JP2004151441A - Toner, image forming method, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for higher speed fixing, which excels in low-temperature fixability, high-temperature off-set resistance and prevention of coiling round, and to provide an image forming method and an image forming apparatus. <P>SOLUTION: An unfixed toner image is formed by the toner which contains at least a binder resin at least containing a hybrid resin, coloring matter and wax and in which, in a molecular weight distributions by GPC (Gel Permeation Chromatography) of the THF (Tetrahydrofuran) soluble contents of the toner, the content (M1) of the component of the molecular weight below 10,000 is 40 to 70mass%, the content (M2) of the component of the molecular weight from 10,000 to 50,000 is 25 to 50mass%, the content (M3) of the component of the molecular weight exceeding 50,000 is 2 to 25mass%, and the content of the component of the molecular weight of ≥100,000 is ≤10mass% and which satisfies M1≥M2>M3. The image is formed by bringing the unfixed toner image by a pressurizing member into pressurized contact with a flexible metallic sleeve heated by a heating member and by fixing the image to a recording material. <P>COPYRIGHT: (C)2004,JPO

Description

【００９３】
結着樹脂のＴＨＦ可溶分は、結着樹脂をＴＨＦのソックスレー抽出器にかけ、ＴＨＦ可溶分を抽出し、抽出液を固化して分離することが可能である。
【００９４】
結着樹脂のＴＨＦ不溶分の含有量は、結着樹脂約１ｇを秤量し（ｗ３ｇ）、円筒濾紙（例えば東洋濾紙製Ｎｏ．８６Ｒ）に入れてソックスレー抽出器にかけ、溶媒としてＴＨＦ２００ｍｌを用いて１０時間抽出し、ＴＨＦ溶媒によって抽出された可溶分をエバポレートした後、１００℃で数時間真空乾燥し、ＴＨＦ可溶樹脂成分の質量を（ｗ４ｇ）を秤量する。ＴＨＦ不溶分は、下記式から求められる。
【００９５】
【数２】

【００９６】
本発明に用いられる結着樹脂は、結着樹脂のＴＨＦ可溶分中の分子量１万未満の成分における三価以上の多価カルボン酸類及びその無水物の含有量ｗ１（ｍｏｌ％）と、ＴＨＦ可溶分中の分子量１万以上の成分における三価以上の多価カルボン酸類及びその無水物の含有量ｗ２（ｍｏｌ％）とが下記関係
０≦ｗ１＜３０
０＜ｗ２＜５０
ｗ２＞ｗ１
を満たすことが好ましく、下記関係
１＜ｗ１＜２５
２＜ｗ２＜３０
を満たすことがより好ましく、下記関係
３≦ｗ１＜２０
３＜ｗ２≦２０
を満足することがさらに好ましく、結着樹脂のＴＨＦ可溶分がこのような関係を満足することが、上述した本発明のトナーを得る上で好ましい。
【００９７】
さらに、ｗ１とｗ２の差が下記関係
０＜ｗ２−ｗ１＜１０
を満足することが、より一層好ましい。
【００９８】
さらに、本発明に用いられる結着樹脂は、結着樹脂のＴＨＦ可溶分のＧＰＣの分子量分布において、分子量１万未満の成分の含有量（ｍ１）が４０〜７５質量％、分子量１万乃至５万の成分の含有量（ｍ２）が２３〜４５質量％、分子量５万を超える成分の含有量（ｍ３）が２〜２５質量％、分子量１０万以上の成分の含有量（ｍ４）が１３質量％未満であり、かつｍ１≧ｍ２＞ｍ３を満足することで、好ましくは、分子量１万未満の成分の含有量（ｍ１）が５０〜７５質量％、分子量１万乃至５万の成分の含有量（ｍ２）が２３〜４５質量％、分子量５万を超える成分の含有量（ｍ３）が２〜２５質量％、分子量１０万以上の成分の含有量（ｍ４）が１０質量％未満であり、かつｍ１≧ｍ２＞ｍ３＞ｍ４を満足することで、上述した本発明のトナーを得ることができる。
【００９９】
また、前記第一の形態の結着樹脂においては、結着樹脂のＴＨＦ不溶分が３０質量％以下であることが、上述した本発明のトナーを得る上で好ましく、１〜２０質量％であることが、上述した本発明のトナーを得る上でより好ましい。
【０１００】
また、前記第二の形態の結着樹脂においては、結着樹脂のＴＨＦ不溶分の含有量が１〜５０質量％であることが、上述した本発明のトナーを得る上で好ましく、２〜４０質量％であることが、上述した本発明のトナーを得る上でより好ましく、５〜３０質量％であることが、上述した本発明のトナーを得る上でさらに好ましい。
【０１０１】
本発明に用いられるポリエステル樹脂及びハイブリッド樹脂に含まれるポリエステルユニットを構成するポリエステル系モノマーとしては、通常使用されるアルコール成分モノマー及び酸成分モノマーが用いられ、例えば以下のものが挙げられる。
【０１０２】
アルコール成分モノマーとしては、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、２−エチル−１，３−ヘキサンジオール、水素化ビスフェノールＡ、下記（ア）式で表されるビスフェノール誘導体及び下記（イ）式で示されるジオール類がある。
【０１０３】
【化１】

【０１０４】
【化２】

【０１０５】
酸成分モノマーとしては、フタル酸、テレフタル酸、イソフタル酸、無水フタル酸の如きベンゼンジカルボン酸類又はその無水物又はその低級アルキルエステル類；こはく酸、アジピン酸、セバシン酸、アゼライン酸の如きアルキルジカルボン酸類又はその無水物又はその低級アルキルエステル、またさらに炭素数６〜１８のアルキル基あるいはアルケニル基で置換されたこはく酸もしくはその無水物；フマル酸、マレイン酸、シトラコン酸、イタコン酸、メサコン酸の如き不飽和ジカルボン酸又はその無水物が挙げられる。さらに、酸成分モノマーとして、後述する三価以上の多価カルボン酸類も挙げられる。
【０１０６】
さらに酸成分モノマーとしては、マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和ジカルボン酸のハーフエステル類；マレイン酸ジメチル、フマル酸ジメチルの如き不飽和ジカルボン酸ジエステル類が挙げられる。
【０１０７】
本発明のトナーにおいて、結着樹脂は、三価以上の多価カルボン酸又はその無水物によって架橋されていることが好ましい。架橋成分としては、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸やその無水物、ベンゾフェノンテトラカルボン酸が好ましいものとして挙げられる。
【０１０８】
本発明のトナーにおいて、結着樹脂は三価以上の多価カルボン酸の他に多価アルコールによって架橋されていても良い。多価アルコールとしてはグリセリン、ペンタエリスリトール、ソルビット、ソルビタン、さらには例えば、ノボラック型フェノール樹脂のオキシアルキレンエーテルが挙げられる。
【０１０９】
本発明に用いられる、ビニル系樹脂及びハイブリッド樹脂中に含まれるビニル系重合体ユニットを構成するビニル系モノマーとしては、通常使用されるものを用いることができ、例えば、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−フェニルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ブチルスチレン、ｐ−ｔｅｒｔ−トリブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−メトキシスチレン、ｐ−クロルスチレン、３，４−ジクロルスチレン、ｍ−ニトロスチレン、ｏ−ニトロスチレン、ｐ−ニトロスチレンの如きスチレン及びその誘導体；エチレン、プロピレン、ブチレン、イソブチレンの如き不飽和モノオレフィン類；ブタジエン、イソプレンの如き不飽和ポリエン類；塩化ビニル、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類；酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニルの如きビニルエステル類；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸−ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸−ｎ−オクチル、メタクリル酸ドデシル、メタクリル酸−２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα−メチレン脂肪族モノカルボン酸エステル類；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸−ｎ−ブチル、アクリル酸イソブチル、アクリル酸−ｎ−オクチル、アクリル酸ドデシル、アクリル酸−２−エチルヘキシル、アクリル酸ステアリル、アクリル酸−２−クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類；ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類；ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類；Ｎ−ビニルピロール、Ｎ−ビニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニルピロリドンの如きＮ−ビニル化合物；ビニルナフタリン類；アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体が挙げられる。
【０１１０】
さらに、ビニル系モノマーとしては、アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα，β−不飽和酸；クロトン酸無水物、ケイヒ酸無水物の如きα，β−不飽和酸無水物、該α，β−不飽和酸と低級脂肪酸との無水物；アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらのモノエステルの如きカルボキシル基を有するモノマーが挙げられる。
【０１１１】
さらに、ビニル系モノマーとしては、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどのアクリル酸又はメタクリル酸エステル類；４−（１−ヒドロキシ−１−メチルブチル）スチレン、４−（１−ヒドロキシ−１−メチルヘキシル）スチレンの如きヒドロキシ基を有するモノマーが挙げられる。
【０１１２】
またさらに、マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和ジカルボン酸ハーフエステル類；マレイン酸ジメチル、フマル酸ジメチルの如き不飽和ジカルボン酸ジエステル類；マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和ジカルボン酸類；マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和ジカルボン酸無水物類もビニル系モノマーとして使用できるが、本発明における結着樹脂を製造するのに使用される全モノマー成分を基準としてポリエステル系モノマー成分の割合を算出するときには、本発明ではこれらに限りポリエステル系モノマー成分として算出する。
【０１１３】
さらに、前記ビニル系樹脂及びビニル系重合体ユニットは、必要に応じて以下に例示するような架橋性モノマーで架橋された重合体であっても良い。
【０１１４】
芳香族ジビニル化合物としては、例えばジビニルベンゼン、ジビニルナフタレンが挙げられ；アルキル鎖で結ばれたジアクリレート化合物類としては、例えばエチレングリコールジアクリレート、１，３−ブチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，５−ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；エーテル結合を含むアルキル鎖で結ばれたジアクリレート化合物類としては、例えばジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコール＃４００ジアクリレート、ポリエチレングリコール＃６００ジアクリレート、ジプロピレングリコールジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；芳香族基及びエーテル結合を含む鎖で結ばれたジアクリレート化合物類としては、例えばポリオキシエチレン（２）−２，２−ビス（４−ヒドロキシジフェニル）プロパンジアクリレート、ポリオキシエチレン（４）−２，２−ビス（４−ヒドロキシフェニル）プロパンジアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたものが挙げられ；ポリエステル型ジアクリレート類としては、例えば商品名ＭＡＮＤＡ（日本化薬）が挙げられる。
【０１１５】
多官能の架橋剤としては、ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの；トリアリルシアヌレート、トリアリルトリメリテートが挙げられる。
【０１１６】
これらの架橋剤は、他のビニル系モノマー成分１００質量部に対して、０．０１〜１０．０質量部（さらに好ましくは０．０３〜５質量部）用いることが好ましい。
【０１１７】
本発明ではビニル系重合体成分及び／又はポリエステル樹脂成分中に、両樹脂成分と反応し得るモノマー成分を含むことが好ましい。ポリエステル樹脂成分を構成するモノマーのうちビニル系重合体と反応し得るものとしては、例えば、フマル酸、マレイン酸、シトラコン酸、イタコン酸の如き不飽和ジカルボン酸又はその無水物などが挙げられる。ビニル系重合体成分を構成するモノマーのうちポリエステル樹脂成分と反応し得るものとしては、カルボキシル基又はヒドロキシ基を有するものや、アクリル酸もしくはメタクリル酸エステル類などが挙げられる。
【０１１８】
ビニル系樹脂とポリエステル樹脂の反応生成物を得る方法としては、先に挙げたビニル系樹脂及びポリエステル樹脂のそれぞれと反応しうるモノマー成分を含むポリマーが存在しているところで、どちらか一方もしくは両方の樹脂の重合反応をさせることにより得る方法が好ましい。
【０１１９】
前記ビニル系樹脂及びビニル系重合体ユニットを製造する場合に用いられる重合開始剤としては、例えば２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、ジメチル−２，２’−アゾビスイソブチレート、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、２−カルバモイルアゾイソブチロニトリル、２，２’−アゾビス（２，４，４−トリメチルペンタン）、２−フェニルアゾ−２，４−ジメチル−４−メトキシバレロニトリル、２，２’−アゾビス（２−メチルプロパン）、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイド、シクロヘキサノンパーオキサイドの如きケトンパーオキサイド類；２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキジイソプロピル）ベンゼン、イソブチルパーオキサイド、オクタノイルパーオキサイド、デカノイルパーオキサイド、ラウロイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、ベンゾイルパーオキサイド、ジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジ−ｎ−プロピルパーオキシジカーボネート、ジ−２−エトキシエチルパーオキシジカーボネート、ジメトキシイソプロピルパーオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）パーオキシカーボネート、アセチルシクロヘキシルスルホニルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシネオデカノエイト、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエイト、ｔ−ブチルパーオキシイソプロピルカーボネート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシアリルカーボネート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート、ジ−ｔ−ブチルパーオキシアゼレートが挙げられる。
【０１２０】
前記ビニル系樹脂及びビニル系重合体ユニットを製造する場合に用いられる重合開始剤として、以下に例示する多官能性重合開始剤を単独で使用しても良いし、又は単官能性重合開始剤と併用しても良い。
【０１２１】
多官能構造を有する多官能重合開始剤の具体例としては、１，１−ジ−ｔ−ブチルパーオキシ−３，３，３−トリメチルシクロヘキサン、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、２，５−ジメチル−２，５（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔ−ブチルパーオキシ）ヘキサン、トリス（ｔ−ブチルパーオキシ）トリアジン、１，１−ジ−ｔ−ブチルパーオキシシクロヘキサン、２，２−ジ−ｔ−ブチルパーオキシブタン、４，４−ジ−ｔ−ブチルパーオキシバレリックアシッド−ｎ−ブチルエステル、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート、ジ−ｔ−ブチルパーオキシアゼレート、ジ−ｔ−ブチルパーオキシトリメチルアジペート、２，２−ビス（４，４−ジ−ｔ−ブチルパーオキシシクロヘキシル）プロパン及び２，２−ｔ−ブチルパーオキシオクタンの如き、パーオキサイド基のような重合開始機能を有する官能基を１分子内に２つ以上有する多官能性重合開始剤；及びジアリルパーオキシジカーボネート、トリブチルパーオキシマレイン酸、ｔ−ブチルパーオキシアリルカーボネート及びｔ−ブチルパーオキシイソプロピルフマレートの如き、パーオキサイド基の如き重合開始機能を有する官能基と重合性不飽和基との両方を１分子内に有する多官能性重合開始剤が挙げられる。
【０１２２】
これらのうち、より好ましいものは、１，１−ジ−ｔ−ブチルパーオキシ−３，３，５−トリメチルシクロヘキサン、１，１−ｔ−ブチルパーオキシシクロヘキサン、ジ−ｔ−ブチルパーオキシヘキサハイドロテレフタレート、ジ−ｔ−ブチルパーオキシアゼレート、２，２−ビス−（４，４−ジ−ｔ−ブチルパーオキシシクロヘキシル）プロパン、及びｔ−ブチルパーオキシアリルカーボネートである。
【０１２３】
本発明において結着樹脂は、少なくともハイブリッド樹脂成分を含有する。本発明において、ハイブリッド樹脂とは、ポリエステル樹脂成分とビニル系重合体成分とが化学的に結合している成分のことであり、このような成分を少なくとも一部含むものを意味する。そして、化学的に結合しているポリエステル樹脂成分側が、ポリエステルユニットであり、化学的に結合しているビニル系重合体成分が、ビニル系重合体ユニットである。
【０１２４】
具体的には、ポリエステルユニットと、（メタ）アクリル酸の如きカルボン酸を有するビニル系モノマー類や（メタ）アクリル酸エステルの如きカルボン酸エステル基を有するビニル系モノマー類を含んで重合されたビニル系重合体ユニットとが、エステル化反応やエステル交換反応によって形成するものである。その共重合の形態としては、ビニル系重合体ユニットを幹重合体とし、ポリエステルユニットを枝重合体としたグラフト共重合あるいはブロック共重合であることが好ましい。
【０１２５】
したがって、本発明において具体的に、ハイブリッド樹脂成分とは、ポリエステルユニットとビニル系重合体ユニットの少なくとも一部が下記に示す結合部位を介して結合するものである。
【０１２６】
【化３】

【０１２７】
本発明において、ハイブリッド樹脂の製造方法としては、例えば以下の（１）〜（７）に示す製造方法を挙げることができる。
【０１２８】
（１）ビニル系重合体とポリエステル樹脂を別々に製造した後、有機溶剤に溶解／膨潤させ、エステル化触媒、必要に応じてアルコール類を添加して、加熱することによりエステル化反応又は／及びエステル交換反応を行った後、有機溶媒を留去する。この製造方法では前記反応時にワックス類を添加しても良い。
【０１２９】
（２）ビニル系重合体の存在下に、ポリエステル系モノマーを添加し、重合並びにビニル系重合体とのエステル化反応又は／及びエステル交換反応を行う。この製造方法では、反応時に、必要に応じてさらにビニル系モノマーを添加し重合しても良い。また、この製造方法では、有機溶剤が適宜使用される。また、この製造方法では、前記（１）と同様に、反応時にワックス類を添加しても良い。
【０１３０】
（３）ポリエステル樹脂の存在下に、ビニル系モノマーを添加し、重合並びにエステル化反応又は／及びエステル交換反応を行う。この製造方法では、反応時に、必要に応じてさらにポリエステル系モノマーを添加し重合しても良い。また、この製造方法では、前記（２）と同様に有機溶剤を適宜使用することができ、前記（１）と同様に反応時にワックスを添加しても良い。
【０１３１】
（４）ビニル系重合体及びポリエステル樹脂存在下に、ビニル系モノマー及び／又はポリエステル系モノマーを添加し、重合並びにエステル化反応又は／及びエステル交換反応を行う。この製造方法でも、前記（２）と同様に有機溶剤を適宜使用することができ、前記（１）と同様に反応時にワックスを添加しても良い。
【０１３２】
（５）ビニル系モノマー及びポリエステル系モノマーを混合して付加重合及び縮重合反応並びにエステル化反応又は／及びエステル交換反応を行う。この製造方法でも、前記（２）と同様に有機溶剤を適宜使用することができ、前記（１）と同様に反応時にワックスを添加しても良い。
【０１３３】
（６）上記（１）〜（５）で製造されたハイブリッド樹脂成分を含有する樹脂を、さらにビニル系重合体及び／又はポリエステル系樹脂と、例えば有機溶剤に溶解／膨潤させるなどして混合して、有機溶剤を留去する。
【０１３４】
（７）上記（１）〜（５）で製造されたハイブリッド樹脂成分を含有する樹脂の存在下に、さらにビニル系モノマー及び／又はポリエステル系モノマーを添加し、重合並びにエステル化反応又は／及びエステル交換反応を行う。この製造方法でも、前記（２）と同様に有機溶剤を適宜使用することができ、前記（１）と同様に反応時にワックスを添加しても良い。
【０１３５】
上記（１）〜（４）及び（６）の製造方法において、ビニル系重合体及び／又はポリエステル樹脂には、分子量や架橋度の異なる複数種類の重合体を使用することができる。
【０１３６】
上記（１）〜（７）の製造方法の中でも、特に（３）の製造方法が、分子量制御が容易であり、ハイブリッド樹脂成分の生成を制御することができ、かつワックスを添加する場合にはその分散状態を制御できる点で好ましい。
【０１３７】
本発明のトナーは、ワックスを含有する。本発明において、トナーは、示差熱分析（ＤＳＣ）における吸熱ピークを６０乃至１２０℃の温度領域に少なくとも一つ以上有することが好ましい。このような熱特性を有するトナーは、ＤＳＣにおける吸熱ピークを６０乃至１２０℃の温度領域に少なくとも一つ以上有するワックスを含有することにより達成することができる。
【０１３８】
トナーの示差熱分析における吸熱ピークが６０℃以上１２０℃以下に少なくとも一つ以上有することで、トナーが定着し始める低温領域からワックスが作用し、より定着性を高めることができ、低温定着性、耐高温オフセット性、及び耐ブロッキング性をより高めることができる。吸熱ピークが６０℃未満にある場合、耐ブロッキング性が悪化しやすく、吸熱ピークが１２０℃を超える場合は、低温定着性が悪化しやすい。
【０１３９】
ワックス及びトナーのＤＳＣ吸熱ピークは、示差熱分析測定装置（ＤＳＣ測定装置）、ＤＳＣ−７（パーキンエルマー社製）、ＤＳＣ２９２０（ＴＡインスツルメンツジャパン社製）や他機種を用いて、ＡＳＴＭ Ｄ３４１８−８２に準じて測定することができる。具体例としては、測定試料を２〜１０ｍｇの範囲で正確に秤量し、これをアルミパン中に入れ、リファレンスとして空のアルミパンを用い、測定温度範囲３０〜１６０℃の間で、昇温速度１０℃／ｍｉｎで、常温常湿下で測定を行う。
【０１４０】
本発明に用いられるワックスは、ＧＰＣの測定による重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が１．０〜２．０であることが好ましい。前記分子量比が上記範囲にあると、分子量分布が極めてシャープになり、好ましい。本発明においては、分子量分布が極めてシャープなワックスを使用することにより、離型効果の発現が素早く、さらに一層良好な耐定着巻きつき性及び耐高温オフセット性を達成する一方で、さらに耐ブロッキング性も悪化させることがないので好ましい。
【０１４１】
さらに、第一の形態のトナーにおいては、結着樹脂は、ハイブリッド樹脂からなることにより、これらのワックスが均一に分散されることから、この効果は顕著に現れる。シャープに溶けるワックスを用いることで離型効果を発揮し、ハイブリッド樹脂を用いることでワックス分散性が向上することから、ワックス分散性と離型効果を両立し、かつこれらをより向上させることができる。
【０１４２】
さらに、第二の形態においては、トナーに用いられる結着樹脂は、ポリエステル樹脂とハイブリッド樹脂からなるが、ポリエステル樹脂とハイブリッド樹脂の相溶性が良く、これらのワックスはハイブリッド樹脂への分散が良好であるため、結着樹脂中にワックスが均一に分散され、上述の効果は顕著に現れる。シャープに溶けるワックスを用いることで離型効果を発揮し、ポリエステル樹脂とハイブリッド樹脂を用いることでワックス分散性が向上し、離型効果をより効率的に発揮することができる。
【０１４３】
ワックスの分子量は、以下の条件で測定することができる。
装置：ＧＰＣ−１５０Ｃ（ウォーターズ社）
カラム：ＧＭＨ−ＨＴ３０ｃｍ、２連（東ソー社製）
温度：１３５℃溶媒：ｏ−ジクロロベンゼン（０．１質量％アイオノール添加）
流速：１．０ｍｌ／ｍｉｎ
試料：０．１５質量％のワックスを０．４ｍｌ注入
【０１４４】
以上の条件で測定し、ワックスの分子量算出にあたっては単分散ポリスチレン標準試料により作成した分子量校正曲線を使用する。さらに、Ｍａｒｋ−Ｈｏｕｗｉｎｋ粘度式から導き出される換算式に基づいてポリエチレン換算することでワックスの分子量を算出する。
【０１４５】
ワックスは、数平均分子量が２００乃至２０００（より好ましくは３００乃至１５００、さらに好ましくは３５０乃至１０００）であることが、結着樹脂への分散性、耐低温オフセット性、耐高温オフセット性、耐ブロッキング性、多数枚耐久性の点で、より好ましい。
【０１４６】
ワックスとしては、炭素と水素から成る低分子量炭化水素ワックス、ＯＨ基を有する長鎖アルキルアルコールワックス、ＣＯＯＨ基を有する長鎖アルキルカルボン酸ワックス、エステルワックスなどが挙げられる。
【０１４７】
低分子量炭化水素ワックスとしては、パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタムなどの石油系ワックス及びその誘導体；低分子量ポリエチレンの如き低分子量ポリオレフィンワックス；フィッシャートロプシュワックスの如きポリメチレンワックスが挙げられる。低分子量ポリオレフィンワックスは、通常Ｍｗ／Ｍｎの値が２．０を超えているので、Ｍｗ／Ｍｎが１．０乃至２．０になり、かつ、ＤＳＣ吸熱メインピークが６０乃至１２０℃になるように精製することが好ましい。
【０１４８】
長鎖アルキルアルコールワックスとしては、炭素数２０個乃至２００個を有する長鎖アルキルアルコールの混合物が挙げられ、長鎖アルキルカルボン酸ワックスとしては、炭素数２０個乃至２００個を有する長鎖アルキルカルボン酸の混合物が挙げられる。
【０１４９】
エステルワックスとしては、カルナバワックスを精製したワックス、キャンデリラワックスを精製したワックス、炭素数１５個乃至４５個の長鎖アルキルアルコールと炭素数１５個乃至４５個の長鎖アルキルカルボン酸とのエステル化合物を主成分とするワックスが挙げられる。本発明のトナーには、より有効な離型効果を発揮するために、シャープな分子量分布を有する傾向にある低分子量炭化水素ワックスが好ましい。
【０１５０】
本発明において、トナーには、帯電性をより安定させるために、荷電制御剤として金属化合物を結着樹脂１００質量部に対し０．１〜１０質量部、トナー粒子中に配合（内添）、又はトナー粒子と混合（外添）することが好ましい。荷電制御剤によって、現像システムに応じた最適な荷電量コントロールが可能となる。
【０１５１】
荷電制御剤として金属化合物を用い、かつ、Ｗ２＞Ｗ１を満たすことによって、トナー分子量分布において高分子量側に多く存在する多価カルボン酸と、金属化合物との間で架橋が進み、非オフセット領域が広がる。さらに、低分子量側成分は、高分子量側成分ほどではないが適度に架橋され、その結果、トナー中のワックスの分散性が良好になる。
【０１５２】
本発明のトナーを負荷電性に制御する荷電制御剤としては、例えば有機金属錯体、キレート化合物が有効であり、モノアゾ金属化合物、アセチルアセトン金属化合物、芳香族ハイドロキシカルボン酸、芳香族ダイカルボン酸系の金属化合物がある。他には、芳香族ハイドロキシカルボン酸、芳香族モノカルボン酸、芳香族ポリカルボン酸、及びそれらの金属塩、それらの無水物、それらのエステル類、ビスフェノールのごときフェノール誘導体類がある。
【０１５３】
本発明のトナーを正荷電正に制御する荷電制御剤としては、例えばニグロシン及び脂肪族金属塩等による変性物；トリブチルベンジルアンモニウム−１−ヒドロキシ−４−ナフトスルホン酸塩、テトラブチルアンモニウムテトラフルオロボレート等の四級アンモニウム塩、及びこれらの類似体であるホスホニウム塩の如きオニウム塩及びこれらのレーキ顔料、トリフェニルメタン染料及びこれらのレーキ顔料（レーキ化剤としては燐タングステン、燐モリブデン酸、燐タングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フエリシアン化物、フェロシアン化物等）、高級脂肪酸の金属塩；ジブチルスズオキサイド、ジオクチルスズオキサイド、ジシクロヘキシルスズオキサイド等のジオルガノスズオキサイド；ジブチルスズボレート、ジオクチルスズボレート、ジシクロヘキシルスズボレートの如きジオルガノスズボレート類；これらを単独で用い、あるいは二種類以上組み合わせて用いることができる。
【０１５４】
上述した荷電制御剤は微粒子状として用いることが好ましい。
【０１５５】
本発明では、分子中に金属原子を有する芳香族ヒドロキシカルボン酸を用いることが好ましく、耐久初期の帯電性の立ち上がりが良好な、アルミニウムの芳香族ヒドロキシカルボン酸化合物を使用することが好ましい。また、アルミニウムの芳香族ヒドロキシカルボン酸化合物を使用することで、良好な架橋効果を得ることができる。
【０１５６】
本発明では、長期にわたる耐久において帯電性が安定している、モノアゾ鉄化合物を使用することも好ましい。
【０１５７】
さらに本発明では、長期にわたり帯電性を維持するために、アルミニウムの芳香族ヒドロキシカルボン酸化合物とモノアゾ鉄化合物を併用して使用することが好ましい。特に、アルミニウムの芳香族ヒドロキシカルボン酸化合物を０．１〜１質量部、モノアゾ鉄化合物を０．５〜３質量部トナー中に含有することが、架橋効果と帯電性能を適切に制御するうえで好ましい。
【０１５８】
本発明で好ましく用いられる金属化合物における、ヒドロキシカルボン酸部位及びアゾ化合物部位の例を下記に示す。
【０１５９】
【化４】

【０１６０】
【化５】

【０１６１】
【化６】

【０１６２】
【化７】

【０１６３】
【化８】

【０１６４】
さらに上記ヒドロキシカルボン酸及びアゾ化合物を用いた金属化合物の具体例を下記に示す。
【０１６５】
【化９】

【０１６６】
【化１０】

【０１６７】
【化１１】

【０１６８】
【化１２】

【０１６９】
本発明のトナーは着色剤を含む。本発明に用いられる着色剤は、イエロー、マゼンタ、シアン、及びブラックの、通常使用される着色剤から適宜選択される。
【０１７０】
イエロー着色剤としては、縮合アゾ化合物、イソインドリノン化合物、アンスラキノン化合物、アゾ金属錯体、メチン化合物、アリルアミド化合物に代表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１７、６２、７４、８３、９３、９４、９５、９７、１０９、１１０、１１１、１２０、１２７、１２８、１２９、１４７、１６８、１７４、１７６、１８０、１８１、１９１が好適に用いられる。
【０１７１】
マゼンタ着色剤としては、縮合アゾ化合物、ジケトピロロピロール化合物、アンスラキノン、キナクリドン化合物、塩基染料レーキ化合物、ナフトール化合物、ベンズイミダゾロン化合物、チオインジゴ化合物、ペリレン化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントレッド２、３、５、６、７、２３、４８：２、４８：３、４８：４、５７：１、８１：１、１４４、１４６、１６６、１６９、１７７、１８４、１８５、２０２、２０６、２２０、２２１、２５４が特に好ましい。
【０１７２】
シアン着色剤としては、銅フタロシアニン化合物及びその誘導体、アンスラキノン化合物、塩基染料レーキ化合物などが利用できる。具体的には、Ｃ．Ｉ．ピグメントブルー１、７、１５、１５：１、１５：２、１５：３、１５：４、６０、６２、６６が特に好適に利用できる。
【０１７３】
黒色着色剤として、カーボンブラック、磁性体、以下に示すイエロー／マゼンタ／シアン着色剤を用い、黒色に調色されたものが利用される。
【０１７４】
本発明において、着色剤は、黒色着色剤として磁性体以外の染料及び顔料を用いる場合には、樹脂１００質量部に対し、０．１〜１０質量部トナーに含有され、磁性体を用いた場合には、他の着色剤と異なり、樹脂１００質量部に対し３０〜２００質量部がトナーに含有される。
【０１７５】
磁性体としては、鉄、コバルト、ニッケル、銅、マグネシウム、マンガン、アルミニウム又はケイ素の元素を含む金属酸化物がある。中でも、四三酸化鉄、γ−酸化鉄など、酸化鉄を主成分とするものが好ましい。
【０１７６】
本発明のトナーには、トナー帯電性コントロールの観点からケイ素元素又はアルミニウム元素の如き他の金属元素を含有する磁性体を用いても良い。これらの磁性粒子は、窒素吸着法によるＢＥＴ比表面積が２〜３０ｍ^２／ｇ、特に３〜２８ｍ^２／ｇであることが良く、さらにモース硬度が５〜７であることが好ましい。なお、比表面積はＢＥＴ法にしたがって試料表面に窒素ガスを吸着させ、ＢＥＴ多点法を用いて比表面積を算出することができる。
【０１７７】
磁性体の形状としては、８面体、６面体、球状、針状、鱗片状があるが、８面体、６面体、球体、不定形型の異方性の少ないものが画像濃度を高める上で好ましく、球状であることが特に好ましい。さらに、画像濃度をより高める上で、シリカを含有した磁性体が特に好ましい。
【０１７８】
磁性体の平均粒径としては、０．０５〜１．０μｍが好ましく、さらに好ましくは０．１〜０．６μｍ、さらには０．１〜０．４μｍが好ましい。磁性体の平均粒径の測定は、磁性粉の透過型電子顕微鏡写真を撮影し、４万倍に拡大したものにつき、粒径０．０１μｍ以上の粒子を任意に２５０個選定後、投影径の中のＭａｒｔｉｎ径（定方向に投影面積を２等分する線分の長さ）を測定し、これを個数平均径で表す方法等により求められる。
【０１７９】
本発明においては、帯電安定性、現像性、保存性向上のため、シリカ、アルミナ、チタニア等の酸化物やその複酸化物等の無機微粉体を外添することが好ましい。さらに無機微粉体はシリカであることが好ましい。
【０１８０】
例えば、かかるシリカは、ケイ素ハロゲン化合物やアルコキシドの蒸気相酸化により生成されたいわゆる乾式シリカ、又はヒュームドシリカと称される乾式シリカ、及びアルコキシド、水ガラスから製造されるいわゆる湿式シリカの両者が使用可能であるが、表面及びシリカ微粉体の内部にあるシラノール基が少なく、またＮａ_２Ｏ、ＳＯ_３ ^２−等の製造残滓の少ない乾式シリカが好ましい。
【０１８１】
乾式シリカにおいては、製造工程において例えば、塩化アルミニウム、塩化チタン等他の金属ハロゲン化物をケイ素ハロゲン化物と共に用いることによって、シリカと他の金属酸化物の複合微粉体を得ることも可能であり、前記シリカにはそれらも包含する。
【０１８２】
本発明に用いられる無機微粉体は、ＢＥＴ法で測定した窒素吸着による比表面積が３０ｍ^２／ｇ以上であることが好ましい。特に５０〜４００ｍ^２／ｇの範囲のものが良好な結果を得る上でより好ましい。無機微粉体は、トナー粒子１００質量部に対して０．１〜８質量部添加されることが好ましく、０．５〜５質量部添加されることがより好ましく、１．０を超えて３．０質量部まで使用されることがさらに好ましい。
【０１８３】
本発明に用いられる無機微粉体は、必要に応じ疎水化、帯電性制御の目的で、シリコーンワニス、シリコーンオイル、各種変性シリコーンオイル、シランカップリング剤、官能基を有するシランカップリング剤、その他有機ケイ素化合物、有機チタン化合物の如き処理剤の一種又は二種以上により処理されていることが好ましい。
【０１８４】
無機微粉体の比表面積は、ＢＥＴ法にしたがって、比表面積測定装置オートソープ１（湯浅アイオニクス社製）を用いて試料表面に窒素ガスを吸着させ、ＢＥＴ多点法を用いて算出することができる。安定したトナーの保存性を維持する上で、無機微粉体は、少なくともシリコーンオイルで処理されていることが好ましい。
【０１８５】
本発明のトナーには、シリカ微粉体等の無機微粉体以外の外部添加剤を必要に応じて添加しても良い。このような外部添加剤としては、例えば、帯電補助剤、導電性付与剤、流動性付与剤、ケーキング防止剤、熱ロール定着時の離型剤、滑剤、研磨剤などの働きをする樹脂微粒子が挙げられる。
【０１８６】
本発明のトナーは、結着樹脂、着色剤及びワックスを少なくとも含有する混合物を溶融混練する工程を経て製造されることが好ましい。より具体的に、本発明のトナーを製造する方法としては、上述したようなトナー構成材料をボールミルその他の混合機により十分混合した後、熱ロールニーダー、エクストルーダーの如き熱混練機を用いて良く混練し、冷却固化後、機械的に粉砕し、粉砕粉を分級することによってトナーを得る方法が好ましい。
【０１８７】
本発明のトナーを製造する方法としては、他には、結着樹脂を構成すべき単量体に所定の材料を混合して乳化懸濁液とした後に、重合させてトナーを得る重合法トナー製造法；コア材及びシェル材からなるいわゆるマイクロカプセルトナーにおいて、コア材あるいはシェル材、あるいはこれらの両方に所定の材料を含有させる方法；結着樹脂溶液中に構成材料を分散した後、噴霧乾燥することによりトナーを得る方法が挙げられる。さらに、必要に応じ、所望の添加剤とトナー粒子とをヘンシェルミキサーの如き混合機により十分に混合し、本発明のトナーを製造することができる。このように本発明のトナーは、通常知られている製造方法や、通常使用されている製造装置を用いて製造することが可能である。
【０１８８】
本発明のトナーの製造に使用される製造装置として、例えば混合機としては、ヘンシェルミキサー（三井鉱山社製）；スーパーミキサー（カワタ社製）；リボコーン（大川原製作所社製）；ナウターミキサー、タービュライザー、サイクロミックス（ホソカワミクロン社製）；スパイラルピンミキサー（太平洋機工社製）；レーディゲミキサー（マツボー社製）が挙げられる。
【０１８９】
混練機としては、例えばＫＲＣニーダー（栗本鉄工所社製）；ブス・コ・ニーダー（Ｂｕｓｓ社製）；ＴＥＭ型押し出し機（東芝機械社製）；ＴＥＸ二軸混練機（日本製鋼所社製）；ＰＣＭ混練機（池貝鉄工所社製）；三本ロールミル、ミキシングロールミル、ニーダー（井上製作所社製）；ニーテックス（三井鉱山社製）；ＭＳ式加圧ニーダー、ニダールーター（森山製作所社製）；バンバリーミキサー（神戸製鋼所社製）が挙げられる。
【０１９０】
粉砕機としては、例えばカウンタージェットミル、ミクロンジェット、イノマイザ（ホソカワミクロン社製）；ＩＤＳ型ミル、ＰＪＭジェット粉砕機（日本ニューマチック工業社製）；クロスジェットミル（栗本鉄工所社製）；ウルマックス（日曹エンジニアリング社製）；ＳＫジェット・オー・ミル（セイシン企業社製）；クリプトン（川崎重工業社製）；ターボミル（ターボ工業社製）；スーパーローター（日清エンジニアリング社製）が挙げられる。
【０１９１】
分級機としては、例えばクラッシール、マイクロンクラッシファイアー、スペディッククラッシファイアー（セイシン企業社製）；ターボクラッシファイアー（日新エンジニアリング社製）；ミクロンセパレータ、ターボフレックス（ＡＴＰ）、ＴＳＰセパレータ（ホソカワミクロン社製）；エルボージェット（日鉄鉱業社製）、ディスパージョンセパレータ（日本ニューマチック工業社製）；ＹＭマイクロカット（安川商事社製）が挙げられる。
【０１９２】
粗粒等を篩い分けるために用いられる篩い装置としては、例えばウルトラソニック（晃栄産業社製）；レゾナシープ、ジャイロシフター（徳寿工作所社）；バイブラソニックシステム（ダルトン社製）；ソニクリーン（新東工業社製）；ターボスクリーナー（ターボ工業社製）；ミクロシフター（槙野産業社製）；円形振動篩い等が挙げられる。
【０１９３】
次に、本発明において使用される加熱定着装置について説明する。
本発明においては、未定着画像が形成された記録材を、定着部材と加圧部材の間で所定の温度に維持されたニップ部を通過させることにより、上記未定着画像を記録材上に定着させる加熱定着装置において、上記定着部材としての可撓性を有する金属製スリーブ及び通電発熱抵抗層、該金属製スリーブ内面に接触状態にある加熱用部材としての加熱用ヒータ、及び加圧部材を有する加熱定着装置が用いられる。前記金属製スリーブの厚みは２０μｍ〜１００μｍであることが好ましい。
【０１９４】
また、金属製スリーブ内面は接触熱抵抗を低く抑え、定着ニップ部への伝熱を良好にするために、表面粗さＲｚ＝３μｍ以下とすることが好ましい。さらに金属製スリーブ外面の表面粗さをＲｚ＝３μｍ以下とし、接着層としてのプライマ層を含め離型性層を厚み２０μｍ以下で形成することも好ましい構成である。
【０１９５】
これにより、熱伝導性が良好な金属スリーブ内面から加熱用ヒータにより接触加熱することで、画像形成装置の高速化に対応した加熱定着を高い熱効率で実施できる。
【０１９６】
よって、画像形成装置がプリント信号を受信していない状態のスタンバイ中にヒータへの通電をシャットダウンしておくことができ、省エネルギの加熱定着が実現できる。
【０１９７】
また、室温状態から画像形成装置の電源をＯＮした場合でも、即座にプリント信号受信可能になるため、ユーザーを待たせることがない。
【０１９８】
よって画像形成装置が高速化した場合でも、クイックスタート性に優れ、ファーストプリントタイムも速い加熱定着装置を提供することが可能となる。
【０１９９】
また、樹脂製フィルムに比べ剛性の高い金属製スリーブを使用することで、加圧力を高く設定することが可能になり、さらに画像形成装置の高速化に対応することが可能になる。
【０２００】
また、該金属製スリーブ内面に接触し、定着ニップ部を加熱する加熱用ヒータの表面を耐熱性のあるポリイミド樹脂等の樹脂部材とする。これにより、金属製スリーブ内面はスムーズに加熱用ヒータ面を摺動することができ、高耐久の加熱定着が可能となる。
【０２０１】
また、金属製スリーブに上記表面粗さ内の周方向のスジ加工を施すと、金属スリーブの回転をスムーズにし、加熱用ヒータコートを傷つけにくくすることが可能である。
【０２０２】
また、未定着トナー像を記録材上に固着させる加熱定着装置においてトナーと逆極性のバイアスを加圧ローラ側に印加し、金属製スリーブを接地あるいはダイオード接続することで、紙粉、トナー等が金属製スリーブに吸着されることをより一層防止することが可能となる。これにより耐久によって金属製スリーブが汚れる等の問題もなく、高耐久の加熱定着装置を提供できる。
【０２０３】
このような構成の定着装置と上記トナーを組み合わせることで、定着性、高温オフセット性に優れ、巻きつきの発生しないクイックスタート性を有する高速オンデマンド定着を達成することが可能になる。
【０２０４】
（Ａ）画像形成装置例
図１は画像形成装置例の概略構成模型図である。１は感光ドラムであり、ＯＰＣ、アモルファスＳｅ、アモルファスＳｉ等の感光材料がアルミニウムやニッケルなどのシリンダ状の基盤上に形成されている。
【０２０５】
感光ドラム１は矢印の方向に回転駆動され、まず、その表面は帯電装置としての帯電ローラ２によって一様帯電される。
【０２０６】
次に、画像情報に応じてＯＮ／ＯＦＦ制御されたレーザビーム３による走査露光が施され、静電潜像が形成される。
【０２０７】
この静電潜像は、現像装置４で現像、可視化される。現像方法としては、ジャンピング現像法、二成分現像法、ＦＥＥＤ現像法などが用いられ、イメージ露光と反転現像とを組み合わせて用いられることが多い。
【０２０８】
可視化されたトナー像は、転写装置としての転写ローラ５により、所定のタイミングで搬送された記録材Ｐ上に感光ドラム１上より転写される。
【０２０９】
ここで感光ドラム１上のトナー像の画像形成位置と記録材の先端の書き出し位置が合致するようにセンサ８にて記録材Ｐの先端を検知し、タイミングを合わせている。所定のタイミングで搬送された記録材Ｐは感光ドラム１と転写ローラ５に一定の加圧力で挟持搬送される。
【０２１０】
このトナー像が転写された記録材Ｐは加熱定着装置６へと搬送され、定着される。
【０２１１】
一方、感光ドラム１上に残存する転写残りの残留トナーは、クリーニング装置７により感光ドラム１表面より除去される。
【０２１２】
（Ｂ）加熱定着装置６
図２は加熱定着装置６の概略構成模型図である。１０は定着部材、２０は加圧部材であり、互いに圧接させて定着ニップ部を形成させてある。定着部材１０は、加熱用部材としてのヒータ１１、断熱ステイホルダ１２、定着スリーブ１３等からなる。加圧部材２０は耐熱性弾性加圧ローラである。
【０２１３】
ａ）定着スリーブ１３
定着スリーブ１３は熱容量の小さなスリーブであり、クイックスタートを可能にするために厚１００μｍ以下の厚みで耐熱性、高熱伝導性を有するＳＵＳ、Ａｌ、Ｎｉ、Ｃｕ、Ｚｎ等の金属部材を単独あるいは合金部材を基層とした金属製スリーブ（フィルム）である。
【０２１４】
また、長寿命の加熱定着装置を構成するために充分な強度を持ち、耐久性に優れた金属製スリーブとして、厚さ２０μｍ以上の厚みが必要である。よって金属製スリーブ１３の厚みとしては２０μｍ以上１００μｍ以下が最適である。
【０２１５】
さらにオフセット防止や記録材の分離性を確保するために表層にはＰＴＦＥ（ポリテトラフルオロエチレン）、ＰＦＡ（テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体）、ＦＥＰ（テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体）、ＥＴＦＥ（エチレン−テトラフルオロエチレン共重合体）、ＣＴＦＥ（ポリクロロトリフルオロエチレン）、ＰＶＤＦ（ポリビニリデンフルオライド）等のフッ素樹脂、シリコーン樹脂等の離型性の良好な耐熱樹脂を混合ないし単独で被覆したものである。
【０２１６】
被覆の方法としては、金属製スリーブ基材の外面に接着層としてのプライマー層を塗布した後に上記離型性層をディッピング、粉体スプレー等の塗布によるものや、あるいはチューブ状に形成されたものを金属製スリーブの表面に被せる方式のものであっても良い。
【０２１７】
なお、金属製スリーブの内外面の表面性及び離型性層の厚み等については後記ｅ）項で詳述する。
【０２１８】
ｂ）加熱用ヒータ１１
加熱用ヒータ１１は定着スリーブである金属製スリーブ１３の内部に具備され、これにより記録材Ｐ上のトナー像を溶融、定着させるニップ部の加熱を行う。加熱用ヒータ近傍の構成模型図を図３に示す。図３において、加熱用ヒータ１１は、アルミナ、ＡｌＮ（チッ化アルミ）等の高絶縁性のセラミックスやポリイミド、ＰＰＳ、液晶ポリマー等の耐熱性樹脂からなる基板１１ａの表面に長手方向に沿って、例えばＡｇ／Ｐｄ（銀パラジウム）、ＲｕＯ_２、Ｔａ_２Ｎ等の通電発熱抵抗層１１ｂをスクリーン印刷等により、厚み１０μｍ程度、幅１〜５ｍｍ程度の線状もしくは細帯状に塗工して形成し、通電発熱抵抗層１１ｂの表面には、金属製スリーブ１３との摺擦に耐えることが可能な薄層のフッ素樹脂層、ポリイミド、ポリアミドイミド、ＰＥＥＫ等の耐熱性樹脂層からなる摺動層を設けた通電加熱用部材である。
【０２１９】
上記基板１１ａの背面（定着ニップ部Ｎと反対側）には通電発熱抵抗層１１ｂの発熱に応じて昇温した加熱用ヒータ１１の温度を検知するためのサーミスタ等の温度検知素子１４が配設されている。この温度検知素子１４の信号に応じて、図５に示す長手方向端部にある電極部１１ｆ及び１１ｇから通電発熱抵抗層１１ｂに印加される電圧のデューティー比や波数等を適切に制御することで、定着ニップ部Ｎ内での温調温度を略一定に保ち、記録材Ｐ上のトナー像を定着するのに必要な加熱を行う。温度検知素子１４から不図示の温度制御部へのＤＣ通電は不図示のＤＣ通電部及びＤＣ電極部を介して不図示のコネクターにより達成している。
【０２２０】
ヒータ基板１１ａとして熱伝導性の良好なＡｌＮ（チッ化アルミ）等を用いた場合には、図４のように、通電発熱抵抗層１１ｂを上記基板１１ａに対して定着ニップ部Ｎと反対側に形成してあっても良い。図４において、１１ｄは基板１１ａ上に形成された通電発熱抵抗層１１ｄと温度検知素子１４の間の耐電圧を満足するために設けたガラスコート、フッ素樹脂層等の保護層である。また、１１ｅは上述の１１ｃと同様に金属製スリーブとの摺擦に耐えることが可能な薄層のフッ素樹脂層、ポリイミド、ポリアミドイミド、ＰＥＥＫ等の耐熱性樹脂層からなる摺動層である。
【０２２１】
また、上記金属製スリーブ１３の内面において、加熱用ヒータ１１の定着ニップ部Ｎ側の形状を曲面とすることで、金属製スリーブ１３に屈曲負荷を与えないようにした方が長寿命の定着部材が形成される。あるいは、ヒータの金属製基板上の定着ニップ部とは反対側に絶縁層、通電発熱抵抗層を順次積層してなる金属製加熱用ヒータであり、該金属製基板は定着ニップ部側が金属製スリーブと同方向に湾曲した形状であっても良い。
【０２２２】
ｃ）断熱ステイホルダ１２
断熱ステイホルダ１２は、加熱用ヒータ１１を保持し、定着ニップ部Ｎと反対方向への放熱を防ぐための断熱部材であり、液晶ポリマー、フェノール樹脂、ＰＰＳ、ＰＥＥＫ等により形成されており、金属製スリーブ１３が余裕をもってルーズに外嵌されていて、矢印の方向に回転自在に配置されている。また、金属製スリーブ１３は内部の加熱用ヒータ１１及び断熱ステイホルダ１２に摺擦しながら回転するため、加熱用ヒータ１１及び断熱ステイホルダ１２と金属製スリーブ１３の間の摩擦抵抗を小さく抑える必要がある。このため加熱用ヒータ１１及び断熱ステイホルダ１２の表面に耐熱性グリース等の潤滑剤を少量介在させてある。これにより金属製スリーブ１３はスムーズに回転することが可能となる。
【０２２３】
ｄ）加圧ローラ２０
加圧ローラ２０は、芯金２１の外側に、シリコーンゴムやフッ素ゴム等の耐熱ゴムあるいはシリコーンゴムを発泡して形成された弾性層２２からなり、この上にＰＦＡ、ＰＴＦＥ、ＦＥＰ等の離型性層２３を形成してあってもよい。
【０２２４】
定着部材１０は上記の加圧部材２０の方向に図４に示すように断熱ステイホルダ１２の一部、もしくは断熱ステイホルダと嵌合等により取り付けられた部材を介してバネ等の加圧手段１７により、長手方向両端部から加熱定着に必要な定着ニップ部Ｎを形成するべく十分に加圧されている。
【０２２５】
また、加圧ローラ２０の芯金２１端部に取り付けられた駆動ギア１６により加圧ローラ２０を回転駆動し、加圧ローラ表面と金属製フィルム表面の摩擦により金属製フィルムを所定の速度に従動回転させる。
【０２２６】
以上が加熱定着装置６の構成であるが、図２において記録材Ｐは不図示の供給手段によって適宜供給され、耐熱性の定着入口ガイド１５に沿って加熱部材１０と加圧部材２０によって形成される定着ニップ部Ｎに搬送される。
【０２２７】
ｅ）金属製スリーブ１３の内外面の表面粗さ等について
ここで金属製スリーブ１３の内外面の表面粗さ、離型性層の厚み等に関して以下に説明する。
【０２２８】
まず、金属製スリーブ１３の内面は上記加熱用ヒータ１１と所定の接触幅をもって接触することで加熱用ヒータ１１より発した熱を定着ニップ部Ｎへ伝熱する必要があり、従来使用されてきた輻射熱による加熱を行う熱ローラ定着装置（図１３）とは思想が異なる。よって加熱用ヒータ１１と接触伝熱する金属製スリーブ１３内面の表面粗さは、熱効率に大いに影響する。特に加熱用ヒータ１１の摺動層１１ｃ（図３）あるいは１１ｅ（図４）の表面と金属製スリーブ１３の内面との接触熱抵抗が大きくなると、熱効率が悪化し、定着不良を起こしてしまう。仮に熱伝導グリース等を介在させた場合でも熱効率の高い加熱定着装置を構成するためには、所定以下の表面粗さに抑えることが好ましい。
【０２２９】
また、金属製スリーブ１３の外面には、離型性層を形成するが、離型性層は一般にフッ素樹脂より形成されるため、金属製スリーブ１３の熱伝導性に比べ極端に低い熱伝導性となる。よって、あまり厚く形成すると、熱伝導の悪化を招き画像形成装置の高速化に対し、定着ニップ部Ｎで記録材Ｐ上のトナー像に対し十分な熱供給ができなくなる。よって薄い離型性層を金属製スリーブ１３上に形成する必要がある。このとき、金属製スリーブ１３外面の表面粗さは所定以下に抑えることが好ましい。すなわち薄い離型性層では、金属製スリーブ１３外面の表面粗さを緩和する効果が得られず、金属製スリーブ１３外面に離型性層を塗布形成した後の表面粗さは金属スリーブ１３素管の表面粗さと同等か若干小さい粗さの表面粗さとなる。よって、金属製スリーブ１３素管の表面粗さが大きいと離型性層を塗布形成後も大きな表面粗さとなり、定着ニップ部Ｎで記録材Ｐとの密着力が得られず、定着不良を引き起こす可能性が大きくなる。
【０２３０】
以上のことから、金属製スリーブ１３の外面の表面粗さを所定以下とし、接着層としてのプライマー層を含み離型性層を所定以下の厚みで塗布形成することにより、十分な定着性能が得られ、画像形成装置の高速化に対応可能となる。
【０２３１】
また、金属製スリーブ１３に周方向に所定以下の表面粗さを有する凹凸形状を施すことにより、金属製スリーブ１３の回転をよりスムーズにすると共に加熱用ヒータ１１の表面にコーティングした離型性層を傷つけにくくする。これによりさらに高耐久の高速対応可能な加熱定着用金属製スリーブ１３を提供する。
【０２３２】
前記図２における金属製スリーブ１３の製法を以下に示す方法により達成し、金属製スリーブ１３に周方向に適度な凹凸を形成する。
【０２３３】
図６から図１０に金属製スリーブ１３の主な製法を示す。まず、図６において、３１は金属製スリーブ１３の基材であり、０．１ｍｍ〜０．５ｍｍ程度のＳＵＳ、Ａｌ、Ｎｉ、Ｃｕ、Ｚｎ等の単独ないし、合金状態で形成される金属平板（プランク）である。３２は一般的な深絞り製法における円形内型（ポンチ）、３３は円筒容器状の外型（ダイス）であり、金属材料の表面に超硬メッキ等を施した金型である。図６において、金属平板３１を内型３２と外型３３の間に挟み矢印の方向に内型３２を外型３３の方向へ押し込む。また、金属平板３１と外型３３の間には粘度の高い潤滑油、あるいは黒鉛、二硫化モリブデン等の固体潤滑剤を介在させ、絞り性を良くしてある。以上の工程を通常は２〜４回程度、異なる金型で深絞り加工することにより、図７に示すようなカップ状の金属製円筒部材３４を製造する。
【０２３４】
次に、この金属製円筒部材３４が所定の厚みに形成されるようにしごき加工を施す。しごき加工としては、圧延加工、引き抜き加工、絞り加工等どのような加工を途中に経緯してもよいが、最終加工としては、以下に示すような加工方法により金属製スリーブの周方向に所定以下の凹凸を有する加工を施す。例えば、図８及び９に示すような加工方法がある。図８は一般的な絞りスピニング加工であり、固定台３６ｃに取り付けられた軸３６ｂに回転自在に取り付けられた押し当てローラ３６ａを金属製内型３５と所定の距離だけ常に離間した状態で金属製内型３５方向へ押し付られるようになっている。金属製内型３５に取り付けられた上記カップ状に深絞り加工を施した金属製円筒部材３４をはめ込み、押え部材３７によって金属製円筒部材３４のカップ形状底部が金属製内型３５に密着状態となって固定される。この状態で金属製内型３５、金属製円筒部材３４、押え部材３７を図の矢印の方向に回転させながら、紙面右方へ徐々に送り込む。端部からは金属製内型３５と所定距離を保って回転自在のローラが押し当てられる。
【０２３５】
これにより、金属製円筒部材３４の端部から徐々にしごき加工により薄肉化され、最終的には図１０に示すように本実施例における金属製スリーブ１３の所定厚みにまで加工されたカップ状の金属製円筒部材３９がしごき加工により形成される。
【０２３６】
金属製円筒部材３９には、周方向に絞りスピニング加工時のローラ押し当ての凹凸跡３９ａが残る。最終的には、金属製円筒部材３９のカップ形状底部を切り落とすことにより、本実施例の金属製スリーブ１３を得る。
【０２３７】
また、図９に示すように、押し当てローラの代わりに段階的に内径が小さく形成された連続ダイス３８ａ、３８ｂ、３８ｃの内側に金属製内型３５と押え部材３７により固定された金属製円筒部材３４を回転させながら送り込みしごき加工により薄肉化しながら周方向の凹凸形状を付与させる方式であっても良い。
【０２３８】
その他、へら絞り加工等、金属製スリーブ１３の周方向に所定量以下の凹凸を形成できる方法であれば、どのようなしごき加工の加工方法であっても構わない。
【０２３９】
以上の製法で製造した金属製スリーブ１３を用いて、未定着画像が形成された記録材Ｐを加熱定着する場合、熱伝導の観点から、上記周方向の凹凸は３μｍ以下に抑えることが好ましい。
【０２４０】
金属製スリーブ１３の周方向に３μｍ以下の凹凸を形成する。好ましくは、長手方向の表面粗さＲｚを３μｍ以下とし、周方向の表面粗さＲｚ’との関係をＲｚ＞Ｒｚ’とすることで、加熱定着装置の回転駆動を低く抑え、回転をスムーズにすると共に、耐久による金属製スリーブ内面に接触する加熱用ヒータの樹脂コートを傷つけにくくし、加熱定着装置のさらなる高耐久、高速化を達成することが可能になる。
【０２４１】
さらに、金属製スリーブ１３と加圧部材である加圧ローラ２０の間に電位差を形成し、かつ金属製スリーブ１３を接地状態、もしくはダイオードを介して接地状態とすることで金属製スリーブ１３に紙粉やトナーを付着しにくい構成とすることで、耐久を通じて離型性を維持する加熱定着装置を提供することが可能になる。
【０２４２】
加熱定着装置のより詳しい構成を図１１及び１２に示す。図１１及び１２において、加圧部材である加圧ローラ２０の弾性層２２は、導電性シリコーンゴム、導電性シリコーンスポンジ等からなる導電性付与された弾性層であり、加圧ローラ芯金２１あるいは、導電性弾性層２２に導電性カーボンチップ等よりなるチップ電極２５を介してバイアス印加手段２４によってトナー像と逆極性のバイアスを印加する。
【０２４３】
図では、トナーが現像部でマイナス帯電される画像形成装置を元に図示しており、加圧ローラ芯金部２１には、プラスバイアスが印加される構成となっている。
【０２４４】
よってトナーが現像部でプラス帯電される画像形成装置の場合、加圧ローラ芯金２１には、マイナスバイアスが印加される構成となる。
【０２４５】
また、金属製スリーブ１３の端部では、接着層としてのプライマー層、フッ素樹脂層からなる離型性層がコーティングされていない金属製スリーブ素材がむき出しになっている部位１３ａを設け、この部位１３ａよりアモルファス導電繊維よりなる導電ブラシ１８を介して接地状態に構成されている。
【０２４６】
あるいは、トナー像と同電位の電荷が金属製フィルムに保持されるようにダイオード接続されていても良い。
【０２４７】
以上の構成により、加圧ローラ２０側に積極的にバイアス印加する構成とすることで、金属製スリーブ１３には、紙粉、トナー等が吸着されにくくなる。
【０２４８】
よってパルプ材を主原料とするカット紙等に形成されたトナー像を加熱定着する場合の上記加熱定着装置においては、表面粗さＲｚ＝３μｍ以下とした金属製スリーブ１３の表面の離型性層には、静電気的にも紙粉やトナーの汚染が発生しづらく、耐久によって離型性が損なわれることがないため、長寿命の加熱定着装置が提供される。
【０２４９】
（その他）
・ 定着装置は、オイル系定着であってもオイルレス系であっても同様に効果がある。
・ 加熱用部材（ヒータ）は電磁誘導発熱性部材であってもよい。
・ 本発明の定着装置には、記録材上の画像を仮定着処理する像加熱装置、つや等の画像表面性を改質する像加熱装置等も含むものである。
【０２５０】
本発明の画像形成方法において、記録材上に未定着トナー画像を形成するまでの工程は、前述した本発明のトナーを用いること以外は特に限定されない。本発明の画像形成方法では、例えば感光体の帯電、静電潜像の形成、トナーによる静電潜像の現像、及び記録材へのトナー画像の転写等、公知の工程で記録材上に未定着トナー画像を形成することができる。また、本発明の画像形成方法では、他の工程をさらに採用しても良く、例えば転写後における感光体上のトナーを除去するためのクリーニング工程、現像時に感光体上のトナーを回収する現像兼クリーニング工程、フルカラー画像形成に適用したときの中間転写工程、中間転写体のクリーニング工程、帯電前の感光体の表面電位を揃えるための前露光工程等を任意に採用することができる。
【０２５１】
【実施例】
以下実施例をもって本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
【０２５２】

上記ポリエステル系モノマーをジブチル錫オキシド７．０ｍｍｏｌとともにオートクレーブに仕込み、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置及び攪拌装置を装着し、窒素雰囲気下にて減圧しながら常法にしたがって２１０℃まで加熱し、縮重合反応を行うことにより、ポリエステル樹脂Ａを得た。
【０２５３】
次に、キシレン５０質量部に、ここで得られたポリエステル樹脂Ａ８５質量部、スチレン／２−エチルヘキシルアクリレート（各モノマーの質量％：８４／１６）のビニル系モノマー混合液１５質量部、及びエステル化触媒としてジブチル錫オキサイド０．３質量部をオートクレーブに仕込み、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置及び攪拌装置を装着し、窒素雰囲気下にて減圧しながら常法にしたがって１１０℃まで加熱して溶解・膨潤した。
【０２５４】
次いで、ｔ−ブチルハイドロパーオキサイド１質量部をキシレン１０質量部に溶解したラジカル開始剤溶液を、窒素雰囲気下にて約３０分かけて滴下した。その温度でさらに１０時間保持してラジカル重合反応を終了した。さらに加熱しながら減圧して、脱溶剤することにより、ハイブリッド樹脂成分を含む結着樹脂ａを得た。結着樹脂ａの物性を表１に示す。
【０２５５】
＜結着樹脂製造例２＞
ＢＰＡ−ＰＯ ２５ｍｏｌ％
ＢＰＡ−ＥＯ ２５ｍｏｌ％
ＴＰＡ １４ｍｏｌ％
ＴＭＡ １８ｍｏｌ％
ＦＡ １８ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｂを得た。
【０２５６】
ポリエステル樹脂Ｂを９０質量部、ビニル系モノマー混合液１０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｂを得た。結着樹脂ｂの物性を表１に示す。
【０２５７】
＜結着樹脂製造例３＞
ＢＰＡ−ＰＯ ３１ｍｏｌ％
ＢＰＡ−ＥＯ １９ｍｏｌ％
ＴＰＡ １９ｍｏｌ％
ＴＭＡ ６ｍｏｌ％
ＦＡ ２５ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｃを得た。
【０２５８】
ポリエステル樹脂Ｃを６０質量部、ビニル系モノマー混合液を４０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｃを得た。結着樹脂ｃの物性を表１に示す。
【０２５９】
＜結着樹脂製造例４＞
ＢＰＡ−ＰＯ ２５ｍｏｌ％
ＢＰＡ−ＥＯ ２５ｍｏｌ％
ＴＰＡ １５ｍｏｌ％
ＦＡ ３５ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｄを得た。
【０２６０】
ポリエステル樹脂Ｄを５０質量部、ビニル系モノマー混合液を５０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｄを得た。結着樹脂ｄの物性を表１に示す。
【０２６１】
＜結着樹脂製造例５＞
ＢＰＡ−ＰＯ １５ｍｏｌ％
ＢＰＡ−ＥＯ ３５ｍｏｌ％
ＴＰＡ １５ｍｏｌ％
ＴＭＡ ０．１ｍｏｌ％
ＦＡ ３４．９ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｅを得た。
【０２６２】
ポリエステル樹脂Ｅを９５質量部、ビニル系モノマー混合液を５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｅを得た。結着樹脂ｅの物性を表１に示す。
【０２６３】
＜結着樹脂製造例６＞
ＢＰＡ−ＰＯ ２３ｍｏｌ％
ＢＰＡ−ＥＯ ２７ｍｏｌ％
ＴＰＡ ４ｍｏｌ％
ＴＭＡ ３６ｍｏｌ％
ＦＡ １０ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｆを得た。
【０２６４】
ポリエステル樹脂Ｆを１０質量部、ビニル系モノマー混合液を９０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｆを得た。結着樹脂ｆの物性を表１に示す。
【０２６５】
＜結着樹脂製造例７＞
ＢＰＡ−ＰＯ ２８ｍｏｌ％
ＢＰＡ−ＥＯ ２２ｍｏｌ％
ＴＰＡ ５ｍｏｌ％
ＴＭＡ ３０ｍｏｌ％
ＦＡ １５ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｇを得た。
【０２６６】
ポリエステル樹脂Ｇを９５質量部、ビニル系モノマー混合液を５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｇを得た。結着樹脂ｇの物性を表１に示す。
【０２６７】
＜結着樹脂製造例８＞
ＢＰＡ−ＰＯ ２１ｍｏｌ％
ＢＰＡ−ＥＯ ２９ｍｏｌ％
ＴＰＡ ３ｍｏｌ％
ＴＭＡ ４０ｍｏｌ％
ＦＡ ７ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｈを得た。
【０２６８】
ポリエステル樹脂Ｈを９５質量部、ビニル系モノマー混合液を５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｈを得た。結着樹脂ｈの物性を表１に示す。
【０２６９】
＜結着樹脂製造例９＞
ＢＰＡ−ＰＯ ３５ｍｏｌ％
ＢＰＡ−ＥＯ １５ｍｏｌ％
ＴＰＡ １５ｍｏｌ％
ＴＭＡ ０．１ｍｏｌ％
ＦＡ ３４．９ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｉを得た。これを結着樹脂ｉとする。結着樹脂ｉの物性を表１に示す。
【０２７０】
＜結着樹脂製造例１０＞
スチレン８３質量％と、アクリル酸−ｎ−ブチル１７質量％とを付加重合してスチレン−アクリル樹脂を得た。これを結着樹脂ｊとする。結着樹脂ｊの物性を表１に示す。
【０２７１】
＜結着樹脂製造例１１＞
ＢＰＡ−ＰＯ ３５ｍｏｌ％
ＢＰＡ−ＥＯ １５ｍｏｌ％
ＴＰＡ １１ｍｏｌ％
ＴＭＡ ２２ｍｏｌ％
ＦＡ １７ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｋを得た。
【０２７２】
ポリエステル樹脂Ｋを８５質量部、ビニル系モノマー混合液を１５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｋを得た。結着樹脂ｋの物性を表１に示す。
【０２７３】
＜結着樹脂製造例１２＞
ＢＰＡ−ＰＯ ３５ｍｏｌ％
ＢＰＡ−ＥＯ １５ｍｏｌ％
ＴＰＡ ３０ｍｏｌ％
ＴＭＡ ５ｍｏｌ％
ＳＡ（こはく酸誘導体） １５ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｌを得た。
【０２７４】
ポリエステル樹脂Ｌを７５質量部、ビニル系モノマー混合液を２５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｌを得た。結着樹脂ｌの物性を表１に示す。
【０２７５】
＜結着樹脂製造例１３＞
ＢＰＡ−ＰＯ ３５ｍｏｌ％
ＢＰＡ−ＥＯ １５ｍｏｌ％
ＴＭＡ １５ｍｏｌ％
ＦＡ ３５ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｍを得た。
【０２７６】
ポリエステル樹脂Ｍを９５質量部、ビニル系モノマー混合液を５質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｍを得た。結着樹脂ｍの物性を表１に示す。
【０２７７】
＜結着樹脂製造例１４＞
ＢＰＡ−ＰＯ １５ｍｏｌ％
ＢＰＡ−ＥＯ ３５ｍｏｌ％
ＴＭＡ ３１ｍｏｌ％
ＦＡ １９ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｎを得た。
【０２７８】
ポリエステル樹脂Ｎを９０質量部、ビニル系モノマー混合液を１０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｎを得た。結着樹脂ｎの物性を表１に示す。
【０２７９】
＜結着樹脂製造例１５＞
ＢＰＡ−ＰＯ １５ｍｏｌ％
ＢＰＡ−ＥＯ ３５ｍｏｌ％
ＴＭＡ ４１ｍｏｌ％
ＦＡ ９ｍｏｌ％
ポリエステル系モノマーの組成を上記のようにして、結着樹脂製造例１と同様にしてポリエステル樹脂Ｏを得た。
【０２８０】
ポリエステル樹脂Ｏを９０質量部、ビニル系モノマー混合液を１０質量部とし、結着樹脂製造例１と同様にしてハイブリッド樹脂成分を含む結着樹脂ｏを得た。結着樹脂ｏの物性を表１に示す。
【０２８１】
＜実施例１＞
・結着樹脂ａ ７０質量部
・結着樹脂ｃ ３０質量部
・磁性体（形状：球形、平均粒径：０．２０μｍ） １００質量部
・アルミニウムのヒドロキシカルボン酸化合物 ０．５質量部
（３，５−ジ−ｔ−ブチルサリチル酸化合物：化学式ＶＩＩＩ）
・モノアゾ鉄化合物（化学式ＶＩ） １質量部
・低分子量ポリエチレン ２質量部
（ＤＳＣ吸熱ピーク１０７℃、Ｍｗ／Ｍｎ＝１．０８）
上記材料をヘンシェルミキサーにて前混合した後、１３０℃に設定した二軸混練押し出し機（ＰＣＭ−３０池貝鉄工社製）によって溶融混練した。得られた混練物を冷却し、カッターミルで粗粉砕した後、ジェット気流を用いた微粉砕機で粉砕し、得られた微粉砕粉末をコアンダ効果を、利用した多分割分級機を用いて分級し、重量平均粒径７．０μｍの磁性トナー粒子を得た。トナー粒子の処方を表２に示す。
【０２８２】
得られた磁性トナー粒子に１００質量部に、ジメチルシリコーンオイルとヘキサメチルジシラザンで処理された乾式シリカを１．２質量部添加し、混合機にて混合してトナー１を得た。得られたトナー１の物性を表３に示す。また、トナーの製造時に用いた結着樹脂として、トナー製造時に用いた比率と同一比率で乾式混合して得られた樹脂組成物の物性を表４に示す。
【０２８３】
なお、処理シリカは、シリカ微粉体に対して１０質量％のヘキサメチルジシラザンで処理した後、ヘキサメチルジシラザンで処理されたシリカに対して１０質量％のジメチルシリコーンオイルでさらに処理したものである。
【０２８４】
上記トナー１について、以下に示す試験を行い評価した。評価結果を表５に示す。
【０２８５】
［定着試験］
本試験に用いた加熱定着装置の基本的構成として、加熱用ヒータ１１としては、図３の（ｂ）及び図４の構成のものを用いた。即ち、ＡｌＮをヒータ基板１１ａとし、このヒータ基板１１ａ上の定着ニップ部Ｎと反対方向に、Ａｇ／Ｐｄの導電剤と、マトリックス成分としての燐酸系ガラスの混合物と、有機溶剤、バインダー、分散剤等とを混合してペースト状にしたものをスクリーン印刷して６００℃で焼成したものを通電発熱抵抗層１１ｂとして用いた。また、ＡｌＮのヒータ基板１１ａの定着ニップ部Ｎ側には、摺動性の良好なポリイミド層１１ｅを、スクリーン印刷にて１０μｍの厚さに形成した。
【０２８６】
また、金属製スリーブ１３は、内径３０ｍｍ、厚み５０μｍの円筒状ステンレス鋼にプライマー層を５μｍ、ＰＦＡ樹脂を１０μｍ、それぞれディッピングによって塗布することによって、外径３０．１３ｍｍの円筒状に形成した。金属製スリーブ１３の内面の表面粗さＲｚを２μｍ、外面の表面粗さＲｚを２μｍとした。
【０２８７】
また、加圧ローラ２０は、直径２０ｍｍのＡｌ芯金２１に、シリコーンゴム層を厚み５ｍｍで形成し、さらに外層にはＰＦＡチューブを被覆して形成した。
【０２８８】
本試験では、画像形成装置の記録材搬送スピードを２７０ｍｍ／ｓｅｃに調整して、加熱用ヒータ１１の温度を任意に制御できるようにした前記加熱定着装置を用いた。
【０２８９】
低温定着性については、前記加熱定着装置において１５０〜２４０℃の温度範囲で加熱用ヒータ１１の温度を５℃おきに制御し、金属製スリーブ外表面の温度が一定になってから、未定着トナー像が形成された記録材Ｐを定着ニップ部Ｎに挿入し、得られた画像を、４．９ｋＰａの荷重をかけたシルボン紙で５往復摺擦し、摺擦前後の画像濃度の濃度低下率が１０％以下になる定着温度を低温定着性とした。この温度が低いほど低温定着性に優れたトナーである。未定着画像としては、普通紙（７５ｇ／ｍ^２）を用い、紙上のトナー現像量を０．６ｍｇ／ｃｍ^２に設定したベタ黒画像の定着を行った。
【０２９０】
耐高温オフセット性については、上記の定着条件と同様に、加圧ローラ表面と金属製フィルム表面が十分に加熱された状態で記録材を挿入し、評価を行った。評価は高温オフセット現象による画像上の汚れを目視で確認し、発生した温度を耐高温オフセット性とした。この温度が高いほど高温オフセット性に優れたトナーである。未定着画像としては、低温低着性の評価で使用したベタ黒画像と同じものを使用した。
【０２９１】
耐定着巻きつき性については、上記耐高温オフセット性の試験と同様にして、上記定着装置の温度を２３０℃とし、加圧ローラ表面と金属製フィルム表面が十分に加熱された状態で記録材を挿入し、Ａ、Ｂ、Ｃ、Ｄの４段階の評価基準で評価を行った。
【０２９２】
上記の評価基準は、Ａが最も良く、ＢがＡについで良く、ＣがＢについで良く、Ｄが最も悪いことを示す。また耐定着巻きつき性の試験では、巻きつきの発生しやすいＢＡＤＧＥＲ ＢＯＮＤ（６０ｇ／ｍ^２）紙を用い、紙上のトナー現像量を１．０ｍｇ／ｃｍ^２に設定したベタ黒画像で評価を行った。
【０２９３】
クイックスタート性については、低温低湿環境（１５℃、１０％）において、上記定着装置、通紙する記録材ともに充分環境になじんで冷えた状態から、上記定着装置の温度を２３５℃に設定し、加熱用ヒータ１１の通電発熱抵抗層１１ｂへの通電を開始してから何秒後に未定着トナー像が形成された記録材を定着ニップ部に挿入すれば定着可能になるかをテストし、この定着開始時間をクイックスタート性とした。この時間が短いほどクイックスタート性に優れることを示す。クイックスタート性試験における定着性に関しては、低温定着性と同様に摺擦前後の画像濃度の濃度低下率が１０％以下になる時間で判断した。
【０２９４】
＜実施例２〜７、比較例１＞
表２に示す材料を用い、トナー１と同様にしてトナー２〜８を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０２９５】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０２９６】
＜実施例８＞
・結着樹脂ｉ ３０質量部
・結着樹脂ｋ ７０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・アルミニウムの芳香族ヒドロキシカルボン酸化合物 ０．５質量部
（ジ−ｔ−ブチルサリチル酸化合物：化学式ＶＩＩＩ）
・モノアゾ鉄化合物（化学式ＶＩ） １質量部
・低分子量ポリエチレン ２質量部
（ＤＳＣ吸熱ピーク１０６．７℃、Ｍｗ／Ｍｎ＝１．２）
上記材料を用い、トナー１と同様にしてトナー９を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０２９７】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０２９８】
＜実施例９＞
・結着樹脂ｉ ３０質量部
・結着樹脂ｍ ７０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・アルミニウムの芳香族ヒドロキシカルボン酸化合物 １質量部
（ジ−ｔ−ブチルサリチル酸化合物：化学式ＶＩＩＩ）
・低分子量ポリエチレン ２質量部
（ＤＳＣ吸熱ピーク１０６．７℃、Ｍｗ／Ｍｎ＝１．２）
上記材料を用い、トナー１と同様にしてトナー１０を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０２９９】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３００】
＜実施例１０＞
・結着樹脂ｉ ７０質量部
・結着樹脂ｍ ３０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・モノアゾ鉄化合物（化学式ＶＩ） ３質量部
・高級アルコール ２質量部
（ＤＳＣ吸熱ピーク９９℃、Ｍｗ／Ｍｎ＝１．９）
上記材料を用い、トナー１と同様にしてトナー１１を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３０１】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３０２】
＜比較例２＞
・結着樹脂ｉ ５質量部
・結着樹脂ｋ ９５質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・アルミニウムの芳香族ヒドロキシカルボン酸化合物 ２質量部
（ジ−ｔ−ブチルサリチル酸化合物）
・モノアゾ鉄化合物（化学式ＶＩ） １質量部
・フィッシャートロプシュワックス ４質量部
（ＤＳＣ吸熱ピーク８８℃、Ｍｗ／Ｍｎ＝１．３）
上記材料を用い、トナー１と同様にしてトナー１２を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３０３】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３０４】
＜実施例１１＞
・結着樹脂ｉ ７０質量部
・結着樹脂ｌ ３０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・モノアゾ鉄化合物（化学式ＶＩ） ２質量部
・フィッシャートロプシュワックス ４質量部
（ＤＳＣ吸熱ピーク８８℃、Ｍｗ／Ｍｎ＝１．３）
上記材料を用い、トナー１と同様にしてトナー１３を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３０５】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３０６】
＜実施例１２＞
・結着樹脂ｉ ９０質量部
・結着樹脂ｌ １０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・モノアゾ化合物のクロム錯体（化学式ＶＩＩ） ３質量部
・低分子量ポリプロピレン ４質量部
（ＤＳＣ吸熱ピーク１４５℃、Ｍｗ／Ｍｎ＝８．８）
上記材料を用い、トナー１と同様にしてトナー１４を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３０７】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３０８】
＜比較例３＞
・結着樹脂ｉ １０質量部
・結着樹脂ｎ ９０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・モノアゾ鉄化合物（化学式ＶＩ） ２質量部
・低分子量ポリプロピレン ４質量部
（ＤＳＣ吸熱ピーク１４５℃、Ｍｗ／Ｍｎ＝８．８）
上記材料を用い、トナー１と同様にしてトナー１５を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３０９】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３１０】
＜比較例４＞
・結着樹脂ｊ ５０質量部
・結着樹脂ｌ ５０質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・クロムの芳香族ヒドロキシカルボン酸化合物 １質量部
（ジ−ｔ−ブチルサリチル酸化合物：化学式ＩＸ）
・低分子量ポリエチレン ２質量部
（ＤＳＣ吸熱ピーク１２６℃、Ｍｗ／Ｍｎ＝１．２）
上記材料を用い、トナー１と同様にしてトナー１６を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３１１】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３１２】
＜比較例５＞
・結着樹脂ｉ ５質量部
・結着樹脂ｏ ９５質量部
・磁性体（形状：球状、平均粒径：０．２０μｍ） １００質量部
・モノアゾクロム化合物（化学式ＶＩＩ） １質量部
・低分子量ポリプロピレン ４質量部
（ＤＳＣ吸熱ピーク１４５℃、Ｍｗ／Ｍｎ＝８．８）
上記材料を用い、トナー１と同様にしてトナー１７を得た。得られたトナーの物性を表３に、得られたトナーの樹脂組成物の物性を表４に示す。
【０３１３】
また上記のトナーについて、トナー１と同様に試験を行い評価した。評価結果を表５に示す。
【０３１４】
【表１】

【０３１５】
【表２】

【０３１６】
【表３】

【０３１７】
【表４】

【０３１８】
【表５】

【０３１９】
【発明の効果】
本発明は、少なくとも加熱用部材と、加圧部材と、該加熱用部材と加圧部材の間に介在し、加熱用部材からの熱を被加熱材に接触して与える可撓性を有する円筒状金属素管を基層として形成される加熱用金属製スリーブとを具備し、該加熱用金属製スリーブと加圧部材の間で形成される加熱ニップ相当部において、該金属製スリーブ内面に加熱用部材を接触配置しており、未定着トナー画像が形成された記録材を、金属製スリーブと加圧部材により互いに圧接してなる定着ニップ間を通過させることにより、上記未定着画像を記録材上に定着させる定着手段と、結着樹脂、着色剤及びワックスを少なくとも含有し、結着樹脂は、ビニル系重合体ユニットとポリエステルユニットとを有するハイブリッド樹脂を少なくとも含有し、トナーのテトラヒドロフラン可溶分のゲルパーミエーションクロマトグラフィーの分子量分布において、分子量１万未満の成分の含有量が４０〜７０質量％であり、分子量１万乃至５万の成分の含有量が２５〜５０質量％であり、分子量５万を超える成分の含有量が２〜２５質量％であり、分子量１０万以上の成分の含有量が１０質量％末満であり、かつ分子量１万未満の成分の含有量をＭ１とし、分子量１万乃至５万の成分の含有量をＭ２とし、分子量５万を超える成分の含有量をＭ３としたときにＭ１≧Ｍ２＞Ｍ３を満足するトナーとを用いることから、金属製スリーブと加圧部材の間で形成される加熱ニップ相当部において、該金属製スリーブ内面に加熱用部材を接触配置していることを特徴とするフィルム加熱方式の加熱定着装置において、低温低着性、耐高温オフセット性に優れ、かつ優れた耐定着巻きつき性を有するトナーを提供することができ、また定着性能、クイックスタート性を達成する高速オンデマンド定着を実現できる画像形成方法及び画像形成装置、及びこの方法や装置に適するトナーを提供することができる。
【図面の簡単な説明】
【図１】本発明の画像形成装置における一実施の形態を示す概略構成図である。
【図２】図１に示す定着装置の概略構成を示す図である。
【図３】図２に示す定着部材の一例における定着ニップ部近傍を示す図である。
【図４】図２に示す定着部材の他の例における定着ニップ部近傍を示す図である。
【図５】図１に示す定着装置における定着部材と加圧部材の配置例を示す図である。
【図６】本発明に用いられる円筒状金属素管の製造例を説明する図である。
【図７】図５に示す製造例で得られる円筒状金属素管の中間製造物を示す図である。
【図８】図７に示す中間生成物の表面粗さ及び厚みを調整するための加工の一例を説明する図である。
【図９】図７に示す中間生成物の表面粗さ及び厚みを調整するための加工の他の例を説明する図である。
【図１０】図８又は図９に示す加工により形成された円筒状金属素管を示す図である。
【図１１】本発明に用いられる定着装置の他の実施の形態を示す概略構成図である。
【図１２】図１１に示す定着装置を正面から見た概略構成図である。
【図１３】従来のローラ加熱方式の定着装置の一例を示す概略構成図である。
【図１４】従来のフィルム加熱方式の定着装置の一例を示す概略構成図である。
【符号の説明】
１ 感光ドラム
２ 帯電ローラ
３ レーザビーム
４ 現像装置
５ 転写ローラ
６ 加熱定着装置
７ クリーニング装置
８ センサ
１０、６０ 定着部材
１１、６１ 加熱用ヒータ
１１ａ ヒータ基板
１１ｂ 通電発熱抵抗層
１１ｃ、１１ｅ 摺動層
１１ｄ 保護層
１１ｆ、１１ｇ 電極部
１２、６２ 断熱ステイホルダ
１３ 定着スリーブ（金属製スリーブ）
１３ａ 部位
１４、６４ 温度検知素子
１５ 定着入口ガイド
１６ 駆動ギア
１７ 加圧手段
１８ 導電ブラシ
２０ 加圧部材（加圧ローラ）
２１、５１ 芯金
２２、５２ 弾性層
２３、４３、５３ 離型性層
２４ バイアス印加手段
２５ チップ電極
３１ 金属平板
３２ 内型
３３ 外型
３４、３９ 金属製円筒部材
３５ 金属製内型
３６ａ 押し当てローラ
３６ｂ 軸
３６ｃ 固定台
３７ 押さえ部材
３８ａ〜３８ｃ 連続ダイス
３９ａ 凹凸跡
４０ 定着ローラ
４１ ハロゲンランプ
４２ 中空芯金
４４ サーミスタ
５０ 加圧ローラ
６３ 定着フィルム
Ｎ 定着ニップ部
Ｐ 記録材[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a toner used in an image forming method such as electrophotography, electrostatic recording, electrostatic printing, and toner jet, and an image forming method and an image forming apparatus using the toner.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, in a fixing device provided in an image forming apparatus employing an electrophotographic method, an electrostatic recording method, or the like, a recording material carrying an unfixed toner image is pressed against each other, and a fixing roller and a pressure roller are rotated. A so-called heat fixing device for fixing a recording material by passing through a nip portion formed by the above-mentioned method is widely used.
[0003]
FIG. 13 shows an example of a conventional heat fixing device. Reference numeral 40 denotes a fixing roller provided with a heating means, and a halogen lamp 41 is disposed inside a hollow aluminum core bar 42 having a thickness of about 1 mm to 4 mm so as to satisfy mechanical strength. Is sufficient to melt the toner on the recording material P from the inside of the hollow cored bar 42 by applying the current.
[0004]
In order to improve the absorption of radiant heat by the halogen lamp 41, a material having a black absorption rate of 90% or more (for example, Okitsumo (trade name) or the like) is generally applied to the inside of the hollow metal core 42, The roughness of the inner surface is rough for the purpose of preventing reflection and increasing the absorptance, and is Rz = 10 μm or more.
[0005]
Further, in order to fix the toner on the recording material P without offsetting the recording material P, a polytetrafluoroethylene (PTFE), a perfluoroalkoxy, and the like having excellent releasability are provided outside the hollow cored bar 42. A release layer 43 such as a tetrafluoroethylene copolymer (PFA) is formed.
[0006]
The releasable layer 43 is formed into a tubular shape on the outer surface of the hollow core metal 42 having a surface roughness of Rz = 5 μm or more by blasting or etching the outer surface, or is formed by electrostatic spraying or dipping coating. Etc., and has an adhesive strength to the hollow cored bar 42.
[0007]
In some cases, a conductive member such as carbon black is mixed into the release layer 43 in order to prevent offset generated by charging up the surface of the fixing roller 40 due to conveyance of the recording material P.
[0008]
Further, the hollow core 42 of the fixing roller 40 is electrically grounded or grounded via a diode element, or is biased by a bias applying unit (not shown), and the surface of the fixing roller is charged up and offset. This prevents images from occurring.
[0009]
The thermistor 44 is in contact with the surface of the fixing roller 40, detects the temperature of the fixing roller surface, and turns on the power supply to the halogen lamp 41 so as to heat the toner image on the recording material P at an appropriate temperature. / Off control.
[0010]
On the other hand, a pressing roller 50 presses the fixing roller 40 at both ends in the roller longitudinal direction by a pressing spring (not shown) to pinch and convey the recording material P. The pressing roller 50 has an elastic layer formed of silicone rubber or a sponge elastic layer 52 formed by foaming silicone rubber on the outside of the cored bar 51, and further has an outer layer such as PTFE, PFA, FEP or the like similar to the fixing roller 40. The moldable layer 53 is formed in a tubular shape or by coating.
[0011]
Therefore, a fixing nip portion N having a sufficient nip width can be formed between the rollers 40 and 50 by the elasticity of the pressure roller 50. The toner image on the recording material P nipped and conveyed in the fixing nip portion N can be fixed by heating from the fixing roller 40.
[0012]
In particular, a method in which power is not supplied to the heat fixing device during standby and power consumption is minimized, more specifically, a toner image is fixed on a recording material via a thin film between a heater and a pressure roller. An example of a heat fixing method using a film heating method is known (for example, see Patent Documents 1 to 4).
[0013]
FIG. 14 shows a schematic configuration of an example of a film heating type fixing device. That is, in FIG. 14, a heating member (heating body, hereinafter referred to as a heater) 61 fixedly supported by a stay holder (support) 62 and a heat-resistant thin film (hereinafter, referred to as a fixing film) 63 are provided on the heater 61. The elastic pressure roller 50 has a fixing nip portion N having a predetermined nip width formed therebetween by a pressing means and pressed against the fixing nip portion N.
[0014]
The heater 61 is heated and controlled to a predetermined temperature by energization.
[0015]
The fixing film 63 is conveyed and moved in the direction of the arrow while being in close contact with and sliding on the surface of the heater 61 in the fixing nip portion N by a driving means (not shown) or the rotational force of the pressing roller 50. Alternatively, it is a rolled end-shaped web member.
[0016]
In a state where the heater 61 is heated and controlled to a predetermined temperature, and the fixing film 63 is conveyed and moved in the direction of the arrow, the heating material between the fixing film 63 of the fixing nip N and the pressure roller 50 is When the recording material P on which the unfixed toner image is formed and carried is introduced, the recording material P is brought into close contact with the surface of the fixing film 63 and is conveyed by nipping the fixing nip portion N together with the fixing film 63. In the fixing nip portion N, the recording material / toner image is heated by the heater 61 via the fixing film 63, and the toner image on the recording material P is heated and fixed. The recording material portion that has passed through the fixing nip N is separated from the surface of the fixing film 63 and conveyed.
[0017]
In general, a ceramic heater is used for the heater 61 as a heating member. For example, silver palladium (Ag / Ag / Ag) is applied on the surface of the ceramic substrate (the surface facing the fixing film 63) having electrical insulation, good thermal conductivity, and low heat capacity such as alumina along the substrate length (the direction perpendicular to the drawing). Pd) ・ Ta₂A heat generating resistance layer of N or the like is formed by screen printing or the like, and the surface on which the heat generation resistance layer is formed is further covered with a thin glass protective layer. In the ceramic heater 61, when current is applied to the energized heating resistor layer, the energized heating resistor layer generates heat, and the entire heater including the ceramic substrate / glass protection layer rapidly rises in temperature. The temperature rise of the heater 61 is detected by the temperature detecting means 64 provided on the back surface of the heater 61, and is fed back to a power supply control unit (not shown). The power supply control unit controls power supply to the power supply heat generating resistance layer such that the heater temperature detected by the temperature detection unit 64 is maintained at a predetermined substantially constant temperature (fixing temperature). That is, the heater 61 is heated and adjusted to a predetermined fixing temperature.
[0018]
The fixing film 63 has a considerably small thickness of 20 to 70 μm in order to efficiently apply the heat of the heater 61 to the recording material P as a material to be heated in the fixing nip portion N. The fixing film 63 has a three-layer configuration of a film base layer, a conductive primer layer, and a release layer. The film base layer side is the heater side, and the release layer is the pressure roller side. The film base layer is made of highly insulating polyimide, polyamideimide, PEEK, or the like, and has a heat resistance, a high elasticity and a flexible thickness of about 15 to 60 μm. Further, the mechanical strength such as the tear strength of the entire fixing film 63 is maintained by the film base layer. The conductive primer layer is formed as a thin layer having a thickness of about 2 to 6 μm, and is electrically connected to ground to prevent charge-up of the entire fixing film. The releasable layer is a toner offset preventing layer for the fixing film 63 and is formed by coating a fluororesin having good releasability, such as PFA, PTFE, and FEP, to a thickness of about 5 to 14 μm. Further, in order to reduce the charge-up on the surface of the fixing film 63 and prevent the electrostatic offset, similarly to the fixing roller 40 of FIG.³Ωcm-10⁶A conductive member of about Ωcm such as carbon black is mixed.
[0019]
The stay holder 62 is formed of, for example, a heat-resistant plastic member and holds the heater 61 and also serves as a conveyance guide for the fixing film 63. Therefore, in order to enhance the slidability with the fixing film 63, grease or the like having high heat resistance is interposed between the fixing film 63 and the outer peripheral surfaces of the heater 61 and the stay holder 62. The pressing member 50 has the same configuration as the pressing roller of the above-described fixing roller type heat fixing device.
[0020]
Further, in order to form a fixing nip portion N required for heat fixing between the fixing film 63 and the pressing roller 50, both ends of the stay holder 62 are pressed toward the pressing roller 50 by a pressing spring (not shown). ing. As a result, the heater 61 attached to the stay holder 62 is brought into close contact with the fixing film 63 over part of the circumferential direction of the pressure roller 50 and over the entire area in the longitudinal direction.
[0021]
Further, the pressure roller 50 is driven to rotate, and accordingly, the fixing film 63 is driven to rotate by the surface of the pressure roller 50. In this state, power is supplied to the current-carrying resistance layer formed on the heater 61 through connectors formed at both ends of the heater 61 by connectors (not shown). As a result, the temperature of the current-carrying resistance layer rises, and the toner image on the recording material nipped and conveyed in the fixing nip is heated and fixed.
[0022]
However, when the above-described heat fixing device is used, there are the following problems.
[0023]
First, in the case of a heat fixing device using the fixing roller 40, since the thickness of the fixing roller core metal 42 satisfies mechanical strength, about 1 to 4 mm is required, which has a large heat capacity. Therefore, it is necessary to preheat the fixing roller 40 to a predetermined temperature before the image forming apparatus receives the print signal. This is because it is difficult to heat the fixing roller 40 from room temperature to a fixable temperature in a short time until the recording material P on which the unfixed toner image is formed is conveyed to the heat fixing device. It is necessary to heat and raise the temperature to some extent in a standby state before receiving a print signal.
[0024]
For this reason, when the power of the image forming apparatus is turned on after the fixing roller 40 is cooled down to the room temperature, it is necessary to heat and heat the fixing roller 40 until the image forming apparatus can receive a print signal. there were.
[0025]
In addition, since it is necessary to heat the fixing roller 40 to a predetermined temperature by energizing the heater 41 during standby, a large amount of energy is used for the heating.
[0026]
Further, even when the thickness of the cored bar 42 is reduced, if the fixing roller is heated by the radiant heat of the heater 41 as in the above-described conventional example, the thermal efficiency is not good. When the recording material conveyance speed increases due to the increase in the speed of the apparatus, preheating is also required.
[0027]
Also, if the thickness of the cored bar 42 is reduced to increase the temperature rising speed, the strength of the cored bar 42 is not sufficient. There was a problem with sex. When pressure is applied with a weak pressing force in consideration of durability, fixing of the toner becomes insufficient.
[0028]
On the other hand, the heat fixing device of the film heating type does not require the power supply to the heater 61 in the standby state as described above. Even if the image forming apparatus receives the print signal and then supplies the power to the heater 61, the recording is performed. Heating can be performed before the material P reaches the heat fixing device. Therefore, from the viewpoint of energy saving, the film fixing type heat fixing device is an excellent heat fixing device that does not waste energy.
[0029]
However, the fixing film 63 is formed of a resin layer having poor heat conductivity, and is not suitable for speeding up the image forming apparatus. That is, when the speed of the image forming apparatus is increased, the speed at which the heating by the heater 61 is applied to the recording material P via the fixing film 63 must be increased in accordance with the increase in the speed of the apparatus. In the case of 63, there is a limit even if a countermeasure such as mixing of a heat conductive filler is taken, and it is impossible to cope with further speeding up.
[0030]
In addition, when a high pressure is applied, the toner image can be pressed against the recording material P with a strong adhesive force, and the fixing performance is improved. However, in the case of a resin film, the inner surface is scraped due to durability, and may be damaged. It was difficult to achieve both high speed and durability.
[0031]
Further, when a large amount of the thermally conductive filler is added to the resin fixing film 63, mechanical strength such as tear strength is lost. For example, when regulating the position in the thrust direction by a regulating member at the end or the like. In addition, since the fixing film 63 rotates in a state where the end thereof is shifted to the end surface of the regulating member or the like, a problem such as a tear of the end of the fixing film 63 occurs, and the durability is deteriorated.
[0032]
Further, if an attempt is made to control the approach to the end, the structure becomes complicated, which leads to an increase in the size and cost of the device.
[0033]
Therefore, a system using a resin film is not suitable for increasing the speed of a heat fixing device having a simple configuration and satisfying both the fixing property and the durability.
[0034]
Until now, various toners have been proposed to achieve both low-temperature fixing performance and high-temperature offset resistance. Needs to adjust the toner characteristics to the fixing device.
[0035]
Conventionally, as a resin for a toner, a polyester resin or a vinyl copolymer such as a styrene resin is mainly used. Polyester resin inherently has excellent low-temperature fixability, so it exhibits excellent low-temperature and low-adhesion properties in combination with a film heating type heat fixing device, but on the other hand, it causes offset phenomenon at high temperatures It also has the problem of being easy to do.
[0036]
In particular, in the heat fixing device of the film heating type, when small-size paper such as a postcard is printed continuously, heat is supplied to the paper at the fixing nip, so that the temperature rise can be suppressed, but the non-paper-passing part is not heated. At the end of the fixing nip, the heat from the heating heater is not deprived by the paper, but is stored in the pressure roller and rises considerably. As a result, when small-size paper is continuously passed and normal-size paper such as A4 is passed, there is a problem that the end of the fixing device is likely to be offset at high temperature. This problem becomes more remarkable in order to increase the speed of the apparatus because it is necessary to set the set temperature even higher.
[0037]
Attempts to increase the viscosity by increasing the molecular weight of the polyester resin to compensate for this problem not only impair the low-temperature fixability, but also degrade the pulverizability during toner production and make the toner finer. It will be appropriate.
[0038]
Vinyl-based copolymers such as styrene-based resins have excellent pulverizability during toner production, and have excellent high-temperature offset resistance due to easy high-molecular weight reduction, but lower molecular weight to improve low-temperature fixability In this case, the developability deteriorates.
[0039]
In order to effectively utilize the advantages of these two types of resins and to compensate for each other's problems, some methods of mixing and using these resins have been studied. For example, a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer is known (for example, see Patent Document 5). However, since the polyester resin and the vinyl copolymer have essentially poor compatibility, it is difficult to satisfy the low-temperature fixing property and the high-temperature offset resistance unless the mixing ratio of these resins is appropriate. Further, since the dispersibility of an internal additive such as a colorant or a wax added during the production of the toner cannot be sufficiently increased, a problem tends to occur in the developability. In particular, in recent years, this problem is remarkable in a toner in which fine particles are advanced.
[0040]
Further, when the speed of the heat fixing device of the film heating type is increased, the separation speed of the recording material and the film cannot keep up with the process speed, and the phenomenon that the recording material winds around the fixing device and the fixing winding is liable to occur.
[0041]
Further, a toner is known which contains a polymer obtained by polymerizing a monomer in the presence of a polyester resin (for example, see Patent Documents 6 and 7). Further, a toner characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester resin is known (for example, see Patent Documents 8 and 9). Further, a toner is known which contains a polymer obtained by esterifying an acid value-containing styrenic resin and a polyester resin (for example, see Patent Document 10). In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, the melting rate of the wax and the like are not sufficiently taken into consideration. There are issues to be left.
[0042]
Further, a toner using two kinds of polyester resins having different softening points and a toner using two kinds of polyester resins having different molecular weights are known (for example, see Patent Documents 11 and 12). However, the high-temperature offset resistance is within the range of the polyester resin, and there is a problem to be improved when used in a high-speed film heating type heat fixing device.
[0043]
Further, a toner using a resin obtained by mixing a polyester resin with a hybrid resin obtained by performing an addition polymerization reaction with a vinyl resin monomer and a polycondensation reaction with a polyester resin monomer in parallel is known. (For example, see Patent Document 13). Further, toners using two types of hybrid resins having different softening points obtained by performing an addition polymerization reaction with a vinyl resin monomer and a condensation polymerization reaction with a polyester resin monomer in parallel are known (for example, Patent Document 14). However, in these methods, the balance between the crosslinking on the low molecular weight side and the crosslinking on the high molecular weight side of the toner is not good, and there is still a problem to be improved in the low-temperature fixing property and the high-temperature offset resistance. In addition, when used in a high-speed film heating type heat fixing device, there is a problem that the fixing winding resistance is not sufficient.
[0044]
Further, in a toner containing at least a binder resin, a colorant and a wax, the binder resin contains a vinyl resin, a polyester resin, and a hybrid resin component having a vinyl polymer unit and a polyester unit. , The amount of tetrahydrofuran-soluble and insoluble components, the amount of ethyl acetate-soluble and insoluble components, the amount of chloroform-soluble components and the amount of insoluble components, and the molecular weight distribution of THF-soluble components by GPC measurement were defined. A toner is known (for example, see Patent Document 15).
[0045]
Although this toner has good fixability and excellent offset resistance, it is still insufficient in combination with a film heating type heat fixing device, and there is room for improvement, particularly in terms of fixing wrap resistance.
[0046]
There is a long-awaited need for an optimal toner that can better solve the various problems described above and is compatible with a high-speed on-demand fixing device.
[0047]
[Patent Document 1]
JP-A-63-313182
[Patent Document 2]
JP-A-2-15778
[Patent Document 3]
JP-A-4-44075
[Patent Document 4]
JP-A-4-204980
[Patent Document 5]
JP-A-54-114245
[Patent Document 6]
JP-A-56-116043
[Patent Document 7]
JP-A-58-159546
[Patent Document 8]
JP-A-58-102246
[Patent Document 9]
JP-A-1-156759
[Patent Document 10]
JP-A-2-881
[Patent Document 11]
JP-A-4-338973
[Patent Document 12]
JP-A-8-166688
[Patent Document 13]
JP-A-8-54754
[Patent Document 14]
JP-A-8-44108
[Patent Document 15]
U.S. Pat. No. 5,977,752
[0048]
[Problems to be solved by the invention]
An object of the present invention is to provide a toner which has solved the above-mentioned problems, and an image forming method and an image forming apparatus using the toner.
[0049]
That is, an object of the present invention is to provide a film heating system in which a heating member is arranged in contact with an inner surface of a metal sleeve in a portion corresponding to a heating nip formed between a metal sleeve and a pressing member. An object of the present invention is to provide a toner having excellent low-temperature and low-wear properties, high-temperature offset resistance, and excellent fixing wrap resistance in a heat fixing device, and an image forming method and an image forming apparatus using the toner.
[0050]
That is, an object of the present invention is to provide a toner corresponding to high-speed on-demand fixing that achieves fixing performance and quick start property, an image forming method and an image forming apparatus using the toner.
[0051]
[Means for Solving the Problems]
That is, the present invention, as a means for solving the above-mentioned problems, includes at least a heating member, a pressing member, and a heat-insulating member interposed between the heating member and the pressing member so that heat from the heating member contacts the material to be heated. And a heating metal sleeve formed as a base layer of a flexible cylindrical metal tube provided as a base, and a heating nip equivalent portion formed between the heating metal sleeve and the pressing member. A heating member is arranged in contact with the inner surface of the metal sleeve, and the recording material on which the unfixed toner image is formed is passed through a fixing nip formed by pressing the metal sleeve and the pressing member together. A toner applied to an image forming method using a fixing unit for fixing the unfixed image on a recording material, the toner including at least a binder resin, a colorant and a wax, wherein the binder resin is a vinyl polymer unit In a molecular weight distribution of gel-permeation chromatography of a toner, which contains at least a hybrid resin having a polyester unit and which is soluble in tetrahydrofuran, the content of components having a molecular weight of less than 10,000 is 40 to 70% by mass, and the molecular weight is 10,000. The content of the component having a molecular weight of 100 to 50,000 is from 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 is from 2 to 25% by mass, and the content of the component having a molecular weight of 100,000 or more is less than 10% by mass. When the content of components having a molecular weight of less than 10,000 is M1, the content of components having a molecular weight of 10,000 to 50,000 is M2, and the content of components having a molecular weight of more than 50,000 is M3, M1 ≧ M2 > M3 is provided.
[0052]
Further, the present invention has at least a heating member, a pressing member, and a flexibility interposed between the heating member and the pressing member to apply heat from the heating member to the material to be heated. A heating metal sleeve formed with a cylindrical metal tube as a base layer; a heating nip corresponding to a heating nip formed between the heating metal sleeve and the pressing member; The unfixed toner image is formed by passing the recording material on which an unfixed toner image is formed through a fixing nip formed by pressing a metal sleeve and a pressing member together. The present invention provides an image forming method and an image forming apparatus using a fixing unit for fixing an image thereon, and provides an image forming method and an image forming apparatus using the toner of the present invention described above.
[0053]
BEST MODE FOR CARRYING OUT THE INVENTION
In a high-speed film-heating type heat fixing device, it is important how the synergistic effect of the combination of the binder resin and the wax is enhanced.
[0054]
The fixing film made of metal used in the present invention has a stronger fixing film strength than a conventionally used fixing film made of a resin such as polyimide, polyamide imide, or PEEK. The film hardly adheres to the heater at the portion where the heater contacts the inner surface of the film. Therefore, the gap between the heater and the film is large at the part where the recording material enters and exits from the nip, and the gap between the heater and the film is small at the center of the nip, and the fixing nip is uneven with respect to the recording material traveling direction. It is no longer a face.
[0055]
As a result, when the recording material passes through the nip portion, the toner image on the recording material is disturbed and rubbed against the film, so that the separability between the film and the recording material is easily deteriorated, and winding is liable to occur. In order to achieve excellent fixing performance and high-temperature offset resistance and to suppress winding, it is important to combine a toner suitable for the configuration of the fixing device.
[0056]
The present inventors have ascertained that the binder resin of the toner has at least a hybrid resin having a vinyl polymer unit and a polyester unit, and the molecular weight distribution of a component having a molecular weight of less than 10,000 in the THF-soluble GPC molecular weight distribution of the toner. The content (M1) is 40 to 70% by mass, the content of the component having a molecular weight of 10,000 to 50,000 (M2) is 25 to 50% by mass, and the content of the component having a molecular weight exceeding 50,000 (M3) is 2 to 25% by mass. %, The content of the component having a molecular weight of 100,000 or more (M4) is less than 10% by mass, and M1 ≧ M2> M3. It has been found that, as compared with the case where a conventional toner is used, excellent low-temperature fixing property and high-temperature anti-offset property can be achieved, and very excellent fixing winding resistance can be obtained.
[0057]
The hybrid resin has a higher affinity for the wax than the polyester resin and easily carries the wax, but the resin and the wax are more likely to phase-separate than the vinyl resin, so that the wax dissolution rate during heating is faster. Therefore, the wax easily melts on the toner surface by heating at the time of fixing, and when used in a heat fixing device of a film heating type using a metal fixing film, the low-temperature low-wear property and the high-temperature offset resistance are improved. It works.
[0058]
In the toner of the present invention, the content of components having a molecular weight of less than 10,000 is 40 to 70% by mass and the content of components having a molecular weight of 10,000 to 50,000 is The content is 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 is 2 to 25% by mass, the content of the component having a molecular weight of 100,000 or more is less than 10% by mass, and the molecular weight is 1 When the content of a component having a molecular weight of less than 10,000 is M1, the content of a component having a molecular weight of 10,000 to 50,000 is M2, and the content of a component having a molecular weight exceeding 50,000 is M3, M1 ≧ M2> M3 is satisfied.
[0059]
In the toner of the present invention, by controlling the molecular weight of the binder resin as described above, the phase separation speed between the wax and the resin is dramatically improved, so that the recording material and the fixing film are easily separated, and the anti-fixing winding is improved. The tackiness is greatly improved.
[0060]
A component having a molecular weight of less than 10,000 is a component which is well soluble at low temperatures and greatly contributes to low-temperature low-adhesion. Therefore, if the content (M1) of less than 10,000 is less than 40% by mass, high-speed fixing is sufficient. In some cases, an excellent fixing property cannot be obtained. If it exceeds 70% by mass, plasticization due to the wax melted out during heating progresses, and the hot offset resistance may be deteriorated.
[0061]
Since the components having a molecular weight of 10,000 to 50,000 have a function of increasing the dissolution rate of the wax, if the content (M2) of the components having a molecular weight of 10,000 to 50,000 is less than 25% by mass, sufficient dissolution of the wax occurs. The speed cannot be obtained, and the winding resistance to fixing tends to deteriorate. If the amount exceeds 50% by mass, the load at the time of kneading the toner is increased, and the wax dispersion diameter in the toner becomes too small, so that the wax release effect may not be exhibited.
[0062]
When the content (M3) of the component having a molecular weight exceeding 50,000 exceeds 25% by mass, the low-temperature fixability may be deteriorated. If the amount is less than 2% by mass, the elasticity of the toner becomes too small, the melt viscosity of the toner at the time of fixing becomes low, the wax hardly dissolves on the toner surface, and the high-temperature offset resistance may deteriorate.
[0063]
A component having a molecular weight of 100,000 or more exerts an effect on high-temperature offset with a small amount. Therefore, by setting the content (M4) of the component having a molecular weight of 100,000 or more to less than 10% by mass, low-temperature fixability is not impaired. High-temperature offset properties can be improved.
[0064]
Further, when M1 ≧ M2> M3 is satisfied, the wax is most likely to dissolve on the toner surface, and the effect of improving low-temperature low-wear property, high-temperature offset property, and fixing wrap resistance is great.
[0065]
The molecular weight of the THF-soluble component of the toner of the present invention and the binder resin described below is measured by gel permeation chromatography (GPC). As an example of a specific GPC measurement method, the toner is extracted in advance with a THF (tetrahydrofuran) solvent for 10 hours using a Soxhlet extractor, and the obtained extract is used as a sample. 801, 802, 803, 804, 805, 806, and 807 are connected, and a standard polystyrene resin calibration curve is used. The content of the component having a molecular weight of less than 10,000 (M1 or m1), the content of the component having a molecular weight of 10,000 to 50,000 (M2 or m2), the content of the component having a molecular weight exceeding 50,000 (M3 or m3) and the molecular weight of 100,000 The content (M4 or m4) of the above components is defined as mass% in terms of the area ratio of the GPC chromatogram. The lower limit of the molecular weight range of the content (M1) of the component having a molecular weight of less than 10,000 is set to 800 in consideration of noise at the time of measuring the molecular weight.
[0066]
The THF-soluble component of the toner particles can be separated as a solid by subjecting the toner to a Soxhlet extractor of THF to extract the THF-soluble component, and distilling off THF from the extract. The molecular weight distribution can be adjusted by the type of the binder resin, the mixing ratio of the units in the hybrid resin, the degree of polymerization in each unit, and the like.
[0067]
The binder resin contains at least a trivalent or higher polycarboxylic acid or an anhydride thereof as a constituent monomer, and is included in a component having a molecular weight of less than 10,000 in a molecular weight distribution of gel permeation chromatography of a tetrahydrofuran-soluble component of a toner. The total content of the trivalent or higher polyvalent carboxylic acids and their anhydrides in the monomer unit constituting the polyester component is W1 (mol%), and constitutes the polyester component contained in the component having a molecular weight of 10,000 or more. Assuming that the total content of the trivalent or higher polycarboxylic acids and their anhydrides in the monomer unit is W2 (mol%), W1 and W2 have the following relationship.
0 ≦ W1 <30
0 <W2 <50
W2> W1
Is preferably satisfied.
[0068]
When W1 and W2 are within this range, the linearity of the low molecular weight component and the degree of crosslinking of the high molecular weight component are properly maintained, and the low-temperature fixability and the high-temperature offset resistance can be sufficiently enhanced. it can. Furthermore, the wax carrying force of the hybrid resin is increased, and the dispersibility of the wax in the binder resin can be appropriately maintained, so that the anti-fixing wrapping property can be improved. When W1 is 30 or more, the crosslinking of the low molecular weight component is excessively advanced, and the low-temperature fixability tends to deteriorate. When W2 is 50 or more, the crosslinking of the high molecular weight component proceeds too much, the elasticity of the toner becomes too large, and the low-temperature fixability tends to deteriorate.
[0069]
In the present invention, the component having a molecular weight of 10,000 or more in the toner is a component that affects the high-temperature offset resistance, and since the restoring force of the toner at a high temperature is important, the trivalent or more polyvalent carboxylic acid or its anhydride is used. It is important that the substance is sufficiently crosslinked. On the other hand, the components of the toner having a molecular weight of less than 10,000 are components that affect the low-temperature fixability, and it is important that the toner be well melted at a low temperature. .
[0070]
Therefore, by satisfying the relationship W2> W1, the high molecular weight side of the toner is crosslinked more than the low molecular weight side by the trivalent or higher polyvalent carboxylic acid and its anhydride, the elastic force (restoring force) increases, and the high temperature resistance is increased. The offset property is improved, and the polymer is less crosslinked at the low molecular weight side than at the high molecular weight side, so that it is well melted even at a low temperature and has excellent wax dispersibility. As a result, the low-temperature fixing property and the high-temperature offset resistance can be highly compatible, and the developing property is excellent. When W1 and W2 satisfy W2 ≦ W1, the low-temperature fixability tends to decrease, and fixing wrapping tends to occur.
[0071]
In the present invention, the total contents W1 and W2 mean the content of one of the contained trivalent or higher polycarboxylic acid units when only one of the units or the anhydride unit is contained. When both are contained, it means the total amount of both contents.
[0072]
In the present invention, as a form of the binder resin, a mixture of two or more types of hybrid resins (hereinafter, also referred to as a “first form”), a mixture of a polyester resin and a hybrid resin (hereinafter, also referred to as a “second form”) ), A mixture of a vinyl resin and a hybrid resin (hereinafter also referred to as a “third mode”), and a mixture of a polyester resin, a vinyl resin and a hybrid resin (hereinafter also referred to as a “fourth mode”). No.
[0073]
According to the study of the present inventors, when a vinyl resin is blended with a hybrid resin, the dispersibility of the vinyl resin and the hybrid resin in the toner tends to be reduced. In particular, the first mode and the second mode are preferable. That is, in the present invention, it is preferable to employ the first and second embodiments in order to further enhance the effect of the molecular weight distribution described below.
[0074]
In the present invention, W1 and W2 have the following relationship:
1 <W1 <25
2 <W2 <30
It is more preferable to satisfy the following relationship
3 ≦ W1 <20
3 <W2 ≦ 20
It is more preferable to satisfy the following.
[0075]
In the case of 1 <W1, crosslinking is also performed on the low molecular weight side, so that plasticization of the low molecular weight by the wax hardly occurs and the high-temperature offset resistance hardly deteriorates, which is preferable. In the case of 2 <W2, it is preferable because a crosslinked structure is formed in the high molecular weight component to such an extent that the above-mentioned high temperature offset resistance of the toner can be sufficiently exhibited.
[0076]
Furthermore, in the present invention, when the difference between W1 and W2 satisfies the following relationship, the low molecular weight component and the high molecular weight component can exert their roles in a well-balanced manner, and the low molecular weight component This is preferred because the compatibility between the polymer and the high molecular weight component is improved, and the wax dispersion is improved.
0 <W2-W1 <10
[0077]
Further, in the present invention, from the above viewpoint, it is more preferable to satisfy the following relationship.
0.1 × W2 <W2-W1 <0.5 × W2
[0078]
In the first embodiment, the toner preferably has a THF-insoluble content of 25% by mass or less, more preferably 1 to 15% by mass. If the content of the THF-insoluble component in the toner exceeds 25% by mass, the fixability of the toner tends to decrease.
[0079]
In the second embodiment, the content of the THF-insoluble component in the toner is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and still more preferably 5 to 30% by mass. . If the content of the THF-insoluble component is less than 1% by mass, the high-temperature offset resistance may be affected. If it exceeds 50% by mass, the fixability tends to be poor.
[0080]
In the first embodiment, the content (Wa:% by mass) of the vinyl polymer unit in the component having a molecular weight of less than 10,000 in the THF-soluble component of the toner and the component having a molecular weight of 10,000 or more in the THF-soluble component are determined. It is preferable that the content (Wb: mass%) of the vinyl polymer unit satisfies the following relationship.
| Wa-Wb | <20
[0081]
By satisfying | Wa−Wb | <20, the difference in the content of the vinyl polymer unit contained in the low molecular weight component and the high molecular weight component is not so large. As a result, the low molecular weight component and the high molecular weight Since the compatibility of the side components is improved and the rate of dissolution of the wax is increased, the anti-fixing wrapping property is improved.
[0082]
Further, in the first embodiment, it is preferable that Wa and Wb satisfy Wa ≧ Wb, and the following relationship is satisfied.
0 <Wa <50
0 <Wb <30
It is more preferable to satisfy the following relationship:
5 <Wa <30
0 <Wb <20
Is more preferably satisfied.
[0083]
In the first embodiment, when the molecular weight of the toner is less than 10,000, the crosslinking component is small and the viscosity is low as described above. Therefore, when 0 <Wa <50 is satisfied, the viscosity of the toner having a molecular weight of less than 10,000 increases, and the dispersibility of the wax becomes good. Further, if the vinyl-based polymer unit does not have a molecular weight of 10,000 or more in the toner, the compatibility between the low molecular weight side and the high molecular weight side may be deteriorated. Therefore, in order to improve the compatibility between the low molecular weight side and the high molecular weight side, it is preferable to satisfy 0 <Wb <30.
[0084]
In the first embodiment, by setting Wa ≧ Wb, the low molecular component of the toner contains a large amount of the vinyl polymer unit, and the kneading share is uniformly applied during the production of the toner. Becomes more uniform in wax dispersibility. As a result, more excellent fixing winding resistance can be obtained.
[0085]
In the present invention, fractionation of each molecular weight component of the toner and the binder resin can be obtained by, for example, the following method. In the sample, additives other than the polymer component are separated in advance. As a fractionation method, a solvent time at which the molecular weight becomes 10,000 is measured in advance, and a sample is fractionated before and after that. Specific examples of the measuring device and the measuring conditions are shown below.
Apparatus configuration: LC-908 (manufactured by Nippon Kagaku Kogyo Co., Ltd.), JRS-86 (company; repeat injector), JAR-2 (company; autosampler), FC-201 (Gilson; hula cushion collector)
Column configuration: JAIGEL-1H to 5H (20φ × 600mm: preparative column)
Measurement conditions: temperature; 40 ° C., solvent; THF, flow rate: 5 ml / min, detector; RI
[0086]
A sample having a molecular weight of less than 10,000 and a sample having a molecular weight of 10,000 or more separated by the preparative column are hydrolyzed with 6 mol / l of NaOH. After the hydrolysis, the obtained solution is filtered, the solution is adjusted to pH 5 to 6, and extracted with ether, and the ether layer and the aqueous layer are separated.
[0087]
Methanol is added to the obtained ether layer, and the insoluble matter and the soluble matter are separated by filtration. The soluble component is methyl-esterified with diazomethane, and the acidic component (including the polycarboxylic acid component or its anhydride) and the alcohol component having low water solubility are identified by GC / MS, and the content is determined by the GC peak area. . The insoluble content is defined as a styrene / acryl component, the weight is measured to determine the content of the styrene / acryl component, and the styrene / acryl component ratio is determined from H-NMR.
[0088]
On the other hand, the aqueous layer is trimethylsilylated with a trimethylsilylating agent (for example, bis (trimethylsilyl) acetamide or the like), the alcohol component is identified by GC / MS, and the content is determined from the GC peak area.
[0089]
From the obtained results, the polyester component in the THF-soluble component of the toner is set to 100 mol%, and the mol% of the polyvalent carboxylic acid component is calculated.
[0090]
Specific examples for measuring the contents Wa and Wb of the vinyl polymer unit in the toner will be described below.
By the above method, components having a molecular weight of less than 10,000 and components having a molecular weight of 10,000 or more are separated. 0.2 to 0.3 g of the sample is weighed, dissolved in 6 mol / l NaOH, and hydrolyzed at 180 ° C. for 6 hours. This is extracted with ether, the polyester-based monomer component soluble in the aqueous layer is removed, and the ether layer is collected. Next, methanol is added to the ether layer until the vinyl polymer component is precipitated, and the vinyl polymer component is collected by filtration, and the mass ratio of the vinyl polymer component in the hybrid resin is determined.
[0091]
The content of the THF-insoluble component of the toner particles was determined by weighing about 1 g of the toner (W3 g), placing it in a cylindrical filter paper (for example, No. 86R made by Toyo Filter Paper), applying a Soxhlet extractor, and extracting with 200 ml of THF as a solvent for 10 hours. After evaporating a soluble component extracted with a THF solvent, the resultant is dried under vacuum at 100 ° C. for several hours, and the weight of the THF-soluble resin component (W4 g) is weighed. The mass of the components other than the binder resin component such as the colorant and the wax in the toner is measured in advance, and is set to W5 g. The THF-insoluble content is obtained from the following equation.
[0092]
(Equation 1)

[0093]
The THF-soluble component of the binder resin can be separated by subjecting the binder resin to a THF Soxhlet extractor to extract the THF-soluble component, and solidifying the extract.
[0094]
The content of the THF-insoluble content of the binder resin was determined by weighing about 1 g of the binder resin (w3 g), placing it in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), applying a Soxhlet extractor, and using 200 ml of THF as a solvent. After extracting for a time and evaporating the soluble matter extracted with the THF solvent, the resultant is vacuum-dried at 100 ° C. for several hours, and the mass of the THF-soluble resin component (w4 g) is weighed. The THF-insoluble content is obtained from the following equation.
[0095]
(Equation 2)

[0096]
The binder resin used in the present invention includes a content w1 (mol%) of a trivalent or higher polyvalent carboxylic acid and its anhydride in a component having a molecular weight of less than 10,000 in a THF-soluble component of the binder resin, and THF The content w2 (mol%) of trivalent or higher polyvalent carboxylic acids and their anhydrides in the components having a molecular weight of 10,000 or more in the soluble component has the following relationship.
0 ≦ w1 <30
0 <w2 <50
w2> w1
Preferably satisfy the following relationship
1 <w1 <25
2 <w2 <30
It is more preferable to satisfy the following relationship
3 ≦ w1 <20
3 <w2 ≦ 20
Is more preferable, and it is more preferable that the THF-soluble component of the binder resin satisfies such a relationship for obtaining the toner of the present invention described above.
[0097]
Furthermore, the difference between w1 and w2 is
0 <w2-w1 <10
Is more preferably satisfied.
[0098]
Furthermore, in the binder resin used in the present invention, the content (m1) of the component having a molecular weight of less than 10,000 is 40 to 75% by mass, and the molecular weight is 10,000 to The content (m2) of the 50,000 component is 23 to 45% by mass, the content (m3) of the component having a molecular weight exceeding 50,000 is 2 to 25% by mass, and the content (m4) of the component having a molecular weight of 100,000 or more is 13 By satisfying m1 ≧ m2> m3, the content (m1) of the component having a molecular weight of less than 10,000 is preferably 50 to 75% by mass, and the content of the component having a molecular weight of 10,000 to 50,000 is preferably contained. An amount (m2) of 23 to 45% by mass, a content of a component having a molecular weight of more than 50,000 (m3) of 2 to 25% by mass, and a content of a component having a molecular weight of 100,000 or more (m4) of less than 10% by mass; By satisfying m1 ≧ m2> m3> m4, the present invention described above It is possible to obtain a toner.
[0099]
Further, in the binder resin of the first embodiment, the THF-insoluble content of the binder resin is preferably 30% by mass or less for obtaining the toner of the present invention described above, and more preferably 1 to 20% by mass. Is more preferable for obtaining the toner of the present invention described above.
[0100]
In the binder resin of the second embodiment, the content of the THF-insoluble component in the binder resin is preferably 1 to 50% by mass in order to obtain the toner of the present invention described above. It is more preferable to obtain the toner of the present invention described above, and it is more preferable that the amount be 5 to 30% by weight to obtain the toner of the present invention described above.
[0101]
As the polyester-based monomer constituting the polyester unit contained in the polyester resin and the hybrid resin used in the present invention, commonly used alcohol component monomers and acid component monomers are used, and examples thereof include the following.
[0102]
As the alcohol component monomer, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6- There are hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (A), and diols represented by the following formula (A).
[0103]
Embedded image

[0104]
Embedded image

[0105]
Examples of the acid component monomer include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or their anhydrides or lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid Or an anhydride thereof or a lower alkyl ester thereof, or a succinic acid or an anhydride thereof further substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms; such as fumaric acid, maleic acid, citraconic acid, itaconic acid and mesaconic acid; And unsaturated dicarboxylic acids or anhydrides thereof. Further, examples of the acid component monomer include trivalent or higher polyvalent carboxylic acids described below.
[0106]
Further, as the acid component monomers, maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl Half esters of unsaturated dicarboxylic acids such as methyl succinate half ester, methyl fumarate half ester and methyl mesaconate half ester; and unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate.
[0107]
In the toner of the present invention, the binder resin is preferably cross-linked by a trivalent or higher polycarboxylic acid or an anhydride thereof. Preferred examples of the crosslinking component include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride, and benzophenonetetracarboxylic acid.
[0108]
In the toner of the present invention, the binder resin may be cross-linked by a polyhydric alcohol in addition to the trivalent or higher polycarboxylic acid. Examples of the polyhydric alcohol include glycerin, pentaerythritol, sorbit, sorbitan, and, for example, oxyalkylene ether of a novolak type phenol resin.
[0109]
As the vinyl-based monomer constituting the vinyl-based polymer unit contained in the vinyl-based resin and the hybrid resin used in the present invention, a commonly used vinyl-based monomer can be used, for example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-butylstyrene, p-tert-tributylstyrene, pn-hexylstyrene, pn- Octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitro Styrene and its derivatives such as styrene and p-nitrostyrene; ethylene, propylene, Unsaturated monoolefins such as butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate and vinyl benzoate. Vinyl esters: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic esters such as phenyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate; Acrylic esters such as isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyls such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone Compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.
[0110]
Further, vinyl monomers include α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride; An anhydride of the α, β-unsaturated acid and a lower fatty acid; monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid and monoesters thereof.
[0111]
Further, examples of vinyl monomers include acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, Monomers having a hydroxy group such as (1-hydroxy-1-methylhexyl) styrene are exemplified.
[0112]
Furthermore, methyl maleate half ester, maleic acid ethyl half ester, butyl maleate half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl methyl succinate half Unsaturated dicarboxylic acid half esters such as esters, methyl fumarate half ester and methyl mesaconate half ester; unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate; maleic acid, citraconic acid, itaconic acid and alkenyl succinic acid Unsaturated dicarboxylic acids such as acid, fumaric acid and mesaconic acid; unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride Anhydrides can also be used as the vinyl-based monomer, but when calculating the ratio of the polyester-based monomer component based on all the monomer components used for producing the binder resin in the present invention, the polyester in the present invention is limited to these. It is calculated as a system monomer component.
[0113]
Further, the vinyl resin and the vinyl polymer unit may be a polymer cross-linked with a cross-linkable monomer as exemplified below as necessary.
[0114]
Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butane. Diol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; and an alkyl chain containing an ether bond. Examples of the linked diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol # 400 dia. Relates, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced by methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond include: For example, polyoxyethylene (2) -2,2-bis (4-hydroxydiphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and acrylates of the above compounds Is replaced by methacrylate; examples of polyester-type diacrylates include, for example, trade name MANDA (Nippon Kayaku).
[0115]
Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Nurate and triallyl trimellitate are exemplified.
[0116]
These crosslinking agents are preferably used in an amount of 0.01 to 10.0 parts by mass (more preferably 0.03 to 5 parts by mass) based on 100 parts by mass of the other vinyl monomer component.
[0117]
In the present invention, the vinyl polymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those which can react with the vinyl polymer include, for example, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, and anhydrides thereof. Among the monomers constituting the vinyl polymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
[0118]
As a method for obtaining a reaction product of a vinyl resin and a polyester resin, where a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resin and polyester resin is present, one or both of the two may be used. A method obtained by polymerizing a resin is preferable.
[0119]
Examples of the polymerization initiator used for producing the vinyl resin and the vinyl polymer unit include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl- 4-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide Ketone peroxides such as cyclohexanone peroxide; 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxy Dicarbonate, di-2-ethoxyethylperoxydicarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butyl Peroxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate Include di -t- butyl peroxy azelate.
[0120]
As the polymerization initiator used when producing the vinyl-based resin and vinyl-based polymer unit, a polyfunctional polymerization initiator exemplified below may be used alone, or a monofunctional polymerization initiator. You may use together.
[0121]
Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,3-trimethylcyclohexane and 1,3-bis (t-butylperoxyisopropyl). Benzene, 2,5-dimethyl-2,5 (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris (t-butylperoxy) triazine 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t -Butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate, 2,2-bis (4,4-di Polyfunctional polymerization initiators having two or more functional groups having a polymerization initiation function such as peroxide groups in one molecule, such as t-butylperoxycyclohexyl) propane and 2,2-t-butylperoxyoctane And a functional group having a polymerization initiation function such as a peroxide group, such as diallyl peroxydicarbonate, tributyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate, and polymerizable unsaturated. And polyfunctional polymerization initiators having both groups in one molecule.
[0122]
Among these, more preferred are 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-t-butylperoxycyclohexane, and di-t-butylperoxyhexahydro. Terephthalate, di-t-butylperoxyazelate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.
[0123]
In the present invention, the binder resin contains at least a hybrid resin component. In the present invention, a hybrid resin is a component in which a polyester resin component and a vinyl polymer component are chemically bonded, and means a resin containing at least a part of such a component. And the polyester resin component side chemically bonded is the polyester unit, and the vinyl polymer component chemically bonded is the vinyl polymer unit.
[0124]
Specifically, vinyl polymerized by containing a polyester unit and a vinyl monomer having a carboxylic acid such as (meth) acrylic acid or a vinyl monomer having a carboxylic acid ester group such as (meth) acrylic acid ester It is formed by an esterification reaction or a transesterification reaction with the system polymer unit. The form of the copolymerization is preferably graft copolymerization or block copolymerization using a vinyl polymer unit as a trunk polymer and a polyester unit as a branch polymer.
[0125]
Accordingly, specifically, in the present invention, the hybrid resin component is one in which at least a part of the polyester unit and the vinyl polymer unit are bonded via the bonding site shown below.
[0126]
Embedded image

[0127]
In the present invention, examples of the method for producing a hybrid resin include the following production methods (1) to (7).
[0128]
(1) After separately producing a vinyl polymer and a polyester resin, they are dissolved / swelled in an organic solvent, an esterification catalyst and, if necessary, an alcohol are added, and the esterification reaction or / and After the transesterification, the organic solvent is distilled off. In this production method, waxes may be added during the reaction.
[0129]
(2) In the presence of a vinyl polymer, a polyester monomer is added, and polymerization and an esterification reaction and / or a transesterification reaction with the vinyl polymer are performed. In this production method, during the reaction, a vinyl monomer may be further added, if necessary, for polymerization. In this production method, an organic solvent is appropriately used. Further, in this production method, similarly to the above (1), waxes may be added during the reaction.
[0130]
(3) In the presence of a polyester resin, a vinyl monomer is added, and polymerization and an esterification reaction and / or a transesterification reaction are performed. In this production method, during the reaction, a polyester-based monomer may be further added, if necessary, for polymerization. Further, in this production method, an organic solvent can be appropriately used as in the above (2), and a wax may be added during the reaction as in the above (1).
[0131]
(4) In the presence of a vinyl polymer and a polyester resin, a vinyl monomer and / or a polyester monomer are added, and polymerization, an esterification reaction and / or a transesterification reaction are performed. Also in this production method, an organic solvent can be appropriately used in the same manner as in the above (2), and a wax may be added during the reaction in the same manner as in the above (1).
[0132]
(5) A vinyl-based monomer and a polyester-based monomer are mixed to carry out addition polymerization and polycondensation, and esterification and / or transesterification. Also in this production method, an organic solvent can be appropriately used in the same manner as in the above (2), and a wax may be added during the reaction in the same manner as in the above (1).
[0133]
(6) The resin containing the hybrid resin component produced in the above (1) to (5) is further mixed with a vinyl polymer and / or polyester resin by, for example, dissolving / swelling in an organic solvent. To remove the organic solvent.
[0134]
(7) In the presence of the resin containing the hybrid resin component produced in the above (1) to (5), a vinyl-based monomer and / or a polyester-based monomer is further added to carry out polymerization and esterification reaction and / or esterification. Perform an exchange reaction. Also in this production method, an organic solvent can be appropriately used in the same manner as in the above (2), and a wax may be added during the reaction in the same manner as in the above (1).
[0135]
In the production methods of the above (1) to (4) and (6), a plurality of types of polymers having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer and / or the polyester resin.
[0136]
Among the production methods (1) to (7), the production method (3) is particularly easy to control the molecular weight, can control the production of the hybrid resin component, and when the wax is added. This is preferable in that the dispersion state can be controlled.
[0137]
The toner of the present invention contains a wax. In the present invention, it is preferable that the toner has at least one endothermic peak in differential thermal analysis (DSC) in a temperature range of 60 to 120 ° C. The toner having such thermal characteristics can be achieved by containing a wax having at least one endothermic peak in DSC in a temperature range of 60 to 120 ° C.
[0138]
By having at least one endothermic peak in the differential thermal analysis of the toner at not less than 60 ° C. and not more than 120 ° C., the wax acts from a low temperature region where the toner starts to be fixed, so that the fixing property can be further improved, and the low temperature fixing property can be improved. High-temperature offset resistance and blocking resistance can be further improved. When the endothermic peak is below 60 ° C., the blocking resistance tends to deteriorate, and when the endothermic peak exceeds 120 ° C., the low-temperature fixability tends to deteriorate.
[0139]
The DSC endothermic peaks of the wax and the toner were measured by using a differential thermal analyzer (DSC measuring apparatus), DSC-7 (manufactured by PerkinElmer), DSC2920 (manufactured by TA Instruments Japan), or another model using ASTM D3418-82. It can be measured according to. As a specific example, a measurement sample is accurately weighed in the range of 2 to 10 mg, placed in an aluminum pan, and an empty aluminum pan is used as a reference. The measurement is performed at 10 ° C./min under normal temperature and normal humidity.
[0140]
The wax used in the present invention preferably has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC of 1.0 to 2.0. When the molecular weight ratio is in the above range, the molecular weight distribution becomes extremely sharp, which is preferable. In the present invention, by using a wax having an extremely sharp molecular weight distribution, the release effect is quickly exhibited, and further excellent fixing wrapping resistance and high-temperature offset resistance are achieved, while blocking resistance is further improved. Is also preferable because it does not deteriorate.
[0141]
Further, in the toner of the first embodiment, since the binder resin is made of a hybrid resin, and these waxes are uniformly dispersed, this effect is remarkably exhibited. By using a wax that dissolves sharply, a release effect is exhibited, and by using a hybrid resin, the wax dispersibility is improved, so that both the wax dispersibility and the release effect can be achieved, and these can be further improved. .
[0142]
Furthermore, in the second embodiment, the binder resin used for the toner is made of a polyester resin and a hybrid resin, and the polyester resin and the hybrid resin have good compatibility, and these waxes are well dispersed in the hybrid resin. Because of this, the wax is uniformly dispersed in the binder resin, and the above-mentioned effects are remarkably exhibited. By using a wax that dissolves sharply, a releasing effect is exhibited, and by using a polyester resin and a hybrid resin, the wax dispersibility is improved, and the releasing effect can be exhibited more efficiently.
[0143]
The molecular weight of the wax can be measured under the following conditions.
Equipment: GPC-150C (Waters)
Column: GMH-HT 30 cm, 2 stations (Tosoh Corporation)
Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% by mass ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml of 0.15 mass% wax injected
[0144]
The molecular weight of the wax is measured under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the wax. Further, the molecular weight of the wax is calculated by converting into a polyethylene based on a conversion formula derived from the Mark-Houwink viscosity formula.
[0145]
The wax has a number average molecular weight of 200 to 2,000 (more preferably 300 to 1500, and still more preferably 350 to 1000), and the dispersibility in the binder resin, the low-temperature offset resistance, the high-temperature offset resistance, and the blocking resistance. It is more preferable in view of the properties and the durability of a large number of sheets.
[0146]
Examples of the wax include a low-molecular-weight hydrocarbon wax composed of carbon and hydrogen, a long-chain alkyl alcohol wax having an OH group, a long-chain alkyl carboxylic acid wax having a COOH group, and an ester wax.
[0147]
Examples of the low molecular weight hydrocarbon wax include petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam and derivatives thereof; low molecular weight polyolefin wax such as low molecular weight polyethylene; and polymethylene wax such as Fischer-Tropsch wax. Since the low molecular weight polyolefin wax usually has a Mw / Mn value of more than 2.0, the Mw / Mn becomes 1.0 to 2.0 and the DSC endothermic main peak becomes 60 to 120 ° C. It is preferable to purify the product.
[0148]
Examples of the long-chain alkyl alcohol wax include a mixture of long-chain alkyl alcohols having 20 to 200 carbon atoms, and examples of the long-chain alkyl carboxylic acid wax include long-chain alkyl carboxylic acids having 20 to 200 carbon atoms. And mixtures thereof.
[0149]
Examples of the ester wax include a wax obtained by purifying carnauba wax, a wax obtained by purifying candelilla wax, and an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms. The main component is a wax. For the toner of the present invention, a low molecular weight hydrocarbon wax which tends to have a sharp molecular weight distribution is preferable in order to exhibit a more effective releasing effect.
[0150]
In the present invention, in order to further stabilize the chargeability, a metal compound as a charge control agent is added to the toner particles in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin (internal addition). Alternatively, it is preferable to mix (externally add) with the toner particles. The charge control agent makes it possible to control the amount of charge optimally according to the development system.
[0151]
By using a metal compound as the charge control agent and satisfying W2> W1, crosslinking progresses between the polyvalent carboxylic acid, which is more frequently present on the high molecular weight side in the toner molecular weight distribution, and the metal compound, and the non-offset region is reduced. spread. Further, the low molecular weight component is appropriately crosslinked, though not as much as the high molecular weight component, and as a result, the wax dispersibility in the toner is improved.
[0152]
As the charge control agent for controlling the toner of the present invention to negative charge, for example, an organic metal complex, a chelate compound is effective, a monoazo metal compound, an acetylacetone metal compound, an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid-based There are metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, aromatic polycarboxylic acids, metal salts thereof, anhydrides thereof, esters thereof, and phenol derivatives such as bisphenol.
[0153]
Examples of the charge controlling agent for controlling the toner of the present invention to be positively charged include those modified with nigrosine and an aliphatic metal salt; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate Quaternary ammonium salts, such as onium salts such as phosphonium salts, and their lake pigments, triphenylmethane dyes, and these lake pigments (as the lacking agent, there are phosphorous tungsten, phosphomolybdic acid, phosphorous tungsten). Molybdic acid, tannic acid, lauric acid, gallic acid, phenylic acid, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borane DOO, dioctyl tin borate, such as dicyclohexyl tin borate diorgano tin borate such; using these alone or may be used in combination of two or more kinds.
[0154]
The charge control agent described above is preferably used in the form of fine particles.
[0155]
In the present invention, it is preferable to use an aromatic hydroxycarboxylic acid having a metal atom in the molecule, and it is preferable to use an aromatic hydroxycarboxylic acid compound of aluminum, which has a good chargeability in the early stage of durability. Further, by using an aromatic hydroxycarboxylic acid compound of aluminum, a good crosslinking effect can be obtained.
[0156]
In the present invention, it is also preferable to use a monoazo iron compound, which has stable chargeability in long-term durability.
[0157]
Further, in the present invention, in order to maintain the chargeability over a long period of time, it is preferable to use an aromatic hydroxycarboxylic acid compound of aluminum and a monoazo iron compound in combination. In particular, when the aromatic hydroxycarboxylic acid compound of aluminum is contained in the toner in an amount of 0.1 to 1 part by mass and the monoazo iron compound in the amount of 0.5 to 3 parts by mass, the crosslinking effect and the charging performance are appropriately controlled. preferable.
[0158]
Examples of the hydroxycarboxylic acid site and the azo compound site in the metal compound preferably used in the present invention are shown below.
[0159]
Embedded image

[0160]
Embedded image

[0161]
Embedded image

[0162]
Embedded image

[0163]
Embedded image

[0164]
Further, specific examples of metal compounds using the above hydroxycarboxylic acids and azo compounds are shown below.
[0165]
Embedded image

[0166]
Embedded image

[0167]
Embedded image

[0168]
Embedded image

[0169]
The toner of the present invention contains a colorant. The colorant used in the present invention is appropriately selected from commonly used colorants of yellow, magenta, cyan, and black.
[0170]
As the yellow colorant, compounds represented by a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, and an allylamide compound are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.
[0171]
Examples of the magenta colorant include a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.
[0172]
As the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 can be particularly preferably used.
[0173]
As a black colorant, a carbon black, a magnetic substance, and a yellow / magenta / cyan colorant shown below and toned to black are used.
[0174]
In the present invention, when a dye and a pigment other than a magnetic substance are used as a black colorant, the colorant is contained in the toner in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin, and when a magnetic substance is used. Unlike the other colorants, the toner contains 30 to 200 parts by mass with respect to 100 parts by mass of the resin.
[0175]
As the magnetic material, there is a metal oxide containing an element of iron, cobalt, nickel, copper, magnesium, manganese, aluminum or silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable.
[0176]
In the toner of the present invention, a magnetic material containing another metal element such as a silicon element or an aluminum element may be used from the viewpoint of controlling the chargeability of the toner. These magnetic particles have a BET specific surface area of 2 to 30 m by a nitrogen adsorption method.²/ G, especially 3 to 28 m²/ G, and preferably a Mohs hardness of 5 to 7. The specific surface area can be calculated by adsorbing nitrogen gas on the sample surface according to the BET method and using the BET multipoint method.
[0177]
Examples of the shape of the magnetic material include an octahedron, a hexahedron, a sphere, a needle, and a scale, but an octahedron, a hexahedron, a sphere, and an amorphous type having little anisotropy are preferable for increasing image density. It is particularly preferred that they are spherical. Further, in order to further increase the image density, a magnetic material containing silica is particularly preferable.
[0178]
The average particle size of the magnetic material is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.6 μm, and further preferably 0.1 to 0.4 μm. The average particle size of the magnetic material was measured by taking a transmission electron micrograph of the magnetic powder and arbitrarily selecting 250 particles having a particle size of 0.01 μm or more per 40,000-fold magnification. The inside Martin diameter (the length of a line segment bisecting the projected area in a fixed direction) is measured, and this is obtained by a method or the like expressing this as a number average diameter.
[0179]
In the present invention, it is preferable to externally add an inorganic fine powder such as an oxide such as silica, alumina, or titania or a double oxide thereof in order to improve charging stability, developability, and storage stability. Further, the inorganic fine powder is preferably silica.
[0180]
For example, as such silica, both so-called dry silica produced by vapor phase oxidation of a silicon halide and an alkoxide, or dry silica called fumed silica, and so-called wet silica produced from alkoxide and water glass are used. Although possible, there are few silanol groups on the surface and inside the silica fine powder, and Na₂O, SO₃ ^2-Dry silica with little production residue such as is preferred.
[0181]
In the case of fumed silica, for example, in the production process, by using other metal halides such as aluminum chloride and titanium chloride together with silicon halide, it is also possible to obtain a composite fine powder of silica and other metal oxides, Silica also includes them.
[0182]
The inorganic fine powder used in the present invention has a specific surface area of 30 m by nitrogen adsorption measured by the BET method.²/ G or more. Especially 50-400m²/ G is more preferable for obtaining good results. The inorganic fine powder is preferably added in an amount of 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, and more than 1.0 to 3 parts by mass based on 100 parts by mass of the toner particles. More preferably, it is used up to 0 parts by mass.
[0183]
The inorganic fine powder used in the present invention may be, for the purpose of hydrophobicity and charge control, if necessary, silicone varnish, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organic compounds. It is preferable to be treated with one or two or more treating agents such as a silicon compound and an organic titanium compound.
[0184]
The specific surface area of the inorganic fine powder can be calculated according to the BET method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device, Auto Soap 1 (manufactured by Yuasa Ionics), and using the BET multipoint method. it can. In order to maintain stable storage stability of the toner, the inorganic fine powder is preferably treated at least with silicone oil.
[0185]
External additives other than inorganic fine powder such as silica fine powder may be added to the toner of the present invention as needed. Examples of such external additives include, for example, charge assisting agents, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, release agents at the time of hot roll fixing, lubricants, and resin fine particles that function as abrasives. No.
[0186]
The toner of the present invention is preferably manufactured through a step of melt-kneading a mixture containing at least a binder resin, a colorant and a wax. More specifically, as a method for producing the toner of the present invention, after sufficiently mixing the above-described toner constituent materials with a ball mill or other mixer, a heat kneader such as a hot roll kneader or an extruder may be used. It is preferable to knead the mixture, solidify it by cooling, mechanically grind it, and classify the crushed powder to obtain a toner.
[0187]
As a method for producing the toner of the present invention, another method is to mix a predetermined material with a monomer to constitute a binder resin to form an emulsion suspension, and then polymerize to obtain a toner. Manufacturing method: In a so-called microcapsule toner composed of a core material and a shell material, a method in which a predetermined material is contained in the core material and / or the shell material; and after the constituent materials are dispersed in a binder resin solution, spray drying is performed. To obtain a toner. Further, if desired, the desired additive and toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention. As described above, the toner of the present invention can be manufactured using a generally known manufacturing method or a generally used manufacturing apparatus.
[0188]
As a manufacturing apparatus used for manufacturing the toner of the present invention, for example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); Burizer, Cyclomix (manufactured by Hosokawa Micron); Spiral Pin Mixer (manufactured by Taiheiyo Kiko Co., Ltd.); and Ledige Mixer (manufactured by Matsubo).
[0189]
Examples of the kneading machine include a KRC kneader (manufactured by Kurimoto Iron Works); a bus co-kneader (manufactured by Buss); a TEM extruder (manufactured by Toshiba Machine); a TEX twin-screw kneading machine (manufactured by Nippon Steel Works). PCM kneader (Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Netex (manufactured by Mitsui Mining); MS-type press kneader; kneader router (manufactured by Moriyama Seisakusho) A Banbury mixer (manufactured by Kobe Steel Ltd.).
[0190]
Examples of the pulverizer include a counter jet mill, a micron jet, an innomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industries); a cross jet mill (manufactured by Kurimoto Tekkosho); (Manufactured by Nisso Engineering Co., Ltd.); SK Jet O Mill (manufactured by Seishin Enterprise Co., Ltd.); krypton (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turbo Kogyo Co., Ltd.); and super rotor (manufactured by Nisshin Engineering Co., Ltd.).
[0191]
Classifiers include, for example, Crasheal, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); micron separator, turboflex (ATP), TSP separator (manufactured by Hosokawa Micron) Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industries Co., Ltd.); and YM Micro Cut (manufactured by Yaskawa Corporation).
[0192]
Examples of the sieving apparatus used for sifting coarse particles and the like include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheep, Gyro Shifter (manufactured by Tokuju Kosakusho); Vibrasonic System (manufactured by Dalton); Turbo Screener (manufactured by Turbo Kogyo); Microshifter (manufactured by Makino Sangyo); circular vibrating sieve.
[0193]
Next, the heat fixing device used in the present invention will be described.
In the present invention, the unfixed image is fixed on the recording material by passing the recording material on which the unfixed image is formed through a nip portion maintained at a predetermined temperature between the fixing member and the pressing member. The heating and fixing device includes a flexible metal sleeve and a current-carrying resistance layer as the fixing member, a heating heater as a heating member in contact with the inner surface of the metal sleeve, and a pressure member. A heat fixing device is used. The thickness of the metal sleeve is preferably 20 μm to 100 μm.
[0194]
In addition, the inner surface of the metal sleeve preferably has a surface roughness Rz of 3 μm or less in order to keep the contact thermal resistance low and improve the heat transfer to the fixing nip. Further, it is also a preferable configuration that the surface roughness of the outer surface of the metal sleeve is set to Rz = 3 μm or less, and the release layer including the primer layer as the adhesive layer is formed to have a thickness of 20 μm or less.
[0195]
With this, by performing contact heating from the inner surface of the metal sleeve having good thermal conductivity by the heater for heating, it is possible to perform the heat fixing corresponding to the high speed of the image forming apparatus with high thermal efficiency.
[0196]
Accordingly, the power supply to the heater can be shut down during standby when the image forming apparatus is not receiving the print signal, and energy-saving heat fixing can be realized.
[0197]
Further, even when the power of the image forming apparatus is turned on from the room temperature state, the print signal can be received immediately, so that the user does not have to wait.
[0198]
Therefore, even when the speed of the image forming apparatus is increased, it is possible to provide a heat fixing device which is excellent in quick start performance and has a fast first print time.
[0199]
Further, by using a metal sleeve having higher rigidity than a resin film, it is possible to set a high pressing force, and it is possible to cope with an increase in the speed of the image forming apparatus.
[0200]
Further, the surface of the heater for heating the fixing nip portion which is in contact with the inner surface of the metal sleeve is made of a heat-resistant resin member such as a polyimide resin. As a result, the inner surface of the metal sleeve can smoothly slide on the surface of the heater for heating, and heat fixing with high durability becomes possible.
[0201]
Further, when the metal sleeve is subjected to the circumferential streak processing within the above surface roughness, the rotation of the metal sleeve can be made smooth and the heating heater coat can be hardly damaged.
[0202]
Further, in a heat fixing device for fixing an unfixed toner image on a recording material, a bias having a polarity opposite to that of the toner is applied to the pressure roller side, and the metal sleeve is grounded or diode-connected, so that paper powder, toner, and the like are removed. It is possible to further prevent the metal sleeve from being sucked. Thus, a highly durable heat fixing device can be provided without a problem such as contamination of the metal sleeve due to durability.
[0203]
By combining the above-described toner with the fixing device having such a configuration, it is possible to achieve high-speed on-demand fixing that is excellent in fixing property and high-temperature offset property and has a quick start property in which winding does not occur.
[0204]
(A) Example of image forming apparatus
FIG. 1 is a schematic configuration model diagram of an example of an image forming apparatus. Reference numeral 1 denotes a photosensitive drum on which a photosensitive material such as OPC, amorphous Se, or amorphous Si is formed on a cylindrical base such as aluminum or nickel.
[0205]
The photosensitive drum 1 is driven to rotate in the direction of the arrow, and its surface is first uniformly charged by a charging roller 2 as a charging device.
[0206]
Next, scanning exposure is performed by a laser beam 3 that is ON / OFF controlled according to image information, and an electrostatic latent image is formed.
[0207]
This electrostatic latent image is developed and visualized by the developing device 4. As a development method, a jumping development method, a two-component development method, an FEED development method, or the like is used, and a combination of image exposure and reversal development is often used.
[0208]
The visualized toner image is transferred from the photosensitive drum 1 onto the recording material P conveyed at a predetermined timing by a transfer roller 5 as a transfer device.
[0209]
Here, the sensor 8 detects the leading end of the recording material P so that the image forming position of the toner image on the photosensitive drum 1 and the writing start position of the leading end of the recording material coincide with each other, and the timing is adjusted. The recording material P conveyed at a predetermined timing is nipped and conveyed by the photosensitive drum 1 and the transfer roller 5 with a constant pressing force.
[0210]
The recording material P to which the toner image has been transferred is conveyed to the heat fixing device 6 and fixed.
[0211]
On the other hand, the transfer residual toner remaining on the photosensitive drum 1 is removed from the surface of the photosensitive drum 1 by the cleaning device 7.
[0212]
(B) Heat fixing device 6
FIG. 2 is a schematic structural model diagram of the heat fixing device 6. Reference numeral 10 denotes a fixing member, and reference numeral 20 denotes a pressing member, which are pressed against each other to form a fixing nip portion. The fixing member 10 includes a heater 11 as a heating member, a heat insulating stay holder 12, a fixing sleeve 13, and the like. The pressure member 20 is a heat-resistant elastic pressure roller.
[0213]
a) Fixing sleeve 13
The fixing sleeve 13 is a sleeve having a small heat capacity. In order to enable quick start, a metal member such as SUS, Al, Ni, Cu, or Zn having a thickness of 100 μm or less and having heat resistance and high thermal conductivity is used alone or in an alloy. It is a metal sleeve (film) having a member as a base layer.
[0214]
Further, a metal sleeve having sufficient strength and excellent durability for constituting a heat fixing device having a long service life is required to have a thickness of 20 μm or more. Therefore, the thickness of the metal sleeve 13 is optimally 20 μm or more and 100 μm or less.
[0215]
Further, in order to prevent offset and secure the separation property of the recording material, the surface layer is made of PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), and FEP (tetrafluoroethylene-hexafluoropropylene). Heat-resistant resins with good mold release properties, such as fluororesins, silicone resins, etc., such as polymers), ETFE (ethylene-tetrafluoroethylene copolymer), CTFE (polychlorotrifluoroethylene), PVDF (polyvinylidene fluoride). They are mixed or coated individually.
[0216]
As a method of coating, after applying a primer layer as an adhesive layer on the outer surface of the metal sleeve base material, dipping the release layer, applying a powder spray or the like, or forming a tube-like May be applied to the surface of the metal sleeve.
[0219]
The surface properties of the inner and outer surfaces of the metal sleeve and the thickness of the releasable layer will be described in detail in section e) below.
[0218]
b) Heating heater 11
The heating heater 11 is provided inside a metal sleeve 13 which is a fixing sleeve, and heats a nip portion where the toner image on the recording material P is melted and fixed. FIG. 3 shows a schematic diagram of the configuration near the heater for heating. In FIG. 3, a heater 11 is provided along a longitudinal direction on a surface of a substrate 11a made of a highly insulating ceramic such as alumina, AlN (aluminum nitride) or a heat-resistant resin such as polyimide, PPS, or liquid crystal polymer. For example, Ag / Pd (silver palladium), RuO₂, Ta₂N is formed by coating a heating or heating resistor layer 11b of N or the like into a linear or narrow band having a thickness of about 10 μm and a width of about 1 to 5 mm by screen printing or the like, and a metal sleeve is formed on the surface of the heating and heating resistor layer 11b. 13 is a heating member provided with a sliding layer made of a thin fluororesin layer capable of withstanding rubbing with No. 13 and a heat-resistant resin layer of polyimide, polyamideimide, PEEK or the like.
[0219]
A temperature detecting element 14 such as a thermistor for detecting the temperature of the heating heater 11 which has been heated in accordance with the heat generated by the energized heat generating resistance layer 11b is disposed on the back surface (the side opposite to the fixing nip portion N) of the substrate 11a. Have been. By appropriately controlling the duty ratio, the wave number, and the like of the voltage applied from the electrode portions 11f and 11g at the longitudinal ends shown in FIG. The temperature necessary for fixing the toner image on the recording material P is maintained while maintaining the temperature of the regulated temperature in the fixing nip N substantially constant. DC conduction from the temperature detecting element 14 to a temperature control unit (not shown) is achieved by a connector (not shown) via a DC conduction unit (not shown) and a DC electrode unit.
[0220]
In the case where AlN (aluminum nitride) having good thermal conductivity is used as the heater substrate 11a, as shown in FIG. 4, the heat-generating resistor layer 11b is placed on the side opposite to the fixing nip portion N with respect to the substrate 11a. It may be formed. In FIG. 4, reference numeral 11d denotes a protective layer such as a glass coat or a fluororesin layer provided to satisfy the withstand voltage between the current-generating resistance layer 11d and the temperature detecting element 14 formed on the substrate 11a. Reference numeral 11e denotes a sliding layer composed of a thin fluororesin layer capable of withstanding rubbing with the metal sleeve, and a heat-resistant resin layer of polyimide, polyamideimide, PEEK or the like, similar to 11c described above.
[0221]
In addition, by fixing the inner surface of the metal sleeve 13 on the fixing nip portion N side of the heating heater 11 to a curved surface so as not to apply a bending load to the metal sleeve 13, a longer-life fixing member can be used. Is formed. Alternatively, the heater is a metal heating heater in which an insulating layer and an energization heating resistance layer are sequentially laminated on a side of the metal substrate opposite to the fixing nip portion, and the metal substrate has a metal sleeve on the fixing nip portion side. The shape may be curved in the same direction.
[0222]
c) Heat insulation stay holder 12
The heat insulating stay holder 12 is a heat insulating member that holds the heater 11 for heating and prevents heat radiation in a direction opposite to the fixing nip portion N, and is formed of a liquid crystal polymer, a phenol resin, PPS, PEEK, or the like. A sleeve 13 is loosely fitted around the sleeve 13 and is rotatably arranged in the direction of the arrow. Further, since the metal sleeve 13 rotates while rubbing against the internal heater 11 and the heat insulating stay holder 12, it is necessary to reduce the frictional resistance between the metal heater 13 and the heater 11 and the heat insulating stay holder 12. There is. Therefore, a small amount of lubricant such as heat-resistant grease is interposed between the surfaces of the heater 11 and the heat insulating stay holder 12. Thereby, the metal sleeve 13 can rotate smoothly.
[0223]
d) Pressure roller 20
The pressure roller 20 includes an elastic layer 22 formed by foaming heat-resistant rubber such as silicone rubber or fluorine rubber or silicone rubber on the outer side of a cored bar 21, and a releasing agent such as PFA, PTFE, or FEP is formed thereon. The active layer 23 may be formed.
[0224]
As shown in FIG. 4, the fixing member 10 is provided with a part of the heat insulating stay holder 12 as shown in FIG. Thus, pressure is sufficiently applied from both ends in the longitudinal direction to form a fixing nip portion N necessary for heat fixing.
[0225]
Further, the pressure roller 20 is rotationally driven by the drive gear 16 attached to the end of the metal core 21 of the pressure roller 20, and the metal film is driven at a predetermined speed by friction between the pressure roller surface and the metal film surface. Rotate.
[0226]
The configuration of the heat fixing device 6 has been described above. In FIG. 2, the recording material P is appropriately supplied by a supply unit (not shown), and is formed by the heating member 10 and the pressing member 20 along the heat-resistant fixing entrance guide 15. To the fixing nip N.
[0227]
e) Surface roughness of the inner and outer surfaces of the metal sleeve 13
Here, the surface roughness of the inner and outer surfaces of the metal sleeve 13 and the thickness of the release layer will be described below.
[0228]
First, it is necessary to transfer the heat generated from the heater 11 to the fixing nip N by contacting the inner surface of the metal sleeve 13 with the heater 11 with a predetermined contact width. The idea is different from that of the heat roller fixing device (FIG. 13) that performs heating by radiant heat. Therefore, the surface roughness of the inner surface of the metal sleeve 13 that contacts and conducts heat with the heater 11 greatly affects the thermal efficiency. In particular, when the contact thermal resistance between the surface of the sliding layer 11c (FIG. 3) or 11e (FIG. 4) of the heater 11 and the inner surface of the metal sleeve 13 increases, the thermal efficiency deteriorates, and fixing failure occurs. Even if thermal conductive grease or the like is interposed, it is preferable to suppress the surface roughness to a predetermined value or less in order to configure a heat fixing device having high thermal efficiency.
[0229]
Further, a release layer is formed on the outer surface of the metal sleeve 13, but since the release layer is generally formed of a fluororesin, the thermal conductivity is extremely lower than the thermal conductivity of the metal sleeve 13. It becomes. Therefore, if the thickness is too large, heat conduction is deteriorated, and sufficient heat cannot be supplied to the toner image on the recording material P at the fixing nip portion N in order to speed up the image forming apparatus. Therefore, it is necessary to form a thin release layer on the metal sleeve 13. At this time, the surface roughness of the outer surface of the metal sleeve 13 is preferably suppressed to a predetermined value or less. That is, the effect of reducing the surface roughness of the outer surface of the metal sleeve 13 cannot be obtained with the thin release layer, and the surface roughness after the release layer is formed on the outer surface of the metal sleeve 13 is reduced. The surface roughness is equal to or slightly smaller than the surface roughness of the tube. Therefore, if the surface roughness of the metal sleeve 13 is large, the surface roughness becomes large even after the release layer is formed, and the adhesion to the recording material P is not obtained at the fixing nip portion N. More likely to cause.
[0230]
From the above, it is possible to obtain sufficient fixing performance by setting the surface roughness of the outer surface of the metal sleeve 13 to a predetermined value or less, and applying and forming a release layer including a primer layer as an adhesive layer to a predetermined thickness or less. Therefore, it is possible to cope with an increase in the speed of the image forming apparatus.
[0231]
In addition, by providing the metal sleeve 13 with an uneven shape having a surface roughness of a predetermined value or less in the circumferential direction, the rotation of the metal sleeve 13 becomes smoother, and the release layer coated on the surface of the heater 11 for heating. Hardly hurt. Thus, the heat-fixing metal sleeve 13 with higher durability and higher speed can be provided.
[0232]
The manufacturing method of the metal sleeve 13 in FIG. 2 is achieved by the following method, and moderate unevenness is formed on the metal sleeve 13 in the circumferential direction.
[0233]
6 to 10 show a main method of manufacturing the metal sleeve 13. FIG. First, in FIG. 6, reference numeral 31 denotes a base material of the metal sleeve 13 which is made of SUS, Al, Ni, Cu, Zn, or the like of about 0.1 mm to 0.5 mm alone or in a metal plate ( Plank). Numeral 32 denotes a circular inner die (punch) in a general deep drawing method, and numeral 33 denotes a cylindrical container-shaped outer die (die), which is a die having a surface of a metal material plated with a super hard metal or the like. 6, the metal plate 31 is sandwiched between the inner mold 32 and the outer mold 33, and the inner mold 32 is pushed in the direction of the arrow in the direction of the arrow. A high-viscosity lubricating oil or a solid lubricant such as graphite or molybdenum disulfide is interposed between the metal plate 31 and the outer mold 33 to improve the drawability. The above process is usually performed about 2 to 4 times by deep drawing with different molds, thereby producing a cup-shaped metal cylindrical member 34 as shown in FIG.
[0234]
Next, ironing is performed so that the metal cylindrical member 34 is formed to a predetermined thickness. As the ironing process, any process such as rolling, drawing, drawing, etc. may be performed in the middle, but as the final process, a predetermined amount or less in the circumferential direction of the metal sleeve by a processing method as described below. Processing with irregularities is applied. For example, there is a processing method as shown in FIGS. FIG. 8 shows a general drawing spinning process, in which a pressing roller 36a rotatably mounted on a shaft 36b mounted on a fixed base 36c is always separated from a metal inner mold 35 by a predetermined distance, and is made of metal. The inner mold 35 is pressed in the direction. A deeply drawn metal cylindrical member 34 attached to the cup shape attached to the metal inner mold 35 is fitted into the cup shape, and the cup-shaped bottom of the metal cylindrical member 34 is brought into close contact with the metal inner mold 35 by the pressing member 37. Be fixed. In this state, the metal inner mold 35, the metal cylindrical member 34, and the pressing member 37 are gradually fed rightward on the paper while rotating in the direction of the arrow in the figure. From the end, a rotatable roller is pressed against the metal inner mold 35 at a predetermined distance.
[0235]
As a result, the thickness of the metal cylindrical member 34 is gradually reduced from the end by ironing, and finally, as shown in FIG. The metal cylindrical member 39 is formed by ironing.
[0236]
The metal cylindrical member 39 has a trace 39a of the roller pressing at the time of drawing and spinning in the circumferential direction. Finally, the metal sleeve 13 of this embodiment is obtained by cutting off the cup-shaped bottom of the metal cylindrical member 39.
[0237]
As shown in FIG. 9, a metal cylinder fixed by a metal inner mold 35 and a pressing member 37 inside continuous dies 38 a, 38 b, and 38 c having stepwise smaller inner diameters instead of the pressing roller. A method may be used in which the member 34 is fed while being rotated, and is provided with unevenness in the circumferential direction while being thinned by ironing.
[0238]
In addition, any ironing processing method may be used as long as it can form irregularities of a predetermined amount or less in the circumferential direction of the metal sleeve 13 such as a spatula drawing process.
[0239]
When the recording material P on which an unfixed image has been formed is heated and fixed using the metal sleeve 13 manufactured by the above-described manufacturing method, it is preferable to suppress the above-mentioned circumferential unevenness to 3 μm or less from the viewpoint of heat conduction.
[0240]
Irregularities of 3 μm or less are formed in the circumferential direction of the metal sleeve 13. Preferably, by setting the surface roughness Rz in the longitudinal direction to 3 μm or less and the relationship with the surface roughness Rz ′ in the circumferential direction to Rz> Rz ′, the rotational driving of the heat fixing device is suppressed low, and the rotation is smoothly performed. At the same time, the resin coat of the heater for contact with the inner surface of the metal sleeve due to durability is hardly damaged, and it is possible to achieve higher durability and higher speed of the heat fixing device.
[0241]
Further, a potential difference is formed between the metal sleeve 13 and the pressing roller 20 as a pressing member, and the metal sleeve 13 is grounded or is grounded via a diode, so that paper is applied to the metal sleeve 13. By adopting a configuration in which powder or toner does not easily adhere, it is possible to provide a heat fixing device that maintains releasability through durability.
[0242]
11 and 12 show a more detailed configuration of the heat fixing device. 11 and 12, the elastic layer 22 of the pressing roller 20, which is a pressing member, is an elastic layer provided with conductivity made of conductive silicone rubber, conductive silicone sponge, or the like. Then, a bias having a polarity opposite to that of the toner image is applied to the conductive elastic layer 22 by a bias applying unit 24 via a chip electrode 25 made of a conductive carbon chip or the like.
[0243]
In the figure, the image forming apparatus is illustrated based on an image forming apparatus in which toner is negatively charged in a developing unit, and a positive bias is applied to the pressure roller core 21.
[0244]
Therefore, in the case of an image forming apparatus in which the toner is positively charged in the developing section, a negative bias is applied to the pressure roller core 21.
[0245]
At the end of the metal sleeve 13, there is provided a portion 13a where a metal sleeve material not coated with a primer layer as an adhesive layer and a release layer made of a fluororesin layer is exposed. It is configured to be grounded via a conductive brush 18 made of a more amorphous conductive fiber.
[0246]
Alternatively, it may be diode-connected so that a charge having the same potential as the toner image is held on the metal film.
[0247]
With the above-described configuration, by positively applying a bias to the pressure roller 20 side, paper powder, toner, and the like are less likely to be attracted to the metal sleeve 13.
[0248]
Therefore, in the above-mentioned heat fixing device for heating and fixing a toner image formed on cut paper or the like made mainly of pulp material, the release layer on the surface of the metal sleeve 13 having a surface roughness Rz of 3 μm or less. However, the present invention provides a heat-fixing device having a long service life, because paper dust and toner are less likely to be contaminated by static electricity, and the releasability is not impaired by durability.
[0249]
(Other)
The fixing device is similarly effective whether it is an oil-based fixing device or an oil-less fixing device.
-The heating member (heater) may be an electromagnetic induction heating member.
The fixing device of the present invention also includes an image heating device for temporarily fixing an image on a recording material, an image heating device for improving the image surface properties such as gloss, and the like.
[0250]
In the image forming method of the present invention, the steps up to forming an unfixed toner image on a recording material are not particularly limited, except that the above-described toner of the present invention is used. In the image forming method of the present invention, for example, charging of a photoreceptor, formation of an electrostatic latent image, development of an electrostatic latent image with toner, transfer of a toner image to a recording material, and the like are performed on a recording material in a known manner. A toner image can be formed. Further, in the image forming method of the present invention, other steps may be further adopted, for example, a cleaning step for removing the toner on the photoconductor after the transfer, and a development step for collecting the toner on the photoconductor at the time of development. A cleaning step, an intermediate transfer step when applied to full-color image formation, a cleaning step of the intermediate transfer body, a pre-exposure step for equalizing the surface potential of the photoconductor before charging, and the like can be arbitrarily adopted.
[0251]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
[0252]

The polyester-based monomer was charged into an autoclave together with 7.0 mmol of dibutyltin oxide, equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device. The polyester resin A was obtained by heating to 210 ° C. and performing a polycondensation reaction.
[0253]
Next, 85 parts by mass of the polyester resin A obtained here, 50 parts by mass of xylene, 15 parts by mass of a vinyl monomer mixture of styrene / 2-ethylhexyl acrylate (mass% of each monomer: 84/16), and esterification 0.3 parts by mass of dibutyltin oxide as a catalyst was charged into an autoclave, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device were attached. Heated to ℃ to dissolve and swell.
[0254]
Next, a radical initiator solution in which 1 part by mass of t-butyl hydroperoxide was dissolved in 10 parts by mass of xylene was added dropwise over about 30 minutes under a nitrogen atmosphere. The radical polymerization reaction was completed by holding at that temperature for further 10 hours. The pressure was reduced while heating, and the solvent was removed to obtain a binder resin a containing a hybrid resin component. Table 1 shows the physical properties of the binder resin a.
[0255]
<Binder resin production example 2>
BPA-PO 25mol%
BPA-EO 25mol%
TPA 14mol%
TMA 18mol%
FA 18mol%
Polyester resin B was obtained in the same manner as in Binder resin production example 1 with the composition of the polyester-based monomer as described above.
[0256]
Using 90 parts by mass of the polyester resin B and 10 parts by mass of the vinyl-based monomer mixed solution, a binder resin b containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1. Table 1 shows the physical properties of the binder resin b.
[0257]
<Binder resin production example 3>
BPA-PO 31mol%
BPA-EO 19mol%
TPA 19mol%
TMA 6mol%
FA 25mol%
Polyester resin C was obtained in the same manner as in Binder Resin Production Example 1 with the composition of the polyester-based monomer as described above.
[0258]
Using 60 parts by mass of the polyester resin C and 40 parts by mass of the vinyl-based monomer mixture, a binder resin c containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1. Table 1 shows the physical properties of the binder resin c.
[0259]
<Binder resin production example 4>
BPA-PO 25mol%
BPA-EO 25mol%
TPA 15mol%
FA 35mol%
Polyester resin D was obtained in the same manner as in Binder resin production example 1 with the composition of the polyester-based monomer as described above.
[0260]
A binder resin d containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin D was 50 parts by mass and the vinyl monomer mixture was 50 parts by mass. Table 1 shows the physical properties of the binder resin d.
[0261]
<Binder resin production example 5>
BPA-PO 15mol%
BPA-EO 35mol%
TPA 15mol%
TMA 0.1mol%
FA 34.9 mol%
A polyester resin E was obtained in the same manner as in Binder Resin Production Example 1, except that the composition of the polyester-based monomer was as described above.
[0262]
A binder resin e containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that the polyester resin E was 95 parts by mass and the vinyl-based monomer mixture was 5 parts by mass. Table 1 shows the physical properties of the binder resin e.
[0263]
<Binder resin production example 6>
BPA-PO 23mol%
BPA-EO 27mol%
TPA 4mol%
TMA 36mol%
FA 10mol%
Polyester resin F was obtained in the same manner as in Binder Resin Production Example 1 with the composition of the polyester-based monomer as described above.
[0264]
Binder resin f containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that polyester resin F was 10 parts by mass and the vinyl-based monomer mixture was 90 parts by mass. Table 1 shows the physical properties of the binder resin f.
[0265]
<Binder resin production example 7>
BPA-PO 28mol%
BPA-EO 22mol%
TPA 5mol%
TMA 30mol%
FA 15mol%
A polyester resin G was obtained in the same manner as in Binder Resin Production Example 1, except that the composition of the polyester-based monomer was as described above.
[0266]
A binder resin g containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that 95 parts by mass of the polyester resin G and 5 parts by mass of the vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin g.
[0267]
<Binder resin production example 8>
BPA-PO 21mol%
BPA-EO 29mol%
TPA 3mol%
TMA 40mol%
FA 7mol%
A polyester resin H was obtained in the same manner as in Binder Resin Production Example 1, except that the composition of the polyester-based monomer was as described above.
[0268]
Binder resin h containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that 95 parts by mass of polyester resin H and 5 parts by mass of the vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin h.
[0269]
<Binder resin production example 9>
BPA-PO 35mol%
BPA-EO 15mol%
TPA 15mol%
TMA 0.1mol%
FA 34.9 mol%
Polyester resin I was obtained in the same manner as in Binder resin production example 1 with the composition of the polyester-based monomer as described above. This is called binder resin i. Table 1 shows the physical properties of the binder resin i.
[0270]
<Binder resin production example 10>
83% by mass of styrene and 17% by mass of n-butyl acrylate were subjected to addition polymerization to obtain a styrene-acrylic resin. This is called binder resin j. Table 1 shows the physical properties of the binder resin j.
[0271]
<Binder resin production example 11>
BPA-PO 35mol%
BPA-EO 15mol%
TPA 11mol%
TMA 22mol%
FA 17mol%
Polyester resin K was obtained in the same manner as in binder resin production example 1 with the composition of the polyester-based monomer as described above.
[0272]
A binder resin k containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that the polyester resin K was 85 parts by mass and the vinyl monomer mixture was 15 parts by mass. Table 1 shows the physical properties of the binder resin k.
[0273]
<Binder resin production example 12>
BPA-PO 35mol%
BPA-EO 15mol%
TPA 30mol%
TMA 5mol%
SA (succinic acid derivative) 15mol%
A polyester resin L was obtained in the same manner as in Binder Resin Production Example 1, except that the composition of the polyester-based monomer was as described above.
[0274]
Binder resin 1 containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that 75 parts by mass of polyester resin L and 25 parts by mass of the vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin l.
[0275]
<Binder resin production example 13>
BPA-PO 35mol%
BPA-EO 15mol%
TMA 15mol%
FA 35mol%
Polyester resin M was obtained in the same manner as in binder resin production example 1 with the composition of the polyester-based monomer as described above.
[0276]
A binder resin m containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 1, except that 95 parts by mass of the polyester resin M and 5 parts by mass of the vinyl-based monomer mixture were used. Table 1 shows the physical properties of the binder resin m.
[0277]
<Binder resin production example 14>
BPA-PO 15mol%
BPA-EO 35mol%
TMA 31mol%
FA 19mol%
A polyester resin N was obtained in the same manner as in Binder Resin Production Example 1, except that the composition of the polyester-based monomer was as described above.
[0278]
A binder resin n containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that the polyester resin N was 90 parts by mass and the vinyl-based monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin n.
[0279]
<Binder resin production example 15>
BPA-PO 15mol%
BPA-EO 35mol%
TMA 41mol%
FA 9mol%
A polyester resin O was obtained in the same manner as in Binder Resin Production Example 1 with the composition of the polyester-based monomer as described above.
[0280]
A binder resin o containing a hybrid resin component was obtained in the same manner as in Binder resin production example 1, except that the polyester resin O was 90 parts by mass and the vinyl-based monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin o.
[0281]
<Example 1>
・ Binder resin a 70 parts by mass
・ Binder resin c 30 parts by mass
・ 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Hydroxycarboxylic acid compound of aluminum 0.5 parts by mass
(3,5-di-t-butylsalicylic acid compound: chemical formula VIII)
-Monoazo iron compound (chemical formula VI) 1 part by mass
・ 2 parts by mass of low molecular weight polyethylene
(DSC endothermic peak 107 ° C., Mw / Mn = 1.08)
After the above materials were premixed by a Henschel mixer, they were melt-kneaded by a twin-screw kneading extruder (PCM-30 manufactured by Ikegai Iron Works) set at 130 ° C. After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill, pulverizing it with a fine pulverizer using a jet stream, and classifying the obtained finely pulverized powder using a multi-part classifier utilizing the Coanda effect. Thus, magnetic toner particles having a weight average particle size of 7.0 μm were obtained. Table 2 shows the formulation of the toner particles.
[0282]
To 100 parts by mass of the obtained magnetic toner particles, 1.2 parts by mass of dry silica treated with dimethyl silicone oil and hexamethyldisilazane was added and mixed by a mixer to obtain toner 1. Table 3 shows the physical properties of Toner 1 thus obtained. Table 4 shows the physical properties of the resin composition obtained by dry-mixing the binder resin used in the production of the toner at the same ratio as that used in the production of the toner.
[0283]
The treated silica was obtained by treating silica fine powder with 10% by mass of hexamethyldisilazane, and then further treating the silica treated with hexamethyldisilazane with 10% by mass of dimethyl silicone oil. is there.
[0284]
The toner 1 was evaluated by performing the following test. Table 5 shows the evaluation results.
[0285]
[Fixing test]
As the basic configuration of the heat fixing device used in this test, the heater 11 having the configuration shown in FIG. 3B and FIG. 4 was used. That is, AlN is used as the heater substrate 11a, and a mixture of a conductive agent of Ag / Pd, a phosphoric acid-based glass as a matrix component, an organic solvent, a binder, And the like were paste-formed into a paste, screen-printed, and fired at 600 ° C., and used as the current-carrying resistance layer 11b. On the fixing nip portion N side of the AlN heater substrate 11a, a polyimide layer 11e having good slidability was formed to a thickness of 10 μm by screen printing.
[0286]
The metal sleeve 13 was formed into a cylindrical shape having an outer diameter of 30.13 mm by applying a primer layer of 5 μm and a PFA resin of 10 μm to cylindrical stainless steel having an inner diameter of 30 mm and a thickness of 50 μm by dipping. The surface roughness Rz of the inner surface of the metal sleeve 13 was 2 μm, and the surface roughness Rz of the outer surface was 2 μm.
[0287]
The pressure roller 20 was formed by forming a silicone rubber layer with a thickness of 5 mm on an Al core 21 having a diameter of 20 mm, and further covering the outer layer with a PFA tube.
[0288]
In this test, the above-described heating and fixing device was used in which the recording material conveyance speed of the image forming apparatus was adjusted to 270 mm / sec so that the temperature of the heating heater 11 could be arbitrarily controlled.
[0289]
Regarding the low-temperature fixing property, the temperature of the heating heater 11 is controlled at intervals of 5 ° C. in the temperature range of 150 to 240 ° C. in the above-mentioned heating and fixing device, and after the temperature of the outer surface of the metal sleeve becomes constant, The recording material P on which the image is formed is inserted into the fixing nip portion N, and the obtained image is rubbed reciprocally 5 times with a silbon paper loaded with a load of 4.9 kPa, and the density reduction rate of the image density before and after the rubbing. Is determined as a low-temperature fixing property. The lower the temperature, the better the low-temperature fixability of the toner. As an unfixed image, plain paper (75 g / m²) And the toner development amount on paper is 0.6 mg / cm²The fixing of the solid black image set in was performed.
[0290]
The high-temperature offset resistance was evaluated by inserting the recording material in a state where the surface of the pressure roller and the surface of the metal film were sufficiently heated in the same manner as in the above fixing conditions. In the evaluation, dirt on the image due to the high-temperature offset phenomenon was visually confirmed, and the generated temperature was regarded as high-temperature offset resistance. The higher the temperature is, the more excellent the high-temperature offset property is. The same unfixed image as the solid black image used in the evaluation of low-temperature low-adhesion was used.
[0291]
Regarding the fixing wrap resistance, in the same manner as in the above-mentioned high temperature offset resistance test, the temperature of the fixing device was set to 230 ° C., and the recording material was heated while the pressure roller surface and the metal film surface were sufficiently heated. It was inserted and evaluated according to four-grade evaluation criteria of A, B, C, and D.
[0292]
The above evaluation criteria indicate that A is the best, B is the best after A, C is the best after B, and D is the worst. In addition, in the test for resistance to fixing wrap, a BADGER BOND (60 g / m²) Using paper, the toner development amount on the paper is set to 1.0 mg / cm.²The evaluation was performed using the solid black image set in the above.
[0293]
Regarding the quick start property, in a low-temperature and low-humidity environment (15 ° C., 10%), the temperature of the fixing device is set to 235 ° C. from a state where both the fixing device and the recording material to be passed are sufficiently adjusted to the environment and are cooled. A test is made as to how many seconds after the energization of the heating heater layer 11b of the heating heater 11 is started, if a recording material on which an unfixed toner image is formed is inserted into a fixing nip portion, it is possible to fix the recording material. The start time was defined as quick start. The shorter this time is, the better the quick start property is. The fixability in the quick start property test was determined based on the time when the rate of decrease in image density before and after rubbing was 10% or less, similarly to the low-temperature fixability.
[0294]
<Examples 2 to 7, Comparative Example 1>
Using the materials shown in Table 2, toners 2 to 8 were obtained in the same manner as toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0295]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0296]
<Example 8>
・ Binder resin i 30 parts by mass
・ Binder resin k 70 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Aromatic hydroxycarboxylic acid compound of aluminum 0.5 parts by mass
(Di-t-butylsalicylic acid compound: Chemical formula VIII)
-Monoazo iron compound (chemical formula VI) 1 part by mass
・ 2 parts by mass of low molecular weight polyethylene
(DSC endothermic peak 106.7 ° C., Mw / Mn = 1.2)
Using the above materials, a toner 9 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0297]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0298]
<Example 9>
・ Binder resin i 30 parts by mass
・ Binder resin m 70 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Aromatic hydroxycarboxylic acid compound of aluminum 1 part by mass
(Di-t-butylsalicylic acid compound: Chemical formula VIII)
・ 2 parts by mass of low molecular weight polyethylene
(DSC endothermic peak 106.7 ° C., Mw / Mn = 1.2)
Using the above materials, a toner 10 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0299]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0300]
<Example 10>
・ Binder resin i 70 parts by mass
・ Binder resin 30 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ 3 parts by mass of monoazo iron compound (chemical formula VI)
・ 2 parts by mass of higher alcohol
(DSC endothermic peak 99 ° C, Mw / Mn = 1.9)
Using the above materials, a toner 11 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0301]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0302]
<Comparative Example 2>
・ 5 parts by mass of binder resin i
・ Binder resin k 95 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Aromatic hydroxycarboxylic acid compound of aluminum 2 parts by mass
(Di-t-butylsalicylic acid compound)
-Monoazo iron compound (chemical formula VI) 1 part by mass
・ 4 parts by mass of Fischer-Tropsch wax
(DSC endothermic peak 88 ° C., Mw / Mn = 1.3)
Using the above materials, a toner 12 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0303]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0304]
<Example 11>
・ Binder resin i 70 parts by mass
・ Binder resin 30 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ 2 parts by mass of monoazo iron compound (chemical formula VI)
・ 4 parts by mass of Fischer-Tropsch wax
(DSC endothermic peak 88 ° C., Mw / Mn = 1.3)
Using the above materials, a toner 13 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0305]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0306]
<Example 12>
・ Binder resin i 90 parts by mass
・ Binder resin 10 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Chromium complex of monoazo compound (chemical formula VII) 3 parts by mass
・ 4 parts by mass of low molecular weight polypropylene
(DSC endothermic peak 145 ° C., Mw / Mn = 8.8)
Using the above materials, a toner 14 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0307]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0308]
<Comparative Example 3>
・ Binder resin i 10 parts by mass
・ Binder resin 90 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ 2 parts by mass of monoazo iron compound (chemical formula VI)
・ 4 parts by mass of low molecular weight polypropylene
(DSC endothermic peak 145 ° C., Mw / Mn = 8.8)
Using the above materials, a toner 15 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0309]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0310]
<Comparative Example 4>
.Binder resin j 50 parts by mass
・ Binder resin l 50 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
・ Chromium aromatic hydroxycarboxylic acid compound 1 part by mass
(Di-t-butylsalicylic acid compound: Chemical formula IX)
・ 2 parts by mass of low molecular weight polyethylene
(DSC endothermic peak 126 ° C, Mw / Mn = 1.2)
Using the above materials, a toner 16 was obtained in the same manner as the toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0311]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0312]
<Comparative Example 5>
・ 5 parts by mass of binder resin i
・ Binder resin o 95 parts by mass
100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm)
-Monoazochrome compound (chemical formula VII) 1 part by mass
・ 4 parts by mass of low molecular weight polypropylene
(DSC endothermic peak 145 ° C., Mw / Mn = 8.8)
Using the above materials, Toner 17 was obtained in the same manner as Toner 1. Table 3 shows the physical properties of the obtained toner, and Table 4 shows the physical properties of the resin composition of the obtained toner.
[0313]
The above toner was tested and evaluated in the same manner as toner 1. Table 5 shows the evaluation results.
[0314]
[Table 1]

[0315]
[Table 2]

[0316]
[Table 3]

[0317]
[Table 4]

[0318]
[Table 5]

[0319]
【The invention's effect】
The present invention relates to a cylinder having at least a heating member, a pressing member, and a flexible cylinder interposed between the heating member and the pressing member to apply heat from the heating member to the material to be heated. And a heating metal sleeve formed as a base layer with the metal tube in the form of a heating nip corresponding to a heating nip formed between the heating metal sleeve and the pressing member. The unfixed toner image is formed on the recording material by passing the recording material on which an unfixed toner image is formed through a fixing nip pressed against each other by a metal sleeve and a pressing member. Fixing means, and at least a binder resin, a colorant and a wax, wherein the binder resin contains at least a hybrid resin having a vinyl polymer unit and a polyester unit, and In the molecular weight distribution of the hydrofuran-soluble component by gel permeation chromatography, the content of components having a molecular weight of less than 10,000 is 40 to 70% by mass, and the content of components having a molecular weight of 10,000 to 50,000 is 25 to 50% by mass. The content of components having a molecular weight of more than 50,000 is 2 to 25% by mass, the content of components having a molecular weight of 100,000 or more is less than 10% by mass, and the content of components having a molecular weight of less than 10,000 is When a toner satisfying M1 ≧ M2> M3 is used when M1 is used, the content of components having a molecular weight of 10,000 to 50,000 is M2, and the content of components having a molecular weight of more than 50,000 is M3. In a film fixing type heating and fixing apparatus, a heating member is arranged in contact with an inner surface of the metal sleeve in a portion corresponding to a heating nip formed between the sleeve and the pressing member. An image forming method and image capable of providing a toner having excellent fixability and high-temperature offset resistance and having excellent fixation wrapping resistance, and realizing high-speed on-demand fixing that achieves fixing performance and quick start property. A forming device and a toner suitable for the method and the device can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing one embodiment of an image forming apparatus of the present invention.
FIG. 2 is a diagram illustrating a schematic configuration of a fixing device illustrated in FIG. 1;
FIG. 3 is a diagram illustrating the vicinity of a fixing nip portion in the example of the fixing member illustrated in FIG. 2;
FIG. 4 is a view showing the vicinity of a fixing nip portion in another example of the fixing member shown in FIG. 2;
FIG. 5 is a diagram illustrating an example of the arrangement of a fixing member and a pressing member in the fixing device illustrated in FIG. 1;
FIG. 6 is a diagram illustrating an example of manufacturing a cylindrical metal pipe used in the present invention.
FIG. 7 is a view showing an intermediate product of a cylindrical metal pipe obtained by the production example shown in FIG. 5;
FIG. 8 is a diagram illustrating an example of processing for adjusting the surface roughness and thickness of the intermediate product shown in FIG.
FIG. 9 is a diagram illustrating another example of processing for adjusting the surface roughness and thickness of the intermediate product shown in FIG. 7;
FIG. 10 is a view showing a cylindrical metal pipe formed by the processing shown in FIG. 8 or FIG. 9;
FIG. 11 is a schematic configuration diagram showing another embodiment of a fixing device used in the present invention.
FIG. 12 is a schematic configuration diagram of the fixing device shown in FIG. 11 as viewed from the front.
FIG. 13 is a schematic configuration diagram illustrating an example of a conventional roller heating type fixing device.
FIG. 14 is a schematic configuration diagram illustrating an example of a conventional film heating type fixing device.
[Explanation of symbols]
1 Photosensitive drum
2 Charging roller
3 laser beam
4 Developing device
5 Transfer roller
6 Heat fixing device
7 Cleaning device
8 Sensor
10, 60 fixing member
11,61 Heating heater
11a Heater substrate
11b Heating resistance layer
11c, 11e Sliding layer
11d protective layer
11f, 11g electrode part
12,62 Insulated stay holder
13 Fixing sleeve (metal sleeve)
13a site
14, 64 Temperature sensing element
15 Fixing entrance guide
16 Drive gear
17 Pressurizing means
18 Conductive brush
20 pressure member (pressure roller)
21, 51 core metal
22, 52 elastic layer
23, 43, 53 Release layer
24 bias applying means
25 chip electrode
31 metal plate
32 inner type
33 Outer type
34, 39 Metallic cylindrical member
35 Metal inner mold
36a pressing roller
36b axis
36c fixed base
37 Holding member
38a-38c continuous die
39a Uneven marks
40 fixing roller
41 Halogen lamp
42 hollow metal core
44 Thermistor
50 pressure roller
63 Fixing film
N Fixing nip
P recording material

Claims (38)

At least a heating member, a pressing member, and a flexible cylindrical metal pipe interposed between the heating member and the pressing member and configured to apply heat from the heating member to the material to be heated in contact therewith. Comprising a heating metal sleeve formed as a base layer,
At a portion corresponding to a heating nip formed between the heating metal sleeve and the pressing member, a heating member is arranged in contact with the inner surface of the metal sleeve, and a recording material on which an unfixed toner image is formed is formed. A toner that is applied to an image forming method using a fixing unit that fixes the unfixed image on a recording material by passing between fixing nips that are pressed against each other by a metal sleeve and a pressing member,
At least a binder resin, a colorant and a wax,
The binder resin contains at least a hybrid resin having a vinyl polymer unit and a polyester unit,
In the molecular weight distribution of the tetrahydrofuran-soluble component of the toner by gel permeation chromatography, the content of components having a molecular weight of less than 10,000 is 40 to 70% by mass, and the content of components having a molecular weight of 10,000 to 50,000 is 25 to 50%. % By mass, the content of the component having a molecular weight of more than 50,000 is 2 to 25% by mass, the content of the component having a molecular weight of 100,000 or more is less than 10% by mass,
When the content of a component having a molecular weight of less than 10,000 is M1, the content of a component having a molecular weight of 10,000 to 50,000 is M2, and the content of a component having a molecular weight of more than 50,000 is M3, M1 ≧ M2> M3. A toner characterized by being satisfied. The binder resin contains at least a trivalent or higher polyvalent carboxylic acid or an anhydride thereof as a constituent monomer,
In the molecular weight distribution of the tetrahydrofuran-soluble component of the toner by gel permeation chromatography, in the monomer unit constituting the polyester component contained in the component having a molecular weight of less than 10,000, the trivalent or higher polyvalent carboxylic acid and its anhydride were used. The total content is W1 (mol%), and the total content of the trivalent or higher polycarboxylic acids and their anhydrides in the monomer units constituting the polyester component included in the components having a molecular weight of 10,000 or more is W2 ( mol%),
2. The toner according to claim 1, wherein W1 and W2 satisfy the following relationship.
0 ≦ W1 <30
0 <W2 <50
W2> W1 The binder resin is a mixture of two or more hybrid resins, a mixture of a polyester resin and a hybrid resin, a mixture of a vinyl resin and a hybrid resin, and a mixture of a polyester resin, a vinyl resin and a hybrid resin. The toner according to claim 1, wherein the toner is a mixture selected from a group. 3. The toner according to claim 2, wherein W1 and W2 satisfy the following relationship.
1 <W1 <25
2 <W2 <30 3. The toner according to claim 2, wherein W1 and W2 satisfy the following relationship.
3 ≦ W1 <20
3 <W2 ≦ 20 The toner according to any one of claims 2 to 5, wherein W1 and W2 satisfy the following relationship.
0 <W2-W1 <10 The toner according to any one of claims 2 to 6, wherein W1 and W2 satisfy the following relationship.
0.1 × W2 <W2-W1 <0.5 × W2 The toner according to any one of claims 1 to 7, wherein the binder resin contains a mixture of two or more types of hybrid resins, and the content of the tetrahydrofuran-insoluble content of the toner is 25% by mass or less. The toner as described in the above. 8. The binder resin according to claim 1, wherein the binder resin contains a mixture of two or more kinds of hybrid resins, and a content of a tetrahydrofuran-insoluble content of the toner is 1 to 15% by mass. The toner according to 1. 4. The toner according to claim 3, wherein the binder resin contains a mixture of a polyester resin and a hybrid resin, and a content of a tetrahydrofuran-insoluble content of the toner is 1 to 50% by mass. 5. 4. The toner according to claim 3, wherein the binder resin contains a mixture of a polyester resin and a hybrid resin, and a content of a tetrahydrofuran-insoluble content of the toner is 2 to 40% by mass. 5. The binder resin contains a mixture of two or more types of hybrid resins, and is a vinyl polymer contained in a component having a molecular weight of less than 10,000 in a molecular weight distribution of gel-permeation chromatography of a tetrahydrofuran-soluble component of the toner. When the content of the unit is Wa (% by mass) and the content of the vinyl polymer unit contained in the component having a molecular weight of 10,000 or more is Wb (% by mass),
2. The toner according to claim 1, wherein Wa and Wb satisfy the following relationship.
| Wa-Wb | <20 13. The toner according to claim 12, wherein Wa and Wb satisfy the following relationship.
0 <Wa <50
0 <Wb <30 13. The toner according to claim 12, wherein Wa and Wb satisfy the following relationship.
5 <Wa <30
0 <Wb <20 13. The toner according to claim 12, wherein Wa and Wb satisfy the following relationship.
Wa ≧ Wb The binder resin contains at least a trivalent or higher polyvalent carboxylic acid or an anhydride thereof as a constituent monomer,
In the molecular weight distribution of the gel permeation chromatography of the tetrahydrofuran soluble portion of the binder resin,
The content of components having a molecular weight of less than 10,000 is 40 to 75% by mass, the content of components having a molecular weight of 10,000 to 50,000 is 23 to 45% by mass, and the content of components having a molecular weight of more than 50,000 is 2 to 25% by mass, the content of components having a molecular weight of 100,000 or more is less than 13% by mass, the content of components having a molecular weight of less than 10,000 is defined as m1, and the content of components having a molecular weight of 10,000 to 50,000 is defined as m2. And when the content of the component having a molecular weight exceeding 50,000 is defined as m3, m1 ≧ m2> m3 is satisfied;
In the monomer unit constituting the polyester component included in the component having a molecular weight of less than 10,000, the total content of the trivalent or higher polycarboxylic acids and their anhydrides is represented by w1 (mol%), and the component having a molecular weight of 10,000 or more Assuming that the total content of the trivalent or higher polycarboxylic acids and their anhydrides in the monomer unit constituting the polyester component contained in the above is w2 (mol%), w1 and w2 satisfy the following relationship. The toner according to any one of claims 1 to 15, wherein:
0 ≦ w1 <30
0 <w2 <50
w2> w1 17. The toner according to claim 16, wherein w1 and w2 satisfy the following relationship.
1 <w1 <25
2 <w2 <30 17. The toner according to claim 16, wherein w1 and w2 satisfy the following relationship.
3 ≦ w1 <20
3 <w2 ≦ 20 17. The toner according to claim 16, wherein w1 and w2 satisfy the following relationship.
0 <w2-w1 <10 The binder resin, in the molecular weight distribution of gel permeation chromatography of the tetrahydrofuran soluble component of the binder resin,
When the content of the component having a molecular weight of less than 10,000 is 50 to 75% by mass, the content of the component having a molecular weight of 100,000 or more is less than 10% by mass, and the content of the component having a molecular weight of 100,000 or more is defined as m4. 17. The toner according to claim 16, wherein m1 ≧ m2>m3> m4 is satisfied. 17. The toner according to claim 16, wherein the binder resin contains a mixture of two or more hybrid resins, and a content of a tetrahydrofuran-insoluble component of the binder resin is 30% by mass or less. 17. The toner according to claim 16, wherein the binder resin contains a mixture of two or more hybrid resins, and a content of a tetrahydrofuran-insoluble content of the binder resin is 1 to 20% by mass or less. . 17. The toner according to claim 16, wherein the binder resin contains a mixture of a polyester resin and a hybrid resin, and the binder resin has a tetrahydrofuran-insoluble content of 1 to 50% by mass. 17. The toner according to claim 16, wherein the binder resin contains a mixture of a polyester resin and a hybrid resin, and the content of the tetrahydrofuran-insoluble component of the binder resin is 2 to 40% by mass. The toner according to any one of claims 1 to 24, wherein the toner has one or more endothermic peaks at a temperature rise of 60 to 120 ° C by differential thermal analysis. The toner according to any one of claims 1 to 25, wherein the wax has one or more endothermic peaks at the time of temperature rise by differential thermal analysis in a temperature range of 60 to 120 ° C. 27. The wax according to claim 1, wherein a ratio of a number average molecular weight to a weight average molecular weight in a molecular weight distribution by gel permeation chromatography is 1.0 to 2.0. Toner. The toner according to any one of claims 1 to 27, wherein a metal compound is contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. The toner according to claim 28, wherein the metal compound is an organic metal compound. The toner according to claim 28, wherein the metal compound is a metal-containing aromatic hydroxycarboxylic acid compound. The toner according to claim 28, wherein the metal compound is an aromatic hydroxycarboxylic acid compound of aluminum. The toner according to claim 28, wherein the metal compound is a monoazo iron compound. 29. The toner according to claim 28, comprising a mixture of an aromatic hydroxycarboxylic acid compound of aluminum and a monoazo iron compound. 34. A magnetic toner containing a magnetic material as the colorant, wherein the content of the magnetic material is 30 to 200 parts by mass with respect to 100 parts by mass of the binder resin. The toner according to claim 1. The heating metal sleeve is formed using a flexible cylindrical metal tube as a base layer, and the inner and outer surfaces of the cylindrical metal tube have a surface roughness of Rz = 3 μm or less. The image forming method according to any one of claims 1 to 34, wherein the thickness of the releasable layer including the adhesive layer on the outer surface is formed to be 20 µm or less. toner. The toner according to any one of claims 1 to 35, wherein the toner is manufactured through a step of melt-kneading a mixture containing at least the binder resin, the colorant, and the wax. An image using a fixing unit that fixes the unfixed toner image on the recording material by passing the recording material on which the unfixed toner image is formed between fixing nips that are pressed against each other by a fixing member and a pressing member. Formation method,
The toner is the toner according to any one of claims 1 to 36,
The fixing means has at least a heating member, a pressing member, and a flexibility interposed between the heating member and the pressing member to apply heat from the heating member to the material to be heated. A heating metal sleeve formed as a cylindrical metal tube as a base layer,
At a portion corresponding to a heating nip formed between the heating metal sleeve and the pressure member, a heating member is disposed in contact with the inner surface of the metal sleeve, and a recording material on which an unfixed toner image is formed, An image forming method, wherein the unfixed image is fixed on a recording material by passing through a fixing nip pressed against each other by a metal sleeve and a pressing member. An image having a fixing unit for fixing the unfixed toner image on the recording material by passing the recording material on which the unfixed toner image is formed between fixing nips pressed against each other by a fixing member and a pressing member. A forming device, wherein the toner is the toner according to any one of claims 1 to 36;
The fixing means has at least a heating member, a pressing member, and a flexibility interposed between the heating member and the pressing member to apply heat from the heating member to the material to be heated. A heating metal sleeve formed as a cylindrical metal tube as a base layer,
At a portion corresponding to a heating nip formed between the heating metal sleeve and the pressure member, a heating member is disposed in contact with the inner surface of the metal sleeve, and a recording material on which an unfixed toner image is formed, An image forming apparatus, wherein the unfixed image is fixed on a recording material by passing between fixing nips which are pressed against each other by a metal sleeve and a pressing member.

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