle deteriorates, and the development Affects the sex.
[0034]
In the present invention, the acid value of the binder resin is determined by the following method.
[0035]
<Measurement of acid value>
Basic operation conforms to JIS K-0070.
1) The binder resin pulverized product 0.5 to 2.0 (g) is precisely weighed to obtain the weight W (g) of the binder resin.
2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.
3) Using a 0.1N KOH methanol solution, titration is performed using a potentiometric titrator (for example, using a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette. All automatic titrations are available.)
4) The amount of KOH solution used at this time is S (ml), and at the same time, a blank is measured, and the amount of KOH solution used at this time is B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
[0036]
Acid value (mgKOH / g) = ((SB) × f × 5.61) / W
[0037]
The toner of the present invention has at least one peak in the molecular weight region of 4,000 to 30,000 in the molecular weight distribution by THF-soluble GPC, and at least one peak in the molecular weight region of 100,000 to 500,000. Having at least one peak or shoulder, preferably at least one peak in the region of molecular weight 5,000 to 20,000 and at least one peak in the region of molecular weight 100,000 to 350,000 Or the thing with a shoulder is good.
[0038]
By having at least one peak in the molecular weight region of 4,000 to 30,000, good low-temperature fixability and blocking resistance can be achieved. When the peak is less than 4,000, the blocking resistance deteriorates, and when the molecular weight exceeds 30,000, sufficient fixability cannot be obtained. Further, by having at least one peak or shoulder in the molecular weight range of 100,000 to 500,000, low temperature fixability can be obtained even when a carboxyl group and a glycidyl group react to form a crosslinking component or when no reaction occurs. Good offset resistance is achieved without loss. When the peak is less than 100,000, a sufficient effect on the offset resistance cannot be obtained, and when it exceeds 500,000, a sufficient effect on the offset resistance can be obtained. Low temperature fixability is adversely affected. In addition, if such a peak is not present in the molecular weight distribution, the resin cannot have an appropriate elasticity, so that kneading share cannot be applied at the time of melt kneading at the time of toner production, the dispersibility of the material deteriorates, and fixing Both the stability and durability stability deteriorate.
[0039]
Further, the peak area having a molecular weight of 100,000 or more is desirably 5 to 40% of the total peak area, and more preferably 10 to 35%. When the peak area is less than 5%, the toner is easily peeled off from the transparency (trapene). On the other hand, when it exceeds 40%, sufficient fixability cannot be achieved. In the present invention, the total peak area refers to the peak area of a region having a molecular weight of 500 or more.
[0040]
When the THF-insoluble matter in the binder resin in the toner is contained in an amount of 5 to 50% by mass, good releasability from a heating member such as a fixing roller is exhibited. In particular, when applied to a high-speed machine, there is an effect of reducing the amount of toner offset to a heating member such as a fixing roller. The THF insoluble matter in the binder resin in the toner is preferably 5 to 35% by mass. When the amount is less than 5% by mass, the above effect is hardly exhibited. When the amount exceeds 50% by mass, not only the fixability is deteriorated but also the chargeability tends to be nonuniform in the toner.
[0041]
The glass transition temperature (Tg) of the toner of the present invention is preferably 50 to 70 ° C. When Tg is less than 50 ° C., blocking resistance deteriorates, and when it exceeds 70 ° C., fixability deteriorates.
[0042]
In the present invention, the molecular weight distribution by GPC using the toner and binder resin THF (tetrahydrofuran) as a solvent is measured under the following conditions.
[0043]
<Measurement of molecular weight distribution by GPC>
The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 manufactured by Tosoh Corporation or Showa Denko KK is 10²-10⁷It is appropriate to use a standard polystyrene sample of about 10 points. An RI (refractive index) detector is used as the detector. In addition, as a column, it is better to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko, TSKgel G1000H (H_XL), G2000H (H_XL), G3000H (H_XL), G4000H (H_XL), G5000H (H_XL), G6000H (H_XL), G7000H (H_XL), A combination of TSKgull column.
[0044]
The sample is prepared as follows.
[0045]
Place the sample in THF and let stand for several hours, then shake well and mix well with THF (until the sample is no longer united) and let stand for more than 12 hours. At that time, the standing time in THF should be 24 hours or more. Thereafter, a sample processed filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.
[0046]
In the present invention, the THF-insoluble content of the resin component in the toner and the THF-insoluble content of the raw material binder resin are measured as follows.
[0047]
<Measurement of THF-insoluble matter>
Binder resin and toner 0.5-1.0 g are weighed (W1 g), cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha Co., Ltd.) is put into a Soxhlet extractor, and extracted for 10 hours using 200 ml of THF as a solvent. After evaporating the soluble component solution extracted with the solvent, it is vacuum dried at 100 ° C. for several hours, and the amount of the THF soluble resin component is weighed (W2 g). The weight other than the resin component in the toner is determined (W3g). The THF-insoluble content can be obtained from the following formula.
[0048]
[Expression 1]

[0049]
In the present invention, the binder resin contains a resin obtained by reacting a carboxyl group-containing vinyl resin and a glycidyl group-containing vinyl resin. When both are reacted, this reaction may be performed either during the production of the binder resin or during the production of the toner.
[0050]
In order to obtain the carboxyl group-containing vinyl resin, which is a feature of the present invention, a design in which the acid value of the high molecular weight component is high and the acid value of the low molecular weight component is low is preferable. This is because the high molecular weight component is selectively reacted to improve the offset resistance without affecting the low-temperature fixability.
[0051]
In order to obtain the carboxyl group-containing vinyl resin of the present invention, the following can be used as monomers of the vinyl polymer for both the high molecular weight component and the low molecular weight component.
[0052]
For example, unsaturated dibasic acid and anhydride monomers such as maleic acid, citraconic acid, dimethylmaleic acid, itaconic acid, alkenyl succinic acid, and anhydrides thereof; fumaric acid, metaconic acid, dimethyl fumaric acid; And monoesters of the above unsaturated dibasic acids. Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and anhydrides thereof; anhydrides between the α, β-unsaturated acids and anhydrides with lower fatty acids; These anhydride monomers. Alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid and anhydrides and monoesters thereof. Among these, maleic acid, maleic acid half ester, and maleic anhydride are particularly preferably used as the monomer for obtaining the binder resin of the present invention.
[0053]
Furthermore, the following are mentioned as a comonomer of a vinyl polymer.
[0054]
For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Styrene such as styrene and its derivatives; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride Vinyl acetate, vinyl propionate, vinyl benzoate, etc. Esters: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Α-methyl aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate , Acrylic acid esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl Vinyl ethers such as ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, and other N- Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .; esters of the aforementioned α, β-unsaturated acids, diesters of dibasic acids; Used in two or more.
[0055]
Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.
[0056]
The reason why the styrene copolymer is preferred is that the carboxyl group present in the polymer chain of the styrene copolymer effectively interacts with the glycidyl group in the vinyl resin containing glycidyl group, and the release agent, magnetic substance This is to improve the dispersibility with the raw materials such as.
[0057]
As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.
[0058]
The binder resin used in the present invention may be a polymer crosslinked with a crosslinkable monomer as exemplified below if necessary.
[0059]
Aromatic divinyl compounds, such as divinylbenzene, divinylnaphthalene, etc .; diacrylate compounds linked by alkyl chains, such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, and acrylates of the above compounds replaced by methacrylate; diacrylate compounds linked by an alkyl chain containing an ether bond For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 40 Diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and acrylates of the above compounds replaced with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond, such as poly Oxyethylene (2) -2,2-bis (4-hydroxydiphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxydiphenyl) propane diacrylate, and acrylates of the above compounds What replaced it with methacrylate; Furthermore, polyester type diacrylate compounds, for example, brand name MANDA (Nippon Kayaku), is mentioned. Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; For example, lucyanurate and triallyl trimellitate;
[0060]
These crosslinking agents are preferably used in an amount of about 0.01 to 5 parts by mass (more preferably about 0.03 to 3 parts by mass) with respect to 100 parts by mass of other monomer components.
[0061]
The selection of the initiator, the type of solvent and the reaction conditions when producing the resin of the present invention is an important factor for obtaining the target resin of the present invention. Examples of initiators include benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate. Organic peroxides such as dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t-butylperoxide; azobisisobutyronitrile, Azo and diazo compounds such as diazoaminoazobenzene can be used.
[0062]
As a method for synthesizing the low molecular weight component polymer of the carboxyl group-containing vinyl resin according to the present invention, a known method can be used. However, in the bulk polymerization method, a low molecular weight polymer can be obtained by polymerizing at a high temperature to increase the termination reaction rate, but there is a problem that the reaction is difficult to control. On the other hand, in the solution polymerization method, a low molecular weight polymer can be obtained under mild conditions by utilizing the difference in radical chain transfer by a solvent and adjusting the initiator amount and reaction temperature. Preferred for obtaining components.
[0063]
As a solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene is used. When using a styrene monomer, xylene, toluene or cumene is preferred. The solvent is appropriately selected depending on the polymer to be polymerized. The reaction temperature varies depending on the solvent to be used, the polymerization initiator, and the polymer to be polymerized, but it is usually preferable to carry out the reaction at 70 to 230 ° C. In solution polymerization, it is preferable to carry out by 30-400 mass parts of monomers with respect to 100 mass parts of solvents. Furthermore, it is also preferable to mix other polymers in the solution at the end of the polymerization, and several types of polymers can be mixed.
[0064]
Examples of the method for synthesizing the high molecular weight component polymer include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method and a suspension polymerization method. Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed using a water-soluble polymerization initiator. In this method, the reaction heat can be easily adjusted, and the termination reaction rate is low because the phase in which the polymerization is carried out (the oil phase consisting of the polymer and the monomer) and the aqueous phase are separate, resulting in a high polymerization rate. A product having a high degree of polymerization is obtained. Furthermore, because the polymerization process is relatively simple and the polymerization product is fine particles, it is easy to mix with additives such as colorants and charge control agents in the production of toner. There is an advantage as a method for producing a binder resin for toner.
[0065]
However, because of the added emulsifier, the polymer tends to be impure, and an operation such as salting out is necessary to take out the polymer, and the suspension polymerization method is convenient to avoid this inconvenience.
[0066]
However, the most preferred method for synthesizing the high molecular weight component polymer in the carboxyl group-containing vinyl resin of the present invention is the solution polymerization method. This is because the solution polymerization method can be performed under mild conditions, so that a carboxyl group necessary for crosslinking can be introduced into the high molecular weight component while controlling the distance between crosslinking points.
[0067]
In addition, a polymer component polymer synthesized by a solution polymerization method exhibits good compatibility even when mixed with a low molecular weight component polymer. As a result, it has been shown that this has an effect of further improving the developability, and from such a viewpoint, the synthesis by the solution polymerization method is preferable.
[0068]
The monomer having a glycidyl group unit constituting the glycidyl group-containing vinyl resin may be a compound having a vinyl group and an epoxy group, and examples thereof include esters of glycidyl alcohol and unsaturated carboxylic acid, and unsaturated glycidyl ether. Examples thereof include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether, allyl β-methyl glycidyl ether, and the like.
[0069]
In particular, a glycidyl monomer represented by the following general formula is preferably used.
[0070]
[Chemical formula 5]

(Wherein R^' ₁, R^' ₂And R^' _ThreeRepresents hydrogen, an alkyl group, an aryl group, an aralkyl group, a carboxyl group and an alkoxycarbonyl group. )
[0071]
A monomer having such a glycidyl group unit can be obtained alone or in combination and copolymerized with a vinyl monomer by a known polymerization method to obtain the glycidyl group-containing vinyl resin.
[0072]
The glycidyl group-containing vinyl resin has a weight average molecular weight (Mw) of preferably 5,000 to 30,000, more preferably 6,000 to 20,000, and still more preferably 7,000 to 15,000. good. When Mw is less than 5,000, even if the molecular weight is increased in the crosslinking reaction in the binder resin, there are many cases where the molecular chain is broken in the kneading step, and the effect on the offset resistance may be reduced. When Mw exceeds 30,000, the fixability may be affected.
[0073]
The glycidyl group-containing vinyl resin preferably has an epoxy value of 0.1 to 1.0 eq / kg. When it is less than 0.1 eq / kg, the crosslinking reaction is difficult to occur, the amount of high molecular weight components and THF insolubles produced is small, and the effect on offset resistance is reduced. If it exceeds 1.0 eq / kg, the cross-linking reaction tends to occur, but on the other hand, there are many molecular chain breaks in the kneading step, and the effect on offset resistance is reduced.
[0074]
The epoxy value of the glycidyl group-containing vinyl resin is determined by the following method.
[0075]
<Measurement of epoxy value>
Basic operation conforms to JIS K-7236.
(1) 0.5-2.0 (g) of the sample is precisely weighed, and the weight of the binder resin is defined as W (g).
(2) A sample is put into a 300 (ml) beaker and dissolved in 10 ml of chloroform and 20 ml of acetic acid.
(3) To this solution is added 10 ml of tetraethylammonium bromide acetic acid solution.
(4) Titrate with a potentiometric titrator using 0.1 mol / l perchloric acid acetic acid solution. (For example, automatic titration using a potentiometric titrator AT-400 (win workstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.)
(5) The amount of perchloric acid acetic acid solution used at this time is S (ml), and a blank is measured at the same time. The amount of perchloric acid acetic acid solution used at this time is B (ml).
(6) The epoxy value is calculated by the following formula. f is a factor of the perchloric acid acetic acid solution.
[0076]
Epoxy value (eq / kg) = 0.1 × f × (SB) / W
[0077]
Examples of the vinyl monomer copolymerized with the carboxyl group-containing monomer and the glycidyl group-containing monomer include the following.
[0078]
For example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl Styrene derivatives such as styrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Class: Vinyl acetate, vinyl propionate, vinyl benzoate Vinyl esters such as: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid (2-ethylhexyl), stearyl methacrylate, Α-methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acrylic acid esters such as n-octyl acid, dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), phenyl acrylate; Vinyl ethers such as til ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone N-vinyl compounds such as: vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; esters of the aforementioned α, β-unsaturated acids, dibasic acid diesters; Monomers are used alone or in combination of two or more.
[0079]
Among these, a combination of monomers that becomes a styrene copolymer and a styrene-acrylic copolymer is preferable.
[0080]
Examples of magnetic materials used in the present invention include iron oxides such as magnetite, maghemite, and ferrite; metals such as iron, cobalt, and nickel; and these metals and aluminum, cobalt, copper, lead, magnesium, manganese, selenium, titanium, Metal alloys such as tungsten and vanadium and mixtures thereof are used, and those containing non-ferrous elements on the surface or inside of the magnetic material are preferred.
[0081]
As the magnetic substance used in the present invention, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements and mixtures thereof are preferably used.
[0082]
Among them, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, titanium, zirconium, tin, lead, zinc, calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium, cadmium, indium It is preferably a magnetic iron oxide containing at least one element selected from silver, palladium, gold, mercury, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium, and bismuth. . In particular, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, and transition metal elements in the fourth period are preferable elements. These elements may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as oxides, or may exist on the surface as oxides or hydroxides. Moreover, it is a preferable form to contain as an oxide.
[0083]
A magnetic material containing these elements is well-familiar with the binder resin and has very good dispersibility.
[0084]
In addition, these magnetic materials have a uniform particle size distribution and, together with their dispersibility in the binder resin, can stabilize the chargeability of the toner. Further, in recent years, the toner particle diameter has been reduced, and even when the weight average particle diameter is 10 μm or less, the charging uniformity is promoted, the aggregation property of the toner is reduced, the image density is improved, the fog is improved, etc. Developability is improved. In particular, the effect is remarkable in a toner having a weight average particle diameter of 6.0 μm or less, and an extremely fine image can be obtained. A weight average particle diameter of 2.5 μm or more is preferable because a sufficient image density can be obtained.
[0085]
The content of these different elements is preferably 0.05 to 10% by mass based on the iron element of magnetic iron oxide. More preferably, it is 0.1-7 mass%, Most preferably, it is 0.2-5 mass%, Furthermore, it is 0.3-4 mass%. If it is less than 0.05% by mass, the effect of containing these elements cannot be obtained, and good dispersibility and charging uniformity cannot be obtained. On the other hand, if it exceeds 10% by mass, the discharge of charge increases, resulting in insufficient charging, and the image density may be lowered or fog may increase.
[0086]
In addition, in the content distribution of these different elements, it is preferable that many exist in the direction closer to the surface of the magnetic body. For example, the ratio (B / A) × 100 of the content B of different elements existing in the iron element dissolution rate of iron oxide to 20% by mass and the total content A of different elements of the magnetic iron oxide is 40% or more. It is preferable that Furthermore, 40 to 80% is preferable, and 60 to 80% is particularly preferable. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved. Further, the amount contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component, with respect to 100 parts by mass of the resin component.
[0087]
Furthermore, the sphericity (Ψ) of the magnetic iron oxide used in the present invention is preferably 0.8 or more. When the sphericity (Ψ) is smaller than 0.8, the individual particles of magnetic iron oxide come into contact with each other, and in the case of small magnetic iron oxide particles having a particle size of 0.1 to 1.0 μm, Even with a strong shear force, the magnetic iron oxides cannot be easily separated from each other, so that the magnetic iron oxides may not be sufficiently dispersed in the toner.
[0088]
In some cases, the magnetic iron oxide used in the toner of the present invention may be treated with a silylating agent, a silane coupling agent, a titanium coupling agent, titanate, aminosilane, or the like.
[0089]
The amount of element in the magnetic iron oxide of the present invention is measured by performing fluorescent X-ray analysis using a fluorescent X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to JIS K0119 general X-ray fluorescence analysis rules. did. Regarding the element distribution, the amount of element while dissolving hydrochloric acid was measured and quantified by plasma emission spectroscopy (ICP), and the dissolution rate was determined from the concentration of each element at the time of dissolution relative to the concentration of each element at the time of total dissolution.
[0090]
The sphericity (Ψ) of magnetic iron oxide was photographed at 10,000 times at an applied voltage of 100 kV using a sample of magnetic iron oxide treated on a collodion film copper mesh with an electron microscope (Hitachi H-700H). The baking magnification is 3 times and the final magnification is 30,000 times. Thus, the shape is observed, the maximum length (μm) and the minimum length (μm) of each particle are measured, 100 particles are selected at random, calculated according to the following formula, and then the calculated values are averaged.
[0091]
Sphericality = Minimum length of magnetic iron oxide (μm) / Maximum length of magnetic iron oxide (μm)
[0092]
Other colorants that can be used in the toner include any suitable pigment or dye.
[0093]
Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, Bengala, phthalocyanine blue, and indanthrene blue. These are used in an amount sufficient to maintain the optical density of the fixed image. It is preferable to use 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass of pigment with respect to 100 parts by mass of the resin. For the same purpose, further dyes are used. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and it is preferable to use 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight of the dye with respect to 100 parts by weight of the resin. .
[0094]
Examples of the wax as a release agent used in the present invention include the following. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxidation of aliphatic hydrocarbon wax such as oxidized polyethylene wax Or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax; animal waxes such as beeswax, lanolin, whale wax; minerals such as ozokerite, ceresin, petrolactam Waxes based on fatty acid esters such as montanic acid ester wax and caster wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax That. Further, a saturated straight chain such as palmitic acid, stearic acid, montanic acid, or a long-chain alkyl carboxylic acid having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol; Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide An aliphatic amide such as lauric acid amide; a saturated fatty acid bisamide such as methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; Unsaturated fatty acid amides such as oleic acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, Aromatic bisamides such as N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (generally referred to as metal soap); aliphatic hydrocarbon waxes Wax grafted with vinyl monomers such as styrene and acrylic acid; partially esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; methyl having hydroxyl group obtained by hydrogenating vegetable oil Ester compound And the like.
[0095]
Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures Polyolefins; Polyolefins polymerized using radiation, electromagnetic waves or light; Low molecular weight polyolefins obtained by thermally decomposing high molecular weight polyolefins; Paraffin wax, microcrystalline wax, Fischer-Tropsch wax; Jindole method, Hydrocol method, Age method Synthetic hydrocarbon wax synthesized by the following: a synthetic wax having a compound having one carbon atom as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group; a hydrocarbon wax and a functional group A mixture of wax; styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, waxes of such vinyl monomers with maleic anhydride graft modified.
[0096]
In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal method, low molecular weight solid fatty acids, low molecular weight solids. An alcohol, a low molecular weight solid compound, and other impurities are preferably used.
[0097]
The wax used in the present invention preferably has a melting point of 65 to 160 ° C., more preferably 65 to 130 ° C., particularly 70 ° C. to 120 ° C. in order to balance the fixing property and the offset resistance. It is preferable that it is ° C. If it is less than 65 degreeC, blocking resistance will fall, and if it exceeds 160 degreeC, an offset-proof effect will become difficult to express.
[0098]
In the toner of the present invention, the total content of these waxes is 0.2 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. It is. Moreover, you may use together with other waxes, as long as it does not have a bad influence.
[0099]
In the present invention, the melting point of the wax is defined as the melting point of the wax at the peak top temperature of the endothermic peak of the wax measured by DSC.
In the present invention, the DSC measurement using a differential scanning calorimeter for wax or toner is preferably performed using a differential scanning calorimeter with high accuracy of internal heat input compensation. For example, DSC-7 manufactured by Perkin Elmer can be used.
[0100]
The measurement method is performed according to ASTM D3418-82. The DSC curve used in the present invention is a DSC curve measured when the temperature is raised after raising the temperature once, taking the previous history, then lowering the temperature in the range of 10 ° C./min, and the temperature of 0 to 200 ° C. Is used.
[0101]
In the toner of the present invention, conventionally known pigments or dyes such as carbon black and copper phthalocyanine can be used as coloring materials that can be added.
[0102]
The toner of the present invention is preferably used as a negatively chargeable toner by adding a charge control agent.
[0103]
Specific examples of the negative charge control agent include monoazo dyes described in JP-B No. 41-20153, JP-B No. 42-27596, JP-B No. 44-6397, JP-B No. 45-26478, and the like. Nitrohumic acid and salts thereof described in JP-A-50-133838 or C.I. I. Dyes and pigments such as 14645, salicylic acid, naphthoic acid, dicarboxylic acid described in JP-B-55-42752, JP-B-58-41508, JP-B-58-7384, JP-B-59-7385, etc. Examples thereof include metal complexes of acids such as Zn, Al, Co, Cr, Fe, and Zr, sulfonated copper phthalocyanine pigments, styrene oligomers introduced with nitro groups and halogens, and chlorinated paraffins. In particular, an azo metal complex represented by the general formula (I) and a basic organic acid metal complex represented by the general formula (II) are excellent in dispersibility and effective in reducing the image density stability and fog. preferable.
[0104]
[Chemical 6]

[0105]
[Chemical 7]

[0106]
Among them, the azo metal complex represented by the above formula (I) is more preferable, and the azo iron complex represented by the following formula (III) or (IV) in which the central metal is Fe is most preferable.
[0107]
[Chemical 8]

[0108]
[Chemical 9]

[0109]
Next, specific examples of the azo iron complex represented by the above formula (III) are shown below.
[0110]
[Chemical Formula 10]

[0111]
Embedded image

[0112]
Embedded image

[0113]
Specific examples of the charge control agent represented by the above formulas (I), (II), and (IV) are shown below.
[0114]
Embedded image

[0115]
Embedded image

[0116]
Embedded image

[0117]
These metal complex compounds can be used alone or in combination of two or more.
[0118]
The use amount of these charge control agents is preferably 0.1 to 5.0 parts by mass per 100 parts by mass of the binder resin from the viewpoint of the charge amount of the toner.
[0119]
On the other hand, there are the following substances that control the toner to be positively charged.
[0120]
Modified products by nigrosine and fatty acid metal salts, etc., quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and oniums such as phosphonium salts which are analogs thereof Salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds, 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.
[0121]
The toner of the present invention is preferably mixed with inorganic fine powder or hydrophobic inorganic fine powder. For example, it is preferable to add and use silica fine powder.
[0122]
As the silica fine powder used in the present invention, both a so-called dry process produced by vapor phase oxidation of a silicon halide compound or a so-called wet silica produced from water glass or the like can be used. However, dry silica having less silanol groups on the surface and inside and having no production residue is preferable.
[0123]
Further, the silica fine powder used in the present invention is preferably hydrophobized. The hydrophobizing treatment is performed by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferable method, a dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane coupling agent or with a silane coupling agent and simultaneously with an organosilicon compound such as silicone oil. Is mentioned.
[0124]
Examples of silane coupling agents used for hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane. , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyl Examples thereof include tetramethyldisiloxane and 1,3-diphenyltetramethyldisiloxane.
[0125]
Examples of the organosilicon compound include silicone oil. A preferred silicone oil has a viscosity of approximately 3 × 10 at 25 ° C.^-Five~ 1x10^-3m²For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil, etc. are preferable.
[0126]
Silicone oil treatment can be performed by, for example, mixing silica fine powder treated with a silane coupling agent and silicone oil directly using a mixer such as a Henschel mixer, or adding silicone oil to the base silica. It is good also by the method of injecting. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, and then mixed with the base silica fine powder to remove the solvent.
[0127]
An external additive other than silica fine powder may be added to the toner in the present invention, if necessary.
[0128]
Examples thereof include resin fine particles and inorganic fine particles that function as a charge auxiliary agent, a conductivity imparting agent, a fluidity imparting agent, an anti-caking agent, a release agent at the time of heat roll fixing, a lubricant, and an abrasive.
[0129]
For example, lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride are preferable, and among them, polyvinylidene fluoride is preferable. Alternatively, a polishing agent such as cerium oxide, silicon carbide, strontium titanate, etc., among which strontium titanate is preferable. Alternatively, for example, a fluidity imparting agent such as titanium oxide or aluminum oxide, particularly a hydrophobic one is preferable. A small amount of an anti-caking agent, or a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide or tin oxide, or white and black fine particles having opposite polarity can be used in small amounts.
[0130]
The inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is preferably used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) with respect to 100 parts by mass of the toner.
[0131]
In order to produce the toner according to the present invention, the toner constituent materials as described above are sufficiently mixed by a ball mill or other mixer, and then kneaded well using a heat kneader such as a hot roll, a kneader or an extruder, and cooled. After solidification, a method of obtaining toner by mechanical pulverization / classification is preferable. Otherwise, a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsion suspension, and then polymerized. A method for producing a polymerized toner for obtaining a toner, a method for containing a predetermined material in a core material or a shell material, or both of them in a so-called microcapsule toner comprising a core material and a shell material, and a constituent material in a solution in a binder resin A method of obtaining toner by spray drying after dispersion can be applied. Further, the toner according to the present invention can be produced by sufficiently mixing desired additives with a mixer such as a Henschel mixer, if necessary.
[0132]
For example, as a mixer, Henschel mixer (Mitsui Mining Co., Ltd.); Super mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); (Manufactured by Taiheiyo Kiko Co., Ltd.); Ladige mixer (manufactured by Matsubo Co., Ltd.), and kneading machines such as KRC kneader (manufactured by Kurimoto Iron Works); (Manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); Mining company); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) It is below. As a pulverizer, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries Ltd.); Turbo Mill (manufactured by Turbo Industry Co., Ltd.). Classifiers include: Classy, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nisshin Engineering); Micron Separator, Turbo Flex (ATP), TSP Separator (manufactured by Hosokawa Micron) An elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), a dispersion separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); Ultrasonic (Made by Sakae Sangyo Co., Ltd.); Resona sieve, Gyroshifter (Deoksugaku Kojo Co., Ltd.); Vibrasonic system (Made by Dalton); Soniclean (Shinto) (Industry company); Turbo screener (Turbo industry company); Micro shifter (Ogino industry company); Circular vibration sieve, etc.
[0133]
【Example】
Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, this does not limit the embodiment of the present invention. The number of parts in the examples is part by mass.
[0134]
<Example of production of low molecular weight component (B-1)>
Into a four-necked flask, 300 parts of xylene is charged, and the inside of the container is sufficiently replaced with nitrogen while stirring, and then heated to reflux.
[0135]
Under this reflux, a mixture of 75 parts of styrene, 25 parts of acrylate-n-butyl and 2 parts of di-tert-butyl peroxide (initiator 1) was added dropwise over 4 hours, and then held for 2 hours to conduct polymerization. Completed to obtain a low molecular weight polymer solution (B-1).
[0136]
<Production example of low molecular weight component (B-2)>
Polymerization was carried out in the same manner as in the production example of low molecular weight component B-1 using 80 parts of styrene, 20 parts of acrylic acid-n-butyl, and 2.5 parts of initiator 1 to obtain a low molecular weight polymer solution B-2. .
[0137]
<Example of production of low molecular weight component (B-3)>
Polymerization was carried out in the same manner as in the production example of low molecular weight component B-1 using 78 parts of styrene, 22 parts of acrylic acid-n-butyl, and 2 parts of initiator 1 to obtain a low molecular weight polymer solution B-3.
[0138]
<Example of production of low molecular weight component (B-4)>
Polymerization was carried out in the same manner as in the production example of low molecular weight component B-1 using 60 parts of styrene, 40 parts of acrylic acid-n-butyl, and 1.5 parts of initiator 1 to obtain a low molecular weight polymer solution B-4. .
[0139]
<Example of production of low molecular weight component (B-5)>
Polymerization is carried out in the same manner as in the production example of low molecular weight component B-1 using 75 parts of styrene, 20 parts of acrylic acid-n-butyl, 5 parts of monobutyl maleate, and 2.5 parts of initiator 1, and a low molecular weight polymer solution. B-5 was obtained.
[0140]
<Example of production of low molecular weight component (B-6)>
Polymerization was carried out in the same manner as in the production example of low molecular weight component B-1 using 80 parts of styrene, 20 parts of acrylic acid-n-butyl, and 2 parts of initiator 1 to obtain a low molecular weight polymer solution B-6.
[0141]
<Production example of high molecular weight component (A-1)>
Into a four-necked flask, 300 parts of xylene is charged, and the inside of the container is sufficiently replaced with nitrogen while stirring, and then heated to reflux.
[0142]
Under this reflux, 70 parts of styrene, 25 parts of acrylate-n-butyl, 5 parts of monobutyl maleate and 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane (initiator 2; halved) (A period of 10 hours, temperature: 92 ° C.) 1 part of a mixed solution was dropped over 4 hours and then held for 2 hours to complete the polymerization to obtain a high molecular weight component (A-1) solution.
[0143]
<Production example of high molecular weight component (A-2)>
In the same manner as in the production example of the high molecular weight component (A-1), 70 parts of styrene, 27 parts of acrylic acid-n-butyl, 3 parts of monobutyl maleate and 1 part of initiator 2 were used, and the high molecular weight component (A-2) A solution was obtained.
[0144]
<Production example of high molecular weight component (A-3)>
Similar to the production example of the high molecular weight component (A-1), 72 parts of styrene, 23 parts of acrylic acid-n-butyl, 5 parts of acrylic acid and 1 part of the initiator 2 were used to prepare a high molecular weight component (A-3) solution. Got.
[0145]
<Production example of high molecular weight component (A-4)>
In the same manner as in the production example of the high molecular weight component (A-1), 70 parts of styrene, 27 parts of acrylic acid-n-butyl, 3 parts of methacrylic acid and 1 part of initiator 2 were used to prepare a high molecular weight component (A-4) solution. Got.
[0146]
<Production example of high molecular weight component (A-5)>
Similarly to the production example of the high molecular weight component (A-1), 75 parts of styrene, 25 parts of n-butyl acrylate and 1 part of initiator 2 were used to obtain a high molecular weight component (A-5) solution.
[0147]
<Production example of high molecular weight component (A-6)>
In the same manner as in the production example of the high molecular weight component (A-1), 65 parts of styrene, 25 parts of acrylic acid-n-butyl, 10 parts of monobutyl maleate, and 1 part of initiator 2 were used, and the high molecular weight component (A-6) A solution was obtained.
[0149]
<Production example of high molecular weight component (A-8)>
Into a four-necked flask, 180 parts of degassed water and 20 parts of a 2% by weight aqueous solution of polyvinyl alcohol were added, and then 70 parts of styrene, 25 parts of acrylic acid-n-butyl, 5 parts of monobutyl maleate, 0. A mixed solution in which 005 parts and initiator 2 were mixed at 0.1 part was added and stirred to obtain a suspension.
[0150]
After sufficiently replacing the inside of the flask with nitrogen, the temperature was raised to 85 ° C. to initiate polymerization. After maintaining at the same temperature for 24 hours, 0.1 part of benzoyl peroxide (half-life 10 hours temperature: 72 ° C.) was added. The polymerization was completed by holding for another 12 hours. Thereafter, the high molecular weight polymer was separated by filtration, washed with water and dried to obtain a high molecular weight component (A-8).
[0151]
<Production example of high molecular weight component (A-9)>
Similarly to the production example of the high molecular weight component (A-8), 70 parts of styrene, 26 parts of acrylate-n-butyl, 4 parts of monobutyl maleate, 0.005 part of divinylbenzene and 1 part of initiator 2 were used. A high molecular weight component (A-9) was obtained.
[0152]
<Production of carboxyl group-containing vinyl resin (C-1)>
In a four-necked flask, 200 parts of a xylene solution of the low molecular weight component (B-1) (corresponding to 50 parts of a low molecular weight component) is added, and the temperature is raised and stirred under reflux. On the other hand, 200 parts (corresponding to 50 parts of high molecular weight component) of the above high molecular weight component (A-1) solution is put into another container and refluxed. After the low molecular weight component (B-1) solution and the high molecular weight component (A-1) solution are mixed under reflux, the organic solvent is distilled off, and the resulting resin is cooled, solidified and pulverized to contain a carboxyl group. A vinyl resin (C-1) was obtained. The results of molecular weight distribution, acid value, etc. are shown in Table 1.
[0153]
<Production example of carboxyl group-containing vinyl resin (C-2 to 10)>
A high molecular weight component solution, a high molecular weight component polymer (A-2 to 9) and a low molecular weight component solution (B-2 to 6) are combined as shown in Table 1 to produce a carboxyl group-containing vinyl resin (C-1). In the same manner as in the examples, carboxyl group-containing vinyl resins (C-2 to 10) were obtained. The results of molecular weight distribution, acid value, etc. are shown in Table 1.
[0154]
<Production example of carboxyl group-containing vinyl resin (C-11)>
Similar to the production example of the high molecular weight component (A-1), using 70 parts of styrene, 20 parts of n-butyl acrylate, 10 parts of monobutyl maleate, 0.005 part of divinylbenzene and 1 part of initiator 1, One carboxyl group-containing vinyl resin (C-11) was obtained in the distribution. The results of molecular weight distribution, acid value, etc. are shown in Table 1.
[0155]
<Production example of glycidyl group-containing vinyl resin (D-1)>
Into a four-necked flask, 300 parts of xylene is charged, and the inside of the container is sufficiently replaced with nitrogen while stirring, and then heated to reflux.
[0156]
Under this reflux, a mixture of 75 parts of styrene, 18 parts of acrylic acid-n-butyl, 7 parts of glycidyl methacrylate and 2 parts of di-tert-butyl peroxide was added dropwise over 4 hours, and then held for 2 hours for polymerization. And the solvent was distilled off under reduced pressure. In this way, a glycidyl group-containing vinyl resin (D-1) was obtained.
[0157]
<Production example of glycidyl group-containing vinyl resin (D-2)>
In the same manner as in the production example of the glycidyl group-containing vinyl resin (D-1), 75 parts of styrene, 21 parts of acrylic acid-n-butyl, 4 parts of glycidyl methacrylate and 3 parts of initiator 1 were used. D-2) was obtained. Table 2 shows the results of molecular weight distribution and epoxy value.
[0158]
<Production example of glycidyl group-containing vinyl resin (D-3)>
As in the production example of the glycidyl group-containing vinyl resin (D-1), 75 parts of styrene, 18 parts of acrylic acid-n-butyl, 7 parts of glycidyl methacrylate and 1.5 parts of initiator 1 were used, and glycidyl group-containing vinyl was used. Resin (D-3) was obtained. Table 2 shows the results of molecular weight distribution and epoxy value.
[0159]
<Production example of glycidyl group-containing vinyl resin (D-4)>
Glycidyl group-containing vinyl using 75 parts of styrene, 20 parts of n-butyl acrylate, 5 parts of glycidyl methacrylate and 0.5 part of initiator 1 as in the production example of glycidyl group-containing vinyl resin (D-1). Resin (D-4) was obtained. Table 2 shows the results of molecular weight distribution and epoxy value.
[0160]
<Production example of glycidyl group-containing vinyl resin (D-5)>
In the same manner as in the production example of the glycidyl group-containing vinyl resin (D-1), 70 parts of styrene, 15 parts of acrylic acid-n-butyl, 15 parts of glycidyl methacrylate and 2 parts of initiator 1 were used. D-5) was obtained. Table 2 shows the results of molecular weight distribution and epoxy value.
[0161]
<Wax>
The wax used in the examples is as shown in Table 3.
[0162]
<Example of production of magnetic iron oxide particles>
Magnetic iron oxide particles were produced by adding a salt of an element present inside the magnetite to adjust the pH, and magnetic iron oxide particles 1 to 5 shown in Table 4 were obtained. Magnetic iron oxide particles 1 and 3 added silicate, magnetic iron oxide particles 2 added phosphate, and magnetic iron oxide particles 4 added magnesium salt to generate magnetite particles. In particular, magnetite particles were generated without adding a salt, and then the pH was adjusted by adding a zirconium salt to precipitate zirconia on the surface of the magnetite particles to obtain magnetic iron oxide particles 5.
[0163]
[Example 1]
Using 93 parts of the carboxy group-containing vinyl resin obtained in Production Example C-1 and 7 parts of the glycidyl group-containing vinyl resin obtained in Production Example D-3 (corresponding to 2.5 mol in terms of glycidyl group blending ratio) in a Henschel mixer After mixing, the mixture was kneaded at 180 ° C. with a twin-screw kneading extruder, cooled and pulverized to obtain a binder resin 1.
[0164]
・ 100 parts of the above binder resin 1
・ 90 parts of magnetic iron oxide particles 1
・ Wax e 4 parts
・ Azo-based iron complex compound A 2 parts
[0165]
The above materials were premixed with a Henschel mixer and then melt kneaded with a twin screw kneading extruder set at 130 ° C.
[0166]
The obtained kneaded product is cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder is classified using a multi-division classifier utilizing the Coanda effect. Thus, toner particles having a weight average particle diameter of 6.5 μm were obtained. 100 parts of toner particles are hydrophobized with 15% by weight of hexamethyldisilazane and 15% by weight of dimethyl silicone for 80% methanol wettability and a BET specific surface area of 120 m.²/ G hydrophobic silica fine powder 1.2 parts and 1.0 part of strontium titanate are externally added and mixed to negatively charge toner No. 1 was prepared.
[0167]
Table 5 shows the toner internal formulation and physical property values.
[0168]
This toner No. 1 was remodeled from a commercially available LBP printer (LBP-930, manufactured by Canon Inc.) to 1.5 times the printing speed, and 15,000 in an environment of 15 ° C., 10% RH and 30 ° C., 80% RH. A sheet print test was performed. Furthermore, this LBP-930 fixing device, which uses a heat roll fixing device, is taken out and operated outside the printer. The fixing roller temperature can be arbitrarily set, and the process speed is modified to 235 mm / sec. Using the external fixing device, the fixing property and the anti-offset property were evaluated. Also, take out a fixing device of a commercially available LBP printer (LBP-430, manufactured by Canon Inc.) using a fixing device made of a pressure member for closely attaching a recording material to a heating body through a film, and even outside the printer. The fixability and offset resistance were evaluated using an external fixer that was operated to allow the fixing film temperature to be arbitrarily set and the process speed was 140 mm / sec. The evaluation results are shown in Tables 6 to 8.
[0169]
“Fixability” refers to 50 g / cm by passing two types of images, solid black and halftone, through a fixing device whose temperature is adjusted to 150 ° C.²The fixed image was rubbed with Silbon paper and evaluated by the reduction rate (%) of the image density before and after rubbing. As for “fixability by tape peeling”, a solid black image is passed through a fixing device whose temperature is adjusted to 180 ° C., a polyester tape is stuck on the fixed image, and 50 g / cm is similarly applied from above.²Then, the film was rubbed with sylbon paper, and then the tape was peeled off. Evaluation was based on the reduction rate (%) of the image density before and after the tape was peeled off. For “bending fixability”, first, a solid black image is passed through a fixing device whose temperature is adjusted to 170 ° C. Then, in order to bend the fixed image in the vertical direction and apply a certain pressure, the fixed image is passed through a fixing device in a room temperature state where temperature control is not applied. Next, the fixed image is once opened, bent in the horizontal direction, and similarly passed through a fixing device not subjected to temperature control. 50 g / cm at the intersection of the vertical and horizontal folds on the fixed image²Was applied, and was rubbed with sylbon paper. Evaluation was based on the reduction rate (%) of the image density before and after rubbing.
[0170]
(Evaluation criteria)
○: Less than 10%
Δ: 10% or more and less than 20%
×: 20% or more
[0171]
“Offset resistance” was evaluated based on the degree of contamination on an image after 3000 sheets of a sample image having an image area ratio of about 5%.
[0172]
(Evaluation criteria)
○: Good
Δ: Slightly dirty
×: Dirt that affects the image
[0173]
“Image density” was a reflection density measurement using an SPI filter with a Macbeth densitometer (manufactured by Macbeth), and a 5 mm square image was measured. “Fog” is performed using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). The fog was evaluated using Ds-Dr as the fog amount. The smaller the number, the better the fog suppression. As the evaluation of “image quality”, an image is formed by forming 100 isolated dots and the number of dots out of 100 can be expressed. The higher the number of dots reproduced, the higher the image quality.
[0174]
These evaluations were performed at the initial stage after 15000 sheets were left outside the apparatus for a day.
[0175]
  [Example 28. Reference examples 1 and 2]
  In the same manner as in Example 1, the toner No. 2-10 were produced. However, toner No. For No. 4, the carboxyl group-containing vinyl resin and the glycidyl group-containing vinyl resin were not kneaded in advance, but were premixed simultaneously with other raw materials and kneaded at 150 ° C. The physical property values thus obtained are shown in Table 5, and the results of similar tests are shown in Tables 6 to 8.
[0176]
[Comparative Examples 1 to 7]
In the formulation shown in Table 5, the toner No. Tables 6 to 8 show the results of manufacturing 11 to 15 and performing the same test.
[0177]
[Table 1]

[0178]
[Table 2]

[0179]
[Table 3]

[0180]
[Table 4]

[0181]
[Table 5]

[0182]
Embedded image

[0183]
Embedded image

[0184]
Embedded image

[0185]
[Table 6]

[0186]
[Table 7]

[0187]
[Table 8]

[0188]
【The invention's effect】
According to the present invention, the toner having the binder resin having the above-described configuration enables low-temperature fixing regardless of the configuration of the fixing device, has excellent offset resistance, and does not cause image defects over time or after standing. High image quality can be obtained stably even when used under low humidity or high humidity.

Claims (15)

In a dry toner having at least a binder resin, a colorant, a charge control agent and a release agent,
The binder resin, which is reacted mosquitoes carboxyl group-containing vinyl resin and a glycidyl group-containing vinyl resin,
The carboxyl group-containing vinyl resin has an acid value of 0.1 to 1 mg KOH / g before the reaction with the glycidyl group-containing vinyl resin , and the carboxyl group is at least of maleic acid, maleic acid half ester, and maleic anhydride. It is produced from an acid monomer selected from one or more types,
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the toner, the toner has at least one peak at a molecular weight of 4,000 to 30,000, and further has a molecular weight of 100,000 to 500,000 has at least one peak or shoulder, and the peak area with a molecular weight of 100,000 or more is a ratio of 5 to 40% with respect to the total peak area,
A dry toner comprising 5 to 50% by mass of a THF-insoluble component in a binder resin component in a toner.   In the molecular weight distribution measured by GPC of the THF soluble part of the toner, it has at least one peak at a molecular weight of 4,000 to 30,000, and further has at least one peak or shoulder at a molecular weight of 100,000 to 350,000. The dry toner according to claim 1, wherein the toner is a dry toner.   The dry toner according to claim 1 or 2, wherein the binder resin component in the toner contains 5 to 35% by mass of a THF-insoluble component. The glycidyl group-containing vinyl resin has a weight average molecular weight of 5,000 to 30,000 and an epoxy value of 0.1 to 1 eq / kg before the reaction with the carboxyl group-containing vinyl resin. The dry toner according to any one of claims 1 to 3 . The binder resin, and a carboxyl group-containing vinyl resin and a glycidyl group-containing vinyl resin, per carboxyl group 1 mol of the carboxyl group-containing vinyl resin, as a glycidyl group of the glycidyl group-containing vinyl resin is from 1 to 4 mol dry toner according to any one of claims 1 to 4, wherein the formulation to those reacted. Is the magnetic iron oxide colorant, dry toner according to any one of claims 1 to 5 100 parts by mass of the binder resin, characterized in that it contains 20 to 200 parts by weight. 7. The dry toner according to claim 6 , wherein the magnetic iron oxide is magnetic iron oxide fine particles containing 0.05 to 10% by mass of a different element on the basis of iron element. The ratio (B / A) × 100 of the content B of the different elements present in the magnetic iron oxide up to 20% by mass and the total content A of the different elements of the magnetic iron oxide is 40% or more. The dry toner according to claim 6 or 7 , wherein: Dry toner according to any one of claims 6 to 8 magnetic iron oxide has a sphericity ([psi) is characterized by having a 0.8 or more. Charge control agent, dry toner according to any one of claims 1 to 9, characterized in that it contains an azo metal complex compound represented by the following formula (I).

Charge control agent, dry toner according to any one of claims 1 to 9, characterized in that it contains a basic organometallic compound represented by the following formula (II).

Charge control agent, dry toner according to any one of claims 1 to 9, characterized in that it contains the azo-type iron complex compound represented by the following formula (III).

Charge control agent, dry toner according to any one of claims 1 to 9, characterized in that it contains the azo-type iron complex compound represented by the following formula (IV).

Dry toner according to any one of claims 1 to 13 releasing agent is 100 parts by mass of the binder resin, characterized by containing 0.2 to 20 parts by weight. Dry toner according to any one of claims 1 to 14 the melting point of the releasing agent is characterized in that it is a sixty-five to one hundred sixty ° C..