JP4176216B2 - Toner particles containing a mixture of modified linear polymer, cross-linked polymer and wax - Google Patents

Description

【００４９】
［式中、０≦ｘ≦１２、１０≦ｙ≦９０であり、
Ｒ¹は−ＯＨ、−ＣＯＯＨ、−ＣＯＣｌ、−ＮＨ₂、
【００５０】
【化２】

【００５１】
−ＮＣＯ、−Ｏ−ＣＨ₂−ＣＨＯＨ−ＣＨ₂Ｃｌ、−ＣＯＯ−ＣＨ₂−ＣＨＯＨ−ＣＨ₂Ｃｌ及びＣＯＯＭ（Ｍはアルカリ金属イオン）から成る群より選ばれるメンバーであり、Ｒ²はＣＨ₃又はＨ、好ましくはＨであり、Ｒ³はＣ₂Ｈ₅又はＣＨ₃である］
に対応する化合物を用いるのが好ましい。
【００５２】
驚くべきことに、ポリマーＡがポリマー鎖ＬＰＣとＲ¹がＯＨ又はＣＯＯＨであり、ｘ＝０であり、５５≦ｙ≦９０である上記の式Ｉに従う化合物Ｄを反応させることにより製造されるポリマーである樹脂性マトリックスを含む本発明のトナー粒子は、抗−ホット−オフセット性及び溶融状態における流動性の組み合わせに関して非常に優れた結果を与えることが見いだされた。
【００５３】
本発明の非晶質複合巨大分子化合物中の結晶性もしくは結晶化可能末端鎖及び／又は側鎖の形成のために非常に有用な１官能基性ヒドロキシル末端ポリオレフィン性ポリマーの例は、ＵＮＩＬＩＮ ４２５、ＵＮＩＬＩＮ ５５０、ＵＮＩＬＩＮ ７００（４２５，７００という平均分子量を有するポリオレフィン性アルコールに関するＰＥＴＲＯＬＩＴＥ，６９１０ Ｅａｓｔ １４ｔｈ ｓｔｒｅｅｔ，ＴＵＬＳＡ，Ｏｋｌａｈｏｍａ ７４１１２，ＵＳＡの商品名）又は８７５という平均分子量を有するヒドロキシ末端ポリオレフィン性ポリオキシエチレン性巨大分子に関する同じＰＥＴＲＯＬＩＴＥ社の商品名であるＵＮＩＴＨＯＸ ７２０として商業的に入手可能なポリオレフィン性モノアルコールである。１官能基性カルボキシル末端ポリオレフィンの典型的例は、７００という平均分子量を有するポリオレフィン性モノカルボン酸に関するＰＥＴＲＯＬＩＴＥの商品名であるＵＮＩＣＩＤ ７００である。ヒドロキシル基又はカルボキシル基が末端であり、１０００〜２５００の分子量を有するＰＥＴＲＯＬＩＴＥのさらに別の実験的ポリオレフィン性化合物も用いることができる。
【００５４】
さらに、ポリマー鎖ＬＰＣを４００〜１０００の分子量を有する１つの化合物及び１５００〜２５００の分子量を有する１つの化合物という２種類の化合物Ｄと反応させることにより、本発明のトナー粒子中で用いるためのポリマーＡを非常に有益に製造できることが見いだされた。本発明における化合物Ｄの好ましい組み合わせは、７００もしくは１０００という分子量を有するポリオレフィン性アルコール又はポリオレフィン性カルボン酸と分子量２０００のポリオレフィン性アルコール又はポリオレフィン性カルボン酸の組み合わせである。そのようなポリマーは例えばＥＰ−Ａ−７１２ ８８１に開示されている。
【００５５】
該化合物Ｄがポリシロキサンである場合、式：
【００５６】
【化３】

【００５７】
［式中、
Ｘ’は
【００５８】
【化４】

【００５９】
であり、
Ｙ’はＸ’と同じ意味を有するか又は低級（Ｃ１〜Ｃ４）アルキル基を示し、
Ｚ’及びＺ”は同一か又は異なることができ、低級（Ｃ１〜Ｃ４）アルキル基又はアリール基を示し、
２＜ｍ＜３５であり、
１＜ｎ＜６である］
に対応するポリシロキサンを用いるのが好ましい。
【００６０】
上記の一般式に対応するエポキシ末端ポリシロキサン誘導体はＴｈ．Ｇｏｌｄｓｃｈｍｉｄ ＡＧ，Ｅｓｓｅｎ，ＧｅｒｍａｎｙからＴＥＧＯＭＥＲ Ｅ−Ｓｉ２１３０及びＴＥＧＯＭＥＲ Ｅ−Ｓｉ ２３３０という商品名の下に商業的に入手可能である。
【００６１】
該化合物Ｄを該ポリマー鎖（ＬＰＣ）と反応させる場合、用いられるＬＰＣの重量に対して１０〜５０重量％の化合物Ｄを加えるのが好ましい。ポリマーＡ中でポリマー鎖ＬＰＣと化合物Ｄの間のモル比が０．８≦ＬＰＣ／Ｄ≦１．２５であるようなモル比であることも重要である。
【００６２】
本発明のトナー粒子において有用なポリマーＡを形成するためのポリマー鎖の化合物Ｄによる改質は２つの方法により行うことができる：
１．（ｉ）反応容器中でポリマー鎖と少なくとも１種の化合物Ｄを混合し、
（ｉｉ）該混合物を窒素雰囲気下に、撹拌下で１５０℃〜２５０℃に加熱し、
（ｉｉｉ）相の分離がなくなるまで該加熱を続け、
（ｉｖ）冷却し、ポリマーＡを回収する
段階を含む方法。
【００６３】
２．（ｉ）少なくとも１種の化合物Ｄをジカルボン酸、ジオール、もしそのように望まれるならジアミン又はラクタムあるいはそれらの混合物と混合して重縮合混合物を生成させ、
（ｉｉ）もしそのように望まれるなら適した触媒の存在下に、該重縮合混合物を加熱することによりプレポリマーを生成させ、
（ｉｉｉ）所望の粘弾性に達するまでさらにプレポリマーをジオール及び／又はジカルボン酸と反応させ、
（ｉｖ）反応混合物を冷却し、ポリマーＡを回収する
段階を含む方法。
【００６４】
本発明のトナー粒子中で用いるためのポリマーＬＰＣを改質するために好ましい第１の方法は、反応性末端基を有する完成された鎖ポリマーをある量の少なくとも１種の化合物Ｄと混合し、次いで一緒に反応させる方法である。第２の方法の場合、少なくとも１種の化合物Ｄがポリマー鎖（ＬＰＣ）の生成のための試薬と混合され、本発明のトナー粒子において有用なポリマーＡが１容器合成において直接得られる。
【００６５】
樹脂性マトリックス中のポリマーＢは分枝鎖状もしくは部分的に架橋されたポリマーであり、それは例えばポリイソシアナートとの反応により部分的に架橋された遊離のヒドロキシル又はカルボキシル基を有する付加ポリマーであることができる。それは１〜１０モル％のジビニルベンゼン又はエチレングリコールジアクリレート又はエチレングリコールジメタクリレートから誘導される部分を含むスチレン、アクリレート又はメタクリレートコポリマーであることができる。
【００６６】
ポリマーＢは好ましくは分枝鎖状ポリエステルである。分枝鎖状ポリエステルの製造のために、例えばトリメリト酸などのポリカルボン酸又は例えばトリメチロールプロパン、グルセロール、ペンタエリトリトールなどのポリヒドロキシ化合物を用いることができる。興味深い分枝鎖状ポリエステルはＤＩＡＮＯＬ ２２（ジ−エトキシル化ビスフェノールＡ）、ＤＩＡＮＯＬ ３３（ジ−プロポキシル化ビスフェノールＡ）、テレフタル酸及びトリメリト酸の重縮合により製造されるポリエステルである。ＤＩＡＮＯＬ ２２及びＤＩＡＮＯＬ ３３はオランダのＡＫＺＯ ＣＨＥＭＩＥの商品名である。本発明において用いる場合、ポリマーＢは好ましくは１〜１０モルパーセントの多官能基性モノマーから誘導される部分を含む分枝鎖状ポリエステルである。ポリマーＢは好ましくは１２０℃及び１００ｒａｄ／秒で測定される場合の１〜２．５というｔｇδを有する。本発明のトナー粒子中で用いるためのポリマーＢは４５℃より高い、好ましくは５０℃より高いＴｇ及び１９〜２２Ｊ^1/2／ｃｍ^3/2のヒルデブランド溶解パラメーターを有するのが好ましい。
【００６７】
本発明で用いるための化合物Ｃは以下を包含することができる。それは脂肪族炭化水素ワックス類、例えば低分子量ポリエチレン、低分子量ポリプロピレン、微結晶性ワックス及びパラフィンワックス、脂肪族炭化水素ワックス類の酸化物、例えばポリエチレンワックス酸化物及びそれらのブロックコポリマー；主に脂肪酸エステルから成るワックス類、例えばカルナウバワックス及びモンタン酸エステルワックス；ならびに脂肪酸エステルの一部又は全部を脱酸素化することにより得られるもの、例えば脱酸素化カルナウバワックスを包含することができる。それは飽和直鎖状脂肪酸、例えばパルミチン酸、ステアリン酸及びモンタン酸；不飽和脂肪酸、例えばブラシジン酸、オレオステアリン酸及びパチナチン酸（ｐａｔｉｎａｔｉｃ ａｃｉｄ）；飽和アルコール類、例えばステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール及びメリシルアルコール；多価アルコール、例えばソルビトール；脂肪酸アミド類、例えばリノレン酸アミド、オレイン酸アミド及びラウリン酸アミド；飽和脂肪酸ビスアミド類、例えばメチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド及びヘキサメチレンビスステアリン酸アミド；不飽和脂肪酸アミド類、例えばエチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、Ｎ，Ｎ’−ジオレイルアジピン酸アミド及びＮ，Ｎ’−ジオレイルセバシン酸アミド；芳香族ビスアミド類、例えばｍ−キシレンビスステアリン酸アミド及びＮ，Ｎ’−ジステアリルイソフタル酸アミド；脂肪酸金属塩（通常金属石鹸と呼ばれる）、例えばステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛及びステアリン酸マグネシウム；脂肪酸炭化水素ワックス中にスチレン又はアクリル酸などのビニルモノマーをグラフトすることにより得られるワックス類；多価アルコールを用いる脂肪酸の部分的エステル化生成物、例えばベヘン酸モノグリセリド；ならびに植物脂肪及び油の水素化により得られるヒドロキシル基を有するモノメチルエステル化合物も包含することができる。
【００６８】
本発明のトナー粒子の樹脂性マトリックスにおいて有用な化合物Ｃの例は、Ｍｉｔｓｕｉ Ｐｅｔｒｏｃｈｅｍｉｃａｌ Ｉｎｄｕｓｔｒｉｅｓ，Ｌｔｄ ＪａｐａｎからＭＩＴＳＵＩ ＨＩ−ＷＡＸ １００Ｐ、ＭＩＴＳＵＩ ＨＩ−ＷＡＸ １１０Ｐ、ＭＩＴＳＵＩ ＨＩ−ＷＡＸ １１０５Ａ、ＭＩＴＳＵＩ ＨＩ−ＷＡＸ １１２０Ｈなどの商品名の下にあるいはＨｏｅｃｈｔｓ，ＧｅｒｍａｎｙからＨＯＥＣＨＳＴ−ＷＡＣＨＳ Ｕ、ＨＯＥＣＨＳＴ−ＷＡＣＨＳ ＰＥ５２０、ＨＯＥＣＨＳＴ−ＷＡＣＨＳ ＰＥ１３０、ＨＯＥＣＨＳＴ−ＷＡＣＨＳ ＰＥＤ１２１などの商品名の下に商業的に入手可能なワックス類である。
【００６９】
化合物Ｃは好ましくは４００〜２，５００の分子量、より好ましくは５００〜１，６００の分子量を有する。
【００７０】
本発明の樹脂性マトリックスを有する乾燥トナー粒子のためには、このマトリックス中に１種より多い化合物Ｃが存在するのが有益である。化合物Ｃをその融点Ｍ_pC及びその軟化点Ｔ_sCに関して注意深く選択するとにより、樹脂性マトリックスが組み込まれたトナー粒子の抗−ホット−オフセット性、物理的強度及び溶融状態における流動性を微調整することができる。
【００７１】
本発明で用いるための化合物Ｃは分子量、融点Ｍ_pC及びその軟化点Ｔ_sC及びそのヒルデブランド溶解パラメーターδ_Cに基づいて選択される。これらの値が上記の値の範囲内である時、すなわちＭ_p≦Ｔ_sB＋１０、好ましくはＭ_p≦Ｔ_sB＋５であり、ここでＴ_sBはポリマーＢの軟化点である時そしてＴ_sC≦Ｔ_sB＋２０、好ましくはＴ_sC≦Ｔ_sB＋１５であり、δ_Cが１５〜１９Ｊ^1/2／ｃｍ^3/2である時、トナー粒子に所望の性質を与える樹脂性マトリックスのみでなく、化合物Ｃ（又は１種より多い化合物Ｃ）が非常に均一に分配されている樹脂性マトリックスも製造することができる。樹脂性マトリックス中における化合物Ｃの分配の均一性は該マトリックスの試料をガラス板上で溶融させ、偏光顕微鏡下で溶融試料を観察することにより調べられる。この方法によりポリマーＡ、Ｂ及び化合物Ｃの配合物（すなわちいくつかの樹脂性マトリックス）をその質に従って評価することができる。いずれの場合も樹脂性マトリックス中における化合物Ｃの優れた分散を得るために、ポリマーＡ及び化合物Ｃが１〜１０、好ましくは２〜５の重量比で存在するのが好ましい。化合物Ｃは好ましくは本発明の樹脂性マトリックス中で２〜８重量（ｗｔ／ｗｔ）％の量で、より好ましくは４〜６％ｗｔ／ｗｔの量で存在する。
【００７２】
本発明のトナー粒子は当該技術分野において既知のいずれの方法によっても製造することができるが、用いられる化合物Ｃの融点Ｍ_pより高い温度における溶融混練法により本発明のトナー粒子を製造するのが好ましい。１種より多い化合物Ｃが用いられる場合、溶融混練法は好ましくは化合物Ｃの最も高い融点より高い温度で好適に行われる。かくして本発明は：
−反応性末端基を有するポリマー鎖（ＬＰＣ）ならびに反応性末端基を有し、炭素数が２０〜２５０である長鎖脂肪族化合物及びポリシロキサンから成る群より選ばれる長鎖化合物Ｄを反応させることにより製造されるポリマーであるポリマーＡであり、ポリマーＡ中のＬＰＣ／Ｄのモル分率が０．８≦ＬＰＣ／Ｄ≦１．２５であるようなモル分率であるポリマーＡを、１２０℃及び１００ｒａｄ／秒において測定される１．０≦ｔｇδ≦２．５であるような粘弾性損失ｔｇδ、１１０℃≦Ｔ_sB≦１３５℃であるような軟化点Ｔ_sBを有するポリマーＢならびに８５℃≦Ｍ_p≦１３５℃であり、Ｍ_p≦Ｔ_sB＋１０であるような融点Ｍ_p及びＴ_sC≦Ｔ_sB＋２０℃であるような軟化点Ｔ_sC、１５Ｊ^1/2／ｃｍ^3/2≦δ_C≦１９Ｊ^1/2／ｃｍ^3/2であるようなヒルデブランド溶解パラメーターδ_Cを有する少なくとも１種の化合物Ｃと混合し、ポリマーＡ、ポリマーＢ及び少なくとも１種の化合物Ｃの混合物を生成させ、
−該融点ＭＣ_pより高い温度で該混合物を溶融混練し、
−該溶融混練された混合物を冷却する
段階を含む乾燥トナー粒子の製造のための方法も包含する。
【００７３】
本発明は：
−該ポリマーＡを少なくとも１種の該化合物Ｃと混合し、
−該融点Ｍ_pより高い温度で該混合物を溶融混練し、
−該混合物に該ポリマーＢを加え、溶融混練を続け、
−該溶融混練された混合物を冷却する
段階を含む乾燥トナー粒子の製造のための方法も含む。
【００７４】
後者の方法の場合、ポリマーＡ及び化合物Ｃが化合物Ｃの融点より高い温度で溶融混練されたら、ポリマーＢの添加の後に高められた温度における溶融混練を続ける必要はない。
【００７５】
本発明の樹脂性マトリックスを含むトナー粒子はいずれの通常のトナー成分、例えば電荷調節剤、着色及び黒の両方の顔料、無機充填剤、微細磁性材料などをも含むことができる。トナー粒子において有用な電荷調節剤、顔料及び他の添加剤の記載は例えばＥＰ Ａ ６０１ ２３５に見いだすことができる。
【００７６】
本発明の樹脂性マトリックスを含むトナー粒子は、多成分乾燥現像薬中で用いられる場合、いずれの既知の担体材料と混合することもできる。適した担体粒子は、例えばＥＰ−Ａ−２８９ ６６３；ＥＰ−Ａ−５５９ ２５０；ＥＰ−Ａ−６５６ １３０及び１９９７年８月２０日出願のヨーロッパ出願９７２０２５５１に開示されているような担体粒子である。例えば疎水化されたシリカなどの既知の流動性向上剤を該トナー粒子と混合することができる。トナー粒子は単成分乾燥現像薬（磁性及び非−磁性の両方）として用いられることができるか又は担体粒子と混合して多成分現像薬を形成することができる。
【００７７】
本発明の樹脂性マトリックスを含むトナー粒子は、１〜５０μｍ、好ましくは３〜２０μｍ、より好ましくは３〜１０μｍの体積平均直径を有することができる。該トナー粒子の粒度分布はいずれの型のものであることもできる。しかし０．５より小さい、より好ましくは０．３の変動係数（平均で割った標準偏差）（Ｖ）の数又は体積のいずれかによるガウス粒度分布又は正規粒度分布を有するのがより好ましい。トナー粒子はいずれの形を有していることもでき、粒子は不規則、丸形などであることができる。
【００７８】
本発明のトナー粒子は、定着が「接触溶融」ステーションで行われ、ホット−オフセットを防ぐために非常に少量の外部剥離剤が溶融ステーションの被加熱ローラーに適用される静電記録又は磁気記録画像形成法において用いられるために特に有用である。かくして本発明のトナー粒子は：
−該トナー粒子を最終的受像基質に画像通りに適用し、
−Ｓｉ−原子を有する表面を有する加熱されたローラーを含む溶融ステーションで該トナー粒子を該基質に定着させる
段階を含み、
−該加熱されたローラー上の該表面上に外部剥離剤を、最高で１６０ｍｇ／ｍ²の剥離剤が該基質に適用されるような量で加える
ことを特徴とする乾燥トナー粒子を用いる画像形成法において用いられる。該量は好ましくは最高で８０ｍｇ／ｍ²の剥離剤が該基質に適用されるような量、より好ましくは最高で４０ｍｇ／ｍ²が適用されるような量である。
【００７９】
該量の剥離剤は好ましくはＴｈｅ Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ＩＳ＆Ｔ’ｓ Ｅｌｅｖｅｎｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｇｒｅｓｓ ｏｎ Ａｄｖａｎｃｅｓ ｉｎ Ｎｏｎ−Ｉｍｐａｃｔ Ｐｒｉｎｔｉｎｇ Ｔｅｃｈｎｏｌｏｇｉｅｓ，ｐａｇｅ ２１９−２２２におけるＲ．Ｂｕｃｈｅｒ ｅｔ ａｌ．による“Ｉｎｎｏｖａｔｉｖｅ Ｒｅｌｅａｓｅ Ａｇｅｎｔ Ｄｅｌｉｖｅｒｙ Ｓｙｓｔｅｍｓ”という標題の文献に記載されているようなＮＯＭＥＸ−フェルト（ＮＯＭＥＸはＤｕ Ｐｏｎｔ ｄｅ Ｎｅｍｏｕｒｓ，Ｗｉｌｍｉｎｇｔｏｎ，ＵＳの商品名である）の表面を有する供給ローラーにより被加熱ローラーに適用される。この会議はＨｉｌｔｏｎ Ｈｅａｄにおいて２９．１０．９５から０３．１１．９５に開かれた。会議録はＩＳ＆Ｔ，Ｓｐｒｉｎｇｆｉｅｌｄ，ＵＳ １９９５により出版されている。そのようなローラーを用いると、典型的にｍ²当たり１〜１０ｍｇの外部剥離剤が適用される。かくして本発明のトナー粒子を用い、１〜１０ｍｇ／ｍ²の外部剥離剤しか適用されなくてもホット−オフセットに伴う問題なしで接触溶融を行うことができる。
【００８０】
被加熱ローラーを有する「接触溶融」ステーションが組み込まれた画像形成法であり、外部剥離剤が被加熱ローラーに適用されない（本文書の目的の場合、外部剥離剤を適用しないことは、それが１ｍｇ／ｍ²未満であることを意味する）方法において本発明のトナー粒子を用いることさえ原則的に可能である。
【００８１】
被加熱ローラーは当該技術分野において既知のいずれの材料から作られていることもできるが、好ましくはＳｉ−原子を含有する化合物及びＦ−原子を含有する化合物から成る群より選ばれる化合物を含む表面を有する被加熱ローラーであることができる。表面にＳｉ−原子を含有する化合物及びＦ−原子を含有する化合物の両方を有する表面を持つローラーならびに表面にＦ−原子を有する化合物を含むがＳｉ−原子を有する化合物を含まないローラーは本発明のトナー粒子の定着に非常に適している。
【００８２】
【実施例】
改質剤ＤによるポリマーＬＰＣの改質
１．ポリマーＡ１の製造
ＡＴＬＡＣ Ｔ５００（酸価 ２０、Ｍ_w＝１２，０００、Ｍ_n＝４，０００、１００℃のＴ_sp、１２０℃及び１００ｒａｄ／秒においてｔｇδ＝７ならびに２０Ｊ^1/2／ｃｍ^3/2のヒルデブランド値）という商品名の下に販売されている市販の線状ポリエステルである７０重量（ｗｔ／ｗｔ）部のポリマー鎖（ＬＰＣ）ならびに１０部ｗｔ／ｗｔのＵＮＩＬＩＮ７００（片側の末端が−ＣＨ₃基であり、他の末端がＨＯ−基である−ＣＨ₂−ＣＨ₂−基から成り、７００の平均分子量及び１７Ｊ^1/2／ｃｍ^3/2のヒルデブランド値を有する１官能基性ポリオレフィン性分子）ならびに分子量Ｍｗ＝２０００であり、ヒルデブランド値が１７Ｊ^1/2／ｃｍ^3/2である２０部ｗｔ／ｗｔの実験的同族体を反応容器中で混合した。かくして１種のＬＰＣと共に２種の化合物Ｄが存在した。混合物を２４５℃に３０分間加熱し、反応混合物を介して泡立てられる窒素流により撹拌した。この反応時間の間、反応により生成する水を蒸留して除いた。これは重量平均分子量Ｍ_wが約１２，０００のポリマーＡ１を与えた。
【００８３】
２．ポリマーＡ２の製造
ビス−プロポキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン（Ａ）、ビス−エトキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン（Ｂ）、テレフタル酸（Ｃ）及びトリメリト酸（Ｄ）から作られ、Ａ／Ｂ＝７０モル％／３０モル％、Ｃ／Ｄ＝６０モル％／４０モル％及びＡ＋Ｂ／Ｃ＋Ｄ＝１００モル％／７０モル％であるポリエステルである（このポリエステルは３０という酸価、Ｍ_w＝１４，０００、Ｍ_n＝２，０００、１０５℃というＴ_sp、１２０℃及び１００ｒａｄ／秒においてｔｇδ＝４．５及び２０Ｊ^1/2／ｃｍ^3/2というヒルデブランド値を有する）である７０重量（ｗｔ／ｗｔ）部のポリマー鎖（ＬＰＣ）ならびに１０部ｗｔ／ｗｔのＵＮＩＬＩＮ７００（片側の末端が−ＣＨ₃基であり、他の末端がＨＯ−基である−ＣＨ₂−ＣＨ₂−基から成り、７００の平均分子量及び１７Ｊ^1/2／ｃｍ^3/2のヒルデブランド値を有する１官能基性ポリオレフィン性分子）ならびに分子量Ｍｗ＝２０００であり、ヒルデブランド値が１７Ｊ^1/2／ｃｍ^3/2である２０部ｗｔ／ｗｔの実験的同族体を反応容器中で混合した。かくして１種のＬＰＣと共に２種の化合物Ｄが存在した。混合物を２４５℃に３０分間加熱し、反応混合物を介して泡立てられる窒素流により撹拌した。この反応時間の間、反応により生成する水を蒸留して除いた。これは重量平均分子量Ｍ_wが約１２，０００のポリマーＡ２を与えた。
【００８４】
トナー粒子の製造
トナー粒子ＴＯＮ１
６０部ｗｔ／ｗｔの上記のポリマーＡ１を、ビス−エトキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン、ビス−プロポキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン、テレフタル酸及びトリメリト酸の架橋されたポリエステルであり、１１８℃という軟化点、１２０℃及び１００ｒａｄ／秒におけるｔｇδ＝２及び２０Ｊ^1/2／ｃｍ^3/2というヒルデブランド溶解因子を有する３０重量部のポリマーＢと混合した。この混合物に３重量部のシアンＣｕ−フタロシアニン顔料ならびに約２，０００という分子量、ＤＳＣにより決定される１２２℃という融点及びＪＩＳＫ２２０７試験法により決定される１３０℃という軟化点及び１６Ｊ^1/2／ｃｍ^3/2というヒルデブランド溶解因子を有する７重量部のポリオレフィンワックスを加えた。
【００８５】
混合物を１３０℃において溶融均一化し、冷却し、粉砕し、分類し、ＣＯＵＬＴＥＲ ＣＯＵＮＴＥＲ（商品名）により決定される８．５μｍという体積平均直径ｄ_v50及び６．３μｍという数平均直径ｄ_n50を有するシアントナー粒子を得た。
【００８６】
トナー粒子ＴＯＮ２
６０部ｗｔ／ｗｔの上記のポリマーＡ２を、ビス−エトキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン、ビス−プロポキシル化２，２−ビス（４−ヒドロキシフェニル）プロパン、テレフタル酸及びトリメリト酸の架橋されたポリエステルであり、１１８℃という軟化点、１２０℃及び１００ｒａｄ／秒におけるｔｇδ＝２及び２０Ｊ^1/2／ｃｍ^3/2というヒルデブランド溶解因子を有する３０重量部のポリマーＢと混合した。この混合物に３重量部のシアンＣｕ−フタロシアニン顔料ならびに約２，０００という分子量、ＤＳＣにより決定される１２２℃という融点及びＪＩＳＫ２２０７試験法により決定される１３０℃という軟化点及び１６Ｊ^1/2／ｃｍ^3/2というヒルデブランド溶解因子を有する７重量部のポリオレフィンワックスを加えた。
【００８７】
混合物を１３０℃において溶融均一化し、冷却し、粉砕し、分類し、ＣＯＵＬＴＥＲ ＣＯＵＮＴＥＲ（商品名）により決定される８．５μｍという体積平均直径ｄ_v50及び６．３μｍという数平均直径ｄ_n50を有するシアントナー粒子を得た。
【００８８】
トナー粒子ＴＯＮ３
ポリマー鎖（ＬＰＣ）が改質されないことを除いてトナー粒子ＴＯＮ１の製造を繰り返した。
【００８９】
トナー粒子ＴＯＮ４
ワックスを加えないことを除いてトナー粒子ＴＯＮ３の製造を繰り返した。
【００９０】
トナー粒子ＴＯＮ５
ワックスを加えないことを除いてトナー粒子ＴＯＮ１の製造を繰り返した。
【００９１】
現像薬の製造
それぞれのトナー粒子（ＴＯＮ１〜ＴＯＮ５）を用い、０．５％（ｗｔ／ｗｔ）のＡＥＲＯＳＩＬ Ｒ９７２ ５（疎水性シリカに関するＤｅｇｕｓｓａ，Ｇｅｒｍａｎｙの商品名）を加え、５％ｗｔ／ｗｔのこのトナー粒子とシリカの混合物を５０μｍという体積平均粒径ｄ_v50を有するシリコーン−コーテッドフェライト担体粒子と混合することにより現像薬を製造した。
【００９２】
印刷及び定着実施例
ＸＣ３０５カラーコピー機（Ａｇｆａ−Ｇｅｖａｅｒｔ Ｎ．Ｖ，Ｍｏｒｔｓｅｌ，Ｂｅｌｇｉｕｍの商品名）において現像薬を用い、紙基質上に画像を形成した。画像はｃｍ２当たり１ｍｇのトナーを含有した。画像を被加熱ローラーを含む４種類の「接触溶融」ステーションＡ〜Ｄにおいて定着した。ある程度の修正をして基本的に該ＸＣ３０５カラーコピー機の溶融装置を用いた。標準設計においてこの装置の溶融ステーションは典型的５〜６ｍｍ接触領域を示す二重シリコーンコーテッドローラー対を含む。温度設定は１６０〜１７５℃の範囲内で可変とし、温度を実施例における可変パラメーターとした。すべての実施例において、溶融は装置の標準設計の速度及び圧力の条件下で行った。
【００９３】
溶融ステーションＡ：
通常ＤＩＮ Ａ４ページ上にコピー当たり４０〜８０ｍｇのシリコーン油（すなわち６４０〜１，２８０ｍｇ／ｍ²）を供給する標準的給油装置、すべてのこすり取り装置及び清浄化ウェブを溶融ステーションから取り除いた。被加熱ローラーはシリコーン表面を有し、５，０００コピーという寿命を有するローラーであった。この溶融ステーションでは、被加熱ローラー上で外部剥離剤を用いずに接触溶融を行った。
【００９４】
溶融ステーションＢ
５０，０００コピーの寿命を有する被加熱ローラーを用いる以外は溶融ステーションＡの場合と同じ構成を用いた。この溶融ステーションでも、被加熱ローラー上で外部剥離剤を用いずに接触溶融を行った。
【００９５】
溶融ステーションＣ
被加熱ローラー上で少量の外部剥離剤（シリコーン油）を被加熱ローラーに適用する以外は溶融ステーションＢの場合と同じ構成を用いた。被加熱ローラーに送達されるべきシリコーン油の量は、画像上にｍ²当たり１．６ｍｇのシリコーン油がもたらされるように調整した。これは通常より４０〜８０倍少ない。シリコーン油は、Ｔｈｅ ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ ＩＳ＆Ｔ’ｓ Ｅｌｅｖｅｎｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｇｒｅｓｓ ｏｎ Ａｄｖａｎｃｅｓ ｉｎ Ｎｏｎ−Ｉｍｐａｃｔ Ｐｒｉｎｔｉｎｇ Ｔｅｃｈｎｏｌｏｇｉｅｓ，ｐａｇｅ ２１９−２２２におけるＲ．Ｂｕｃｈｅｒ ｅｔ ａｌ．による“Ｉｎｎｏｖａｔｉｖｅ Ｒｅｌｅａｓｅ Ａｇｅｎｔ ＤｅｌｉｖｅｒｙＳｙｓｔｅｍｓ”という標題の文献に記載されているようなＮＯＭＥＸ−フェルト（ＮＯＭＥＸはＤｕ Ｐｏｎｔ ｄｅ Ｎｅｍｏｕｒｓ，Ｗｉｌｍｉｎｇｔｏｎ，ＵＳの商品名である）の表面を有する供給ローラーにより被加熱ローラーに適用された。この会議はＨｉｌｔｏｎ Ｈｅａｄにおいて２９．１０．９５から０３．１１．９５に開かれた。会議録はＩＳ＆Ｔ，Ｓｐｒｉｎｇｆｉｅｌｄ，ＵＳ １９９５により出版されている。
【００９６】
溶融ステーションＤ：
純粋なシリコーン表面を有するローラーの代わりにシリコーン、ポリフルオロアクリレート表面を有するローラーを用いる以外は溶融ステーションＣの場合と同じ構成を用いた。これらのローラーは引っ掻き傷に対して非常に抵抗性であり、約５００，０００コピーという寿命を有する。しかし該ローラーは比較的高い表面エネルギーを有し、シリコーン表面を有するローラーより容易にホット−オフセットを引き起こし得る。
【００９７】
溶融ステーションのそれぞれに関して定着ウィンドウを決定した。最初に定着が適切に成される定着温度をＴ１の記号で表した。これは種々のトナーを用いて画像を印刷し、種々の温度で画像を定着し、得られる定着の質を４つの課題について評価することにより査定して行った：
画像の質：視覚検査
滑らかさ：視覚検査
感触：画像の表面の感触
トナー付着性：プラスチックナイフを用いて手動でトナーを引っ掻き取る。
【００９８】
評価は課題のそれぞれに関して４〜１の尺度で行い、４は優であり、３は良であり、２は境界的であり、１は許容不可であった。画像が上記の課題のそれぞれに関して少なくとも３の採点を得た場合に定着は適切であると理解した。その画像の定着温度を温度Ｔ１とした。
【００９９】
次いでさらにもっと高い温度で定着を行い、ホット−オフセットの最初の兆候が発生する温度Ｔ２を記した。Ｔ２からＴ１を引き去ることにより定着ウィンドウを決定し、℃で示す。定着ステーションＡ及びＢの両方は外部剥離剤なしで運転され、定着ステーションＣ及びＤは少量の外部剥離剤を用いて運転されたので、定着ステーションＡ及びＢで得られるそれぞれのトナー粒子ＴＯＮ１〜ＴＯＮ５に関する定着ウィンドウを平均して外部剥離剤が存在しない場合の定着ウィンドウに関する１つの数字を得、同様に定着ステーションＣ及びＤで得られるそれぞれのトナー粒子ＴＯＮ１〜ＴＯＮ５に関する定着ウィンドウを平均し、いくらかの外部剥離剤が存在する場合の定着ウィンドウに関する１つの数字を得た。これらの数字を表１にまとめる。
【０１００】
【表１】

【０１０１】
表１
本発明のトナー粒子であるトナー粒子ＴＯＮ１及びＴＯＮ２が最も良い結果：最も広い定着ウィンドウ及び最も良い画像の質を与えることが明らかである。
【０１０２】
ポリマー鎖ＬＰＣが化合物Ｄにより改質されていないことを除いてトナー粒子ＴＯＮ１に等しく、かくして本発明のトナー粒子でないトナー粒子ＴＯＮ３は、より狭い定着ウィンドウを与えた。
【０１０３】
他の２つの本発明でないトナー粒子（ＴＯＮ４及びＴＯＮ５）は明らかに不満足な結果を与えた。
【０１０４】
本発明の主たる特徴及び態様は以下の通りである。
【０１０５】
１．樹脂性マトリックス及びワックスを含む乾燥トナー粒子であって、
該樹脂性マトリックスが
２，０００〜２０，０００の重量平均分子量（Ｍｗ）、１２０℃及び１００ｒａｄ／秒におけるｔｇδ＞３ならびに９０℃≦Ｔ_sLPC≦１２０℃であるような低い軟化点Ｔ_sLPCを有し、反応性末端基を有し且つ炭素数が２０〜２５０の長鎖脂肪族化合物及びポリシロキサンから成る群より選ばれる改質剤（Ｄ）により改質されてポリマーＡを形成しており、該改質剤及び該ポリマーが０．８〜１．２５のモル比ＬＰＣ／Ｄで存在しているポリマー（ＬＰＣ）ならびに
１１０℃≦Ｔ_sB≦１３５℃であるような軟化点Ｔ_sBを有し、該樹脂性マトリックスの少なくとも２５重量％を構成する非−線状ポリマーの混合物を含有し、
該ワックスが８５℃≦Ｍ_p≦１３５℃であり且つＭ_p≦Ｔ_sB＋１０であるような融点Ｍ_pを有する
ことを特徴とする乾燥トナー粒子。
【０１０６】
２．該樹脂性マトリックスが該化合物Ｄにより改質された該ポリマーＬＰＣ及び該非−線状ポリマーＢの該混合物から成る上記１項に記載の乾燥トナー粒子。
【０１０７】
３．該ポリマーＢがさらに１２０℃及び１００ｒａｄ／秒で測定される１．０≦ｔｇδ≦２．５であるような粘弾性損失ｔｇδを有し、
該ワックスがさらにＴ_sC≦Ｔ_sB＋２０℃であるような軟化点Ｔ_sC及び１５Ｊ^1/2／ｃｍ^3/2≦δ_C≦１９Ｊ^1/2／ｃｍ^3/2であるようなヒルデブランド溶解パラメーターδ_Cを有し、そして
該ポリマーＢ、該線状ポリマー鎖ＬＰＣならびに該化合物Ｃ及びＤがδ_C＝δ_D＜δ_LPC＝δ_Bであるようなヒルデブランド溶解パラメーターδを有する
上記１又は２項に記載の乾燥トナー粒子。
【０１０８】
４．乾燥トナー粒子を用いる画像形成法であって：
−該トナー粒子を最終的受像基質に画像通りに適用し、
−表面を有する加熱されたローラーを含む溶融ステーションで該トナー粒子を該基質に定着させる
段階を含み、
−該トナー粒子が樹脂性マトリックス及びワックスを含み、
該樹脂性マトリックスが
２，０００〜２０，０００の重量平均分子量（Ｍｗ）、１２０℃及び１００ｒａｄ／秒におけるｔｇδ＞３ならびに９０℃≦Ｔ_sLPC≦１２０℃であるような低い軟化点Ｔ_sLPCを有し、反応性末端基を有し且つ炭素数が２０〜２５０の長鎖脂肪族化合物及びポリシロキサンから成る群より選ばれる改質剤（Ｄ）により改質されてポリマーＡを形成しており、該改質剤及び該ポリマーが０．８〜１．２５のモル比ＬＰＣ／Ｄで存在しているポリマー（ＬＰＣ）ならびに
１１０℃≦Ｔ_sB≦１３５℃であるような軟化点Ｔ_sBを有し、該樹脂性マトリックスの少なくとも２５重量％を構成する非−線状ポリマー
の混合物を含有し、
該ワックスが８５℃≦Ｍ_p≦１３５℃であり且つＭ_p≦Ｔ_sB＋１０であるような融点Ｍ_pを有する
ことを特徴とするものであり、
−該加熱されたローラー上の該表面上に外部剥離剤を、最高で１６０ｍｇ／ｍ²の剥離剤が該最終的受像基質に適用されるような量で加える
ことからなる方法。
【０１０９】
５．該加熱されたローラーの該表面上に、１〜１０ｍｇ／ｍ²の剥離剤が該最終的受像基質に適用されるような量で外部剥離剤を加える上記４項に記載の方法。
【０１１０】
６．該加熱されたローラーの該表面上に外部剥離剤が適用されない上記４項に記載の方法。[0001]
Field of the Invention
The present invention relates to dry toner particles, and more particularly to dry toner particles useful in electrostatic or magnetic recording image forming methods wherein toner particles are fixed to a final image receiving component by the simultaneous application of heat and pressure.
[0002]
BACKGROUND OF THE INVENTION
For example, in image forming methods such as electronic (photographic) recording, magnetic recording, and ionography, a latent image is formed, which is developed by attracting so-called toner particles. In the case of DEP, so-called toner particles are deposited image-wise on the substrate. The toner particles are basically polymer particles including a polymer resin as a main component and various components mixed with the toner resin. Apart from the colorless toner used, for example, for finishing functions, the toner particles contain at least one black and / or colored substance, for example a colored pigment.
[0003]
In the various image forming methods described above, the toner particles can be present in a liquid or dry developer composition.
[0004]
In most cases, the use of a dry developer composition is preferred. The main advantage of using a dry developer composition is that it is not necessary to remove the liquid phase after development. Avoiding the need to vent (mainly organic) liquids is desirable from both an economic and ecological point of view.
[0005]
After development of the latent image (eg, in electronic (photographic) recording, magnetic recording, ionography, etc.), the developed image is transferred to a substrate. In the case of DEP (direct electrostatic printing), the toner image is deposited directly on the substrate.
[0006]
The visible image of the electrostatically or magnetically attracted toner particles on this substrate is not permanent, but by adhering the toner particles to each other and the substrate by softening or melting and then cooling. Must be fixed. Fixing is usually done on a somewhat porous paper by impregnating or forcing a softened or melted toner mass into the bumps on the paper surface.
[0007]
There are various types of fusing methods used to fuse a toner powder image to its support. Some are based primarily on fixing when melted by heat, others based on softening by solvent vapor or by applying a cold stream at high pressure under ambient temperature conditions. In the case of heat-based melting methods, two main types must be considered: a “non-contact” melting method and a “contact” melting method. In the case of the contactless melting method, there is no direct contact of the toner image with the solid heating body.
[0008]
In the case of “contact” fusing, a support that supports the unfixed toner image is supported by a heating roller, also called a fuser roller, and a support, which acts as a pressure roller, and another one called a pressure roller. It is transported through a nip formed by a roller. This roller can be heated to some extent to avoid large losses of heat during the copy cycle. The last-mentioned fusing method is widely used in low-speed and high-speed fusing systems because the surface of the heating roller is pressed against the toner image surface of the sheet to be fixed, resulting in significantly higher thermal efficiency. . This fusing system allows the toner to melt to the point where "splitting" occurs because the melt cohesive force and melt viscosity are too low when the fuser roller imparts too much heat energy to the toner and paper. It must be carefully monitored in that it is transferred to the roller from which toner contamination can transfer onto and adhere to the next copy sheet in the next copy cycle; such phenomenon is referred to as “hot-offset”. Called and needs proper cleaning. To avoid these phenomena, an external release agent, such as silicone oil, that wets the melter roller can be used. The application of an external liquid stripper means extra consumables, requires adapting the device, and makes the device more expensive. The release agent inevitably also transfers to the copier, which can give an oily feel and uneven glossy prints due to the presence of oil.
[0009]
Thus, in toner particles designed to be fixed in a “contact” process, special resins and / or special to minimize the need for external release agents or to avoid the use of such release agents altogether. It is preferable to use additives.
[0010]
Several proposals have been made in the art. All of these proposals overcome some of the problems associated with toner particle fusing in the “contact” melting process.
[0011]
EP-A-276 147 discloses the addition of long chain aliphatic alcohols as toner components to toner particles to avoid the above problems. The disclosure suggests that any conventional toner resin can be used when such an alcohol is added. JP-A-5967554 also discloses the addition of long-chain compounds to toner particles.
[0012]
In US-A-5 344 737, in order to avoid the hot-offset phenomenon, the formula H in which 30 ≦ n ≦ 50 and 3 ≦ m ≦ 16 _Three C-(-CH ₂ ) _n -(-O-CH ₂ -CH ₂ ) _m It is disclosed to add a component having —OH to a toner composition.
[0013]
For example, DE-A-195 20 580 may use a polyester containing a moiety derived from a long-chain aliphatic dicarboxylic acid (eg, eicosane dicarboxylic acid) or containing a long-chain mono-carboxylic acid as a toner resin. Proposed. US-A-5 578 409 also describes the use of polyester toner resins modified with long chain fatty acids or alcohols. EP-A-712 881 describes the modification of amorphous polymers with two types of long chain fatty acids or alcohols.
[0014]
EP-A-298 279 discloses the incorporation of a multiphase polyorganosiloxane block or graft condensation copolymer in a toner resin. EP-A-740 217 describes modification of polymers for use in toner particles by reacting polymers containing free hydroxyl or acid groups with certain polysiloxanes.
[0015]
EP-A-716 351 includes a high softening point polyester, a low softening point polyester, and a long chain alkyl compound selected from the group consisting of a long chain alcohol having 23 to 252 carbon atoms and a long chain acid having 22 to 251 carbon atoms. Toner particles are disclosed. Modification by reacting a polyester with a long-chain alkyl compound selected from the group consisting of a high-softening point polyester, a low-softening point polyester, a long-chain alcohol having 23 to 252 carbon atoms, and a long-chain acid having 22 to 251 carbon atoms Also disclosed are toner particles comprising a mixture of the polyesters as a toner resin. Toner particles with such a toner resin are very resistant to hot-offset.
[0016]
The above disclosure allows for the production of dry toner particles having an acceptable to excellent degree of hot-offset (ie exhibiting a very low hot-offset). The toner particles need to have other properties as well as hot-offset properties. During use, the toner particles are also subjected to severe mechanical stress, such as by mixing, during transport through the device, by a doctor blade that adjusts the thickness of the toner layer. When toner particles are used in full-color development, due to the excellent mixed flow of four colors (Y, M, C, K), the particles have very good fluidity during fixing and yet are excellent Must exhibit hot-offset properties. Similar excellent melt flowability is achieved by black pigments with varying amounts of gray scale (tone range) in black-and-white electrostatic recording images fixed to the final substrate as disclosed in EP-A-768 577. This is indispensable when the toner particles can be spread by realizing the various gray shades required by using superposition of toner particles containing. For such images, if there is no very good mixing of toner particles when fused, there can be undesirable high surface relief that makes the image very sensitive to scratches.
[0017]
Therefore, there is a need for toner particles that have excellent hot-offset properties even with very small amounts of external release agents, and at the same time sufficiently strong to withstand mechanical stresses and have excellent fluidity when melted. Still exists.
[0018]
OBJECT AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide dry toner particles that combine high mechanical strength and excellent fluidity at elevated temperatures with excellent hot-offset properties.
[0019]
It is a further object of the present invention to provide toner particles that can be used in electrostatic or magnetic recording imaging processes that include a “contact” fusing step for fixing the image to the final substrate.
[0020]
A further object of the present invention is to provide toner particles useful in a full color image forming method in which the color of an original is faithfully expressed.
[0021]
A further object of the present invention is that the dry toner particles are fixed to the final image receiving part by a “contact” fusing device comprising a heated roller and no external release agent is present on the heated roller to avoid hot-offset. It is to provide a method for electrostatic or magnetic recording imaging that may or may not be present.
[0022]
Other objects and advantages of the present invention will become apparent from the following detailed description.
[0023]
An object of the present invention is dry toner particles comprising a resinous matrix and a wax,
The resinous matrix
Weight average molecular weight of 2,000 to 20,000 (M _w ), Tgδ> 3 at 120 ° C. and 100 rad / sec and 90 ° C. ≦ T _sLPC Low softening point T such that ≦ 120 ° C. _sLPC And having a reactive terminal group and a modifier (D) selected from the group consisting of a long-chain aliphatic compound having 20 to 250 carbon atoms and polysiloxane, the modifier And a polymer (LPC) in which the polymer is present in a molar ratio LPC / D of 0.8 to 1.25, and
110 ℃ ≦ T _sB ≦ 135 ° C. softening point T _sB A non-linear polymer comprising at least 25% by weight of the resinous matrix
Containing a mixture of
The wax is 85 ° C. ≦ M _p ≦ 135 ° C. and M _p ≦ T _sB Melting point M such that +10 _p Have
This is realized by providing dry toner particles characterized in that.
[0024]
[Definition]
In this document, the Hildebrand solubility factor of two compounds (eg of compounds C and D) is equal (ie, δ _C = Δ _D ), The difference in factors is 2J ^1/2 / Cm ^3/2 Means less than.
[0025]
In this document, two compounds (eg, compounds A and B) have different Hildebrand solubility factors (ie, δ _B ≠ δ _A ), The difference in factors is 2J ^1/2 / Cm ^3/2 Means bigger.
[0026]
The term “non-linear polymer” is used to indicate both heavily branched polymers and fully or partially crosslinked polymers.
[0027]
Detailed Description of the Invention
Electrostatic recording (electrophotography, ionography, direct electrostatic printing) where dry toner particles are used to form an image on the final substrate and the toner particles are fixed on the substrate in a contact fusing station that includes heated rollers (DEP)) or a magnetic recording image forming apparatus, it is desirable that a very simple contact melting apparatus can be used. The simpler the melting device, the cheaper, the smaller and more reliably it can be produced. In many cases, however, the problem of hot-offset (deposition of toner particles on the fuser roller rather than on the final substrate) is a device for applying an external release agent on the image and the amount of release agent applied. Order the use of a complex melting station with built-in equipment. If toner particles having excellent anti-hot-offset properties are used in the imaging system, the fusing station can be simplified. Methods and apparatus for the production of toner particles with excellent anti-hot-offset properties have already been described in the background section of this document, for example EP-A-276 147, JP-A-5967554. U.S. Pat. No. 5,344,737, DE-A-195 20 580, EP-A-712 881, EP-A-298 279, EP-A 740 217, and the like. When toner particles are used in full color development, the particles have excellent fluidity during fixing and excellent resistance due to the excellent mixed flow of four colors (Y, M, C, K). -It must exhibit hot-offset properties. As disclosed in EP-A-768 577, toner particles containing various amounts of (black) pigment in grayscale (tone range) in black-and-white (monochrome) electrostatic recording images fixed to the final substrate The same applies to the case where the image is widened by realizing the various gray shades required by using the superposition of. Combining excellent fluidity when melted in toner particles with excellent anti-hot-offset properties is not so simple.
[0028]
This time, after the experiment, a resinous matrix and a wax were included, and the resinous matrix had a weight average molecular weight (M _w ), Tgδ> 3 and 90 ° C ≦ T at 120 ° C. and 100 rad / sec. _sLPC Very low softening point T such that ≦ 120 ° C. _sLPC And a polymer chain (polymer LPC) modified with a long-chain compound (compound D) to form polymer A has a temperature of 110 ° C. ≦ T _sB ≦ 135 ° C. softening point T _sB Present with a heavily branched or (partially) cross-linked polymer (Polymer B), wherein the wax (Compound C) is 85 ° C. ≦ M _p ≤135 ° C, M _p ≦ T _sB Melting point M for the softening point of a polymer such as +10 _p It has been found that toner particles having an excellent anti-offset property combined with an excellent interflow during melting. Viscosity and tgδ are CARRI available via TA-Instruments, USA
Measured with MED Rheometer CSL 500.
[0029]
In a preferred embodiment, the resinous matrix contains at least 50% by weight of the polymer LPC modified with the compound D and the non-linear polymer B relative to the total weight of the resinous matrix.
[0030]
In a more preferred embodiment of the invention, the resinous matrix of toner particles consists of the mixture of the polymer LPC modified with the compound D and the non-linear polymer B.
[0031]
The polymer LPC having tgδ> 3 at 120 ° C. and 100 rad / sec is preferably a linear polymer.
[0032]
Surprisingly, toner particles comprising a wax and a resinous matrix having a tgδ> 3 at 120 ° C. and 100 rad / sec and containing a polymer modified with Compound D and a non-linear polyester are disclosed herein. It has been found that toner particles having a wax and resinous matrix according to the same melt quality during melt and anti-offset properties do not show excellent quality.
[0033]
Furthermore, when the polymer LPC, compound D, polymer B and compound C have Hildebrand solubility factors within a certain range and related to each other, it is possible to enhance the mixing of the toner particles and to easily improve the gloss of the resulting toner image. It has been found that a satin appearance can be obtained by controlling it. Such toner particles combine excellent anti-hot-offset properties, excellent fluidity in the molten state, and excellent physical strength.
[0034]
The concept of Hildebrand solubility parameters is “The Solubility of Non-electrolytes” by J. H. Hildebrand and R.H. L. Scott, Dover Publications, Inc. , New York, 3th. ed. (1964) and “Properties of Polymers” by D. W. Van Krevelen, 2nd. ed. , Elseviers Scientific Publishing Company, New York, 1976, Chapter 7.
[0035]
In particular, the resinous matrix of toner particles of the present invention contains polymer LPC, polymer B and compound C modified with compound D:
The polymer LPC has a weight average molecular weight of 2,000 to 20,000 (M _w ), Tgδ> 3 and 90 ° C ≦ T at 120 ° C. and 100 rad / sec. _sLPC Low softening point T such that ≦ 120 ° C. _sLPC A polymer having a reactive end group and modified with a modifier (D) selected from the group consisting of a long-chain aliphatic compound having 20 to 250 carbon atoms and a polysiloxane, LPC The molar fraction of / D is such that 0.8 ≦ LPC / D ≦ 1.25,
The polymer B has a viscoelastic loss tgδ such that 1.0 ≦ tgδ ≦ 2.5 measured at 120 ° C. and 100 rad / sec, 110 ° C. ≦ T _sB ≦ 135 ° C. softening point T _sB Comprising at least 25% by weight of the resinous matrix;
Compound C is 85 ° C. ≦ M _p ≤135 ° C, M _p ≦ T _sB Melting point M such that +10 _p And T _sC ≦ T _sB Softening point T such as + 20 ° C. _sC , 15J ^1/2 / Cm ^3/2 ≦ δ _C ≦ 19J ^1/2 / Cm ^3/2 Hildebrand dissolution parameter δ such as _C Have
The polymer B, the polymer chain LPC and the compounds C and D are δ _C = Δ _D <Δ _LPC = Δ _B With Hildebrand solubility parameter δ such that
It is characterized by that.
[0036]
Preferably δ _C 15-19J ^1/2 / Cm ^3/2 And δ _D Is 15-18J ^1/2 / Cm ^3/2 And δ _LPC 19-22J ^1/2 / Cm ^3/2 And δ _B 19-22J ^1/2 / Cm ^3/2 It is. δ _C And δ _D Are preferably equal, and in this specification this is the difference between them ^1/2 / Cm ^3/2 Means not bigger. δ _C And δ _D The difference of 2J ^1/2 / Cm ^3/2 Preferably it is not larger. δ _C = Δ _D And both are δ _LPC = Δ _B 2 units (2J ^1/2 / Cm ^3/2 ) Low is preferred. The difference between δ is 6 units (6J ^1/2 / Cm ^3/2 ) Is preferably not larger. When the difference was larger, the resinous matrix formulation became incompatible and the images printed with toner particles having such a matrix were dull and dull. On the other hand, a slight incompatibility (represented by a Hildebrand solubility factor difference of 2 to 6 units) has a beneficial effect on the appearance of the image, since a very favorable satin appearance was obtained. It is. This effect was described in EP-A-656 129.
[0037]
The polymer chain LPC having tgδ> 3 at 120 ° C. and 100 rad / sec can be any polymer known in the art if it contains at least one reactive end group. The polymer chain LPC is preferably a linear polymer chain. It is for example an addition polymer containing carboxyl groups at the end, for example co (styrene / n-butyl methacrylate), diCOOH end (65/35), polyester, epoxy resin or mixed polycondensates containing polyester and polyamide moieties (block or random). Polymer). A linear mixed polycondensate containing polyester and polyamide moieties is prepared by copolycondensation of at least one di-carboxylic acid, at least one diol and at least one aliphatic diamine or aminocarboxylic acid or lactam. Can do. The diamine, aminocarboxylic acid or lactam is present in the polycondensation mixture up to 30 mol%. Examples of useful diamines, aminocarboxylic acids or lactams are for example hexamethylenediamine, pentamethylenediamine, tetramethylenediamine, 11-amino-undecanoic acid, ε-caprolactam and the like.
[0038]
Epoxy resins useful as the polycondensation backbone in the composite macromolecule of the present invention are linear adducts of bis-phenol A and epichlorohydrin having a Tg of about 54 ° C.
[0039]
The epoxy resin suitably applied is D.I. H. “The Chemistry of Organic Film Forms” by Solomon—John Wiley & Sons, Inc. , New York (1967) p. Linear adducts of bisphenol compounds and epichlorohydrin as described in 180-181, such as EPIKOTE 1004 (EPIKOTE is a registered trademark of Shell Chemical Co).
[0040]
In the most preferred embodiment of the invention, the polymer chain LPC used to form polymer A after reaction with long chain aliphatic compound D is a homo- or copolyester. The homo- or copolyester (hereinafter referred to as polyester) can be prepared by any known polycondensation reaction between at least one dicarboxylic acid and at least one diol. The polyester used in accordance with the present invention may contain an aromatic dicarboxylic acid moiety. Examples of aromatic dicarboxylic acid moieties are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 4,4 'diphenylene dicarboxylic acid, 4,4' diphenyl ether dicarboxylic acid, 4,4 'diphenylmethane dicarboxylic acid, 4,4' diphenyl sulfodicarboxylic Parts such as acids, 5-sulfoisophthalic acid and mixtures of these acid moieties.
[0041]
The polyester to be used as the polymer chain LPC according to the invention can also contain an aliphatic dicarboxylic acid moiety. It can contain, for example, saturated aliphatic dicarboxylic acid moieties derived from malonic acid, succinic acid, glutaric acid, adipic acid, etc. and / or unsaturated aliphatic carboxylic acid moieties derived from, for example, maleic acid, fumaric acid, etc. .
[0042]
Polyesters useful as polymer chain LPCs according to the present invention have a minimum Tg (glass transition temperature) of 45 ° C. Any polyester resin having a Tg higher than 45 ° C. can be used. Preferred polyester resins are (i) difunctional organic acids such as maleic acid, fumaric acid, terephthalic acid and isophthalic acid and (ii) difunctional alcohols such as ethylene glycol, triethylene glycol and aromatic dihydroxy compounds, Preferably bisphenols such as 2,2-bis (4-hydroxyphenyl) -propane or “alkoxylated bisphenols called“ bisphenol A ”, eg propoxylated bisphenols, examples of which are shown in US Pat. No. 4,331,755 It is a linear polycondensation product. For the production of suitable polyester resins, reference is made to GB-P 1,373,220.
[0043]
Since it is preferred to use a linear polymer as the polymer chain LPC in the resinous matrix of the toner particles of the present invention, an interesting linear polyester is the product of ATLAC T500 (Atlas Chemical Industries Inc. Wilmington, Del. USA). ATLAC T500 has a Tg of about 55 ° C and a Tg of 100 ° C. _sp , 4,000 number average molecular weight (M _n ) And 12,000 weight average molecular weight (M _w ) Fumaric acid and propoxylated bisphenol A linear polyester. This polymer is described, for example, in NL 71/16891.
[0044]
Another useful commercial product for use as the linear polymer chain of the present invention is a T _sp , 3,700 number average molecular weight (M _n ) And 12,000 weight average molecular weight (M _w DIACRON FC150, which is a trade name of Mitsubishi Rayon, Japan, relating to a linear polyester resin produced by polycondensation of terephthalic acid, propoxylated bisphenol A and ethylene glycol.
[0045]
Yet another interesting linear polyester for use as the linear polymer chain in the present invention is a Tg of 52-56 ° C, a T of 95 ° C. _sp , 3,500 number average molecular weight (M _n ) And a weight average molecular weight of 8,000 (M _w A saturated polyester based on linear bisphenol A sold by Image Polymers Europe under the trade name ALMACRYL P-501.
[0046]
Another interesting linear polyester is the polycondensation product of terephthalic acid, isophthalic acid, di-ethoxylated bisphenol A and ethylene glycol.
[0047]
The compound D for reacting with reactive end groups on the chain LPC to give polymer A can be a long chain aliphatic compound or a polysiloxane. When an aliphatic long chain compound is used as the compound D, the general formula:
[0048]
[Chemical 1]

[0049]
[Where 0 ≦ x ≦ 12, 10 ≦ y ≦ 90,
R ¹ Is —OH, —COOH, —COCl, —NH ₂ ,
[0050]
[Chemical 2]

[0051]
-NCO, -O-CH ₂ -CHOH-CH ₂ Cl, -COO-CH ₂ -CHOH-CH ₂ A member selected from the group consisting of Cl and COOM (M is an alkali metal ion); ² Is CH _Three Or H, preferably H and R ^Three Is C ₂ H _Five Or CH _Three Is]
It is preferable to use a compound corresponding to.
[0052]
Surprisingly, polymer A has polymer chains LPC and R ¹ The toner particles of the present invention comprising a resinous matrix that is a polymer produced by reacting compound D according to Formula I above wherein OH or COOH, x = 0, and 55 ≦ y ≦ 90. It has been found to give very good results with respect to the combination of anti-hot-offset properties and fluidity in the molten state.
[0053]
Examples of monofunctional hydroxyl-terminated polyolefinic polymers that are very useful for the formation of crystalline or crystallizable end chains and / or side chains in the amorphous composite macromolecular compounds of the present invention are UNILIN 425, UNILIN 550, UNILIN 700 (trade name for PETROLITE, 6910 East 14th street, TULSA, Oklahoma 74112, USA for polyolefinic alcohols having an average molecular weight of 425,700) or hydroxy-terminated polyolefinic polyoxyethylenic having an average molecular weight of 875 It is a polyolefinic monoalcohol commercially available under the same PETROLITE trade name UNITHOX 720 for macromolecules. A typical example of a monofunctional carboxyl-terminated polyolefin is UNICID 700, a trade name of PETROLITE for a polyolefinic monocarboxylic acid having an average molecular weight of 700. Still other experimental polyolefinic compounds of PETROLITE having a hydroxyl or carboxyl group at the end and having a molecular weight of 1000 to 2500 can also be used.
[0054]
Further, the polymer for use in the toner particles of the present invention is obtained by reacting the polymer chain LPC with two types of compounds D, one compound having a molecular weight of 400 to 1000 and one compound having a molecular weight of 1500 to 2500. It has been found that A can be produced very beneficially. A preferred combination of the compounds D in the present invention is a combination of a polyolefin alcohol or polyolefin carboxylic acid having a molecular weight of 700 or 1000 and a polyolefin alcohol or polyolefin carboxylic acid having a molecular weight of 2000. Such polymers are disclosed for example in EP-A-712 881.
[0055]
When the compound D is a polysiloxane, the formula:
[0056]
[Chemical 3]

[0057]
[Where:
X '
[0058]
[Formula 4]

[0059]
And
Y ′ has the same meaning as X ′ or a lower (C1-C4) alkyl group,
Z ′ and Z ″ can be the same or different and represent a lower (C1-C4) alkyl group or an aryl group,
2 <m <35,
1 <n <6]
It is preferable to use a polysiloxane corresponding to the above.
[0060]
Epoxy-terminated polysiloxane derivatives corresponding to the above general formula are described in Th. It is commercially available from Goldschmid AG, Essen, Germany under the trade names TEGOMER E-Si 2130 and TEGOMER E-Si 2330.
[0061]
When reacting the compound D with the polymer chain (LPC), it is preferable to add 10 to 50% by weight of the compound D based on the weight of the LPC used. It is also important that the molar ratio between polymer chain LPC and compound D in polymer A is such that 0.8 ≦ LPC / D ≦ 1.25.
[0062]
Modification of the polymer chain with compound D to form polymer A useful in the toner particles of the present invention can be accomplished in two ways:
1. (I) mixing a polymer chain and at least one compound D in a reaction vessel;
(Ii) heating the mixture to 150-250 ° C. with stirring under a nitrogen atmosphere;
(Iii) Continue the heating until there is no phase separation;
(Iv) Cool and recover polymer A
A method comprising stages.
[0063]
2. (I) mixing at least one compound D with a dicarboxylic acid, a diol, if so desired, a diamine or lactam or mixtures thereof to form a polycondensation mixture;
(Ii) producing a prepolymer by heating the polycondensation mixture in the presence of a suitable catalyst if so desired;
(Iii) further reacting the prepolymer with a diol and / or dicarboxylic acid until the desired viscoelasticity is reached;
(Iv) Cool the reaction mixture and recover polymer A
A method comprising stages.
[0064]
A preferred first method for modifying the polymer LPC for use in the toner particles of the present invention is to mix the finished chain polymer having reactive end groups with an amount of at least one compound D; Next, the reaction is performed together. In the second method, at least one compound D is mixed with a reagent for the production of polymer chains (LPC) and the polymer A useful in the toner particles of the present invention is obtained directly in a one-vessel synthesis.
[0065]
Polymer B in the resinous matrix is a branched or partially crosslinked polymer, for example an addition polymer with free hydroxyl or carboxyl groups partially crosslinked by reaction with a polyisocyanate. be able to. It can be a styrene, acrylate or methacrylate copolymer containing moieties derived from 1 to 10 mol% divinylbenzene or ethylene glycol diacrylate or ethylene glycol dimethacrylate.
[0066]
Polymer B is preferably a branched polyester. For the production of branched polyesters, polycarboxylic acids such as trimellitic acid or polyhydroxy compounds such as trimethylolpropane, glycerol, pentaerythritol and the like can be used. An interesting branched polyester is a polyester produced by polycondensation of DIANOL 22 (di-ethoxylated bisphenol A), DIANOL 33 (di-propoxylated bisphenol A), terephthalic acid and trimellitic acid. DIANOL 22 and DIANOL 33 are trade names of AKZO CHEMIE in the Netherlands. As used in the present invention, polymer B is preferably a branched polyester containing moieties derived from 1 to 10 mole percent polyfunctional monomer. Polymer B preferably has a tgδ of 1 to 2.5 as measured at 120 ° C and 100 rad / sec. Polymer B for use in the toner particles of the present invention has a Tg higher than 45 ° C, preferably higher than 50 ° C and 19-22J. ^1/2 / Cm ^3/2 Preferably, the Hildebrand solubility parameter is
[0067]
Compound C for use in the present invention can include: It includes aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax, oxides of aliphatic hydrocarbon waxes such as polyethylene wax oxide and block copolymers thereof; mainly fatty acid esters Waxes consisting of, for example, carnauba wax and montanic acid ester wax; and those obtained by deoxygenating part or all of the fatty acid ester, such as deoxygenated carnauba wax. It contains saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, oleostearic acid and patinatic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, Polyhydric alcohols such as sorbitol; fatty acid amides such as linolenic acid amide, oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene bis-stearic acid amide, ethylene biscaprin Acid amides, ethylene bis lauric acid amides and hexamethylene bis stearic acid amides; unsaturated fatty acid amides such as ethylene bis oleic acid amides Tylene bisoleic acid amide, N, N′-dioleyl adipic acid amide and N, N′-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N′-distearyl isophthalate Acid amides; fatty acid metal salts (usually called metal soaps) such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; obtained by grafting vinyl monomers such as styrene or acrylic acid into fatty acid hydrocarbon waxes Waxes; partial esterification products of fatty acids using polyhydric alcohols, such as behenic acid monoglycerides; and monomethyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils can also be included.
[0068]
Examples of compound C useful in the resinous matrix of the toner particles of the present invention include Mitssui HI-WAX 100P, MITSUHI HI-WAX 110P, MITSUHI HI-WAX 1105A, MITSUHI H1120A, MITSWI H1120- Waxes that are commercially available under the trade name or under trade names such as HOECHST-WACHS U, HOECHST-WACHS PE520, HOECHST-WACHS PE130, HOECHST-WACHS PED121 from Hoechts, Germany.
[0069]
Compound C preferably has a molecular weight of 400-2500, more preferably 500-1600.
[0070]
For dry toner particles having the resinous matrix of the present invention, it is beneficial that more than one compound C be present in the matrix. Compound C has its melting point M _pC And its softening point T _sC Careful selection with respect to can fine-tune the anti-hot-offset properties, physical strength, and fluidity in the molten state of toner particles incorporating a resinous matrix.
[0071]
Compound C for use in the present invention has a molecular weight, a melting point M _pC And its softening point T _sC And its Hildebrand solubility parameter δ _C Selected based on When these values are within the above range, ie M _p ≦ T _sB +10, preferably M _p ≦ T _sB +5, where T _sB Is the softening point of polymer B and T _sC ≦ T _sB +20, preferably T _sC ≦ T _sB +15 and δ _C 15-19J ^1/2 / Cm ^3/2 In addition to the resinous matrix that imparts the desired properties to the toner particles, it is possible to produce a resinous matrix in which compound C (or more than one compound C) is very uniformly distributed. The uniformity of distribution of compound C in the resinous matrix is examined by melting a sample of the matrix on a glass plate and observing the molten sample under a polarizing microscope. By this method, blends of polymers A, B and compound C (ie several resinous matrices) can be evaluated according to their quality. In any case, in order to obtain an excellent dispersion of compound C in the resinous matrix, it is preferred that polymer A and compound C are present in a weight ratio of 1 to 10, preferably 2 to 5. Compound C is preferably present in the resinous matrix of the present invention in an amount of 2-8 wt (wt / wt)%, more preferably in an amount of 4-6% wt / wt.
[0072]
The toner particles of the present invention can be produced by any method known in the art, but the melting point M of the compound C used. _p The toner particles of the present invention are preferably produced by a melt kneading method at a higher temperature. When more than one compound C is used, the melt kneading process is preferably carried out at a temperature higher than the highest melting point of compound C. Thus, the present invention:
A polymer chain (LPC) having a reactive end group and a long chain compound D having a reactive end group and selected from the group consisting of a long-chain aliphatic compound having 20 to 250 carbon atoms and polysiloxane are reacted Polymer A, which is a polymer produced by the above process, has a mole fraction such that the LPC / D mole fraction in polymer A is 0.8 ≦ LPC / D ≦ 1.25. Viscoelastic loss tgδ such that 1.0 ≦ tgδ ≦ 2.5 measured at 100 ° C. and 100 rad / sec, 110 ° C. ≦ T _sB ≦ 135 ° C. softening point T _sB Polymer B having a B _p ≤135 ° C, M _p ≦ T _sB Melting point M such that +10 _p And T _sC ≦ T _sB Softening point T such as + 20 ° C. _sC , 15J ^1/2 / Cm ^3/2 ≦ δ _C ≦ 19J ^1/2 / Cm ^3/2 Hildebrand dissolution parameter δ such as _C Mixing with at least one compound C having a polymer A, polymer B and at least one compound C mixture,
The melting point MC _p Melt-kneading the mixture at a higher temperature,
-Cool the melt-kneaded mixture
Also included is a method for the production of dry toner particles comprising steps.
[0073]
The present invention is:
The polymer A is mixed with at least one compound C,
The melting point M _p Melt-kneading the mixture at a higher temperature,
-Add the polymer B to the mixture and continue melt kneading;
-Cool the melt-kneaded mixture
Also included is a method for the production of dry toner particles comprising steps.
[0074]
In the latter method, if the polymer A and the compound C are melt-kneaded at a temperature higher than the melting point of the compound C, it is not necessary to continue the melt-kneading at the elevated temperature after the addition of the polymer B.
[0075]
The toner particles comprising the resinous matrix of the present invention can include any conventional toner component, such as charge control agents, both colored and black pigments, inorganic fillers, fine magnetic materials, and the like. A description of charge control agents, pigments and other additives useful in toner particles can be found, for example, in EP A 601 235.
[0076]
The toner particles comprising the resinous matrix of the present invention can be mixed with any known carrier material when used in a multi-component dry developer. Suitable carrier particles are, for example, carrier particles as disclosed in EP-A-289 663; EP-A-559 250; EP-A-656 130 and European application 97202551 filed on August 20, 1997. . For example, known fluidity improvers such as hydrophobized silica can be mixed with the toner particles. The toner particles can be used as a single component dry developer (both magnetic and non-magnetic) or can be mixed with carrier particles to form a multi-component developer.
[0077]
The toner particles containing the resinous matrix of the present invention can have a volume average diameter of 1 to 50 μm, preferably 3 to 20 μm, more preferably 3 to 10 μm. The particle size distribution of the toner particles can be of any type. However, it is more preferred to have a Gaussian or normal particle size distribution by either the number or volume of variation coefficient (standard deviation divided by average) (V) less than 0.5, more preferably 0.3. The toner particles can have any shape, and the particles can be irregular, round, and the like.
[0078]
The toner particles of the present invention can be electrostatically or magnetically recorded for image formation in which fixing takes place at a “contact melting” station and a very small amount of external release agent is applied to the heated roller of the melting station to prevent hot-offset. Particularly useful for use in the law. Thus, the toner particles of the present invention are:
Applying the toner particles image-wise to the final image receiving substrate;
Fixing the toner particles to the substrate in a melting station comprising a heated roller having a surface with Si-atoms
Including stages,
-External release agent on the surface on the heated roller, up to 160 mg / m ² Of release agent is added in an amount that is applied to the substrate
This is used in an image forming method using dry toner particles. The amount is preferably at most 80 mg / m ² Of release agent applied to the substrate, more preferably up to 40 mg / m ² Is such an amount that is applied.
[0079]
The amount of release agent is preferably the same as that described in The Proceedings of IS &T's Eleventh International Congress on Advances in Non-Impact Printing Technologies, page 219-222. Bucher et al. The heated roller is fed by a feeding roller having a surface of NOMEX-Felt (NOMEX is a trade name of Du Pont de Nemours, Wilmington, US) as described in the literature entitled "Innovative Release Agent Delivery Systems" Applied. The conference was held at the Hilton Head from 29.10.95 to 03.11.95. The proceedings are published by IS & T, Springfield, US 1995. With such a roller, typically m ² 1-10 mg of external release agent is applied per unit. Thus, using the toner particles of the present invention, 1 to 10 mg / m ² Even if only an external release agent is applied, contact melting can be performed without problems associated with hot-offset.
[0080]
An imaging method that incorporates a “contact fusing” station with a heated roller, where no external release agent is applied to the heated roller (for purposes of this document, no external release agent is applied / M ² In principle it is even possible to use the toner particles according to the invention in a process (meaning less than).
[0081]
The heated roller can be made of any material known in the art, but preferably comprises a surface comprising a compound selected from the group consisting of compounds containing Si-atoms and compounds containing F-atoms It can be a heated roller having A roller having a surface with both a compound containing Si-atoms on the surface and a compound containing F-atoms and a roller comprising a compound having F-atoms on the surface but no compound having Si-atoms is present in the present invention. It is very suitable for fixing toner particles.
[0082]
【Example】
Modification of polymer LPC by modifier D
1. Production of polymer A1
ATLAC T500 (acid number 20, M _w = 12,000, M _n = 4,000, T at 100 ° C _sp Tgδ = 7 and 20 J at 120 ° C. and 100 rad / sec ^1/2 / Cm ^3/2 Of commercial linear polyester sold under the trade name of Hildebrand of 70 parts by weight (wt / wt) polymer chain (LPC) and 10 parts by weight / wt UNILIN 700 (on one end- CH _Three -CH, wherein the other end is a HO-group ₂ -CH ₂ An average molecular weight of 700 and 17 J ^1/2 / Cm ^3/2 And a molecular weight Mw = 2000, and the Hildebrand value is 17J. ^1/2 / Cm ^3/2 20 parts wt / wt experimental homologue was mixed in a reaction vessel. Thus, there were two compounds D with one LPC. The mixture was heated to 245 ° C. for 30 minutes and stirred with a stream of nitrogen bubbled through the reaction mixture. During this reaction time, water produced by the reaction was distilled off. This is the weight average molecular weight M _w Gave about 12,000 of polymer A1.
[0083]
2. Production of polymer A2
Bis-propoxylated 2,2-bis (4-hydroxyphenyl) propane (A), bis-ethoxylated 2,2-bis (4-hydroxyphenyl) propane (B), terephthalic acid (C) and trimellitic acid ( D) and is a polyester with A / B = 70 mol% / 30 mol%, C / D = 60 mol% / 40 mol% and A + B / C + D = 100 mol% / 70 mol% (this polyester is Acid value of 30, M _w = 14,000, M _n = 2,000, T of 105 ° C _sp Tgδ = 4.5 and 20 J at 120 ° C. and 100 rad / sec ^1/2 / Cm ^3/2 70 parts by weight (wt / wt) of polymer chain (LPC) and 10 parts by weight / wt of UNILIN 700 (with one end at —CH _Three -CH, wherein the other end is a HO-group ₂ -CH ₂ An average molecular weight of 700 and 17 J ^1/2 / Cm ^3/2 And a molecular weight Mw = 2000, and the Hildebrand value is 17J. ^1/2 / Cm ^3/2 20 parts wt / wt experimental homologue was mixed in a reaction vessel. Thus, there were two compounds D with one LPC. The mixture was heated to 245 ° C. for 30 minutes and stirred with a stream of nitrogen bubbled through the reaction mixture. During this reaction time, water produced by the reaction was distilled off. This is the weight average molecular weight M _w Gave about 12,000 of polymer A2.
[0084]
Toner particle manufacturing
Toner particle TON1
60 parts wt / wt of the above polymer A1 is bis-ethoxylated 2,2-bis (4-hydroxyphenyl) propane, bis-propoxylated 2,2-bis (4-hydroxyphenyl) propane, terephthalic acid and Cross-linked polyester of trimellitic acid, softening point of 118 ° C., tg δ = 2 and 20 J at 120 ° C. and 100 rad / sec ^1/2 / Cm ^3/2 And 30 parts by weight of polymer B having the Hildebrand solubility factor. To this mixture was added 3 parts by weight of cyan Cu-phthalocyanine pigment and a molecular weight of about 2,000, a melting point of 122 ° C. determined by DSC, a softening point of 130 ° C. determined by the JIS K2207 test method and 16 J ^1/2 / Cm ^3/2 7 parts by weight of a polyolefin wax having the Hildebrand solubility factor was added.
[0085]
The mixture is melt homogenized at 130 ° C., cooled, ground, classified, and a volume average diameter d of 8.5 μm as determined by COULTER COUNTER (trade name). _v50 And a number average diameter d of 6.3 μm _n50 Cyan toner particles having
[0086]
Toner particle TON2
60 parts wt / wt of the above polymer A2 is bis-ethoxylated 2,2-bis (4-hydroxyphenyl) propane, bis-propoxylated 2,2-bis (4-hydroxyphenyl) propane, terephthalic acid and Cross-linked polyester of trimellitic acid, softening point of 118 ° C., tg δ = 2 and 20 J at 120 ° C. and 100 rad / sec ^1/2 / Cm ^3/2 And 30 parts by weight of polymer B having the Hildebrand solubility factor. To this mixture was added 3 parts by weight of cyan Cu-phthalocyanine pigment and a molecular weight of about 2,000, a melting point of 122 ° C. determined by DSC, a softening point of 130 ° C. determined by the JIS K2207 test method and 16 J ^1/2 / Cm ^3/2 7 parts by weight of a polyolefin wax having the Hildebrand solubility factor was added.
[0087]
The mixture is melt homogenized at 130 ° C., cooled, ground, classified, and a volume average diameter d of 8.5 μm as determined by COULTER COUNTER (trade name). _v50 And a number average diameter d of 6.3 μm _n50 Cyan toner particles having
[0088]
Toner particle TON3
The production of toner particles TON1 was repeated except that the polymer chain (LPC) was not modified.
[0089]
Toner particle TON4
The production of toner particles TON3 was repeated except that no wax was added.
[0090]
Toner particle TON5
The production of toner particles TON1 was repeated except that no wax was added.
[0091]
Development of developer
Using each toner particle (TON1 to TON5), 0.5% (wt / wt) of AEROSIL R972 (trade name of Degussa, Germany for hydrophobic silica) was added, and 5% wt / wt of the toner particles and Volume average particle diameter d of 50 μm of silica mixture _v50 Developers were prepared by mixing with silicone-coated ferrite carrier particles having the following:
[0092]
Examples of printing and fixing
Images were formed on a paper substrate using a developer in an XC305 color copier (trade name of Agfa-Gevaert NV, Mortsel, Belgium). The image contained 1 mg of toner per cm2. The image was fixed in four “contact fusing” stations AD including heated rollers. The XC305 color copier melting device was basically used with some modifications. In the standard design, the melting station of this device includes a pair of double silicone coated rollers exhibiting a typical 5-6 mm contact area. The temperature setting was variable within the range of 160 to 175 ° C., and the temperature was a variable parameter in the examples. In all examples, melting was performed under conditions of speed and pressure of the standard design of the equipment.
[0093]
Melting station A:
Usually 40-80 mg of silicone oil per copy on DIN A4 page (ie 640-1,280 mg / m ² ), The standard lubrication device, all the scraping devices and the cleaning web were removed from the melting station. The heated roller was a roller having a silicone surface and a lifetime of 5,000 copies. In this melting station, contact melting was performed on the heated roller without using an external release agent.
[0094]
Melting station B
The same configuration as in the melting station A was used except that a heated roller having a lifetime of 50,000 copies was used. Even in this melting station, contact melting was performed on the heated roller without using an external release agent.
[0095]
Melting station C
The same configuration as in the melting station B was used except that a small amount of an external release agent (silicone oil) was applied to the heated roller on the heated roller. The amount of silicone oil to be delivered to the heated roller is m on the image. ² Adjusted to yield 1.6 mg of silicone oil per minute. This is 40 to 80 times less than usual. Silicone oils are available from R.I. in The proceeding of IS &T's Eleventh International Congress on Advances in Non-Impact Printing Technologies, page 219-222. Bucher et al. Applied to heated rollers by a supply roller having a surface of NOMEX-Felt (NOMEX is a trade name of Du Pont de Nemours, Wilmington, US) as described in the literature entitled "Innovative Release Agent Delivery Systems" It was done. The conference was held at the Hilton Head from 29.10.95 to 03.11.95. The proceedings are published by IS & T, Springfield, US 1995.
[0096]
Melting station D:
The same configuration as in the melting station C was used except that a roller with a silicone, polyfluoroacrylate surface was used instead of a roller with a pure silicone surface. These rollers are very resistant to scratches and have a lifetime of about 500,000 copies. However, the roller has a relatively high surface energy and can cause hot-offset more easily than a roller with a silicone surface.
[0097]
The fusing window was determined for each of the melting stations. First, the fixing temperature at which fixing is properly performed is represented by a symbol T1. This was done by printing images with various toners, fixing the images at various temperatures, and assessing the quality of the resulting fixing by evaluating four issues:
Image quality: visual inspection
Smoothness: visual inspection
Feel: Feel of the surface of the image
Toner adhesion: The toner is manually scraped with a plastic knife.
[0098]
Evaluation was on a 4 to 1 scale for each of the tasks, with 4 being excellent, 3 being good, 2 being borderline, and 1 being unacceptable. It was understood that fixing was appropriate if the image scored at least 3 for each of the above challenges. The fixing temperature of the image was set to temperature T1.
[0099]
The fixing was then carried out at a much higher temperature and the temperature T2 at which the first sign of hot-offset occurred was noted. The fixing window is determined by subtracting T1 from T2 and is given in ° C. Since both fixing stations A and B were operated without an external release agent and fixing stations C and D were operated with a small amount of external release agent, the respective toner particles TON1-TON5 obtained at fixing stations A and B were Average the fixing windows for the toner particles TON1 to TON5 obtained at fixing stations C and D as well as an average for the fixing window in the absence of an external release agent. One number was obtained for the fixing window in the presence of an external release agent. These numbers are summarized in Table 1.
[0100]
[Table 1]

[0101]
Table 1
It is clear that toner particles TON1 and TON2, the toner particles of the present invention, give the best results: the widest fixing window and the best image quality.
[0102]
Toner particle TON3, which is equal to toner particle TON1 except that polymer chain LPC has not been modified by compound D, and thus non-toner particles of the present invention, gave a narrower fixing window.
[0103]
The other two non-inventive toner particles (TON4 and TON5) clearly gave unsatisfactory results.
[0104]
The main features and aspects of the present invention are as follows.
[0105]
1. Dry toner particles comprising a resinous matrix and a wax,
The resinous matrix
Weight average molecular weight (Mw) from 2,000 to 20,000, tgδ> 3 at 120 ° C. and 100 rad / sec and 90 ° C. ≦ T _sLPC Low softening point T such that ≦ 120 ° C. _sLPC The polymer A is modified with a modifier (D) selected from the group consisting of a long-chain aliphatic compound having 20 to 250 carbon atoms, a reactive end group, and a polysiloxane. A polymer (LPC) in which the modifier and the polymer are present in a molar ratio LPC / D of 0.8 to 1.25, and
110 ℃ ≦ T _sB ≦ 135 ° C. softening point T _sB And comprising a mixture of non-linear polymers comprising at least 25% by weight of the resinous matrix,
The wax is 85 ° C. ≦ M _p ≦ 135 ° C. and M _p ≦ T _sB Melting point M such that +10 _p Have
Dry toner particles characterized by the above.
[0106]
2. 2. Dry toner particles according to claim 1, wherein the resinous matrix comprises the mixture of the polymer LPC modified with the compound D and the non-linear polymer B.
[0107]
3. The polymer B further has a viscoelastic loss tgδ such that 1.0 ≦ tgδ ≦ 2.5 measured at 120 ° C. and 100 rad / sec,
The wax is further T _sC ≦ T _sB Softening point T such as + 20 ° C. _sC And 15J ^1/2 / Cm ^3/2 ≦ δ _C ≦ 19J ^1/2 / Cm ^3/2 Hildebrand dissolution parameter δ such as _C And
The polymer B, the linear polymer chain LPC, and the compounds C and D are δ _C = Δ _D <Δ _LPC = Δ _B With Hildebrand solubility parameter δ such that
3. The dry toner particles as described in 1 or 2 above.
[0108]
4). An image forming method using dry toner particles comprising:
Applying the toner particles image-wise to the final image receiving substrate;
Fixing the toner particles to the substrate in a melting station comprising a heated roller having a surface
Including stages,
The toner particles comprise a resinous matrix and a wax;
The resinous matrix
Weight average molecular weight (Mw) from 2,000 to 20,000, tgδ> 3 at 120 ° C. and 100 rad / sec and 90 ° C. ≦ T _sLPC Low softening point T such that ≦ 120 ° C. _sLPC The polymer A is modified with a modifier (D) selected from the group consisting of a long-chain aliphatic compound having 20 to 250 carbon atoms, a reactive end group, and a polysiloxane. A polymer (LPC) in which the modifier and the polymer are present in a molar ratio LPC / D of 0.8 to 1.25, and
110 ℃ ≦ T _sB ≦ 135 ° C. softening point T _sB A non-linear polymer comprising at least 25% by weight of the resinous matrix
Containing a mixture of
The wax is 85 ° C. ≦ M _p ≦ 135 ° C. and M _p ≦ T _sB Melting point M such that +10 _p Have
It is characterized by that,
-External release agent on the surface on the heated roller, up to 160 mg / m ² Of release agent is added in an amount such that it is applied to the final image receiving substrate.
A method that consists of things.
[0109]
5. 1-10 mg / m on the surface of the heated roller ² 5. The method of claim 4 wherein an external release agent is added in an amount such that a release agent is applied to the final image receiving substrate.
[0110]
6). The method of claim 4 wherein no external release agent is applied on the surface of the heated roller.

Claims (6)

The resin matrix and a wax in a dry toner particles comprising Nde including,
Low softening point such that the resinous matrix has (i) a weight average molecular weight (Mw) of 2,000 to 20,000, tgδ> 3 at 120 ° C. and 100 rad / sec and 90 ° C. ≦ T _sLPC ≦ 120 ° C. T _SLPC a polymer LPC to have a, and the number of carbon atoms having a reactive end group is modified to form a polymer a by a long chain aliphatic compounds der Ru modifier D of 20 to 250, the Polymer A is a polymer LPC obtainable by reacting the polymer LPC with 10 to 50% by weight modifier D based on the weight of the polymer LPC ; (ii) at 110 ° C. ≦ T _sB ≦ 135 ° C. Containing a mixture of non-linear polymers B having a softening point T _sB and constituting at least 25% by weight of the _resinous matrix;
Dry toner particles, characterized in that the wax has a melting point M _p such that 85 ° C. ≦ M _p ≦ 135 ° C. and M _p ≦ T _sB +10.   2. Dry toner particles according to claim 1, wherein the resinous matrix comprises the mixture of the polymer LPC modified with the compound D and the non-linear polymer B. The polymer B further has a viscoelastic loss tgδ such that 1.0 ≦ tgδ ≦ 2.5 measured at 120 ° C. and 100 rad / sec,
Hildebrand solubility parameter such that the softening point _{T sC} and _{^{15J 1/2 / cm 3/2 ≦ δ C}} ≦ 19J 1/2 / cm 3/2 as the wax is a further _{T sC} ≦ _T sB + 20 ℃ has a [delta] _C, and the polymer B, according to claim 1 or having the linear polymer chain LPC and said compounds C and D _{δ C = δ D <δ LPC} = δ Hildebrand solubility parameter such that _B [delta] 3. Dry toner particles according to 2. An image forming method using dry toner particles comprising:
Applying the toner particles image-wise to the final image receiving substrate;
- the step of the heated rollers having a surface with a fusing station comprising Nde including fixing said toner particles to said substrate becomes Nde including,
The toner particles comprise a resinous matrix and a wax, the resinous matrix comprising: (i) a weight average molecular weight (Mw) of 2,000 to 20,000, tgδ> 3 at 120 ° C. and 100 rad / sec and 90 ° C. ≦ _{T sLPC} ≦ 120 a polymer LPC to have a low softening point _{T SLPC} such that ° C., reactive and carbon atoms having a terminal group long-chain aliphatic compounds der Ru modifier 20 to 250 modified to form a polymer a by D, the polymer a is a polymer LPC which can be obtained by reacting a modifier D of 10 to 50% by weight of the polymer LPC based on the weight of the polymer LPC , (ii) has a softening point _{T sB} such that _{110 ℃ ≦ T sB ≦ 135 ℃} , non constitutes at least 25 wt% of該樹oily matrix - line It contains a mixture of polymer B,
The wax is than also that having a melting point _{M p} such that 85 ℃ ≦ _{M p} ≦ 135 ℃ and _{M p} ≦ _T sB +10,
- wherein the addition in an amount such that the external release agent to the surface on the said heated roller, the release agent up to 160 mg / m ² is applied to the final image receiving substrate. 5. The method of claim 4, wherein an external release agent is added on the heated roller surface in an amount such that 1-10 mg / m < ² > of release agent is applied to the final image receiving substrate.   The method of claim 4, wherein no external release agent is applied on the surface of the heated roller.