JP2005055498A - Toner and method for manufacturing the same, and developer, toner-containing vessel, process cartridge, image forming apparatus and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which has good anti-hot-offset properties, reconciles excellent hot storage resistance with excellent low-temperature fixability, and provides shape high image quality because of a sharp charge amount distribution. <P>SOLUTION: The toner contains fine resin particles having a core-shell structure, a weight average molecular weight of 8,000-1,000,000 and a particle diameter of 20-400 nm. Preferred aspects include an aspect where the toner contains an adhesive base obtained by reacting an active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, an aspect where the toner has the fine resin particles in a surface, an aspect where a glass transition temperature of the fine resin particles is 40-150°C, and an aspect where when a glass transition temperature of a resin forming shells in the fine resin particles is represented by TgS and a glass transition temperature of a resin forming cores by TgC, the expression: TgS>TgC is satisfied. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１９６】
−−樹脂微粒子分散液（１）の調製−
撹拌棒及び温度計をセットした反応容器に、前記コア粒子分散液（Ｃ１）１００９質量部、水６８３質量部、メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩（エレミノールＲＳ−３０、三洋化成工業製）２０質量部、スチレン１０３質量部、メタクリル酸８３質量部、アクリル酸ブチル９０質量部、及び過硫酸アンモニウム１質量部を仕込み、４００回転／分で１５分間撹拌したところ、白色の乳濁液が得られた。該乳濁液を加熱して７５℃まで昇温し５時間反応させた。さらに、１％過硫酸アンモニウム水溶液３０部を加え、７５℃で５時間熟成してビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（１）を得た。
前記樹脂微粒子分散液（１）に含まれる樹脂微粒子（１）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、１０５ｎｍであった。また、該樹脂微粒子分散液（１）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、６０℃であり、重量平均分子量（Ｍｗ）は、４００，０００であった。これらを表２に示した。
【０１９７】
−−樹脂微粒子分散液（２）の調製−
前記樹脂微粒子分散液（１）の調製において、スチレンを１０３質量部から１１．４質量部に変え、メタクリル酸を８３質量部から９．２質量部に変え、アクリル酸ブチルを９０質量部から１０質量部変え、及び過硫酸アンモニウムを１質量部から０．１１質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（２）を調製した。
前記樹脂微粒子分散液（２）に含まれる樹脂微粒子（２）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、９５ｎｍであった。また、該樹脂微粒子（２）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、６０℃であり、重量平均分子量（Ｍｗ）は、４００，０００であった。これらを表２に示した。
【０１９８】
−−樹脂微粒子分散液（３）の調製−
前記樹脂微粒子分散液（１）の調製において、スチレンを１０３質量部から１８．９質量部に変え、メタクリル酸を８３質量部から９．２質量部に変え、アクリル酸ブチルを９０質量部から２．６質量部に変え、及び過硫酸アンモニウムを１質量部から０．１１質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（３）を調製した。
前記樹脂微粒子分散液（３）に含まれる樹脂微粒子（３）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、１１２ｎｍであった。また、該樹脂微粒子（３）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は１１０℃であり、重量平均分子量（Ｍｗ）は、４２０，０００であった。これらを表２に示した。
【０１９９】
−−樹脂微粒子分散液（４）の調製−
前記樹脂微粒子分散液（１）の調製において、コア粒子分散液（Ｃ１）をコア粒子分散液（Ｃ２）に変え、スチレンを１０３質量部から１０８質量部に変え、メアクリル酸ブチルを９０質量部から８５質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（４）を調製した。
前記樹脂微粒子分散液（４）に含まれる樹脂微粒子（４）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、１０７ｎｍであった。また、該樹脂微粒子（４）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、７０℃であり、重量平均分子量（Ｍｗ）は、４４０，０００であった。これらを表２に示した。
【０２００】
−−樹脂微粒子分散液（５）の調製−
前記樹脂微粒子分散液（１）の調製において、コア粒子分散液（Ｃ１）をコア粒子分散液（Ｃ３）に変え、スチレンを１０３質量部から１０８質量部に変え、メアクリル酸ブチルを９０質量部から８５質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（５）を調製した。
前記樹脂微粒子分散液（５）に含まれる樹脂微粒子（５）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、１１０ｎｍであった。また、該樹脂微粒子（５）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、７０℃であり、重量平均分子量（Ｍｗ）は、４４０，０００であった。これらを表２に示した。
【０２０１】
−−樹脂微粒子分散液（６）の調製−
前記樹脂微粒子分散液（１）の調製において、スチレンを１０３質量部から１０８質量部に変え、メアクリル酸ブチルを９０質量部から８５質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（６）を調製した。
前記樹脂微粒子分散液（６）に含まれる樹脂微粒子（６）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、９８ｎｍであった。また、該樹脂微粒子（６）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、７０℃であり、重量平均分子量（Ｍｗ）は、４４０，０００であった。これらを表２に示した。
【０２０２】
−−樹脂微粒子分散液（７）の調製−
前記樹脂微粒子分散液（１）の調製において、コア粒子分散液（Ｃ１）をコア粒子分散液（Ｃ４）に変え、スチレンを１０３質量部から１７０質量部に変え、メアクリル酸ブチルを９０質量部から２３質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（７）を調製した。
前記樹脂微粒子分散液（７）に含まれる樹脂微粒子（７）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、９６ｎｍであった。また、該樹脂微粒子（７）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、１１０℃であり、重量平均分子量（Ｍｗ）は、４２０，０００であった。これらを表２に示した。
【０２０３】
−−樹脂微粒子分散液（８）の調製−
前記樹脂微粒子分散液（１）の調製において、コア粒子分散液（Ｃ１）をコア粒子分散液（Ｃ５）に変え、メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩を１２質量部から５質量部に変えた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（８）を調製した。
前記樹脂微粒子分散液（８）に含まれる樹脂微粒子（８）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、３３７ｎｍであった。また、該樹脂微粒子（８）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、６０℃であり、重量平均分子量（Ｍｗ）は、４４０，０００であった。これらを表２に示した。
【０２０４】
−−樹脂微粒子分散液（９）の調製−
前記樹脂微粒子分散液（１）の調製において、コア粒子分散液（Ｃ１）１００９部を用いず、メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩を２０質量部から１０質量部に変え、スチレンを１０３質量部から４８質量部に変え、メタクリル酸を８３質量部から７８質量部に変え、アクリル酸ブチルを９０質量部から１５０質量部に変え、チオグリコール酸ブチルを１２質量部用いた以外は、前記樹脂微粒子分散液（１）の調製と同様にして、ビニル樹脂（スチレン−メタクリル酸−アクリル酸ブチル−メタクリル酸エチレンオキサイド付加物硫酸エステルのナトリウム塩の共重合体）の樹脂微粒子分散液（９）を調製した。
前記樹脂微粒子分散液（９）に含まれる樹脂微粒子（９）について、ＬＡ−９２０で測定した体積平均粒径（Ｄｖ）は、１１３ｎｍであった。また、該樹脂微粒子（７）のシェルを形成する樹脂のガラス転移温度（Ｔｇ）は、３１℃であり、重量平均分子量（Ｍｗ）は、３２，０００であった。これらを表２に示した。
【０２０５】
【表２】

【０２０６】
−−ポリエステル樹脂（１）の合成−−
冷却管、撹拌機及び窒素導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物２２９質量部、ビスフェノールＡプロピレンオキサイド３モル付加物５２９質量部、テレフタル酸２０８質量部、アジピン酸４６質量部及びジブチルチンオキサイド２質量部を入れ、常圧、２３０℃で８時間反応させ、更に１０〜１５ｍｍＨｇの減圧で５時聞反応させた後、該反応容器に無水トリメリット酸４４質量部を入れ、１８０℃、常圧で２時間反応させることにより、ポリエステル樹脂（２）を得た。該ポリエステル樹脂（２）は、重量平均分子量（Ｍｗ）が６，７００であり、ガラス転移温度（Ｔｇ）が４３℃であり、酸価が２５ｍｇＫＯＨ／ｇであった。
【０２０７】
−−ポリエステル樹脂（２）の合成−−
冷却管、撹拌機及び窒素導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物３５９質量部、ビスフェノールＡプロピレンオキサイド２モル付加物１２７３質量部、エチレングリコール９質量部、テレフタル酸２０８質量部、コハク酸８質量部、イソフタル酸４１５質量部及びジブチルチンオキサイド１質量部を入れ、常圧、２３０℃で８時間反応させ、更に１０〜１５ｍｍＨｇの減圧で５時聞反応した後、反応容器に無水トリメリット酸４８部を入れ、１８０℃、常圧で２時間反応させることにより、ポリエステル樹脂（２）を得た。該ポリエステル樹脂（２）は、重量平均分子量（Ｍｗ）が６，８００であり、ガラス転移温度（Ｔｇ）が６０℃であり、酸価が２８．５ｍｇＫＯＨ／ｇであった。
【０２０８】
（実施例１）
前記ポリエステル樹脂（２）９６質量部と、ポリエチレンワックス（融点８５℃）４質量部と、カーボンブラック（三菱化学 ＃４４）１０質量部と、サリチルサンジルコニウム塩１質量部とを、ヘンシェルミキサー中で十分撹拌混合した後、２軸押出機にて混練し、冷却後、体積平均粒径が９．０±０．５μｍとなるように粉砕、分級し、トナー母体粒子Ａを得た。なお、前記混練は、混練機の出口での混練物温度が１３０〜１４０℃となる条件にて行った。前記粉砕及び前記分級は、体積平均粒径が６．０±０．５μｍとなるようにして行った。
前記樹脂微粒子分散液（１）を減圧乾燥器を用いて３０℃で減圧乾燥し、樹脂微粒子（１）を得た。
前記トナー母体粒子Ａ９５質量部、前記樹脂微粒子（１）５質量部、疎水性シリカ０．３質量部、及び酸化チタン０．３質量部を、ヘンシェルミキサーを用いて攪拌混合し（攪拌回転数２０００ｒｐｍで３０秒間を５回）、実施例１のトナー（粉砕トナー）を得た。得られたトナーをＳＥＭで観察したところ、粒子表面に結晶性を有する樹脂が付着していることが確認された。
実施例１のトナー２．５質量部と、シリコンコートフェライトキャリア（芯材粒径４５μｍ）９７．５質量部とを、ターブラーミキサーで攪拌して、実施例１の現像剤を調製した。実施例１のトナー乃至現像剤につき、後述の評価を行い、その結果を表３に示した。
【０２０９】
（実施例２）
−樹脂微粒子形成工程−
−−コアの形成−−
前記コア分散液（Ｃ２）の調製を行った。
−−シェルの形成−−
前記樹脂微粒子分散液（１）の調製を行った。
【０２１０】
−トナー生成工程−
−−水相の調製−−
水９９０質量部、前記樹脂微粒子分散液（１）８３質量部、ドデシルジフェニルエーテルジスルホン酸ナトリウムの４８．５質量％の水溶液（「エレミノールＭＯＮ−７」；三洋化成工業製）３７質量部、及び酢酸エチル９０質量部を混合撹拌し、乳白色の液体（水相）を得た。
【０２１１】
−−低分子ポリエステルの合成−−
冷却管、撹拌機及び窒素導入管の付いた反応容器中に、ビスフェノールＡエチレンオキサイド２モル付加物６８２質量部、ビスフェノールＡプロピレンオキサイド２モル付加物８１質量部、テレフタル酸２８３質量部、無水トリメリット酸２２質量部、及びジブチルチンオキサイド２質量部を仕込み、常圧下、２３０℃にて５時間反応させて、低分子ポリエステルを合成した。
得られた低分子ポリエステルは、数平均分子量（Ｍｎ）が２，１００、重量平均分子量（Ｍｗ）が９，５００、ガラス転移温度（Ｔｇ）が５５℃、酸価が０．５ｍｇＫＯＨ／ｇであり、水酸基価が５１であった。
【０２１２】
−−プレポリマーの合成−−
冷却管、撹拌機及び窒素導入管の付いた反応容器中に、前記低分子ポリエステル４１０質量部、イソホロンジイソシアネート８９質量部、及び酢酸エチル５００質量部を仕込み、１００℃にて５時間反応させて、プレポリマー（前記活性水素基含有化合物と反応可能な重合体）を合成した。
得られたプレポリマーの遊離イソシアネート含有量は、１．５３質量％であった。
【０２１３】
−−ケチミン（前記活性水素基含有化合物）の合成−−
撹拌棒及び温度計をセットした反応容器中に、イソホロンジアミン１７０質量部及びメチルエチルケトン７５質量部を仕込み、５０℃にて５時間反応を行い、ケチミン化合物（前記活性水素基含有化合物）を合成した。
得られたケチミン化合物（前記活性水素基含有化合物）のアミン価は４１８であった。
【０２１４】
−マスターバッチ（ＭＢ）の調製−
水１２００質量部、着色剤としてのカーボンブラック（「Ｐｒｉｎｔｅｘ３５」；デクサ社製、ＤＢＰ吸油量＝４２ｍｌ／１００ｍｇ、ｐＨ＝９．５）５４０質量部、及び前記ポリエステル樹脂（１）１２００質量部をヘンシェルミキサー（三井鉱山社製）で混合した。該混合物を二本ロールで１５０℃にて３０分混練した後、圧延冷却し、パルペライザー（ホソカワミクロン社製）で粉砕して、マスターバッチを調製した。
【０２１５】
−−有機溶媒相の調製−−
撹拌棒及び温度計をセットした反応容器中に、前記ポリエステル樹脂（１）３７８質量部、カルナバワックス１１０質量部、ＣＣＡ（「サリチル酸金属錯体Ｅ−８４」；オリエント化学工業製）２２質量部、及び酢酸エチル９４７質量部を仕込み、撹拌下、８０℃まで昇温し、８０℃のまま５時間保持した後、１時間かけて３０℃まで冷却した。次いで、反応容器中に、前記マスターバッチ５００質量部、及び酢酸エチル５００質量部を仕込み、１時間混合して原料溶解液を得た。
得られた原料溶解液１３２４質量部を反応容器に移し、ビーズミル（「ウルトラビスコミル」；アイメックス社製）を用いて、送液速度１ｋｇ／ｈｒ、ディスク周速度６ｍ／秒、及び０．５ｍｍジルコニアビーズを８０体積％充填した条件で３パスして、前記カーボンブラック、及びカルナバワックスの分散を行った。次いで、該分散液に前記低分子ポリエステルの６５質量％酢酸エチル溶液１３２４質量部を添加した。上記同様の条件のビーズミルで１パスし、分散させ、有機溶媒相（顔料・ワックス分散液）を調製した。
得られた有機溶媒相の固形分濃度は（１３０℃、３０分）は、５０質量％であった。
【０２１６】
−−乳化・分散−−
反応容器中に、前記有機溶媒相７４９質量部、前記プレポリマー１１５質量部、及び前記ケチミン化合物２．９質量部を仕込み、ＴＫ式ホモミキサー（特殊機化製）を用いて５，０００ｒｐｍにて１分間混合した後、反応容器中に前記水相１２００質量部を添加し、ＴＫ式ホモミキサー（特殊機化工業社製）で、回転数１３，０００ｒｐｍにて２０分間混合して、乳化スラリーを調製した。
次に、撹拌機及び温度計をセットした反応容器中に、前記乳化スラリーを仕込み、３０℃にて８時間脱溶剤した後、４５℃にて４時間熟成を行い、分散スラリーを得た。
得られた分散スラリーは、マルチサイザーＩＩ（ベックマンコールター社製）で測定した体積平均粒径が５．８６μｍ、個数平均粒径が５．１１μｍであった。
【０２１７】
−洗浄工程−
前記分散スラリー１００質量部を減圧濾過した後、濾過ケーキにイオン交換水１００質量部を添加し、ＴＫ式ホモミキサーで混合（回転数１２，０００ｒｐｍにて１０分間）した後、濾過した。ここで得た濾過ケーキにイオン交換水１００質量部を添加し、ＴＫ式ホモミキサーで混合（回転数１２，０００ｒｐｍにて１０分間）した後、減圧濾過した。ここで得た濾過ケーキに１０質量％水酸化ナトリウム水溶液１００質量部を添加し、ＴＫ式ホモミキサーで混合（回転数１２，０００ｒｐｍにて１０分間）した後、濾過した。ここで得た濾過ケーキに１０質量％塩酸１００質量部を添加し、ＴＫ式ホモミキサーで混合（回転数１２，０００ｒｐｍにて１０分間）した後、濾過した。ここで得た濾過ケーキにイオン交換水３００質量部を添加し、ＴＫ式ホモミキサーで混合（回転数１２，０００ｒｐｍにて１０分間）した後で濾過する操作を２回行い、最終濾過ケーキを得た。ここで得られた最終濾過ケーキを循風乾燥機で４５℃にて４８時間乾燥し、目開き７５μｍメッシュで篩うと、実施例２のトナー母体粒子が得られた。
【０２１８】
−外添剤処理−
得られた実施例１のトナー母体粒子２．５質量部と、外添剤としてのシリコーンフェライトキャリア（芯材粒径４５μｍ）９７．５質量部をターブラーミキサー（シンマルエンタープライゼス社＋製）を用いて攪拌処理し、実施例２のトナーを製造した。実施例２のトナーについて、実施例１と同様の評価を行った。結果を表３に示す。
【０２１９】
（実施例３）
実施例２において、樹脂微粒子１を樹脂微粒子２に代えた以外は、実施例２と同様にして、実施例３のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２０】
（実施例４）
実施例２において、樹脂微粒子１を樹脂微粒子３に代えた以外は、実施例２と同様にして、実施例４のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２１】
（実施例５）
実施例２において、樹脂微粒子１を樹脂微粒子４に代えた以外は、実施例２と同様にして、実施例５のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２２】
（実施例６）
実施例２において、樹脂微粒子１を樹脂微粒子５に代えた以外は、実施例２と同様にして、実施例６のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２３】
（実施例７）
実施例２において、樹脂微粒子１を樹脂微粒子６に代えた以外は、実施例２と同様にして、比較例２のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２４】
（実施例８）
実施例２において、樹脂微粒子１を樹脂微粒子７に代えた以外は、実施例２と同様にして、実施例８のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２５】
（実施例９）
実施例２において、樹脂微粒子１を樹脂微粒子８に代えた以外は、実施例２と同様にして、実施例９のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２６】
（比較例１）
実施例１において、樹脂微粒子１を樹脂微粒子９に代えた以外は、実施例１と同様にして、比較例１のトナーを製造し、該トナーについて実施例１と同様の評価を行った。結果を表３に示す。
【０２２７】
（比較例２）
実施例２において、樹脂微粒子１を樹脂微粒子９に代えた以外は、実施例２と同様にして、比較例２のトナーを製造し、該トナーについて実施例２と同様の評価を行った。結果を表３に示す。
【０２２８】
＜定着性＞
定着ローラーとしてテフロン^（Ｒ）ローラーを使用した（株）リコー製複写機ＭＦ２２００定着部を改造した装置を用いて、これにリコー製のタイプ６２００紙をセットし複写テストを行った。このときの結果を表３に示した。
定着温度を変化させて、コールドオフセット温度（定着下限温度）と、ホットオフセット温度（耐ホットオフセット温度）とを求めた。従来における低温定着トナーの定着下限温度は、１４０〜１５０℃程度である。なお、低温定着の評価条件は、紙送りの線速度を１２０〜１５０ｍｍ／ｓｅｃ、面圧１．２ｋｇｆ／ｃｍ^２、ニップ幅３ｍｍ、ホットオフセットの評価条件は、紙送りの線速度を５０ｍｍ／ｓｅｃ、面圧２．０ｋｇｆ／ｃｍ^２、ニップ幅４．５ｍｍの条件と設定した。各特性評価の基準は、以下の通りである。
【０２２９】
▲１▼ 低温定着性（５段階評価）
５・・・１２０℃未満
４・・・１２０℃超１４０℃以下
３・・・１４０℃超１５０℃以下
２・・・１５０℃超１６０℃以下
１・・・１６０℃超
【０２３０】
▲２▼ ホットオフセット性（５段階評価）
５・・・２０１℃以上
４・・・２００〜１９１℃
３・・・１９０〜１８１℃
２・・・１８０〜１７１℃
１・・・１７０℃以下
【０２３１】
＜熱保存性＞
ガラス容器に実施例及び比較例で得られた各トナーを充填し、５５℃の恒温槽にて２４時間放置した。このトナーを２４℃に冷却し、針入度試験（ＪＩＳ Ｋ２２３５−１９９１）を行い、針入度を測定した。この値が大きいトナー程、熱に対する保存性が優れていることを意味する。この値が１５ｍｍ未満の場合は、使用上問題が発生する可能性が高い。なお、針入度に基づく熱保存性の判定基準は、以下の通りである。
５・・・貫通
４・・・２５ｍｍ以上
３・・・２０〜２５ｍｍ
２・・・１５〜２０ｍｍ
１・・・１５ｍｍ未満
【０２３２】
＜解像度＞
（株）リコー製ＭＦ−２２００に現像剤をセットし、常温／常湿の環境下において、主走査、副走査方向ともに、６００ｄｏｔ／ｉｎｃｈ、１５０ｌｉｎｅ／ｉｎｃｈ の１ドット独立 網点画像を出力し、ドット抜け及び画像濃度ムラを目視にて以下の４段階で評価した。
４・・・非常に良好
３・・・良好
２・・・実用上は問題ないレベル
１・・・実用上問題があるレベル
【０２３３】
＜耐久性＞
（株）リコー製ＭＦ−２２００に現像剤をセットし、常温／常湿の環境下において１００，０００万枚の連続画像出力を行い、その後の現像剤の帯電量と画質から以下の４段階で評価した。
４・・・初期に比べて帯電量と画質に大きな変化がない
３・・・初期に比べて帯電量が低下しているが画質に大きな変化はない
２・・・地汚れが発生するが実用上問題ないレベル
１・・・実用上問題があるレベルの地汚れが発生する
【０２３４】
＜ガラス転移温度（Ｔｇ）＞
ＴＧ−ＤＳＣシステム（「ＴＡＳ−１００」；理学電機社製）を用いて、下記方法により、トナーのガラス転移温度（Ｔｇ）を測定した。
まず、各トナー約１０ｍｇをアルミニウム製の試料容器に入れ、試料容器をホルダーユニットにのせ、電気炉中にセットした。室温から昇温速度１０℃／ｍｉｎで１５０℃まで加熱した後、１５０℃で１０ｍｉｎ間放置し、室温まで試料を冷却して１０ｍｉｎ放置した。その後、窒素雰囲気下、１５０℃まで昇温速度１０℃／ｍｉｎで加熱して示差走査熱量計（ＤＳＣ）によりＤＳＣ曲線を計測した。得られたＤＳＣ曲線から、ＴＧ−ＤＳＣシステム「ＴＡＳ−１００」中の解析システムを用いて、ガラス転移温度（Ｔｇ）近傍の吸熱カーブの接線とベースラインとの接点からガラス転移温度（Ｔｇ）（℃）を算出した。
【０２３５】
＜重量平均分子量（Ｍｗ）、個数平均分子量（Ｍｎ）、前記比（Ｍｗ／Ｍｎ）＞
各トナー約１ｇを三角フラスコで精評した後、ＴＨＦ（テトラヒドロフラン）１０〜２０ｇを加え、接着性基材濃度５〜１０％のＴＨＦ試料溶液とした。次に、４０℃のヒートチャンバー内でカラムを安定させ、この温度におけるカラムに、溶媒としてＴＨＦを１ｍｌ／ｍｉｎの流速で流し、前記ＴＨＦ試料溶液２０μｌを注入した。そして、試料の分子量は、単分散ポリスチレン標準試料により作成された検量線の対数値とリテンションタイムとの関係から算出した。前記検量線は、ポリスチレン標準試料を用いて作成したものである。なお、前記単分散ポリスチレン標準試料、検出器、カラム等は、上述したものを使用した。
【０２３６】
＜トナー粒径＞
各トナーの体積平均粒径（Ｄｖ）及び個数平均粒径（Ｄｎ）は、粒度測定器（「コールターカウンターＴＡＩＩ」；ベックマンコールター社製）を用い、アパーチャー径１００μｍで測定した。これらの結果から（体積平均粒径（Ｄｖ／個数平均粒径（Ｄｎ））を算出した。
【０２３７】
＜平均円形度＞
トナーの平均円形度は、フロー式粒子像分析装置（「ＦＰＩＡ−２１００」；シスメックス社製）を用いて計測した。具体的には、容器中に、予め不純固形物を除去した水１００〜１５０ｍｌに分散剤としての界面活性剤（アルキルベンゼンスフォン酸塩）を０．１〜０．５ｍｌ添加した。次いで、各トナーを０．１〜０．５ｇ添加して分散させた。得られた分散液を超音波分散器（本多電子社製）で約１〜３分間分散処理して、分散液の濃度を３０００〜１万個／μｌとしてトナーの形状及び分布を測定した。これらの測定結果から平均円形度を算出した。
【０２３８】
＜樹脂微粒子の含有量＞
スチレン−アクリル系共重合体の樹脂微粒子に由来するスチレンモノマーを標識として、トナーを熱分解して熱分解生成物中におけるスチレンモノマーの量を測定し、トナー中における樹脂微粒子の含有量を算出した。即ち、組成が既知であるスチレン−アクリル系共重合体の樹脂微粒子を標識として用い、トナー粒子中にスチレン−アクリル系共重合体の樹脂微粒子の含有量が０．０１質量％、０．１０質量％、１．００質量％、３．００質量％、及び１０．０質量％となるように添加した。得られた組成が既知の各モデルトナーを５９０℃×１２秒の条件で熱分解させて、下記の測定機器及び測定条件に従って熱分解生成物を分析し、各トナーについてスチレンモノマーのピーク面積を求め、トナー中における樹脂微粒子の含有量を算出した。
【０２３９】
〔測定機器及び測定条件〕
分析機器：熱分解ガスクロマトグラフ質量分析計
装置本体：ＱＲ−５０００（島津製作所製）
付属品の熱分解炉：ＪＨＰ−３Ｓ（日本分析工業製）
熱分解温度：５９０℃×１２秒
カラム：「ＤＢ−１」
（Ｌ＝３０ｍ Ｉ．Ｄ．＝０．２５ｍｍ Ｆｉｌｍ＝０．２５μｍ）
カラム温度：４０℃（保持２分）〜３００℃（１０℃／分昇温）
気化室温度：３００℃
【０２４０】
【表３】

【０２４１】
表３に示す通り、実施例１〜８については、低温定着性、耐ホットオフセット性、耐熱保存性及び解像度の評価結果が良好であった。
比較例１、及び２では、コア・シェル構造を有しない樹脂微粒子を用いたトナーの場合耐熱保存性が十分ではなかった。
【０２４２】
【発明の効果】
本発明によると、従来における問題を解決することができ、耐凝集性、帯電性、流動性、転写性、定着性等の諸特性に優れ、耐ホットオフセット性が良好であり、優れた耐熱保存性と低温定着性とを両立し、帯電量分布がシャープで鮮映な高画質が得られるトナー及びその効率的な製造方法、並びに、該トナーを用い、高画質化が可能な、現像剤、トナー入り容器、プロセスカートリッジ、画像形成装置及び画像形成方法を提供することができる。
【図面の簡単な説明】
【図１】図１は、本発明の画像形成装置により本発明の画像形成方法を実施する一の例を示す概略説明図である。
【図２】図２は、本発明の画像形成装置により本発明の画像形成方法を実施する他の例を示す概略説明図である。
【図３】図３は、本発明の画像形成装置（タンデム型カラー画像形成装置）により本発明の画像形成方法を実施する一例を示す概略説明図である。
【図４】図４は、図３に示す画像形成装置における一部拡大概略説明図である。
【符号の説明】
１０ 感光体（感光体ドラム）
１０Ｋ ブラック用感光体
１０Ｙ イエロー用感光体
１０Ｍ マゼンタ用感光体
１０Ｃ シアン用感光体
１４ 支持ローラ
１５ 支持ローラ
１６ 支持ローラ
１７ 中間転写クリーニング装置
１８ 画像形成手段
２０ 帯電ローラ
２１ 露光装置
２２ 二次転写装置
２３ ローラ
２４ 二次転写ベルト
２５ 定着装置
２６ 定着ベルト
２７ 加圧ベルト
２８ シート反転装置
３０ 露光装置
３２ コンタクトガラス
３３ 第１走行体
３４ 第２走行体
３５ 結像レンズ
３６ 読取りセンサ
４０ 現像装置
４１ 現像ベルト
４２Ｋ 現像剤収容部
４２Ｙ 現像剤収容部
４２Ｍ 現像剤収容部
４２Ｃ 現像剤収容部
４３Ｋ 現像剤供給ローラ
４３Ｙ 現像剤供給ローラ
４３Ｍ 現像剤供給ローラ
４３Ｃ 現像剤供給ローラ
４４Ｋ 現像ローラ
４４Ｙ 現像ローラ
４４Ｍ 現像ローラ
４４Ｃ 現像ローラ
４５Ｋ ブラック用現像器
４５Ｙ イエロー用現像器
４５Ｍ マゼンタ用現像器
４５Ｃ シアン用現像器
４９ レジストローラ
５０ 中間転写体
５１ ローラ
５２ 分離ローラ
５３ 定電流源
５５ 切換爪
５６ 排出ローラ
５７ 排出トレイ
５８ コロナ帯電器
６０ クリーニング装置
６１ 現像器
６２ 転写帯電器
６３ 感光体クリーニング装置
６４ 除電器
７０ 除電ランプ
８０ 転写ローラ
９０ クリーニング装置
９５ 転写紙
１００ 画像形成装置
１２０ タンデム型現像装置
１３０ 原稿台
１４２ 給紙ローラ
１４３ ペーパーバンク
１４４ 給紙カセット
１４５ 分離ローラ
１４６ 給紙路
１４７ 搬送ローラ
１４８ 給紙路
１５０ 複写装置本体
２００ 給紙テーブル
３００ スキャナ
４００ 原稿自動搬送装置（ＡＤＦ）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a manufacturing method thereof, a developer using the toner, a container containing a toner, a process cartridge, an image forming apparatus, and The present invention relates to an image forming method.
[0002]
[Prior art]
Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Documents 1 and 2). The fixing method in the electrophotographic method is a heat roller fixing method in which a heat roller is directly pressed against a toner image on a transfer material and fixed because it is excellent in thermal efficiency and can be downsized. Is widely used.
However, in the case of the heat roller fixing method, there is a problem that a large amount of electric power is required for the fixing. For this reason, from the viewpoint of energy saving, various studies have been made to reduce the power consumption of the heating roller. For example, a layer of the heating roller that contacts the toner image transferred onto the transfer material. It has been proposed that the thermal energy efficiency is increased and the start-up time is significantly shortened by making the thickness of the as thin as possible. However, in this case, the specific heat capacity of the heating roller is reduced, and the temperature difference between the portion through which the transfer material passes and the portion through which the transfer material does not pass increases, so that the molten toner adheres to the heating roller. There is a problem that after the heating roller makes a round, a phenomenon that the molten toner is fixed to a non-image portion on the transfer material, that is, a hot offset phenomenon is likely to occur. On the other hand, increasing the thermal energy efficiency by controlling the thermal characteristics of the binder resin itself in the toner has also been studied. However, if the glass transition temperature (Tg) of the binder resin is lowered, the heat-resistant storage stability may be deteriorated. If the molecular weight of the binder resin is reduced and the F1 / 2 temperature is lowered, the hot There is a problem that an offset phenomenon easily occurs. At present, toners that are excellent in low-temperature fixability and hardly cause hot offset phenomenon at low temperatures have not yet been provided.
[0003]
According to the 1999 International Energy Agency (IEA) Demand-side Management (DSM) program, the next generation copier is a copier with a copy speed (CPM) of 30 or more. The power consumption of 10 to 30 W or less (differs depending on the copying speed) is required, and achieving energy saving has become an extremely important issue.
In recent years, various proposals for achieving the energy saving have been made. For example, instead of using styrene-acrylic resin, which has been widely used as a binder resin, for the purpose of lowering the toner fixing temperature, it is proposed to use a polyester resin that has excellent low-temperature fixability and relatively good heat-resistant storage stability. (See Patent Documents 3 to 8). Further, for the purpose of improving the low-temperature fixability of the toner, it has been proposed to add a specific non-olefinic crystalline polymer to the binder resin (see Patent Document 9). In addition, it has been proposed to use a crystalline polyester resin as a binder resin (see Patent Document 10).
However, in these cases, since the molecular structure and molecular weight of the binder resin are not optimized, it is difficult to achieve the performance required in the DSM (Demand-Side Management) program of the International Energy Agency (IEA). is there.
[0004]
By the way, as the method for producing the toner, there are roughly classified a pulverization method and a suspension polymerization method.
The pulverization method is a method for producing a toner by pulverizing and classifying a toner composition obtained by melt-mixing a colorant, a charge control agent, and the like in a binder resin and uniformly dispersing them. The pulverization method has the following problems. That is, a pulverizer or the like for pulverizing the toner composition is required, which increases costs and is not efficient. In addition, toner particles having a wide particle size distribution are easily formed during the pulverization, and in order to obtain a high-resolution and high-gradation image, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more are classified. Therefore, there is a problem that the yield is greatly reduced. Furthermore, it is difficult to uniformly disperse additives such as a colorant and a charge control agent in the binder resin. When a toner in which the additive is not uniformly dispersed is used, there is a problem that fluidity, developability, durability, image quality, and the like are deteriorated.
[0005]
On the other hand, the suspension polymerization method is a method for producing a toner by suspension polymerization of a toner material in a solvent. In the case of the suspension polymerization method, the problems in the pulverization method can be solved, but there are the following problems. That is, since the toner particles obtained are spherical, when a photographic image or the like having a high image area ratio is formed, the transfer residual toner increases, resulting in poor cleaning. Further, when an untransferred image is formed due to a paper feed failure or the like, the toner remains on the photosensitive member, and if it accumulates, the background stain (fogging) of the image occurs. As a result, there is a problem that the charging roller or the like is contaminated and the original charging ability cannot be exhibited.
[0006]
For this reason, an emulsion polymerization method is known in which resin fine particles are associated to produce amorphous toner particles (see Patent Document 11). However, in the case of the emulsion polymerization method, the surfactant remains in a large amount not only on the surface of the toner particles but also inside the toner particles even after the washing step. As a result, the charging stability of the toner particles is lowered and the charge amount distribution is reduced. When an image is formed using the obtained toner, there is a problem that background stains (fogging) occur or the photosensitive member, the charging roller, the developing roller, etc. become dirty and the original charging ability cannot be exhibited. .
Recently, a toner has been proposed in which a resin containing an acidic group having a glass transition temperature and a particle size smaller than that of the toner base particle is fixed to the surface of the toner base particle obtained by the phase inversion emulsification method. (See Patent Document 12). However, in this case, although the heat resistant storage stability is improved to some extent, there is a problem that the low-temperature fixability is still insufficient.
[0007]
Therefore, it has excellent properties such as anti-aggregation, charging, fluidity, transferability, and fixability, good hot offset resistance, excellent heat resistance storage and low-temperature fixability, and high image quality. At present, the obtained toner, its efficient production method, and related technology using the toner have not yet been provided.
[0008]
[Patent Document 1]
US Pat. No. 2,297,691
[Patent Document 2]
Japanese Patent Publication No.43-24748
[Patent Document 3]
JP 60-90344 A
[Patent Document 4]
JP-A 64-15755
[Patent Document 5]
Japanese Patent Laid-Open No. 2-82267
[Patent Document 6]
JP-A-3-229264
[Patent Document 7]
JP-A-3-41470
[Patent Document 8]
JP-A-11-305486
[Patent Document 9]
JP 62-63940 A
[Patent Document 10]
Japanese Patent No. 2931899
[Patent Document 11]
Japanese Patent No. 2537503
[Patent Document 12]
JP 2001-22117 A
[0009]
[Problems to be solved by the invention]
An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is excellent in various properties such as anti-aggregation property, charging property, fluidity, transferability, and fixability, has good hot offset resistance, and has both excellent heat-resistant storage stability and low-temperature fixability. , A toner having a sharp charge distribution and a clear image quality, and an efficient manufacturing method thereof, and a developer, a toner-containing container, a process cartridge, and an image formation using the toner capable of improving the image quality An object is to provide an apparatus and an image forming method.
[0010]
[Means for Solving the Problems]
Means for solving the problems are as follows. That is,
<1> A toner having a weight average molecular weight (Mw) of 8,000 to 1,000,000, a particle size of 20 to 400 nm, and resin fine particles having a core / shell structure. .
<2> The active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are reacted in an aqueous medium to produce an adhesive base material, which is obtained in the form of particles as described in <1> above Toner.
<3> The toner according to any one of <1> to <2>, which has resin fine particles on a surface thereof.
<4> The toner according to any one of <1> to <3>, wherein the resin fine particles have a glass transition temperature (Tg) of 35 to 150 ° C.
<5> When the glass transition temperature of the resin forming the shell in the resin fine particles is TgS and the glass transition temperature of the resin forming the core is TgC, the following formula, TgS> TgC is satisfied: 4>.
<6> The toner according to any one of <1> to <5>, wherein the adhesive base material includes a polyester resin.
<7> After the core monomer used to form the core is polymerized to form the core particle, the shell monomer used to form the shell is polymerized on the surface of the core particle, thereby reducing the weight. A resin fine particle forming step of forming a resin fine particle having an average molecular weight (Mw) of 8,000 to 1,000,000 and a particle size of 20 to 400 nm and having a core-shell structure; An adhesive base material producing step of obtaining a toner while producing an adhesive base material by dispersing and reacting an active hydrogen group containing compound and a polymer capable of reacting with the active hydrogen group containing compound in an aqueous medium. A toner production method comprising:
<8> A developer comprising the toner according to any one of <1> to <6>.
<9> A toner-containing container filled with the toner according to any one of <1> to <6>.
[0011]
The toner of the present invention includes resin fine particles having a weight average molecular weight (Mw) of 8,000 to 1,000,000, a particle diameter of 20 to 400 nm, and a core-shell structure. Since the toner of the present invention contains the resin fine particles, the hot offset resistance is good, the excellent heat storage stability and the low-temperature fixability are compatible, and high image quality can be formed.
In the toner of the present invention, the mode in which the resin fine particles are obtained by seed polymerization, the core monomer used for forming the core and the shell monomer used for forming the shell in the resin fine particles, In which the mass ratio (core monomer: shell monomer) is 50/50 to 99.9 / 0.1, the content of the resin fine particles is 0.5% by mass or more, and the resin fine particles Is an embodiment formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin and a polyester resin, an embodiment in which the polyester resin contains a urea-modified polyester resin, a non-reactive polyester, and an active hydrogen group-containing compound An embodiment in which the mass ratio of the reactable polymer to the non-reactive polyester (polymer: non-reactive polyester) is 5/95 to 50/50, a release agent, a colorant, and An embodiment containing at least one selected from charge control agents, an embodiment in which the glass transition temperature (Tg) is 40 to 70 ° C., an embodiment in which the outflow start temperature (Tfb) is 100 to 170 ° C., insoluble in tetrahydrofuran (THF) A mode in which the content is 1 to 15% by mass, a mode in which the amount of components having a molecular weight of less than 1,000 is 5.0% by mass or less in the molecular weight distribution of soluble components in tetrahydrofuran (THF), In the molecular weight distribution of the solute, an embodiment in which the molecular weight is 1,000 to 30,000 and the component amount of more than 30,000 is 1 to 10% by mass, respectively, and the number average molecular weight is 2,000 to 15,000, An embodiment in which the weight average particle diameter (D4) is 3 to 8 μm, and the ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) is 1.0. An embodiment in which the average circularity is from 0.95 to 1.00, an embodiment in which the toner is at least one selected from cyan, magenta, yellow, and black are preferable.
[0012]
In the toner production method of the present invention, the core monomer used to form the core is polymerized to form the core particle, and then the shell monomer used to form the shell is formed on the surface of the core particle. A resin fine particle forming step of forming resin fine particles having a core-shell structure having a weight average molecular weight (Mw) of 8,000 to 1,000,000 and a particle size of 20 to 400 nm by polymerization; Adhesiveness for obtaining toner while producing adhesive substrate by dispersing and reacting resin fine particles, active hydrogen group-containing compound and polymer capable of reacting with active hydrogen group-containing compound in aqueous medium Including a base material production step. In the method for producing a toner of the present invention, in the resin fine particle forming step, the core monomer used for forming the core is polymerized to form the core particle, and then the shell unit used for forming the shell is formed. A polymer is polymerized on the surface of the core particle, and a resin fine particle having a weight average molecular weight (Mw) of 8,000 to 1,000,000 and a particle size of 20 to 400 nm and having a core / shell structure is formed. Is done. In the adhesive base material production step, the resin fine particles, the active hydrogen group-containing compound, and a polymer capable of reacting with the active hydrogen group-containing compound are dispersed and reacted in the aqueous medium to form an adhesive group. A material is produced and a particulate toner is obtained. As a result, it is possible to efficiently produce a toner having good hot offset resistance, excellent heat resistance storage stability and low-temperature fixability, and capable of forming a high image quality.
In the toner production method of the present invention, the mass ratio between the core monomer used to form the core and the shell monomer used to form the shell (core monomer: shell monomer). (Monomer) is 50/50 to 99.9 / 0.1, and the mass ratio of the polymer capable of reacting with the active hydrogen group-containing compound and the non-reactive polyester (polymer: non-reactive polyester) is The aspect which is 5 / 95-50 / 50, etc. are preferable.
[0013]
The developer of the present invention contains the toner of the present invention. Therefore, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness can be obtained under low-temperature fixing conditions without causing hot offset.
In the developer of the present invention, an embodiment that is either a one-component developer or a two-component developer is preferable.
[0014]
The toner-containing container of the present invention contains the toner of the present invention in a container. Therefore, when image formation is performed by electrophotography using toner contained in the toner-containing container, a high-quality image with high image density and high sharpness can be obtained under low-temperature fixing conditions without causing hot offset. .
[0015]
The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that it does not cause hot offset and has a high image density and a high sharpness under low temperature fixing conditions. A quality image is obtained.
[0016]
The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high quality image with high image density and high sharpness can be obtained under low temperature fixing conditions without causing hot offset.
[0017]
The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high quality image with high image density and high sharpness can be obtained under low temperature fixing conditions without causing hot offset.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
(toner)
The toner of the present invention has a weight average molecular weight (Mw) of 8,000 to 1,000,000, a particle diameter of 20 to 400 nm, a resin fine particle having a core-shell structure, an adhesive substrate, And, if necessary, other components such as a colorant, a release agent, a non-reactive polyester resin, and a charge control agent.
[0019]
-Resin fine particles-
The resin fine particles may be contained in the toner, but are preferably present on the surface of the toner. In this case, it is advantageous in that the resin particles can easily control the hot offset resistance, heat-resistant storage stability, low-temperature fixability, etc. of the toner within a desired range.
[0020]
There is no restriction | limiting in particular as molecular weight of the said resin fine particle, According to the objective, it can select suitably, For example, a weight average molecular weight (Mw) needs to be 8,000-1,000,000, 10 000 to 600,000 is more preferable.
When the weight average molecular weight (Mw) is less than 8,000, the storage stability of the toner deteriorates, and blocking occurs in the developing machine during storage or use of the toner, and exceeds 100,000. As a result, it becomes difficult to control the content of the resin fine particles, and the minimum fixing temperature increases.
The weight average molecular weight (Mw) of the resin fine particles can be measured, for example, as follows. That is, after about 1 g of the resin fine particles are carefully evaluated in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added to obtain a THF sample solution having a resin concentration of 5 to 10%. Next, the column is stabilized in a 40 ° C. heat chamber, and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected. The weight average molecular weight (Mw) of the sample can be calculated from the relationship between the retention time and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. The calibration curve is created using a polystyrene standard sample. The monodisperse polystyrene standard sample is, for example, a molecular weight of 2.7 × 10 manufactured by Tosoh Corporation. ² ~ 6.2 × 10 ⁶ Those in the range can be used. Further, a refractive index (RI) detector can be used as the detector. Examples of the column include TSKgel, G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H, and GMH manufactured by Tosoh Corporation.
[0021]
There is no restriction | limiting in particular as an average particle diameter of the said resin fine particle, According to the objective, it can select suitably, For example, a volume average particle diameter needs to be 20-400 nm, and 40-200 nm is more preferable.
When the volume average particle size is less than 20 nm, the resin fine particles remaining on the surface of the toner may be formed into a film or may cover the entire surface of the toner densely. As a result, the resin fine particles Hinders the adhesion between the adhesive substrate inside the toner and the fixing paper as a transfer material, and the minimum fixing temperature rises, and if it exceeds 400 nm, the resin fine particles remaining on the surface of the toner May protrude greatly as a convex portion, or resin fine particles may remain as a rough multilayer, and the resin fine particles may be detached due to agitation stress during development.
The volume average particle diameter of the resin fine particles can be measured using, for example, a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method.
[0022]
There is no restriction | limiting in particular as glass transition temperature (Tg) of the said resin fine particle, According to the objective, it can select suitably, For example, 35-150 degreeC is preferable and 40-120 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 40 ° C., the storage stability of the toner deteriorates, and blocking may occur during storage or use of the toner. It may be difficult to control the content of the resin fine particles or the minimum fixing temperature may increase.
[0023]
The glass transition temperature is raised from room temperature to 200 ° C. at 10 ° C./min using, for example, a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation), and then at a cooling rate of 10 ° C./min. After cooling to room temperature, when measured at a rate of temperature increase of 10 ° C./min, from the curve portion where the height (h) of the baseline below the glass transition temperature and the baseline above the glass transition temperature is ½ Can be sought.
[0024]
The content (residual amount) of the resin fine particles in the toner is preferably 0.5% by mass or more, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass.
When the content is less than 0.5% by mass, the storage stability of the toner deteriorates, and blocking may be observed during storage or use. When the content exceeds 20% by mass, the resin The fine particles may not completely cover the toner base particles and may be detached from the toner, and a high quality image with excellent sharpness may not be obtained.
The content of the resin fine particles in the toner can be measured by various methods, and a substance or a functional group caused only by the resin fine particles is analyzed using, for example, a pyrolysis gas chromatograph mass spectrometer. By doing so, it can be calculated from the peak area.
[0025]
The resin fine particles are required to have a core / shell structure.
In this case, since no pressure is applied during storage of the toner, the toner is not destroyed and the resin forming the core having a low glass transition temperature is not exposed, so that fusion between the toners is prevented, while the toner At the time of fixing, a pressure is applied to the toner, the toner is destroyed, the resin forming the core having a low glass transition temperature is exposed, and low-temperature fixing is possible, and as a result, the hot offset resistance of the toner is improved. The glass transition temperature of the resin forming the core is TgS in the resin fine particles, and the glass transition temperature of the resin forming the core in the resin fine particles in that both the heat-resistant storage stability and the low-temperature fixability can be achieved. When the temperature is TgC, it is preferable to satisfy the following formula, TgS> TgC, more preferably TgS-TgC> 10 ° C., and TgS-Tg. > 20 ° C., further preferably satisfy the. It is particularly preferable that TgS−TgC> 30 ° C. is satisfied.
In the core-shell structure, the shell may exist on the entire surface of the core, or may exist only on a part of the surface.
[0026]
Mass ratio of the core monomer used to form the core and the shell monomer used to form the shell in the resin fine particles (core monomer: shell monomer) Is not particularly limited and may be appropriately selected depending on the purpose. For example, 50/50 to 99.9 / 0.1 is preferable, 60/40 to 99/1 is more preferable, and 60/40 ~ 90/10 is particularly preferred.
When the mass ratio (core monomer: shell monomer) is within the above range, it is advantageous in that the heat-resistant storage stability of the obtained toner can be improved.
[0027]
The resin fine particles are not particularly limited and may be formed of a material appropriately selected from known materials. Among these, the resin fine particles are formed of a resin capable of forming an aqueous dispersion in an aqueous medium. Preferably, it may be a thermoplastic resin or a thermosetting resin.
The material resin of the resin fine particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin , Melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin fine particles is easily obtained. It is particularly preferred that
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
[0028]
The shell monomer is not particularly limited and can be appropriately selected from known materials depending on the glass transition temperature of the resin forming the core, the type of resin to be synthesized, and the like. And methyl methacrylate.
These may be used individually by 1 type and may use 2 or more types together. Among these, those capable of forming a resin having a glass transition temperature of more than 80 ° C. are preferable. When the glass transition temperature of the resin forming the core is less than 60 ° C., a resin having a glass transition temperature of 80 ° C. or less is formed. It may be possible.
[0029]
There is no restriction | limiting in particular as glass transition temperature (Tg) of resin which forms the said shell, According to the objective, it can select suitably, For example, it is about 50 degreeC or more and about 150 degrees C or less, and exceeds 50 degreeC and 130 degrees C or less. Is preferable, more than 60 ° C and 110 ° C or less is more preferable, and more than 60 ° C and 110 ° C or less is particularly preferable.
When the glass transition temperature (Tg) of the resin forming the shell is 50 ° C. or less, the storage stability of the toner is deteriorated, and it becomes difficult to satisfy the formula, TgS> TgC. Even when the toner is satisfied, the toner may block during storage or use, and if it exceeds 120 ° C., the minimum fixing temperature may increase.
[0030]
The method for producing the toner having the core / shell structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a seed polymerization method, a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, Examples thereof include a dispersion polymerization method. Among these, the seed polymerization method is particularly preferable.
Production conditions for the toner having the core / shell structure by the seed polymerization method are not particularly limited and may be appropriately selected depending on the intended purpose.
[0031]
As the seed polymerization method, for example, the core monomer used for forming the core is polymerized to form core particles, and then the shell monomer used to form the shell is used as the core particles. An embodiment in which polymerization is performed on the surface is preferable.
When the resin fine particles are produced by the seed polymerization method, it is preferable to add the shell monomer as a small liquid to the reaction system. In this case, the core particle surface is covered with small droplets of the monomer for the shell, and a coating layer of the shell is easily formed uniformly on the core particle surface, and the obtained toner is preferable in terms of excellent heat storage stability. .
The method of making the shell monomer into small droplets is not particularly limited and can be appropriately selected according to the purpose. For example, fine dispersion processing is performed using a known ultrasonic emulsifier or the like. Method, etc.
[0032]
The shell monomer is preferably one having a solubility in water (20 ° C.) of 0.1% by mass or more in consideration of rapidity of migration to the core particle surface.
Examples of the shell monomer having a solubility in water (20 ° C.) of 0.1% by mass or more include (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate; amides such as acrylamide and methacrylamide; Examples thereof include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; nitrogen-containing vinyl compounds such as 4-vinylpyridine; vinyl acetate and acrolein. These may be used individually by 1 type and may use 2 or more types together.
[0033]
Even when the shell monomer having a solubility in water (20 ° C.) of less than 0.1% by mass is used in combination with an organic solvent having a solubility in water (20 ° C.) of 5% by mass or more, Transition to the core particle surface can be performed quickly.
Examples of the shell monomer having a solubility in water (20 ° C.) of less than 0.1% by mass include styrene, butyl acrylate, 2-ethylhexyl acrylate, ethylene, propylene, and the like. These may be used individually by 1 type and may use 2 or more types together.
[0034]
Examples of the organic solvent having a solubility in water (20 ° C.) of 5% by mass or more include lower alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and butyl alcohol; ketones such as acetone and methyl ethyl ketone; And cyclic ethers such as dioxane; ethers such as dimethyl ether and diethyl ether; amides such as dimethylformamide.
The amount of the organic solvent used may be an amount such that the solubility of the shell monomer in the dispersion medium (the total amount of water and the organic solvent) is 0.1% by weight or more. Depending on the type of solvent and the type and amount of the monomer for the shell, etc., it cannot be specified unconditionally, but it is usually 0.1 to 50 parts by mass with respect to 100 parts by mass of the aqueous dispersion medium. -40 mass parts is preferable, and 0.1-30 mass parts is more preferable.
The order of adding the organic solvent and the shell monomer to the reaction system is not particularly limited, but promotes the migration of the shell monomer to the surface of the core particles and is excellent in heat resistant storage stability. From the viewpoint of obtaining a toner, it is preferable to first add the organic solvent to the reaction system and then add the shell monomer.
[0035]
The shell monomer having a solubility in water (20 ° C.) of 0.1% by mass or more and the shell monomer having a solubility in water (20 ° C.) of less than 0.1% by mass are used in combination. In this case, a monomer having a solubility in water (20 ° C.) of 0.1 mass or more is added and polymerized, then the organic solvent is added, and then the solubility in water (20 ° C.). It is preferable to polymerize by adding the shell monomer having a content of less than 0.1% by mass.
[0036]
In the present invention, it is preferable that a charge control agent is mixed with the shell monomer from the viewpoint of improving the chargeability of the resulting toner.
There is no restriction | limiting in particular as said charge control agent, It can select suitably from well-known things, Usually, it is 0.01-10 mass parts with respect to 100 mass parts of said monomers for shells, 0. 1-5 mass parts is preferable.
[0037]
The method for polymerizing the shell monomer on the surface of the core particle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) synthesis of the core particle (colored polymer particle) (2) The core particles obtained in another reaction system are charged into a reactor, and the shell monomer is added to the polymerization reaction system. The method of adding and polymerizing is mentioned.
At this time, the monomer for shell can be added all at once in the reaction system, or can be added continuously or intermittently using a pump such as a plunger pump.
[0038]
In addition, when adding the monomer for shell, it is preferable to add a water-soluble polymerization initiator to the reaction system. The water-soluble radical polymerization initiator is presumed to have an action of entering the surface of the core particle to which the shell monomer has migrated and facilitating formation of a polymer layer (shell) on the surface of the core particle. The
There is no restriction | limiting in particular as said water-soluble polymerization initiator, According to the objective, it can select suitably from well-known things, For example, persulfates, such as potassium persulfate and ammonium persulfate; 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis-2-methyl-N-1,1'-bis (hydroxymethyl) -2- Azo-based initiators such as hydroxyethylpropioamide and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide]; a combination of an oil-soluble initiator such as cumene peroxide and a redox catalyst And so on.
The amount of the water-soluble polymerization initiator used is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the shell monomer.
[0039]
The resin fine particles are usually obtained in the state of a dispersion. However, when the toner is produced using the resin fine particles, the dispersion may be used as it is for the production of the toner. Only the resin fine particles contained in the liquid may be used for the production of the toner. In the latter case, the resin fine particles can be obtained by, for example, washing and drying the dispersion. In addition, there is no restriction | limiting in particular as the said washing | cleaning method, According to the objective, it can carry out suitably, The method using water etc. are mentioned. There is no restriction | limiting in particular as said drying method, Although it can carry out in accordance with a well-known method, For example, a vacuum drying method etc. are mentioned suitably.
[0040]
Here, an example of producing a toner having a core / shell structure by the seed polymerization method is as follows. That is, for example, in a reaction vessel equipped with a stir bar and a thermometer, water, sodium salt of ethylene oxide methacrylate adduct sulfate (for example, Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), styrene, methacrylic acid, acrylic Charge butyl acid and ammonium persulfate and stir at 400 rpm for 15 minutes to obtain a white emulsion. Next, this is heated, and the temperature in the system is raised to about 75 ° C. and reacted for about 5 hours. Aqueous dispersion of vinyl resin fine particles (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) by adding an aqueous ammonium persulfate solution and aging at 75 ° C. for about 5 hours. A liquid is obtained.
[0041]
The resin fine particles may be added to a reaction system as a raw material when producing an adhesive base material by the polymerization method, and may be fixed to the surface of toner particles when the adhesive base material is produced. You may make it externally add to the toner particle surface produced | generated by the crushing method.
In the latter case, for example, a known mixing / stirring apparatus can be used. Examples of the mixing / stirring device include Henschel mixer (manufactured by Mitsui Miike), super mixer (manufactured by Kawada Seisakusho), Q mixer (manufactured by Mitsui Mining), mechano-fusion system (manufactured by Hosokawa Micron), and mechano mill (Okada Seiko). Manufactured). When the mixing / stirring device is used, if the mixing / stirring energy is too strong, a toner in which the resin fine particles are fixed to the surface of the toner base particles is obtained. A toner adhered to the surface of the toner is obtained. In this case, the resin fine particles can also function as a fluidity improver.
[0042]
-Adhesive substrate-
The adhesive substrate is not particularly limited as long as it exhibits adhesion to a recording medium such as paper, and examples thereof include those polymerized according to a known method, such as those produced by a pulverization method. It may be produced by a polymerization method. In the latter case, it is preferable to include a polymer obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium.
The adhesive substrate may further contain a non-reactive polyester described later, if necessary.
[0043]
There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 40-70 degreeC is preferable and 55-65 degreeC is more preferable.
If the glass transition temperature (Tg) is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and if it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
[0044]
The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.
[0045]
Storage elastic modulus (TG ′) of the adhesive substrate, that is, the adhesive substrate is 10000 dyne / cm at a measurement frequency of 20 Hz. ² There is no restriction | limiting in particular as temperature which becomes (TG '), Although it can select suitably according to the objective, For example, 100 degreeC or more is preferable and 110 to 200 degreeC is more preferable.
When the storage elastic modulus (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
[0046]
The viscosity temperature (Tη) of the adhesive substrate, that is, the temperature (Tη) at which the viscosity of the adhesive substrate becomes 1000 poise at a measurement frequency of 20 Hz is not particularly limited and may be appropriately selected according to the purpose. However, for example, 180 ° C. or lower is preferable, and 90 to 160 ° C. is more preferable.
When the viscosity temperature (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
[0047]
In addition, the storage elastic modulus (TG ′) of the adhesive base material is preferably higher than the viscosity (Tη) of the adhesive base material from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability. Specifically, the difference ΔT (TG′−Tη) between the storage elastic modulus (TG ′) and the viscosity temperature (Tη) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C. Preferably, it is 20-80 degreeC.
[0048]
In the present invention, the physical properties of the adhesive substrate contained in the toner are directly related to the physical properties such as the flow characteristics of the toner, and the glass transition temperature (Tg) and the storage in the adhesive substrate. The elastic modulus (TG ′), the difference ΔT (TG′−Tη) between the storage elastic modulus (TG ′) and the viscosity temperature (Tη) can be directly used as the physical properties of the toner.
[0049]
There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester-type resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.
[0050]
Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate and urealated with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.
[0051]
-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.
[0052]
The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.
[0053]
Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.
[0054]
In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).
[0055]
As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5. The ratio is preferably 1.2 / 1 to 1 / 1.2, particularly preferably.
When the isocyanate group [NCO] is less than 1 in the mixing equivalent ratio, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance and charging characteristics may be deteriorated. The molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be deteriorated.
[0056]
--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, polyester resins are particularly preferable from the viewpoint of low-temperature fixing characteristics.
[0057]
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.
[0058]
Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) because it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.
[0059]
There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably, For example, it is a polycondensate of a polyol (PO) and polycarboxylic acid (PC), and Examples include those obtained by reacting the polyester resin containing active hydrogen groups with polyisocyanate (PIC).
[0060]
There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.
[0061]
Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.
[0062]
The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.
[0063]
The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.
[0064]
There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.
[0065]
The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.
[0066]
As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
[0067]
Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.
[0068]
The mixing ratio for the polycondensation reaction of the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hydroxyl group in the polyol (PO) The equivalent ratio ([OH] / [COOH]) between [OH] and the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. 5/1 to 1/1 is more preferable, and 1.45 / 1 to 1.3 / 1 is particularly preferable.
When the equivalent ratio ([OH] / [COOH]) exceeds 2/1 in the mixing ratio, unreacted polyol (PO) remains, and the glass transition point (Tg) of the toner is lowered. If the ratio is less than 1/1, unreacted polycarboxylic acid (PC) remains, and the environmental stability of the toner may be deteriorated due to the hygroscopicity of the polycarboxylic acid (PC).
[0069]
There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.
[0070]
There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more. Among these, alicyclic polyisocyanate is preferable.
[0071]
As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferably, it is particularly preferably 2.5 / 1 to 1.5 / 1.
If the isocyanate group [NCO] exceeds 5 in the mixing ratio, the low-temperature fixability may be deteriorated. If it is less than 1, the hot offset resistance may be deteriorated.
[0072]
There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.
[0073]
The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.5 to 3, and more preferably 1.8 to 2.5.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.
[0074]
--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, ethyl acetate, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the cell solves include methyl cell solve. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together. Among these, ethyl acetate is preferable.
[0075]
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include colorants, mold release agents, non-reactive polyester resins, charge control agents, inorganic fine particles, and polymer particles. , Fluidity improvers, cleaning improvers, magnetic materials and the like.
[0076]
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.
[0077]
The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.
[0078]
The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.
[0079]
Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.
[0080]
The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.
[0081]
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.
[0082]
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
When the melt viscosity is less than 5 cps, the mold release property may be deteriorated. When the melt viscosity exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.
[0083]
There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner is deteriorated, and problems such as contamination of other members may be observed.
[0084]
The non-reactive polyester resin can be contained in the toner for the purpose of improving low-temperature fixability, glossiness and the like.
The non-reactive polyester resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, the same non-reactive polyester resin as the urea bond-forming group-containing polyester resin, that is, polyol (PO) And a polycondensate of polycarboxylic acid (PC). The non-reactive polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.
[0085]
There is no restriction | limiting in particular as a weight average molecular weight of the said non-reactive polyester resin, According to the objective, it can select suitably, For example, by a measured value by GPC (gel permeation chromatography), 1,000-30, 000 is preferable, 1,500 to 10,000 is more preferable, and 2,000 to 8,000 is particularly preferable.
When the weight average molecular weight is less than 1,000, the heat-resistant storage stability may be deteriorated, and when it exceeds 10,000, the low-temperature fixability may be deteriorated.
[0086]
As a hydroxyl value of the said non-reactive polyester resin, 5 or more are preferable, 10-120 are more preferable, and 20-80 are still more preferable.
If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
As an acid value of the said non-reactive polyester resin, 1-40 are preferable and 4-30 are more preferable. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
[0087]
When the non-reactive polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the non-reactive polyester resin (PE) is 5 / 95-50 / 50 is preferable.
When the mixing mass ratio of the non-reactive polyester resin (PE) is less than 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability, and is 50 or more. In some cases, the low-temperature fixing may be worsened.
[0088]
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.
[0089]
The content of the charge control agent in the toner varies depending on the type of the adhesive base material, the presence or absence of additives, the dispersion method, and the like, and cannot be defined generally. 0.1-10 mass parts is preferable with respect to part, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charging characteristics of the toner may be deteriorated. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent , And the electrostatic attraction force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.
[0090]
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is 20 to 500 m. ² / G is preferred.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.
The inorganic fine particles can be suitably used as an external additive for the toner.
[0091]
The polymer polymer particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polystyrene, methacrylic acid obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, etc. Examples thereof include particles formed of esters, acrylic acid ester copolymers, silicone resins, polycondensation resins such as benzoguanamine, nylon, and thermosetting resins.
[0092]
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
[0093]
The shape, size, etc. of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose. The molecular weight, molecular weight distribution, fixability, thermal characteristics, image density, and the like are as follows. And average circularity, circularity distribution, weight average particle diameter (D4), ratio of weight average particle diameter (D4) to number average particle diameter (Dn) (D4 / Dn), and the like.
[0094]
As the molecular weight of the toner, for example, the weight average molecular weight (Mw) obtained as the main peak molecular weight of a tetrahydrofuran (THF) soluble component is preferably 1,000 to 30,000, more preferably 1,500 to 10,000. 2000 to 8000 is particularly preferable.
When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
[0095]
As the molecular weight distribution of the weight average molecular weight (Mw), the amount of the component having the weight average molecular weight (Mw) of less than 1,000 is 5 from the viewpoint of achieving both the heat resistant storage stability and the low temperature fixability. It is preferably 0.0% by mass or less. When the amount of the component that is less than 1,000 exceeds 5.0% by mass, the heat-resistant storage stability is deteriorated, and carrier contamination may occur. Further, the amount of the component having the main peak molecular weight exceeding 30,000 is preferably 1% by mass or more, more preferably 1 to 10% by mass, and particularly preferably 3 to 6% by mass. . When the amount of the component exceeding 30,000 is less than 1% by mass, the hot-off resistance may not be sufficient. On the other hand, when the amount exceeds 10% by mass, glossiness, transparency and the like may be deteriorated. is there.
[0096]
The molecular weight distribution of the toner can be measured, for example, as follows. That is, after about 1 g of the toner is thoroughly evaluated in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added to obtain a THF sample solution having an adhesive substrate concentration of 5 to 10%. Next, the column is stabilized in a 40 ° C. heat chamber, and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected. The molecular weight of the sample can be calculated from the relationship between the retention time and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. The calibration curve is created using a polystyrene standard sample. Examples of the monodisperse polystyrene standard sample, detector, column, etc. include those described above.
[0097]
The number average molecular weight (Mn) of the toner is preferably 2,000 to 15,000, and more preferably 2,500 to 12,000.
When the number average molecular weight (Mn) is less than 2,000, the heat resistant storage stability may be deteriorated, and when it exceeds 15,000, the low temperature fixability may be deteriorated.
[0098]
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the toner is not particularly limited and can be appropriately selected according to the purpose. 4 or less is more preferable.
When the ratio (Mw / Mn) exceeds 5, sharp melt properties may be lost and glossiness may be impaired.
[0099]
The toner preferably contains 1 to 15% by mass of a THF insoluble matter that does not dissolve in tetrahydrofuran (THF).
When the amount of the THF-insoluble component is within the numerical range, it is advantageous in that the hot offset resistance can be improved and the mold release width can be increased.
The amount of the THF-insoluble component can be appropriately adjusted by controlling the elongation or crosslinking of the polymer that can react with the active hydrogen group-containing compound by the acid value of the non-reactive polyester.
[0100]
The amount of THF-insoluble matter in the toner can be measured, for example, as follows. That is, about 1.0 g (A) of the toner (the amount of THF-insoluble matter in the resin fine particles can be measured in the same manner) is weighed. To this, about 50 g of THF is added and allowed to stand at 20 ° C. for 24 hours. This is first separated by centrifugation and filtered using JIS standard (P3801) type 5 C filter paper for quantitative determination. The solvent content of this filtrate is vacuum-dried, and the residual amount (B) of only the resin content can be calculated from the following formula, THF-insoluble content (%) = (A−B) / A. The residual amount (B) is the THF dissolved content. However, in the case of the toner, the amount of the THF-insoluble matter (W1) and the amount of the THF-soluble matter (W2) other than the adhesive base material are determined by a separately known method, for example, a thermal loss method using the TG method. From the following formula, THF-insoluble matter (%) = (A−B−W2) / (A−W1−W2) × 100.
[0101]
The fixing property of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the minimum fixing temperature (cold offset property) is preferably 160 ° C. or lower, more preferably 150 ° C. or lower. 140 degrees C or less is still more preferable, 130 degrees C or less is still more preferable, and less than 120 degreeC is especially preferable.
When the minimum fixing temperature exceeds 160 ° C., it is difficult to achieve the performance required in the International Energy Agency (IEA) DSM program.
Further, the temperature at which hot offset occurs (hot offset resistance) is preferably higher than 180 ° C, more preferably higher than 190 ° C, and particularly preferably higher than 200 ° C.
If the temperature at which the hot offset occurs is 180 ° C. or less, the fixing temperature range cannot be obtained, and the actual use cannot be endured.
[0102]
The fixing lower limit temperature and the hot offset generation temperature are, for example, a known copying machine. In the case of the fixing lower limit temperature, the linear velocity of paper feed is 120 to 150 mm / sec, and the surface pressure is 1.2 kgf / cm. ² Under the conditions of a nip width of 3 mm, and the temperature at which the hot offset occurs, the linear speed of paper feed is 50 mm / sec, and the surface pressure is 2.0 kgf / cm ² Evaluation can be made under the condition of a nip width of 4.5 mm.
[0103]
The thermal characteristics of the toner are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 50-100 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 70-150 degreeC is preferable and 75-120 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 70 ° C., the heat resistant storage stability may be deteriorated, and when it exceeds 170 ° C., the low temperature fixability may be deteriorated. The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 100 ° C. or higher is preferable, and 120 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 100 ° C., at least one of heat-resistant storage stability and low-temperature storage stability may deteriorate.
[0104]
The toner image density is, for example, preferably 1.90 or more, more preferably 2.00 or more, as measured by a spectrometer (938 Spectrodensitometer, manufactured by X-Light). 10 or more is particularly preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.), and the amount of developer adhered to copy paper (TYPE 6000 <70W>; manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.05 mg / cm. ² The solid roller image was formed at a fixing roller surface temperature of 160 ± 2 ° C., and the image density at any six locations in the solid image obtained was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Light). It can be measured by measuring and calculating the average value.
[0105]
The average circularity of the toner is, for example, preferably 0.95 to 1.00, and more preferably 0.960 to 0.980. The particles having an average circularity of less than 0.94 are preferably 15% by mass or less.
If the average circularity is less than 0.95, an irregular shape that is too far from the spherical shape may be obtained, and satisfactory transferability and high-quality images without dust may not be obtained.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). Specifically, for example, 0.1 to 0.5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of water from which impure solids have been previously removed, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the measurement sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the concentration of the dispersion is set to 3000 to 10,000 / μl. It is obtained by measuring the shape and distribution of the toner using FPIA-2100 or the like.
[0106]
There is no restriction | limiting in particular as a weight average particle diameter (D4) of the said toner, According to the objective, it can select suitably, For example, 3-8 micrometers is preferable.
When the weight average particle diameter (D4) is less than 3 μm, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may easily occur. In addition, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle diameter may increase.
[0107]
The ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) in the toner is preferably, for example, 1.00 to 1.25, and more preferably 1.05 to 1.25. preferable.
When the ratio (D4 / Dn) is within the preferable numerical range to the more preferable numerical range, the heat resistance storage property, the low temperature fixing property, the hot offset resistance are excellent, and the image when used in a full-color copying machine is excellent. Excellent gloss, and even when used repeatedly as a two-component developer for a long period of time, there is little fluctuation in toner particle size, stable developability, high image quality, and long-term use as a one-component developer. However, there is little fluctuation in the toner particle size, there is no filming on the developing roller, no fusion to the toner blade, etc., and it is advantageous in that stable developability is exhibited and high image quality is obtained. On the other hand, when the ratio (D4 / Dn) exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the toner particle size The fluctuation may be large, and if it is less than 1.05, the chargeability of the toner may not be sufficient, and the cleaning property may be deteriorated. In some cases, the toner is fused to the toner and the charging ability of the carrier is lowered. In addition, in the case of a one-component developer, the toner filming on the developing roller and the toner on the member such as a blade are made thin. Fusion may occur easily.
[0108]
The weight average particle diameter (D4) and the ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) are, for example, a particle size measuring instrument “Coulter Counter TAII manufactured by Coulter Electronics Co., Ltd. Can be measured. Specifically, for example, first, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution. The electrolytic aqueous solution is an approximately 1% NaCl aqueous solution prepared using primary sodium chloride. Next, 2 to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and a particle size measuring device (for example, ISOTON-II (manufactured by Coulter)) is used and an aperture of 100 μm is used as an aperture. The volume distribution and number distribution can be calculated by measuring the volume and number of toner particles or toner. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained. At this time, for example, the channel is 2.00 to less than 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 ˜less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm 20 .20 to less than 25.40 μm; 25.40 to less than 32.00 μm; using 13 channels of 32.00 to less than 40.30 μm and targeting particles with a particle size of 2.00 μm to less than 40.30 μm can do.
[0109]
The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.
[0110]
The toner of the present invention has a weight average molecular weight of 8,000 to 1,000,000, a particle size of 20 to 400 nm, and contains resin fine particles having a core / shell structure, and thus has good hot offset resistance. It achieves both excellent heat-resistant storage stability and low-temperature fixability, and provides a sharp image quality with sharp charge distribution. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.
[0111]
The toner of the present invention can be produced by a known method, and can be suitably produced by the toner production method of the present invention described later.
[0112]
(Toner production method)
The method for producing a toner of the present invention includes a resin fine particle forming step and an adhesive base material generating step, and further includes other steps appropriately selected as necessary.
[0113]
-Resin fine particle formation process-
In the resin fine particle forming step, the core monomer used to form the core is polymerized to form the core particle, and then the shell monomer used to form the shell is polymerized on the surface of the core particle. This is a step of forming resin fine particles having a core-shell structure having a weight average molecular weight (Mw) of 8,000 to 1,000,000 and a particle size of 20 to 400 nm.
In the resin fine particle forming step, for example, core particles and shells are formed. The formation of the core particles is a process for forming the core particles by polymerizing the core monomer. The formation of the shell is a process of polymerizing the shell monomer on the surface of the core particle.
[0114]
The core monomer is not particularly limited and may be formed of a material appropriately selected from known materials. Among these, the core monomer is formed of a resin capable of forming an aqueous dispersion in an aqueous medium. Preferably, it may be a thermoplastic resin or a thermosetting resin. Examples of the core monomer include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin because an aqueous dispersion of fine spherical resin fine particles can be easily obtained. It is particularly preferable that it is formed of a vinyl resin.
The core particles can be formed by polymerizing the core monomer according to a seed polymerization method. In addition, there is no restriction | limiting in particular about the conditions of this polymerization, etc., It can select suitably according to the objective.
[0115]
The shell monomer is as described above, and is not particularly limited, and may be appropriately selected from known materials depending on the glass transition temperature of the resin forming the core, the type of resin to be synthesized, and the like. Examples thereof include styrene and methyl methacrylate. These may be used individually by 1 type and may use 2 or more types together. Among these, those capable of forming a resin having a glass transition temperature of more than 80 ° C. are preferable. When the glass transition temperature of the resin forming the core is less than 60 ° C., a resin having a glass transition temperature of 80 ° C. or less is formed. It may be possible.
The shell monomer is preferably one having a solubility in water (20 ° C.) of 0.1% by mass or more in consideration of rapidity of migration to the core particle surface.
Examples of the shell monomer having a solubility in water (20 ° C.) of 0.1% by mass or more include (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate; amides such as acrylamide and methacrylamide; Examples thereof include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; nitrogen-containing vinyl compounds such as 4-vinylpyridine; vinyl acetate and acrolein. These may be used individually by 1 type and may use 2 or more types together.
[0116]
The mass ratio of the core monomer to the shell monomer (core monomer: shell monomer) is as described above, and is 50/50 to 99.9 / 0.1. Is preferable, 60/40 to 99/1 is more preferable, and 60/40 to 90/10 is particularly preferable. When the mass ratio is within the above range, it is advantageous in that the heat-resistant storage stability of the obtained toner can be improved.
[0117]
As described above, the formation of the shell is preferably performed by adding the shell monomer as a small liquid to the reaction system including the core particles. The method of making the shell monomer into small droplets is as described above, and is not particularly limited and can be appropriately selected according to the purpose. For example, a known ultrasonic emulsifier or the like is used. And a method of performing fine dispersion processing.
[0118]
Even when the shell monomer having a solubility in water (20 ° C.) of less than 0.1% by mass is used in combination with an organic solvent having a solubility in water (20 ° C.) of 5% by mass or more, Transition to the core particle surface can be performed quickly.
Monomer for shell having solubility in water (20 ° C.) of less than 0.1% by mass, organic solvent having solubility in water (20 ° C.) of 5% by mass or more, use amount of organic solvent, organic solvent The order of adding the shell monomer and the shell monomer to the reaction system is as described above.
The shell monomer having a solubility in water (20 ° C.) of 0.1% by mass or more and the shell monomer having a solubility in water (20 ° C.) of less than 0.1% by mass are used in combination. In this case, a monomer having a solubility in water (20 ° C.) of 0.1 mass or more is added, polymerized, the organic solvent is added, and then the solubility in water (20 ° C.) is 0.1 mass. It is preferable to polymerize by adding the shell monomer of less than%.
[0119]
The method for polymerizing the shell monomer on the surface of the core particle is as described above. In the resin fine particle forming step, the resin fine particles are usually obtained in the form of a dispersion, but when the toner is produced using the resin fine particles, the dispersion is used as it is for the production of the toner. Alternatively, only the resin fine particles contained in the dispersion may be used for the production of the toner.
[0120]
-Adhesive substrate production process-
In the adhesive base material generation step, the above-mentioned active hydrogen group-containing compound, a polymer capable of reacting with the above-mentioned active hydrogen group-containing compound, and at least two kinds of the above-described resin fine particles are dispersed in the above-mentioned aqueous medium. And producing a toner while producing an adhesive base material.
In the adhesive substrate generation step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, Synthesis of active hydrogen group-containing compounds).
[0121]
The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles described above in the aqueous medium described above. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared in the organic solvent by containing the active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, It can be carried out by dissolving or dispersing a toner raw material such as a reactive polyester resin.
It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.
The mass ratio of the polymer capable of reacting with the active hydrogen group-containing compound and the non-reactive polyester (polymer: non-reactive polyester) is not particularly limited and may be appropriately selected depending on the intended purpose. However, 5 / 95-50 / 50 is preferable, for example.
If the mass ratio is not within the numerical range, the fixing characteristics may be deteriorated.
[0122]
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are particularly preferable.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferred is 80 to 120 parts by mass.
[0123]
The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be produced by extending or cross-linking both in the phase, or (3) the organic solvent phase is added and mixed in the aqueous medium and then the active hydrogen group-containing The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.
[0124]
As the reaction conditions for generating the adhesive substrate by subjecting the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound to an extension reaction or a crosslinking reaction by the emulsification / dispersion, There is no limitation, and it can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, preferably 2 Time to 24 hours are more preferable, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.
[0125]
In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, Polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent in the aqueous medium phase (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, and the release agent And a method of adding the toner raw materials such as the charge control agent and the non-reactive polyester resin, and dispersing them by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.
[0126]
In the emulsification / dispersion, the usage amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner raw material.
When the amount used is less than 50 parts by mass, the toner raw material is poorly dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost is high. May be.
[0127]
In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.
[0128]
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.
[0129]
Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).
[0130]
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.
[0131]
Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
[0132]
In the emulsification / dispersion, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.
[0133]
In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.
[0134]
The organic solvent is removed from the emulsified slurry obtained in the emulsification / dispersion. The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. And a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation. In addition, there is no restriction | limiting in particular as said dry atmosphere, According to the objective, it can select suitably, For example, the atmosphere etc. which heated gas, such as air, nitrogen, a carbon dioxide gas, and combustion gas, are mentioned. At this time, the heating temperature of the gas is preferably a temperature equal to or higher than the highest boiling point of the solvents used. There is no restriction | limiting in particular as this heating means, According to the objective, it can select suitably, For example, a spray hair dryer, a belt dryer, a rotary kiln etc. are mentioned suitably at the point which can process for a short time.
[0135]
When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, and the like. At this time, it is preferable to remove the dispersant as much as possible. Further, classification and the like can then be performed as desired. The particle size distribution can be controlled by the classification.
The classification can be performed, for example, by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, and the classification operation may be performed after obtaining the powder as a powder after drying. Unnecessary fine particles or coarse particles obtained by the classification can be used in the adhesive base material production step as they are or after drying.
[0136]
Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.
[0137]
Here, a preferred specific example of the toner production method of the present invention is shown below.
-Resin fine particle formation process-
--Formation of core particles--
In a reaction vessel in which a stir bar and a thermometer are set, water, ethylene oxide methacrylate adduct sulfate sodium salt (for example, Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), styrene, methacrylic acid, butyl acrylate, and Charge ammonium persulfate and stir at 400 rpm for 15 minutes to obtain a white emulsion. Next, this is heated, and the temperature in the system is raised to about 75 ° C. and reacted for about 5 hours. Then, by adding an aqueous ammonium persulfate solution and aging at 75 ° C. for about 5 hours, the core particles of vinyl resin (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion (core particle dispersion) is obtained.
[0138]
--Formation of shell--
In the reaction vessel, the core particle dispersion, water, sodium salt of methacrylic acid ethylene oxide adduct sulfate (for example, Eleminol RS-30, manufactured by Sanyo Chemical Industries), styrene, methacrylic acid, butyl acrylate, thioglycolic acid When butyl and ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The emulsion was heated to 75 ° C. and reacted for 5 hours. Further, an aqueous solution of ammonium persulfate was added and aged at 75 ° C. for 5 hours to form a shell made of vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). An aqueous dispersion of resin fine particles polymerized on the surface of the core particles (resin fine particle dispersion) was obtained.
[0139]
-Adhesive substrate production process-
--Synthesis of low molecular weight polyester--
Put a bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 3-mole adduct, terephthalic acid, adipic acid, and dibutyltin oxide in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and normal pressure. After reacting at 230 ° C. for 8 hours and further reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, trimellitic anhydride was put into the reaction vessel and reacted at 180 ° C. under normal pressure for 2 hours. Thus, a low molecular weight polyester is synthesized.
[0140]
--Synthesis of prepolymer--
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, trimellitic anhydride, and dibutyltin oxide are charged. The reaction was carried out at 230 ° C. for 8 hours under normal pressure. Subsequently, it is made to react under reduced pressure of 10-15mHg for 5 hours, and an intermediate polyester (low molecular polyester) is synthesize | combined.
Next, the intermediate polyester, isophorone diisocyanate, and ethyl acetate are charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours to produce a prepolymer (the active hydrogen A polymer capable of reacting with the group-containing compound).
[0141]
--Synthesis of ketimine (the active hydrogen group-containing compound)-
Isophoronediamine and methyl ethyl ketone are charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
[0142]
-Preparation of master batch (MB)-
Water, carbon black as a colorant, and a polyester resin were added, and a mixture was prepared using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture is kneaded with a two-roller at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.
[0143]
-Preparation of organic solvent phase-
The low molecular polyester, carnauba wax, salicylic acid metal complex E-84, and ethyl acetate are charged into a reaction vessel equipped with a stir bar and a thermometer, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. After holding, cool to 30 ° C. over 1 hour. Next, the master batch and ethyl acetate are charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
The obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80 The carbon black and the carnauba wax are dispersed in 3 passes under the condition of volume% filling. Next, a 65% by mass ethyl acetate solution of the low molecular weight polyester is added to the dispersion. One pass is performed in a bead mill under the same conditions as above, and the mixture is dispersed to prepare an organic solvent phase.
[0144]
--Emulsification / Dispersion--
In a reaction vessel, the organic solvent phase, the prepolymer, and the ketimine compound are charged, and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika) to prepare an oil phase mixture. obtain.
Next, water, the resin fine particle dispersion, a 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate, and ethyl acetate are charged into a reaction vessel, and at 3000 rpm with a TK homomixer (manufactured by Tokushu Kika). Mix for 1 minute. Subsequently, the said oil phase liquid mixture is added in reaction container, and it mixes for 20 minutes at 13,000 rpm in TK type | mold homomixer, and prepares an emulsified slurry.
Next, the emulsified slurry is charged into a reaction vessel in which a stirrer and a thermometer are set, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
[0145]
After filtering the dispersion slurry under reduced pressure, ion-exchanged water is added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered. Distilled water (or 10 mass% sodium hydroxide aqueous solution) is added to the filter cake obtained here, and mixed with a TK homomixer (30 minutes at a rotation speed of 12,000 rpm), followed by filtration under reduced pressure. 10 mass% hydrochloric acid is added to the filter cake obtained here, and after mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), the mixture is filtered. Ion exchanged water is added to the filter cake obtained here, and after mixing with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), filtration is performed twice to obtain a final filter cake.
Here, the obtained final filter cake is dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm, whereby toner base particles are obtained.
[0146]
-External additive treatment-
The toner of the present invention is produced by mixing the obtained toner base particles with hydrophobic silica as an external additive and hydrophobized titanium oxide using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.).
[0147]
(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.
[0148]
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
[0149]
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality Is preferred. These may be used alone or in combination of two or more.
In the case of a magnetic carrier, the material is not particularly limited and can be appropriately selected from known materials according to the purpose. Examples thereof include iron powder, magnetite, and ferrite. Among these, white is preferable in terms of color tone.
[0150]
As the particle diameter of the core material, the average particle diameter (volume average particle diameter (D ₅₀ )), 20 to 200 μm is preferable, and 40 to 100 μm is more preferable.
The average particle diameter (volume average particle diameter (D ₅₀ )) Is less than 10 μm, in the distribution of carrier particles, there are many fine powder systems, the magnetization per particle is lowered and carrier scattering may occur, and if it exceeds 150 μm, the specific surface area decreases, Toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.
[0151]
The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.
[0152]
Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.
[0153]
The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
[0154]
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
[0155]
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.
[0156]
When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
[0157]
Since the developer of the present invention contains the toner of the present invention, the developer of the present invention is excellent in hot offset resistance and the like, has both excellent heat storage stability and low-temperature fixability, and has a sharp charge distribution and a sharp image. High image quality can be formed.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.
[0158]
(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the container body containing toner is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.
[0159]
(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the electrophotographic apparatus of the present invention described later.
[0160]
(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
[0161]
The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.
[0162]
-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.
[0163]
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.
[0164]
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
[0165]
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.
[0166]
-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.
[0167]
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.
[0168]
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
[0169]
The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.
[0170]
-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
[0171]
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).
[0172]
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.
[0173]
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.
[0174]
The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
[0175]
The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
[0176]
The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
[0177]
One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.
[0178]
The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.
[0179]
The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.
[0180]
In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.
[0181]
Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.
[0182]
Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 120 shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 120, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.
[0183]
Next, full color image formation (color copy) using the tandem image forming apparatus 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
[0184]
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.
[0185]
Each image information of black, yellow, magenta and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit and cyan image forming unit) in the tandem image forming apparatus 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).
[0186]
On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.
[0187]
The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.
[0188]
The image forming apparatus and the image forming method of the present invention are excellent in hot offset resistance and the like, have both excellent heat-resistant storage stability and low-temperature fixability, and can form a high quality image with sharp charge distribution and sharpness. Since the toner of the invention is used, a high quality image with high image density and high sharpness can be formed even under low temperature fixing conditions without causing hot offset.
[0189]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0190]
-Preparation of core particle dispersion (C1)-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts by mass of water, 20 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 78 parts by mass of styrene, methacrylic acid When 78 parts by mass, 120 parts by mass of butyl acrylate, and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The emulsion was heated to 75 ° C. and reacted for 5 hours. 30 parts of 1% ammonium persulfate aqueous solution was added to the emulsion and aged at 75 ° C. for 5 hours to give a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). Polymer) core particle dispersion (C1) was obtained.
About the core particle (1) contained in the said core particle dispersion liquid (C1), the volume average particle diameter (Dv) measured by LA-920 was 55 nm. Moreover, the glass transition temperature (Tg) of resin which forms this core particle (1) was 48 degreeC, and the weight average molecular weight (Mw) was 450,000. These are shown in Table 1.
[0191]
-Preparation of core particle dispersion (C2)-
In the preparation of the core particle dispersion (C1), styrene is changed from 78 parts by mass to 73 parts by mass, methacrylic acid is changed from 78 parts by mass to 73 parts by mass, and butyl acrylate is changed from 120 parts by mass to 130 parts by mass. Further, a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate ester) was prepared in the same manner as in the preparation of the core particle dispersion (C1) except that 12 parts by mass of butyl thioglycolate was used. A core particle dispersion (C2).
About the core particle (2) contained in the said core particle dispersion liquid (C2), the volume average particle diameter (Dv) measured by LA-920 was 52 nm. Moreover, the glass transition temperature (Tg) of resin which forms this core particle (2) was 42 degreeC, and the weight average molecular weight (Mw) was 25,000. These are shown in Table 1.
[0192]
-Preparation of core particle dispersion (C3)-
In the preparation of the core particle dispersion (C1), the sodium salt of methacrylic acid ethylene oxide adduct sulfate was changed from 20 parts by mass to 15 parts by mass, styrene was changed from 78 parts by mass to 103 parts by mass, and methacrylic acid was changed to 78 parts by mass. The procedure is the same as the preparation of the core particle dispersion (C1) except that the weight is changed from 83 parts by weight to 83 parts by weight, butyl acrylate is changed from 120 parts by weight to 90 parts by weight, and 12 parts by weight of butyl thioglycolate is used. Then, a core particle dispersion (C3) of vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) was prepared.
About the core particle (3) contained in the said core particle dispersion liquid (C3), the volume average particle diameter (Dv) measured by LA-920 was 74 nm. Moreover, the glass transition temperature (Tg) of resin which forms this core particle (3) was 63 degreeC, and the weight average molecular weight (Mw) was 27,000. These are shown in Table 1.
[0193]
-Preparation of core particle dispersion (C4)-
In the preparation of the core particle dispersion (C4), the sodium salt of methacrylic acid ethylene oxide adduct sulfate was changed from 20 parts by mass to 15 parts by mass, styrene was changed from 78 parts by mass to 150 parts by mass, and methacrylic acid was changed to 78 parts by mass. The procedure is the same as the preparation of the core particle dispersion (C1) except that the weight is changed from 83 to 83 parts by weight, butyl acrylate is changed from 120 to 43 parts by weight, and 12 parts by weight of butyl thioglycolate is used. Then, a core particle dispersion liquid (C4) of vinyl resin (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) was prepared.
About the core particle (4) contained in the said core particle dispersion liquid (C4), the volume average particle diameter (Dv) measured by LA-920 was 62 nm. Moreover, the glass transition temperature (Tg) of resin which forms this core particle (4) was 95 degreeC, and the weight average molecular weight (Mw) was 21,000. These are shown in Table 1.
[0194]
-Preparation of core particle dispersion (C5)-
In the preparation of the core particle dispersion (C1), the sodium salt of methacrylic acid ethylene oxide adduct sulfate was changed from 20 parts by mass to 12 parts by mass, styrene was changed from 78 parts by mass to 83 parts by mass, and methacrylic acid was changed to 78 parts by mass. The vinyl resin (styrene-methacrylic acid-acrylic) was prepared in the same manner as in the preparation of the core particle dispersion (C1) except that the weight was changed from 83 parts by weight to 83 parts by weight and butyl acrylate was changed from 120 parts by weight to 110 parts by weight. A core particle dispersion (C5) of butyl acid-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) was prepared.
About the core particle (7) contained in the said core particle dispersion liquid (C5), the volume average particle diameter (Dv) measured by LA-920 was 168 nm. Moreover, the glass transition temperature (Tg) of resin which forms this core particle (5) was 42 degreeC, and the weight average molecular weight (Mw) was 370,000. These are shown in Table 1.
[0195]
[Table 1]

[0196]
--Preparation of resin fine particle dispersion (1)-
In a reaction vessel in which a stir bar and a thermometer are set, 1009 parts by mass of the core particle dispersion (C1), 683 parts by mass of water, and sodium salt of an ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries) ) 20 parts by weight, 103 parts by weight of styrene, 83 parts by weight of methacrylic acid, 90 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were stirred for 15 minutes at 400 rpm, and a white emulsion was obtained. It was. The emulsion was heated to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A fine particle dispersion (1) was obtained.
The resin fine particles (1) contained in the resin fine particle dispersion (1) had a volume average particle diameter (Dv) measured by LA-920 of 105 nm. Further, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particle dispersion (1) was 60 ° C., and the weight average molecular weight (Mw) was 400,000. These are shown in Table 2.
[0197]
--Preparation of resin fine particle dispersion (2)-
In the preparation of the resin fine particle dispersion (1), styrene is changed from 103 parts by mass to 11.4 parts by mass, methacrylic acid is changed from 83 parts by mass to 9.2 parts by mass, and butyl acrylate is changed from 90 parts by mass to 10 parts by mass. A vinyl resin (styrene-methacrylic acid-butyl acrylate-) was prepared in the same manner as in the preparation of the resin fine particle dispersion (1) except that the mass part was changed and the ammonium persulfate was changed from 1 part by mass to 0.11 part by mass. A resin fine particle dispersion (2) of ethylene oxide methacrylate adduct sulfate sodium salt) was prepared.
The resin fine particles (2) contained in the resin fine particle dispersion (2) had a volume average particle size (Dv) measured by LA-920 of 95 nm. Further, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (2) was 60 ° C., and the weight average molecular weight (Mw) was 400,000. These are shown in Table 2.
[0198]
--Preparation of resin fine particle dispersion (3)-
In the preparation of the resin fine particle dispersion (1), styrene is changed from 103 parts by weight to 18.9 parts by weight, methacrylic acid is changed from 83 parts by weight to 9.2 parts by weight, and butyl acrylate is changed from 90 parts by weight to 2 parts. .6 parts by mass, and vinyl resin (styrene-methacrylic acid-acrylic) in the same manner as in the preparation of the resin fine particle dispersion (1) except that ammonium persulfate was changed from 1 part by mass to 0.11 parts by mass. A resin fine particle dispersion (3) of acid butyl-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) was prepared.
With respect to the resin fine particles (3) contained in the resin fine particle dispersion (3), the volume average particle diameter (Dv) measured by LA-920 was 112 nm. Moreover, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (3) was 110 ° C., and the weight average molecular weight (Mw) was 420,000. These are shown in Table 2.
[0199]
--Preparation of resin fine particle dispersion (4)-
In the preparation of the resin fine particle dispersion (1), the core particle dispersion (C1) is changed to the core particle dispersion (C2), styrene is changed from 103 parts by mass to 108 parts by mass, and butyl methacrylate is changed from 90 parts by mass. Except for changing to 85 parts by mass, the vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt co-polymerized in the same manner as in the preparation of the resin fine particle dispersion (1). A resin fine particle dispersion (4) was prepared.
With respect to the resin fine particles (4) contained in the resin fine particle dispersion (4), the volume average particle diameter (Dv) measured by LA-920 was 107 nm. Moreover, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (4) was 70 ° C., and the weight average molecular weight (Mw) was 440,000. These are shown in Table 2.
[0200]
--Preparation of resin fine particle dispersion (5)-
In the preparation of the resin fine particle dispersion (1), the core particle dispersion (C1) is changed to the core particle dispersion (C3), styrene is changed from 103 parts by mass to 108 parts by mass, and butyl methacrylate is changed from 90 parts by mass. Except for changing to 85 parts by mass, the vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt co-polymerized in the same manner as in the preparation of the resin fine particle dispersion (1). A resin fine particle dispersion (5) was prepared.
With respect to the resin fine particles (5) contained in the resin fine particle dispersion (5), the volume average particle diameter (Dv) measured by LA-920 was 110 nm. Further, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (5) was 70 ° C., and the weight average molecular weight (Mw) was 440,000. These are shown in Table 2.
[0201]
--Preparation of resin fine particle dispersion (6)-
In the preparation of the resin fine particle dispersion (1), except that the styrene was changed from 103 parts by mass to 108 parts by mass and the butyl methacrylate was changed from 90 parts by mass to 85 parts by mass, the resin fine particle dispersion (1) In the same manner as in the preparation, a resin fine particle dispersion (6) of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) was prepared.
With respect to the resin fine particles (6) contained in the resin fine particle dispersion (6), the volume average particle diameter (Dv) measured by LA-920 was 98 nm. The glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (6) was 70 ° C., and the weight average molecular weight (Mw) was 440,000. These are shown in Table 2.
[0202]
--Preparation of resin fine particle dispersion (7)-
In the preparation of the resin fine particle dispersion (1), the core particle dispersion (C1) is changed to the core particle dispersion (C4), styrene is changed from 103 parts by weight to 170 parts by weight, and butyl methacrylate is changed from 90 parts by weight. Except for changing to 23 parts by mass, in the same manner as in the preparation of the resin fine particle dispersion (1), a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt A resin fine particle dispersion (7) was prepared.
The resin fine particles (7) contained in the resin fine particle dispersion (7) had a volume average particle size (Dv) measured by LA-920 of 96 nm. Further, the glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (7) was 110 ° C., and the weight average molecular weight (Mw) was 420,000. These are shown in Table 2.
[0203]
--Preparation of resin fine particle dispersion (8)-
In the preparation of the resin fine particle dispersion (1), the core particle dispersion (C1) is changed to the core particle dispersion (C5), and the sodium salt of methacrylic acid ethylene oxide adduct sulfate is changed from 12 parts by mass to 5 parts by mass. Resin of vinyl resin (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) similar to the preparation of the resin fine particle dispersion (1) except that it was changed. A fine particle dispersion (8) was prepared.
With respect to the resin fine particles (8) contained in the resin fine particle dispersion (8), the volume average particle diameter (Dv) measured by LA-920 was 337 nm. The glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (8) was 60 ° C., and the weight average molecular weight (Mw) was 440,000. These are shown in Table 2.
[0204]
--Preparation of resin fine particle dispersion (9)-
In the preparation of the resin fine particle dispersion (1), 1009 parts of the core particle dispersion (C1) is not used, but the sodium salt of the ethylene oxide adduct sulfate is changed from 20 parts by weight to 10 parts by weight, and 103 parts of styrene is obtained. Except for changing from mass parts to 48 parts by mass, changing methacrylic acid from 83 parts by mass to 78 parts by mass, changing butyl acrylate from 90 parts by mass to 150 parts by mass, and using 12 parts by mass of butyl thioglycolate, Resin fine particle dispersion (9) of vinyl resin (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) in the same manner as in the preparation of resin fine particle dispersion (1) Was prepared.
The resin fine particles (9) contained in the resin fine particle dispersion (9) had a volume average particle diameter (Dv) measured by LA-920 of 113 nm. The glass transition temperature (Tg) of the resin forming the shell of the resin fine particles (7) was 31 ° C., and the weight average molecular weight (Mw) was 32,000. These are shown in Table 2.
[0205]
[Table 2]

[0206]
--Synthesis of polyester resin (1)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propylene oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 adipic acid 46 2 parts by weight of dibutyltin oxide and 2 parts by weight of dibutyltin oxide were reacted at normal pressure and 230 ° C. for 8 hours, and further reacted at 10 to 15 mmHg for 5 hours. Then, 44 parts by weight of trimellitic anhydride was added to the reaction vessel. The polyester resin (2) was obtained by reacting at 180 ° C. and normal pressure for 2 hours. The polyester resin (2) had a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25 mgKOH / g.
[0207]
--Synthesis of polyester resin (2)-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 359 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 1273 parts by mass of bisphenol A propylene oxide 2-mole adduct, 9 parts by mass of ethylene glycol, terephthalic acid 208 1 part by mass, 8 parts by mass of succinic acid, 415 parts by mass of isophthalic acid, and 1 part by mass of dibutyltin oxide were reacted at normal pressure at 230 ° C. for 8 hours, and further reacted at 5 to 10 mm under reduced pressure for 10 hours. A polyester resin (2) was obtained by putting 48 parts of trimellitic anhydride in a container and reacting at 180 ° C. and normal pressure for 2 hours. The polyester resin (2) had a weight average molecular weight (Mw) of 6,800, a glass transition temperature (Tg) of 60 ° C., and an acid value of 28.5 mgKOH / g.
[0208]
(Example 1)
In a Henschel mixer, 96 parts by mass of the polyester resin (2), 4 parts by mass of polyethylene wax (melting point 85 ° C.), 10 parts by mass of carbon black (Mitsubishi Chemical # 44), and 1 part by mass of salicylsanzirconium salt are mixed. After sufficiently stirring and mixing, the mixture was kneaded with a twin-screw extruder, cooled, and then pulverized and classified so that the volume average particle size became 9.0 ± 0.5 μm. The kneading was performed under the condition that the temperature of the kneaded material at the outlet of the kneader was 130 to 140 ° C. The pulverization and the classification were performed so that the volume average particle diameter was 6.0 ± 0.5 μm.
The resin fine particle dispersion (1) was dried under reduced pressure at 30 ° C. using a vacuum dryer to obtain resin fine particles (1).
95 parts by mass of the toner base particles A, 5 parts by mass of the resin fine particles (1), 0.3 parts by mass of hydrophobic silica, and 0.3 parts by mass of titanium oxide are stirred and mixed using a Henschel mixer (stirring speed: 2000 rpm). The toner of Example 1 (ground toner) was obtained for 5 times for 30 seconds. When the obtained toner was observed with an SEM, it was confirmed that a crystalline resin adhered to the particle surface.
The developer of Example 1 was prepared by stirring 2.5 parts by mass of the toner of Example 1 and 97.5 parts by mass of a silicon-coated ferrite carrier (core particle diameter: 45 μm) with a Turbler mixer. The toner or developer of Example 1 was evaluated as described below, and the results are shown in Table 3.
[0209]
(Example 2)
-Resin fine particle formation process-
--Formation of core--
The core dispersion (C2) was prepared.
--Formation of shell--
The resin fine particle dispersion (1) was prepared.
[0210]
-Toner generation process-
-Preparation of aqueous phase-
990 parts by weight of water, 83 parts by weight of the resin fine particle dispersion (1), 37 parts by weight of an aqueous solution of 48.5% by weight of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 90 parts by mass were mixed and stirred to obtain a milky white liquid (aqueous phase).
[0211]
--Synthesis of low molecular weight polyester--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride A low molecular weight polyester was synthesized by charging 22 parts by mass of an acid and 2 parts by mass of dibutyltin oxide and reacting at 230 ° C. for 5 hours under normal pressure.
The obtained low molecular weight polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., and an acid value of 0.5 mgKOH / g. The hydroxyl value was 51.
[0212]
--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts by mass of the low molecular weight polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged and reacted at 100 ° C. for 5 hours. A prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.
[0213]
--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen group-containing compound) was 418.
[0214]
-Preparation of masterbatch (MB)-
1200 parts by mass of water, 540 parts by mass of carbon black (“Printex 35”; manufactured by Dexa, DBP oil absorption = 42 ml / 100 mg, pH = 9.5) as a colorant, and 1200 parts by mass of the polyester resin (1) It mixed with the mixer (made by Mitsui Mining). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.
[0215]
-Preparation of organic solvent phase-
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and 947 parts by mass of ethyl acetate was charged, and the temperature was raised to 80 ° C. with stirring. Next, 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carbon black and carnauba wax were dispersed by three passes under the condition of 80% by volume of beads. Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion. An organic solvent phase (pigment / wax dispersion) was prepared by passing through a bead mill under the same conditions as described above for dispersion.
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.
[0216]
--Emulsification / Dispersion--
Into a reaction vessel, 749 parts by mass of the organic solvent phase, 115 parts by mass of the prepolymer, and 2.9 parts by mass of the ketimine compound were charged, and 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika). After mixing for 1 minute, 1200 parts by mass of the aqueous phase was added to the reaction vessel, and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 13,000 rpm for 20 minutes. Prepared.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersed slurry had a volume average particle size of 5.86 μm and a number average particle size of 5.11 μm as measured by Multisizer II (manufactured by Beckman Coulter, Inc.).
[0217]
-Washing process-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. 100 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a TK type homomixer (at 12,000 rpm for 10 minutes), and then filtered under reduced pressure. 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, it mixed with TK type homomixer (10 minutes at 12,000 rpm), and then filtered. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, it mixed with TK type homomixer (10 minutes at 12,000 rpm), and then filtered. Add 300 parts by mass of ion-exchanged water to the filter cake obtained here, mix it with a TK homomixer (10 minutes at 12,000 rpm), and then filter twice to obtain the final filter cake. It was. The final filter cake thus obtained was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having a mesh size of 75 μm, whereby toner base particles of Example 2 were obtained.
[0218]
-External additive treatment-
2.5 parts by mass of the toner base particles obtained in Example 1 and 97.5 parts by mass of a silicone ferrite carrier (core particle size: 45 μm) as an external additive were used as a tumbler mixer (manufactured by Shinmaru Enterprises Co., Ltd. +). The toner of Example 2 was manufactured by stirring. The toner of Example 2 was evaluated in the same manner as in Example 1. The results are shown in Table 3.
[0219]
(Example 3)
In Example 2, the toner of Example 3 was produced in the same manner as in Example 2 except that the resin fine particle 1 was replaced with the resin fine particle 2, and the same evaluation as in Example 2 was performed on the toner. The results are shown in Table 3.
[0220]
Example 4
In Example 2, the toner of Example 4 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 3. The toner was evaluated in the same manner as in Example 2. The results are shown in Table 3.
[0221]
(Example 5)
In Example 2, the toner of Example 5 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 4. The toner was evaluated in the same manner as in Example 2. The results are shown in Table 3.
[0222]
(Example 6)
In Example 2, the toner of Example 6 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 5. The toner was evaluated in the same manner as in Example 2. The results are shown in Table 3.
[0223]
(Example 7)
A toner of Comparative Example 2 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 6 in Example 2, and the same evaluation as in Example 2 was performed on the toner. The results are shown in Table 3.
[0224]
(Example 8)
In Example 2, the toner of Example 8 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 7. The toner was evaluated in the same manner as in Example 2. The results are shown in Table 3.
[0225]
Example 9
In Example 2, the toner of Example 9 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 8. The toner was evaluated in the same manner as in Example 2. The results are shown in Table 3.
[0226]
(Comparative Example 1)
A toner of Comparative Example 1 was produced in the same manner as in Example 1 except that the resin fine particles 1 were replaced with the resin fine particles 9 in Example 1, and the same evaluation as in Example 1 was performed on the toner. The results are shown in Table 3.
[0227]
(Comparative Example 2)
The toner of Comparative Example 2 was produced in the same manner as in Example 2 except that the resin fine particles 1 were replaced with the resin fine particles 9 in Example 2, and the same evaluation as in Example 2 was performed on the toner. The results are shown in Table 3.
[0228]
<Fixability>
Teflon as fixing roller ^(R) Using a device in which the fixing unit of RICOH Co., Ltd. MF2200 Co., Ltd. using a roller was modified, type 6200 paper manufactured by RICOH was set on this and a copying test was performed. The results at this time are shown in Table 3.
The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset temperature resistance) were determined by changing the fixing temperature. The conventional fixing minimum temperature of the low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear velocity is 120 to 150 mm / sec, and the surface pressure is 1.2 kgf / cm. ² The evaluation conditions for the nip width 3 mm and hot offset were as follows: the paper feed linear velocity was 50 mm / sec, and the surface pressure was 2.0 kgf / cm ² The nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.
[0229]
(1) Low-temperature fixability (5-level evaluation)
5 ... Less than 120 ° C
4 ... More than 120 ℃ and 140 ℃ or less
3 ... More than 140 ℃ and less than 150 ℃
2 ... Over 150 ° C and below 160 ° C
1 ... over 160 ° C
[0230]
▲ 2 ▼ Hot offset property (5-level evaluation)
5 ... 201 ° C or higher
4 ... 200-191 ° C
3 ... 190-181 ° C
2 ... 180-171 ° C
1 ... 170 ℃ or less
[0231]
<Heat preservation>
Each toner obtained in Examples and Comparative Examples was filled in a glass container and left in a constant temperature bath at 55 ° C. for 24 hours. The toner was cooled to 24 ° C., a penetration test (JIS K2235-1991) was performed, and the penetration was measured. A toner having a larger value means better heat storage stability. If this value is less than 15 mm, there is a high possibility of problems in use. In addition, the criteria for determining the heat preservation property based on the penetration are as follows.
5 ... Penetration
4 ... 25mm or more
3 ... 20-25mm
2 ... 15-20mm
1 ... less than 15mm
[0232]
<Resolution>
A developer is set in MF-2200 manufactured by Ricoh Co., Ltd., and a 1-dot independent halftone dot image of 600 dots / inch and 150 line / inch is output in the main scanning and sub-scanning directions in an environment of normal temperature / normal humidity. Dot loss and image density unevenness were visually evaluated in the following four stages.
4 ... very good
3 ... Good
2 ... Practical level
1 ... Practical problem level
[0233]
<Durability>
A developer is set in MF-2200 manufactured by Ricoh Co., Ltd., and 100 million continuous images are output in a normal temperature / humidity environment. evaluated.
4 ... No major change in charge amount and image quality compared to the initial stage
3 ... The amount of charge is lower than the initial level, but there is no significant change in image quality
2 ... Level where soiling occurs but there is no practical problem
1 ... Practical level of soiling occurs
[0234]
<Glass transition temperature (Tg)>
Using a TG-DSC system (“TAS-100”; manufactured by Rigaku Corporation), the glass transition temperature (Tg) of the toner was measured by the following method.
First, about 10 mg of each toner was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, and the sample was cooled to room temperature and left for 10 min. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system “TAS-100”, the glass transition temperature (Tg) (Tg) from the contact point of the endothermic curve near the glass transition temperature (Tg) and the base line. ° C) was calculated.
[0235]
<Weight average molecular weight (Mw), number average molecular weight (Mn), said ratio (Mw / Mn)>
After about 1 g of each toner was carefully evaluated in an Erlenmeyer flask, 10-20 g of THF (tetrahydrofuran) was added to obtain a THF sample solution having an adhesive substrate concentration of 5-10%. Next, the column was stabilized in a 40 ° C. heat chamber, and THF as a solvent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution was injected. The molecular weight of the sample was calculated from the relationship between the retention time and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. The calibration curve is prepared using a polystyrene standard sample. The above-mentioned monodisperse polystyrene standard sample, detector, column, etc. were used.
[0236]
<Toner particle size>
The volume average particle diameter (Dv) and number average particle diameter (Dn) of each toner were measured with a particle size measuring device (“Coulter Counter TAII”; manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. From these results, (volume average particle diameter (Dv / number average particle diameter (Dn))) was calculated.
[0237]
<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 ml of water from which impure solids had been removed in advance. Next, 0.1 to 0.5 g of each toner was added and dispersed. The obtained dispersion was dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), and the shape and distribution of the toner were measured with the concentration of the dispersion being 3000 to 10,000 / μl. The average circularity was calculated from these measurement results.
[0238]
<Content of resin fine particles>
Using the styrene monomer derived from the resin fine particles of the styrene-acrylic copolymer as a label, the toner was thermally decomposed to measure the amount of the styrene monomer in the thermal decomposition product, and the content of the resin fine particles in the toner was calculated. . That is, resin fine particles of styrene-acrylic copolymer having a known composition are used as labels, and the content of fine resin particles of styrene-acrylic copolymer in the toner particles is 0.01% by mass and 0.10% by mass. %, 1.00% by mass, 3.00% by mass, and 10.0% by mass. Each model toner having a known composition is thermally decomposed under the conditions of 590 ° C. × 12 seconds, and the thermal decomposition products are analyzed according to the following measuring equipment and measurement conditions to obtain the peak area of the styrene monomer for each toner. The content of resin fine particles in the toner was calculated.
[0239]
[Measurement equipment and measurement conditions]
Analytical instrument: Pyrolysis gas chromatograph mass spectrometer
Device body: QR-5000 (manufactured by Shimadzu Corporation)
Accessory pyrolysis furnace: JHP-3S (manufactured by Nippon Analytical Industry)
Thermal decomposition temperature: 590 ° C x 12 seconds
Column: “DB-1”
(L = 30 m ID = 0.25 mm Film = 0.25 μm)
Column temperature: 40 ° C. (holding 2 minutes) to 300 ° C. (temperature raising 10 ° C./min)
Vaporization chamber temperature: 300 ° C
[0240]
[Table 3]

[0241]
As shown in Table 3, with respect to Examples 1 to 8, the evaluation results of the low temperature fixability, the hot offset resistance, the heat resistant storage stability and the resolution were good.
In Comparative Examples 1 and 2, the toner using resin fine particles having no core / shell structure did not have sufficient heat-resistant storage stability.
[0242]
【The invention's effect】
According to the present invention, conventional problems can be solved, excellent properties such as agglomeration resistance, chargeability, fluidity, transferability, and fixability, good hot offset resistance, and excellent heat-resistant storage. That can achieve high image quality with the use of the toner, and a toner that can achieve high image quality with a sharp charge distribution and sharpness, and an efficient manufacturing method thereof, A container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic explanatory view showing an example in which an image forming method of the present invention is carried out by an image forming apparatus of the present invention.
FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention.
FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem type color image forming apparatus) of the present invention.
FIG. 4 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.
[Explanation of symbols]
10 Photoconductor (Photoconductor drum)
10K black photoconductor
Photosensitive body for 10Y yellow
10M photoconductor for magenta
10C Cyan photoreceptor
14 Support roller
15 Support roller
16 Support roller
17 Intermediate transfer cleaning device
18 Image forming means
20 Charging roller
21 Exposure equipment
22 Secondary transfer device
23 Laura
24 Secondary transfer belt
25 Fixing device
26 Fixing belt
27 Pressure belt
28 Sheet reversing device
30 exposure equipment
32 Contact glass
33 First traveling body
34 Second traveling body
35 Imaging lens
36 Reading sensor
40 Developer
41 Development belt
42K developer container
42Y developer container
42M developer container
42C Developer container
43K developer supply roller
43Y developer supply roller
43M Developer supply roller
43C Developer supply roller
44K development roller
44Y Development roller
44M Development roller
44C Development roller
45K black developer
45Y Yellow developer
45M Magenta developer
45C Cyan developer
49 Registration Roller
50 Intermediate transfer member
51 Laura
52 Separation roller
53 Constant current source
55 switching claw
56 Discharge roller
57 Discharge tray
58 Corona charger
60 Cleaning device
61 Developer
62 Transfer charger
63 Photoconductor cleaning device
64 Static eliminator
70 Static elimination lamp
80 Transfer roller
90 Cleaning device
95 Transfer paper
100 Image forming apparatus
120 Tandem development device
130 Document platen
142 Feed roller
143 Paper Bank
144 Paper cassette
145 Separation roller
146 paper feed path
147 Conveying roller
148 paper feed path
150 Copying machine body
200 Feeding table
300 scanner
400 Automatic Document Feeder (ADF)

Claims (9)

A toner having a weight average molecular weight (Mw) of 8,000 to 1,000,000, a particle diameter of 20 to 400 nm, and resin fine particles having a core-shell structure. The toner according to claim 1, wherein the toner is obtained in the form of particles while producing an adhesive base obtained by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. The toner according to claim 1, further comprising resin fine particles on a surface thereof. The toner according to any one of claims 1 to 3, wherein the resin fine particles have a glass transition temperature (Tg) of 35 to 150 ° C. In the resin fine particles, when the glass transition temperature of the resin forming the shell is TgS and the glass transition temperature of the resin forming the core is TgC, the following formula, TgS> TgC is satisfied. The toner described. The toner according to claim 1, wherein the adhesive substrate contains a polyester resin. After the core monomer used to form the core is polymerized to form the core particle, the shell monomer used to form the shell is polymerized on the surface of the core particle, so that the weight average molecular weight ( Mw) is 8,000 to 1,000,000, and the particle diameter is 20 to 400 nm. The resin fine particle forming step of forming resin fine particles having a core-shell structure, the resin fine particles, and active hydrogen groups An adhesive base material production step of obtaining a toner while dispersing and reacting a containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to produce an adhesive base material. A method for producing a toner. A developer comprising the toner according to claim 1. A toner-filled container filled with the toner according to claim 1.

Images