JP2004225028A - Method for producing aqueous polyester resin fine particle dispersion and electrophotographic toner - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は電子写真用トナー、インキ等の印刷材料、塗料、接着剤、粘着剤、繊維加工、製紙・紙加工、土木用等の分野に用いられるポリエステル樹脂微粒子水性分散体の製造方法と、この製造方法で得られるポリエステル樹脂微粒子を含有する電子写真用トナーに関するものである。
【０００２】
【従来の技術】
ポリエステル樹脂微粒子水性分散体の製造方式としては、例えば、ポリエステル樹脂を微粒子化する分散造粒法等が挙げられる。転相乳化法は、このような分散造粒法のひとつであり、例えば、中和塩構造を有するポリエステル樹脂を水混和性有機溶剤中に溶解してなる樹脂溶液に水性媒体を加えて転相乳化し、次いで、有機溶剤の除去と乾燥とを行う静電荷像現像用トナーの製造方法が知られている。この製造方法では自己水分散性ポリエステル樹脂である中和塩構造を有するポリエステル樹脂を用いているため、乳化剤、懸濁安定剤等の補助材料を用いることなく、ポリエステル樹脂微粒子水性分散体を製造することができる（例えば、特許文献１参照。）。また、中和された酸基含有ポリエステル樹脂と沸点６０〜２００℃の水溶性有機化合物と水とを特定の配合比で配合してなる水系分散体も知られている（例えば、特許文献２および特許文献３参照。）。
【０００３】
前記特許文献１で開示されている転相乳化法は自己水分散性ポリエステル樹脂の有機溶剤溶液を調製することを念頭に考えられているため、自己水分散性ポリエステル樹脂とこのポリエステル樹脂を溶解できる有機溶剤（良溶媒）との組み合わせについての検討のみが提案されていた。そのため、自己水分散性ポリエステル樹脂とこのポリエステル樹脂を溶解しない有機溶剤の組み合わせに対しては適用されていなかった。また、前記転送乳化法は、自己水分散性ポリエステル樹脂とこのポリエステル樹脂を溶解できる有機溶剤（良溶媒）の組み合わせであるが故に、水性媒体中に自己水分散性ポリエステル樹脂を分散させた後も自己水分散性ポリエステル樹脂と有機溶剤との間の親和性が高く、結果として有機溶剤の除去工程後も、高濃度で有機溶剤が樹脂粒子内に残留してしまい、環境衛生上の問題がある。
【０００４】
前記特許文献２および特許文献３には、沸点６０〜２００℃の水溶性有機化合物として前記ポリエステル樹脂を溶解する沸点１００℃以上の有機溶剤と共に前記ポリエステル樹脂を溶解しない沸点１００℃未満の有機溶剤も例示されているが、得られた水系分散体から有機溶剤を除去すること、および、前記ポリエステル樹脂を、このポリエステル樹脂を溶解しない沸点１００℃未満の有機溶剤と組み合わせて用いることに関する記載や示唆はなく、実施例では前記ポリエステル樹脂を溶解する沸点１００℃以上の有機溶剤（良溶媒）を含む有機溶剤をいずれも使用して水系分散体を製造した後、有機溶剤の除去を行うことなくコーティング剤等に用いている。これら前記実施例で得られる水系分散体は、有機溶剤の除去を行ったとしても、高濃度で有機溶剤が樹脂粒子内に残留してしまい、環境衛生上の問題がある。
【０００５】
【特許文献１】
特開平０８−２１１６５５号公報（第２頁、第４〜６頁）
【特許文献２】
特開昭５６−０８８４５４号公報（第２頁、第４頁、第７頁）
【特許文献３】
特開昭５６−１２５４３２号公報（第２頁、第４頁、第７頁）
【０００６】
【発明が解決しようとする課題】
本発明の目的は、樹脂粒子内に残存する残留溶剤が極めて少ないポリエステル樹脂微粒子水性分散体の製造方法と、残存溶剤が極めて少ない電子写真用トナーを提供することである。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下の知見（ａ）〜（ｈ）を見出し、本発明を完成するに至った。
【０００８】
（ａ）ポリエステル樹脂としてアルキル基および／またはアルケニル基とカルボキシル基とを含有するポリエステル樹脂（Ｐ）、および、有機溶剤として前記ポリエステル樹脂（Ｐ）を溶解しないが膨潤させることが可能な沸点１００℃未満の有機溶剤（Ｓ）を用い、この有機溶剤（Ｓ）を前記ポリエステル樹脂（Ｐ）に吸収させて得られた膨潤体は、塩基性化合物を含有する水性媒体中に転送乳化することにより水性媒体中に微粒子状で分散させた自己水分散性のポリエステル樹脂微粒子水性分散体とすることが容易であること。
【０００９】
（ｂ）ポリエステル樹脂として前記アルキル基／およびアルケニル基とカルボキシル基とを含有するポリエステル樹脂を用いているため、アルキル基およびアルケニル基とを含有しないカルボキシル基含有ポリエステル樹脂を用いた時と比べてポリエステル樹脂微粒子水性分散体中のポリエステル樹脂微粒子の安定性が格段に向上し、また、得られるポリエステル樹脂微粒子は不定形の少ない球形であり、粒度分布も狭いこと。
【００１０】
（ｃ）有機溶剤としてポリエステル樹脂（Ｐ）を溶解しない沸点１００℃未満の有機溶剤（Ｓ）を用いているため、得られた水性分散体中の有機溶剤の除去が容易で、残留有機溶剤の極めて少ないポリエステル樹脂微粒子水性分散体が製造できること。
【００１１】
（ｄ）前記ポリエステル樹脂微粒子水性分散体の製造方法において、ポリエステル樹脂（Ｐ）と共に着色剤（Ｃ）を併用することにより、着色剤（Ｃ）で着色されたポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散した分散体が得られること。
【００１２】
（ｅ）前記ポリエステル樹脂微粒子水性分散体の製造方法で得たポリエステル樹脂微粒子水性分散体の着色された微粒子を分離し、乾燥して得られる微粒子を含有させることにより残存溶剤が極めて少ない電子写真用トナーが得られること。
【００１３】
（ｆ）前記着色された微粒子を会合させた後分離し、乾燥して得られる電子写真用トナーは残留溶剤が極めて少なく、画質も向上すること。
【００１４】
（ｇ）前記製造方法で得られたポリエステル樹脂微粒子水性分散体と着色剤（Ｃ）の水性媒体または着色樹脂粒子の水性媒体とを混合し、ポリエステル樹脂の微粒子と着色剤粒子または着色樹脂微粒子を会合させた後分離し、乾燥して得られる電子写真用トナーは残留溶剤が極めて少なく、画質も向上すること。
【００１５】
（ｈ）前記電子写真用トナーは、前記アルキル基／およびアルケニル基とカルボキシル基とを含有するポリエステル樹脂を用いているため不定形の少なく、かつ、粒度分布の狭い球形のトナーであり、また、前記トナーを用いて得られた画像は色調、解像度に優れること。
【００１６】
即ち、本発明は、アルキル基および／またはアルケニル基とカルボキシル基とを含有するポリエステル樹脂（Ｐ）を、前記ポリエステル樹脂（Ｐ）を溶解しないが膨潤させることが可能な沸点１００℃未満の有機溶剤（Ｓ）で膨潤させることにより膨潤体を製造する第１工程と、前記膨潤体を塩基性化合物を含有する水性媒体中に混合して、ポリエステル樹脂（Ｐ）中のカルボキシル基の一部乃至全部の塩基性化合物による中和と、前記膨潤体の水性媒体中への微粒子状での分散とを行うことにより初期水性分散体を製造する第２工程と、前記初期水性分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が前記水性媒体中に分散した分散体を製造する第３工程とからなることを特徴とするポリエステル樹脂微粒子水性分散体の製造方法を提供するものである。
【００１７】
また、本発明は、前記製造方法においてポリエステル樹脂（Ｐ）と共に着色剤（Ｃ）を併用して得られた熱可塑性樹脂微粒子水性分散体からポリエステル樹脂（Ｐ）の微粒子を分離し、乾燥して得られる微粒子を含有することを特徴とする電子写真用トナーを提供するものである。
【００１８】
更に、本発明は、前記製造方法においてポリエステル樹脂（Ｐ）と共に着色剤（Ｃ）を併用して得られた熱可塑性樹脂微粒子水性分散体中のポリエステル樹脂（Ｐ）の微粒子を会合させた後分離し、乾燥して得られることを特徴とする電子写真用トナーを提供するものである。
【００１９】
更に、本発明は、前記製造方法で得られたポリエステル樹脂微粒子水性分散体と着色剤（Ｃ）の水性分散体または着色樹脂粒子の水性分散体とを混合し、分散しているポリエステル樹脂（Ｐ）の微粒子と着色剤粒子または着色樹脂微粒子を会合させた後分離し、乾燥して得られることを特徴とする電子写真用トナーを提供するものである。
【００２０】
【発明の実施の形態】
以下に本発明を詳細に説明する。
本発明で使用するアルキル基および／またはアルケニル基とカルボキシル基とを含有するポリエステル樹脂（Ｐ）の調製方法としては、例えば、
▲１▼アルキル基やアルケニル基を有する二塩基酸と、二価のアルコールとを必須として、必要に応じてその他の二塩基酸やその無水物、三官能以上の多塩基酸やその無水物、一塩基酸、三官能以上のアルコール、一価のアルコール等を混合し、窒素雰囲気中で加熱下に酸価を測定しながら脱水縮合する調製方法、
▲２▼二塩基酸やその無水物と二価のアルコールとを必須として調製した、末端に水酸基を有するポリエステル樹脂（主鎖中にカルボキシル基を有していても良い）を加熱溶解し、そこにアルキル基やアルケニル基を有する酸無水物を投入し、ポリエステル樹脂の末端水酸基に開環付加させる調製方法、
▲３▼二塩基酸やその無水物と二価のアルコールとを必須として調製した、末端にカルボキシル基を有するポリエステル樹脂（主鎖中にカルボキシル基を含有していても良い）を加熱溶融し、そこにアルキル基やアルケニル基を有する脂肪族モノエポキシ化合物を投入し、ポリエステル樹脂の末端カルボキシル基の一部に開環付加させる調製方法等が挙げられる。
【００２１】
前記した調製方法で使用される装置としては、窒素導入口、温度計、攪拌装置、精留塔等を備えた反応容器等の回分式の製造装置が好適に使用できるほか、脱気口を備えた押出機や連続式の反応装置、混練機等も使用できる。また、前記脱水縮合の際、必要に応じて反応系を減圧することによって、エステル化反応を促進することもできる。さらに、エステル化反応の促進のために、種々の触媒を添加することもできる。
【００２２】
ポリエステル樹脂（Ｐ）の有するアルキル基、アルケニル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基、イソノニル基、ドデシル基、ドデセニル基等が挙げられる。
【００２３】
前記調製方法▲１▼で使用する、アルキル基やアルケニル基を有する二塩基酸としては、例えば、ｎ−ブチルコハク酸、ｎ−オクチルコハク酸、ｎ−ドデシルコハク酸、ｎ−ドデセニルコハク酸等の二塩基酸やそれらの無水物が挙げられる。
【００２４】
二価のアルコールとしては、例えば、エチレングリコール、１，２−プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ネオペンチルグリコール等の脂肪族ジオール類；ビスフェノールＡ、ビスフェノールＦ等のビスフェノール類；ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物等のビスフェノールＡアルキレンオキサイド付加物；キシリレンジグリコール、シクロヘキサンジメタノール、水添ビスフェノールＡ等のアラルキレングリコールまたは脂環式のジオール類等が挙げられる。
【００２５】
その他の二塩基酸やその無水物としては、例えば、マレイン酸、フマール酸、イタコン酸、蓚酸、マロン酸、コハク酸、アジピン酸、アゼライン酸、セバチン酸、デカン−１，１０−ジカルボン酸等の脂肪族二塩基酸；フタル酸、テトラヒドロフタル酸およびその無水物、ヘキサヒドロフタル酸およびその無水物、テトラブロムフタル酸およびその無水物、テトラクロルフタル酸およびその無水物、ヘット酸およびその無水物、ハイミック酸およびその無水物、イソフタル酸、テレフタル酸、シクロヘキサンジカルボン酸、２，６−ナフタレンジカルボン酸等の芳香族又は脂環式の二塩基酸等が挙げられる。
【００２６】
三官能以上の多塩基酸やその無水物としては、例えば、トリメリット酸、無水トリメリット酸、メチルシクロヘキセントリカルボン酸、メチルシクロヘキセントリカルボン酸無水物、ピロメリット酸、無水ピロメリット酸等が挙げられる。
【００２７】
一塩基酸としては、例えば、安息香酸、ｐ−ｔｅｒｔ−ブチル安息香酸等が挙げられる。
【００２８】
三官能以上の多価アルコールとしては、例えば、グリセリン、トリメチロールエタン、トリメチロールプロパン、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、２−メチルプロパントリオール、１，３，５−トリヒドロキシベンゼン、トリス（２−ヒドロキシエチル）イソシアヌレート等が挙げられる。
【００２９】
一価のアルコールとしては、例えば、ステアリルアルコール等の高級アルコール等が挙げられる。
【００３０】
調製方法▲２▼の水酸基含有ポリエステル樹脂や、調製方法▲３▼のカルボキシル基含有ポリエステル樹脂を調製するのに用いる、二塩基酸やその無水物と二価のアルコールとしては、例えば、調製方法▲１▼で用いる、その他の二塩基酸やその無水物、二価のアルコール等を用いることができる。また、例えば、調製方法▲１▼で用いる、三官能以上の多塩基酸やその無水物、一塩基酸、三官能以上の多価アルコール、一価のアルコール等も必要に応じて調製しても良い。
【００３１】
調製方法▲２▼で使用する、アルキル基やアルケニル基を有する酸無水物としては、例えば、ｎ−ブチル無水コハク酸、ｎ−ペンチル無水コハク酸、ネオペンチル無水コハク酸、ｎ−ヘキシル無水コハク酸、ｎ−ヘプチル無水コハク酸、ｎ−オクチル無水コハク酸、イソオクチル無水コハク酸、２−エチルヘキシル無水コハク酸、ｎ−ドデシル無水コハク酸、イソドデシル無水コハク酸、ｎ−ドデセニル無水コハク酸、イソドデセニル無水コハク酸、６−ブチル−１，２，４−ベンゼントリカルボン酸無水物、６−ｎ−オクチル−１，２，４−ベンゼントリカルボン酸無水物等が挙げられる。アルキル基やアルケニル基を有する酸無水物は、単独で使用してもよいし、２種以上のものを併用してもよい。
【００３２】
調製方法▲３▼で使用する、アルキル基やアルケニル基を有する脂肪族モノエポキシ化合物としては、例えば、ヒマシ油脂肪酸、ヤシ油脂肪酸、大豆油脂肪酸、桐油脂肪酸等の飽和あるいは不飽和の脂肪酸のモノグリシジルエステルや、イソノナン酸、バ−サチック酸等の分岐脂肪酸のモノグリシジルエステル等が挙げられる。前記した分岐脂肪酸のモノグリシジルエステルの市販品としては、カージュラＥ１０（シェルケミカル社製）等が挙げられる。脂肪族モノエポキシ化合物は、単独で使用してもよいし、２種以上のものを併用してもよい。
【００３３】
前記した▲１▼〜▲３▼の調製方法で用いる、二塩基酸やその無水物、三官能以上の多塩基酸やその無水物、一塩基酸は、それぞれ単独で使用してもよいし、２種以上のものを併用してもよい。また、カルボキシル基の一部または全部がアルキルエステル、アルケニルエステル又はアリールエステルとなっているものも使用できる。
【００３４】
また、前記した▲１▼〜▲３▼の調製方法で用いる、二価のアルコール、三価以上のアルコール、一価のアルコールは、単独で使用してもよいし２種以上のものを併用しても良い。
【００３５】
また、例えば、ジメチロールプロピオン酸、ジメチロールブタン酸、６−ヒドロキシヘキサン酸等の、１分子中に水酸基とカルボキシル基を併有する化合物あるいはそれらの反応性誘導体も前記調製方法▲１▼〜▲３▼で使用できる。
【００３６】
ポリエステル樹脂（Ｐ）は、例えば、前記調製方法▲１▼で得られるアルキル基および／またはアルケニル基とカルボキシル基とを含有するポリエステル樹脂（Ｐ１）であれば良いが、なかでも、調製方法▲２▼で得られる、末端に水酸基を有するカルボキシル基含有ポリエステル樹脂の末端水酸基にアルキル基またはアルケニル基を有する酸無水物を開環付加させて生成する末端構造を有するポリエステル樹脂（Ｐ２）や、調製方法▲３▼で得られる、末端にカルボキシル基を有するポリエステル樹脂の末端カルボキシル基にアルキル基またはアルケニル基を有する脂肪族モノエポキシ化合物を開環付加させて生成する末端構造を有するポリエステル樹脂（Ｐ３）であれば、ポリエステル樹脂を微粒子状で水性媒体中に分散させた際に樹脂微粒子がより安定に分散することから好ましい。この際使用する末端に水酸基を有するポリエステル樹脂や末端にカルボキシル基を有するポリエステル樹脂は、既にアルキル基やアルケニル基を含有していても良いし、含有していなくても良い。
【００３７】
ポリエステル樹脂（Ｐ）は、ポリエステル樹脂（Ｐ２）の有する末端構造やポリエステル樹脂（Ｐ３）の有する末端構造を、それぞれ単独でポリエステル樹脂１分子中に含んでいても良いし、これらの末端構造を両方有していてもよい。
【００３８】
ポリエステル樹脂（Ｐ）は、なかでも、調製方法▲２▼で得られる一般式（１）で表される末端構造や、調製方法▲３▼で得られる一般式（２）または（３）で表される末端構造を有するポリエステル樹脂であれば特に好ましい。
【化１】
【００３９】
前記一般式（１）、（２）及び（３）中のＲ１〜Ｒ４が示している炭素原子数４〜２０のアルキル基や炭素原子数４〜２０のアルケニル基は、直鎖状でも分岐状でも良く、例えば、ブチル基、イソブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ペプチル基、オクチル基、イソオクチル基、ドデシル基、ドデセニル基等が挙げられる。
【００４０】
次に、ポリエステル樹脂（Ｐ）の性状について説明する。
ポリエステル樹脂（Ｐ）は、水性媒体中でポリエステル樹脂微粒子の安定性が良好なことから、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法による重量平均分子量が５，０００〜３００，０００の範囲にあることが好ましく、なかでも、７，０００〜１００，０００の範囲であることが好ましい。
【００４１】
ポリエステル樹脂（Ｐ）の酸価は、１〜１００ｍｇＫＯＨ／ｇの範囲が好ましく、５〜４０ｍｇＫＯＨ／ｇの範囲がより好ましい。
【００４２】
本発明で用いる有機溶剤（Ｓ）は、ポリエステル樹脂（Ｐ）を溶解しないが膨潤させることが可能な沸点〔常圧（１０１．３ＫＰａ）における沸点をいう。以下同様。〕１００℃未満の有機溶剤であればよい。ポリエステル樹脂（Ｐ）を溶解する有機溶剤および／または沸点１００℃以上の有機溶剤を用いた場合は、第３工程での有機溶剤が除去しにくくなるし、また、ポリエステル樹脂（Ｐ）を膨潤させることができない有機溶剤を用いた場合は、第２工程でのポリエステル樹脂（Ｐ）の水性媒体中への分散が困難となるため、いずれも好ましくない。
【００４３】
なお、本発明で用いるポリエステル樹脂（Ｐ）を溶解しない有機溶剤（Ｓ）とは、有機溶剤とポリエステル樹脂（Ｐ）とを組み合わせて用いた場合に、２５℃でのポリエステル樹脂（Ｐ）の前記有機溶剤への溶解度が１５重量％以下となる有機溶剤を意味し、ポリエステル樹脂（Ｐ）の前記有機溶剤への溶解度が０重量％の有機溶剤を意味するものではない。
【００４４】
本発明において、有機溶剤がポリエステル樹脂（Ｐ）を溶解しない有機溶剤（Ｓ）に該当するか否かの判定は、例えば、ＡＳＴＭ Ｄ３１３２−８４（Ｒｅａｐｐｒｏｖｅｄ １９９６）の７．２結果の判断の７．２．１．１〜７．２．１．３に記載された判定法を用いて行うことができる。
【００４５】
前記有機溶剤（Ｓ）に該当するか否かの判定は、具体的には粒子状のポリエステル樹脂（Ｐ）１５重量部と有機溶剤８５重量部をフラスコにとって密栓し、２５℃で１６時間振とうした後の溶解状態を観察し、前記ＡＳＴＭ Ｄ３１３２−８４の７．２．１．１〜７．２．１．３に記載された下記判定区分で、１．「完全な溶液」か、２．「境界線の溶液」か、３．「不溶」かのどの区分に属するか判定することにより行うことができる。
１．「完全な溶液」；明瞭な固形物やゲル粒子を含まない単一の透明な相。
２．「境界線の溶液」；明瞭な相分離を含まない透明または混濁した相。
３．「不溶」；２相に分離：分離したゲル固体相を含む液体又は２相に相分離した液体。
尚、本発明では、粒子状のポリエステル樹脂（Ｐ）として、孔径３ｍｍのスクリーンを通過させたポリエステル樹脂（Ｐ）の粗粉砕物を前記判定に使用した。
【００４６】
本発明の製造方法は、ポリエステル樹脂（Ｐ）と有機溶剤（Ｓ）とを、前記有機溶剤（Ｓ）に該当するか否かの判定において、２．「境界線の溶液」、または、３．「不溶」となる組み合わせで用いる方法であり、この組み合わせでポリエステル樹脂（Ｐ）と有機溶剤（Ｓ）を用いることにより第３工程において脱溶剤が容易に行える。
【００４７】
本発明で用いる有機溶剤（Ｓ）としては、なかでも第３工程での脱溶剤が更に容易に行えることから、２５℃でのポリエステル樹脂（Ｐ）の有機溶剤への溶解度が１０重量％以下となる有機溶剤であることが好ましく、７重量％以下となる有機溶剤であることがより好ましい。このときの溶解度の判定は、有機溶剤が前記樹脂濃度１５重量％で有機溶剤（Ｓ）に該当するか否かの判定を行う代わりに、樹脂濃度が１０重量％または７重量％での判定を行うことにより可能である。
【００４８】
さらに、前記有機溶剤（Ｓ）としては、水性媒体中に分散された粒子状の膨潤体からの除去が容易で、残留溶剤が極めて少ない樹脂粒子が容易に効率良く経済的に製造できることから、水と相溶する有機溶剤（Ｓ１）が好ましい。ただし、この有機溶剤（Ｓ１）としては、水と有機溶剤がすべての混合比で均一相を形成する必要はなく、ポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させて得られる膨潤体の水性媒体への分散を行う際の温度および水と有機溶剤の組成範囲において相溶すれば十分である。該有機溶剤（Ｓ１）は、この条件を満たせるものであれば、単一もしくは混合溶剤のどちらでも差し支えないが、第３工程で有機溶剤（Ｓ１）の除去を行う際の温度において水と相溶するものが好ましく、２５℃で水と相溶するものがより好ましい。なかでも、有機溶剤（Ｓ１）としては、２５℃における水への溶解度が５０重量％以上であることが好ましく、２５℃において全ての割合で水と相溶することが特に好ましい。さらに、有機溶剤（Ｓ１）が混合溶剤の場合は、使用する有機溶剤の沸点がいずれも１００℃未満であることが好ましい。また、有機溶剤（Ｓ１）の沸点は４０〜９０℃であることがより好ましい。更に好ましくは４０〜８５℃であり、最も好ましくは４０〜６０℃である。
【００４９】
前記有機溶剤（Ｓ１）としては、例えば、アセトン（溶解度：全ての割合で水と相溶する。沸点：５６．１℃）等のケトン類；メタノール（溶解度：全ての割合で水と相溶する、沸点：６４．７℃）、エタノール（溶解度：全ての割合で水と相溶する、沸点：７８．３℃）、イソプロピルアルコール（解度：全ての割合で水と相溶する、沸点：８２．２６℃）等のアルコール類；酢酸メチル（溶解度：２４重量％、沸点：５６．９℃）等のエステル類等が挙げらる。これらの有機溶剤（Ｓ１）は単独で用いても良いし、２種以上を混合した混合溶剤を用いても良い。有機溶剤（Ｓ１）として好ましいものはケトン類、アルコール類であり、より好ましいものはアセトン、イソプロピルアルコールであり、最も好ましいものはアセトンである。
【００５０】
前記有機溶剤（Ｓ）の使用量としては、目的とするポリエステル樹脂微粒子水性分散体中の樹脂微粒子の粒径にもよるが、第１工程においてポリエステル樹脂（Ｐ）が有機溶剤（Ｓ）を十分に吸収し、膨潤して微粒子状での分散が容易なのり状の膨潤体とすることができること、第２工程において前記膨潤体の水性媒体への分散が容易であること、分散を完結させるために用いる水性媒体の使用量が抑制でき、ポリエステル樹脂微粒子水性分散体中の有機溶剤の含有量が大きくならず製造効率が良好となることから、前記ポリエステル樹脂（Ｐ）１００重量部に対して５〜３００重量部が好ましく、より好ましくは１０〜２００重量部であり、最も好ましくは２０〜１５０重量部である。
【００５１】
また、水の使用量は、ポリエステル樹脂（Ｐ）と有機溶剤（Ｓ）の合計１００重量部に対して７０〜４００重量部が好ましく、１００〜２５０重量部がより好ましい。
【００５２】
ポリエステル樹脂（Ｐ）中のカルボキシル基の一部乃至全部の中和に使用される塩基性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等のアルカリ化合物；ナトリウム、カリウム、リチウム等のアルカリ金属の炭酸塩；前記アルカリ金属の酢酸塩類；アンモニア水；メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン類；ジエタノールアミン等のアルカノールアミン類等が挙げられる。なかでも、アンモニア水が好ましい。
【００５３】
前記塩基性化合物の使用量は、ポリエステル樹脂（Ｐ）中のカルボキシル基の当量に対して、０．９〜５．０倍当量となる量であることが好ましく、１．０〜３．０倍当量となる量であることがより好ましい。
【００５４】
本発明の製造方法の第１工程で膨潤体を製造する方法としては、特に限定されないが、短時間で前記膨潤体が得られるし、その後第２工程での前記膨潤体の水性媒体中への分散も容易になることから、前記ポリエステル樹脂（Ｐ）と前記有機溶剤（Ｓ）とを共に加熱することにより前記膨潤体を製造することが好ましく、さらに加圧下で前記膨潤体を製造することがより好ましい。この際、前記ポリエステル樹脂（Ｐ）と前記有機溶剤（Ｓ）の加熱温度としては、前記有機溶剤（Ｓ）の沸点以上が好ましく、前記有機溶剤（Ｓ）の沸点〜１８０℃がより好ましく、前記有機溶剤（Ｓ）の沸点＋１０℃〜１２０℃が特に好ましい。また、この系内の加圧圧力としては、ゲージ圧で０．１〜２．０ＭＰａが好ましく、より好ましくはゲージ圧で０．２〜１．５ＭＰａ、更に好ましくはゲージ圧で０．３〜１．０ＭＰａである。系内を加圧する方法としては、例えば、前記膨潤体を得るための加熱により前記有機溶剤（Ｓ）を気化させて系内を加圧する方法、あらかじめ系内に不活性ガスを導入して予備加圧した後、加熱して前記有機溶剤（Ｓ）の気化によりさらに加圧する方法等が挙げられるが、有機溶剤（Ｓ）の還流、沸騰が抑制できると共に、粒度分布の狭いポリエステル樹脂微粒子水性分散体を得られることから、予備加圧する方法が好ましい。予備加圧としては０．０５〜０．５ＭＰａが好ましい。
【００５５】
前記第１工程において前記膨潤体を得た後、第２工程で得られた膨潤体を塩基性化合物を含有する水性媒体中に混合してポリエステル樹脂（Ｐ）中のカルボキシル基の一部乃至全部の塩基性化合物による中和と前記膨潤体の水性媒体中への微粒子状での分散とを行うことにより初期水性分散体を製造する方法としては、特に限定されないが、前記膨潤体の水性媒体中への分散が容易になることから、第１工程において加圧下で前記有機溶剤（Ｓ）の沸点以上の温度に加熱することにより得られた膨潤体を用い、前記膨潤体を加圧下で前記有機溶剤（Ｓ）の沸点以上１２０℃以下の温度で機械的剪断力により前記塩基性化合物を含有する水性媒体中に微粒子状に分散させて初期水性分散体とする方法が好ましい。この際の系の温度としては、前記有機溶剤（Ｓ）の沸点〜１８０℃が好ましく、前記有機溶剤（Ｓ）の沸点＋１０℃〜１２０℃が特に好ましい。また、この系の圧力としては、ゲージ圧で０．１〜２．０ＭＰａが好ましく、より好ましくはゲージ圧で０．２〜１．５ＭＰａ、更に好ましくはゲージ圧で０．３〜１．０ＭＰａである。なお、前記膨潤体の作成とこの分散体の作成とを同一容器内で行う場合、分散体作成開始時の系の加熱加圧条件は、前記膨潤体の作成終了時の温度および圧力と同様であることが好ましい。ここで用いる塩基性化合物を含有する水性媒体の温度としては、前記有機溶剤（Ｓ）の沸点以上１２０℃以下であることが好ましく、なかでも前記有機溶剤（Ｓ）の沸点以上１００℃未満であって、かつ、第２工程開始時の系の温度−２０℃〜第２工程開始時の系の温度の範囲内とすることがより好ましい。
【００５６】
さらに、前記第１工程で膨潤体を製造する際の温度、および、前記第２工程で初期水性分散体を製造する際の温度は、いずれも前記ポリエステル樹脂（Ｐ）の融点や軟化点より低温であることが好ましく、前記ポリエステル樹脂（Ｐ）のガラス転移温度（Ｔｇ）以下の温度であってもよいが、なかでも前記有機溶剤（Ｓ）の沸点以上であって、かつ、ガラス転移温度（Ｔｇ）より１０〜５０℃高い温度であることが好ましい。なお、第１工程で膨潤体を製造する際の温度と第２工程で初期水性分散体を製造する際の温度は同一でも異なっていてもよい。
【００５７】
本発明のポリエステル樹脂微粒子水性分散体の製造方法としては、例えば以下の▲１▼〜▲３▼で示す方法が代表的な製造方法として挙げられる。
▲１▼第１工程として、密閉容器にポリエステル樹脂（Ｐ）と有機溶剤（Ｓ）とを仕込み、加熱下、好ましくは加熱加圧下で、攪拌下にポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させることにより膨潤体を製造した後、第２工程として、得られた膨潤体を塩基性化合物を含有する水性媒体中に混合して、攪拌等の機械的剪断力により、好ましくは加熱加圧下で、塩基性化合物を含有する水性媒体中に微粒子状に分散させて初期水性分散体とし、次いで、第３工程として、得られた初期水性分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散した分散体を製造する方法。
【００５８】
▲２▼前記▲１▼の第１工程と同様にして前記膨潤体を得た後、第２工程として、得られた膨潤体と塩基性化合物を含有する水性媒体とを連続乳化分散機に連続的に供給しながら前記膨潤体中のポリエステル樹脂（Ｐ）のカルボキシル基の一部乃至全部の塩基性化合物による中和と機械的剪断力による前記膨潤体の前記水性媒体中への微粒子状での分散とを行って初期水性分散体とし、次いで、第３工程として、得られた初期水性分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散した分散体を製造する方法。
【００５９】
▲３▼第１工程として、押出機等の溶融混練機により溶融されたポリエステル樹脂樹脂（Ｐ）または合成された溶融状態のポリエステル樹脂（Ｐ）に、圧入等の方法で有機溶剤（Ｓ）を連続的に供給し混合下に前記ポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させることにより膨潤体を製造し、得られた膨潤体を該ポリエステル樹脂（Ｐ）の融点または軟化点未満の温度まで降温させた後、第２工程として、得られた膨潤体と塩基性化合物を含有する水性媒体とを連続乳化分散機に連続的に供給しながら前記膨潤体中のポリエステル樹脂（Ｐ）のカルボキシル基の一部乃至全部の塩基性化合物による中和と機械的剪断力による前記膨潤体の前記水性媒体中への微粒子状での分散とを行って初期水性分散体とし、次いで、第３工程として、得られた初期水性分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散した分散体を製造する方法。
【００６０】
これらの方法の中でも、比較的容易にポリエステル樹脂微粒子水性分散体が得られることから、前記▲１▼または▲２▼の方法が好ましい。前記▲１▼および▲２▼の方法で用いるポリエステル樹脂（Ｐ）の形状としては、比較的短時間で膨潤体とすることができることから、粒子状であることが好ましく、例えば、粒子径１〜７ｍｍのペレット、孔径が２〜７ｍｍのスクリーンを通過させた粗粉砕物、平均粒子径８００μｍ以下の粉体等が挙げられる。
【００６１】
以下に、前記▲１▼、▲２▼の方法によるポリエステル樹脂微粒子水性分散体の製造方法のより具体的な製造例を挙げる。
まず、プロペラ翼付のガラス製２Ｌのオートクレーブを用い、このオートクレーブにポリエステル樹脂（Ｐ）を粉砕して得た粒子状物と有機溶剤（Ｓ）とを仕込み、不活性ガスを導入してオートクレーブ内を０．０５〜０．５ＭＰａとなるように予備加圧し、次いで１０〜３００ｒｐｍの攪拌下で有機溶剤（Ｓ）の沸点以上に昇温して有機溶剤（Ｓ）を一部気化させることによりオートクレーブ内を０．１〜２．０ＭＰａ（ゲージ圧）に加圧した後、５０〜７００ｒｐｍで３〜６０分間攪拌してポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させて膨潤体とする（第１工程）。
【００６２】
予備加圧に用いる不活性ガスとしては、例えば、窒素ガス、ヘリウムガス、ネオンガス、アルゴンガス等が挙げられるが窒素ガスが好ましい。
【００６３】
この工程で得られた前記膨潤体は、有機溶剤（Ｓ）を吸収したポリエステル樹脂（Ｐ）と、ポリエステル樹脂（Ｐ）に吸収されずに残った有機溶剤（Ｓ）との混合物であり、半透明〜白濁のり状の混合物として観察されるものが好ましい。なお、例えば、有機溶剤（Ｓ）としてイソプロピルアルコールを用いた系では、攪拌速度を５０ｒｐｍ程度にゆるめると、イソプロピルアルコールが樹脂相から分離して２相を形成するのが観察されるが、それでもよい。
【００６４】
このようにして膨潤体を得た後、前記▲１▼の方法では、３００〜１５００ｒｐｍで攪拌しながら予め加熱しておいた塩基性化合物を含有する水性媒体、例えばアンモニア水を２〜３０分間かけて加圧注入して転相乳化させて、前記膨潤体が微粒子状に分散した初期水性分散体とする（第２工程）。このとき、前記膨潤体中の有機溶剤（Ｓ）は局部的な沸騰と還流が起こっており、ポリエステル樹脂（Ｐ）と親和性の低い有機溶剤（Ｓ）の分子はポリエステル樹脂（Ｐ）から離れやすく、かつ転相乳化しやすくする環境を形成していると考えられる。
【００６５】
また、前記▲２▼の方法では、膨潤体を得た後、連続乳化分散機、例えば、特開平９−３１１５０２号公報に記載されているスリットを有するリング状固定子とスリットを有するリング状回転子とを同軸状に設けた高速回転型連続乳化分散機等を使用して連続的に塩基性化合物を含有する水性媒体中に該膨潤体を微粒子状で分散させて初期水性分散体とする（第２工程）。この場合、前記膨潤体と前記水性媒体とを所定の温度、圧力条件で連続乳化分散機に送り込み、前記回転子を３００〜１００００ｒｐｍで回転させれば良い。
【００６６】
前記膨潤体が微粒子状で分散した分散体を得た後、得られた分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散したポリエステル樹脂微粒子水性分散体が得られる（第３工程）。前記有機溶剤（Ｓ）の除去方法としては、例えば、減圧チャンバー中にスプレーする方法、脱溶剤缶壁内面に薄膜を形成させる方法、溶剤吸収用充填剤入りの脱溶剤缶を通過させる方法等が挙げられる。前記有機溶剤（Ｓ）を除去する方法の一例として、ロータリーエバポレーターを使用した除去方法を以下に記す。
試料量；５００ｍｌ
容器；２Ｌなす型フラスコ
回転数；６０ｒｐｍ
バス温度；４７℃
減圧度；１３．３ＫＰａから２０分間かけて１．３３ＫＰａに減圧度を高め、引き続き１０分間１．３３ＫＰａで脱溶剤する。
【００６７】
なお、ポリエステル樹脂微粒子水性分散体中の樹脂微粒子を粉体塗料やホットメルト接着剤などとして利用する場合や、生成した粒子をトナーなど粉体として取り出す場合には、樹脂微粒子が分散した分散体からの有機溶剤（Ｓ）の除去は前記分散体の製造後直ちに行うのがよい。有機溶剤（Ｓ）が含有されたまま分散体を長期間保存しておくと分散体中の樹脂微粒子が自然と凝集する傾向を示すからである。
【００６８】
本発明の製造方法においては、アルキル基およびアルケニル基を含有しないカルボキシル基含有ポリエステル樹脂と有機溶剤（Ｓ）を用いても残留溶剤が極めて少ないポリエステル樹脂微粒子水性媒体を調製できるが、後述する実施例と比べて前記水性分散体中のポリエステル樹脂微粒子は不定形粒子を含み、粒度分布も広い。また、保存安定性も十分でなく経時的に樹脂粒子が大きくなる傾向がある。
【００６９】
本発明のポリエステル樹脂微粒子水性分散体の製造方法では、製造条件を種々変更することによりポリエステル樹脂微粒子水性分散体中の樹脂微粒子の平均粒径を０．０１〜５０μｍ程度の範囲内で自由に制御することが可能である。
【００７０】
本発明のポリエステル樹脂微粒子水性分散体の製造方法において、得られる分散体中の樹脂微粒子の平均粒径を小さく制御するためには、例えば、次に記す手段等をとれば良い。
▲１▼ポリエステル樹脂（Ｐ）中のカルボキシル基等の親水性セグメント濃度を高くする。
▲２▼ポリエステル樹脂（Ｐ）に対する塩基性化合物の使用量を大きくする。
▲３▼ポリエステル樹脂（Ｐ）に対する有機溶剤（Ｓ）の使用量を大きくする。
▲４▼分散体製造時の温度を高くする。
▲５▼分散体製造時の攪拌速度を大きくする。
【００７１】
逆に、本発明のポリエステル樹脂微粒子水性分散体の製造方法において、得られる分散体中の樹脂微粒子の平均粒径を大きくするためには、これらの条件を逆にしてやれば良い。なお、ポリエステル樹脂（Ｐ）および有機溶剤（Ｓ）と共に、その他の成分、例えばカーボンブラック等の着色剤（Ｃ）、磁性粉、ワックス、帯電制御剤等の添加剤を用いることによっても、分散体中の樹脂微粒子の平均粒径は大きくなる。
【００７２】
このような本発明の製造方法で得られたポリエステル樹脂微粒子水性分散体中の樹脂微粒子は、得られた分散体の温度、ｐＨ、電解質濃度などの条件を制御することにより分散している樹脂微粒子を会合させて、より大きな粒子に成長させることも可能である。
【００７３】
本発明で使用する有機溶剤（Ｓ）は、後述する分散体中の樹脂微粒子の会合の工程で樹脂微粒子同士の接着剤的役割も担っている。通常第３工程での脱溶剤は、この会合工程を終了した後に行われるが、会合工程前に一旦脱溶剤しておいて貯蔵しておき、会合工程で同一もしくは類似の有機溶剤の必要量を再添加してから会合させ、ついで脱溶剤してもよい。
【００７４】
次に、本発明の電子写真用トナーを説明する。
本発明の電子写真用トナーは、本発明のポリエステル樹脂微粒子水性分散体の製造方法で得られた分散体からポリエステル樹脂（Ｐ）の微粒子を分離し、乾燥して得られる微粒子を含有する電子写真用トナーであり、本発明の方法で得たポリエステル樹脂微粒子水性分散体をそのまま用い、この分散体から樹脂微粒子を分離し、乾燥して得られる樹脂微粒子を用いてなる電子写真用トナー（Ｔ１）や、本発明の方法でトナーサイズより小さい粒径の樹脂微粒子が分散したポリエステル樹脂微粒子水性分散体を得た後、必要に応じて別途製造したトナーサイズより小さい粒径の樹脂微粒子が分散した分散体と混合し、得られた分散体の温度、ｐＨ、電解質濃度などの条件を適宜制御することにより分散体中の樹脂微粒子を会合させてトナーサイズの微粒子とした後、粒子を分離し、乾燥して得られる樹脂微粒子を用いてなる電子写真用トナー（Ｔ２）等が挙げられる。本発明の電子写真用トナーは、画質が向上することから電子写真用トナー（Ｔ２）が好ましい。
【００７５】
本発明の電子写真用トナーとしては、例えば、前記電子写真用トナー（Ｔ１）として以下の（１）に示すトナーや前記電子写真用トナー（Ｔ２）として以下の（２）〜（４）に示すトナー等が例示できる。
【００７６】
（１）本発明のポリエステル樹脂微粒子水性分散体の製造方法において、ポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させる第１工程でポリエステル樹脂（Ｐ）と共に着色剤（Ｃ）を併用することにより得られる着色樹脂微粒子が水性媒体中に分散した分散体を得た後、得られた分散体からポリエステル樹脂（Ｐ）の微粒子を分離し、乾燥して得られる微粒子を用いてなる電子写真用トナー。なお、着色剤（Ｃ）と共にワックス等の添加剤、磁性粉、電荷制御剤等を併用することもできる。この場合、前記分散体中の着色樹脂微粒子の平均粒径はトナーサイズ、例えば１〜１０μｍであることが好ましい。
【００７７】
（２）前記（１）と同様にして着色樹脂微粒子が水性媒体中に分散した分散体を得た後、逆中和剤の添加などの方法で樹脂微粒子の表面電位を減少させて分散している樹脂微粒子同志を会合させて、より大きな平均粒径を有する着色樹脂粒子の分散体とし、次いで有機溶剤（Ｓ）を除去し、微粒子の分離を行った後、乾燥して得られる微粒子を用いてなる電子写真用トナー。なお、前記有機溶剤（Ｓ）の除去は、樹脂微粒子同志の会合前に行ってもよい。また、着色剤（Ｃ）と共にワックス等の添加剤、磁性粉、電荷制御剤等を併用することもできる。この場合、会合前の分散体中の着色樹脂微粒子の平均粒径は０．０１〜１μｍであることが好ましく、会合後の着色樹脂微粒子の平均粒径はトナーサイズであることが好ましい。
【００７８】
（３）前記（１）と同様にして着色樹脂微粒子が水性媒体中に分散した分散体を得た後、前記（２）と同様に樹脂微粒子同士を会合させて、より大きな平均粒径を有する着色樹脂粒子（コア粒子）の分散体とし、次いで別途製造したシェル層用の樹脂微粒子の水性分散体と混合し、前記（２）と同様にして分散している着色樹脂粒子（コア粒子）にシェル層用の樹脂微粒子を会合させて、コア／シェル構造の着色樹脂粒子の分散体とし、次いで有機溶剤（Ｓ）を除去し、微粒子の分離を行った後、乾燥して得られる微粒子を用いてなる電子写真用トナー。なお、前記有機溶剤（Ｓ）の除去は、樹脂微粒子同士の会合前に行ってもよい。この場合、会合前の分散体中の着色樹脂微粒子の平均粒径は０．０１〜１μｍであることが好ましく、会合終了後の着色樹脂微粒子の平均粒径はトナーサイズであることが好ましい。
【００７９】
前記（３）で用いるシェル層用の樹脂微粒子は、コア用の樹脂粒子のガラス転移温度（Ｔｇ）より１〜４０℃高いＴｇを有するポリエステル樹脂（Ｐ）からなる樹脂微粒子か、後述する帯電制御剤を用いて樹脂微粒子を調製した時は該帯電制御剤の使用量を多く用いて調製された樹脂微粒子が好ましい。
【００８０】
（４）ポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させることにより膨潤体を得た後、前記膨潤体を水性媒体中に微粒子状で分散させて分散体とし、次いで得られた分散体から前記有機溶剤（Ｓ）を除去することにより前記ポリエステル樹脂（Ｐ）の微粒子が水性媒体中に分散した分散体を得た後、別途製造した着色剤（Ｃ）の水性分散体もしくは別途製造した着色樹脂微粒子の水性分散体と混合し、逆中和剤の添加などの方法で樹脂微粒子の表面電位を減少させて分散している樹脂微粒子と着色剤粒子若しくは着色樹脂微粒子を会合させて、より大きな平均粒径を有する着色樹脂粒子の分散体とし、次いで微粒子の分離を行った後、乾燥して得られる微粒子を用いてなる電子写真用トナー。この場合、前記着色剤（Ｃ）と共にワックス等の添加剤、磁性粉、電荷制御剤等を併用することもできるし、添加剤、磁性粉、電荷制御剤等を含有した樹脂微粒子の水性分散体を併用して会合させることもできる。また、前記有機溶剤（Ｓ）の除去は、樹脂微粒子と着色剤粒子若しくは着色樹脂微粒子の会合を行った後に行ってもよい。ここで用いる各分散体中の微粒子の平均粒径は０．０１〜１μｍであることが好ましく、会合後の着色樹脂微粒子の平均粒径はトナーサイズであることが好ましい。
【００８１】
前記（４）で用いる別途製造した着色剤（Ｃ）の水性分散体もしくは別途製造した着色樹脂微粒子の水性分散体としては、着色剤（Ｃ）もしくは着色樹脂微粒子が水性媒体中に微粒子状で分散されているものであればよく、特に限定されないが、例えば、界面活性剤などを用いて着色剤（Ｃ）を乳化処理した水性分散体、着色剤（Ｃ）と樹脂を加熱溶融したのち、分散剤を含有する水中に分散した水性分散体、着色剤（Ｃ）を分散させたポリエステル樹脂を有機溶剤に溶解させた後、水を加えて転相乳化した水性分散体、本発明の製造方法でポリエステル樹脂（Ｐ）を有機溶剤（Ｓ）で膨潤させる際に着色剤（Ｃ）を併用することにより得られる水性分散体等が挙げられ、なかでも本発明の製造方法で得られる水性分散体が好ましい。これら水性分散体中における着色剤（Ｃ）の濃度は、目的とするトナーの着色剤濃度の５〜１０倍であることが好ましい。
【００８２】
前記着色剤（Ｃ）としては、例えば、カーボンブラック、ベンガラ、紺青、酸化チタン、ニグロシン染料（Ｃ．Ｉ．Ｎｏ．５０４１５Ｂ）、アニリンブルー（Ｃ．Ｉ．Ｎｏ．５０４０５）、カルコオイルブルー（Ｃ．Ｉ．Ｎｏ．ａｚｏｉｃ Ｂｌｕｅ３）、クロムイエロー（Ｃ．Ｉ．Ｎｏ．１４０９０）、ウルトラマリンブルー（Ｃ．Ｉ．Ｎｏ．７７１０３）、デュポンオイルレッド（Ｃ．Ｉ．Ｎｏ．２６１０５）、キノリンイエロー（Ｃ．Ｉ．Ｎｏ．４７００５）、メチレンブルークロライド（Ｃ．Ｉ．Ｎｏ．５２０１５）、フタロシアニンブルー（Ｃ．Ｉ．Ｎｏ．７４１６０）、マラカイトグリーンオクサレート（Ｃ．Ｉ．Ｎｏ．７４１６０）、マラカイトグリーンオクサレート（Ｃ．Ｉ．Ｎｏ．４２０００）、ランプブラック（Ｃ．Ｉ．Ｎｏ．７７２６６）、ローズベンガル（Ｃ．Ｉ．Ｎｏ．４５４３５）等が挙げられる。
【００８３】
前記着色剤（Ｃ）の含有量は、ポリエステル樹脂（Ｐ）１００重量部に対して１〜２０重量部の範囲内になるよう使用するのが好ましい。これらの着色剤は１種又は２種以上の組み合わせで使用することができる。
【００８４】
以下に本発明の製造方法で言う「会合」という工程と現象について述べる。
一般に、本発明の製造方法により得られるようなポリエステル樹脂微粒子水性分散体中の樹脂微粒子は、その表面電荷に由来する静電反発力により凝集することなく水性媒体中に安定に存在するが、同時に、ファンデルワールス力によって樹脂粒子間には引力が働いている。そこで、何らかの作用で樹脂粒子表面電荷を適宜減少させてやると、静電反発力より引力が大きくなり、樹脂微粒子同志が凝集し始めて、より大きい粒子径に成長した樹脂粒子の分散体となる。これを本発明では会合という。この会合の温度はポリエステル樹脂（Ｐ）のガラス転移温度（Ｔｇ）〜ガラス転移温度＋５０℃が好ましく、会合工程中に系内に存在している有機溶剤（Ｓ）の沸点との関係により、０．１〜１．０ＭＰａ（ゲージ圧）の加圧下に加熱するのが更に好ましい。会合に要する時間は、通常２〜１２時間であり、４〜１０時間が好ましい。また、会合は、穏やかな攪拌下、例えば、アンカー翼で１０〜１００ｒｐｍ程度の回転数による攪拌下で行うと良い。
【００８５】
前記の樹脂粒子表面電荷を減少もしくは失わせる方法としては、例えば、希塩酸、希硫酸、酢酸、蟻酸、炭酸などの酸をいわゆる逆中和剤として添加する方法が挙げられる。この際、必要に応じて塩析剤と呼ばれる塩化ナトリウム、塩化カリウム、硫酸アルミニウム、硫酸第２鉄、塩化カルシウム等の金属塩類やカルシウム、アルミニウム、マグネシウム、鉄等の金属錯体を添加しても良い。又、会合工程において着色剤などを分散処理したり、会合の進行を制御する目的で、必要に応じて界面活性剤を使用してもよい。
【００８６】
前記界面活性剤としては、例えば、ドデシルベンゼンスルフォン酸ナトリウム、ラウリル硫酸ナトリウム、アルキルジフェニルジスルフォン酸ナトリウム等のアニオン界面活性剤、トリメチルステアリルアンモニウムクロリド等のカチオン界面活性剤、アルキルフェノキシポリ（エチレンオキシ）エタノール等のノニオン界面活性剤等が挙げられ、適宜選択して使用することができる。
【００８７】
本発明の電子写真用トナーの製造方法は、粒径が１〜１０μｍの電子写真用トナーを製造するのに特に好ましい。
【００８８】
本発明の製造方法は、形状中に鋭利な尖点部分を含まない球形の樹脂粒子からなるポリエステル樹脂微粒子水性分散体や電子写真用トナーを製造することができる。ここで「球形」とは、真球状はもちろん楕円状、いびつな球状（ポテト状）等を含む幅広い概念を言う。
【００８９】
本発明のポリエステル樹脂微粒子水性分散体の製造方法や本発明の電子写真用トナーにおいては、磁性粉、ワックス等の添加剤を必要に応じて用いても良い。これらは、ポリエステル樹脂（Ｐ）と予め混練して混練物としておくのが良い。これらの添加剤は、それぞれ単独で使用しても良いし、２種以上を併用しても良い。
【００９０】
磁性粉としては、例えば、マグネタイト、フェライト、コバルト、鉄、ニッケル等の金属単体やその合金等が挙げられる。
【００９１】
ワックスは、電子写真用トナー用のオフセット防止剤として使用できる。ワックスとしては、例えば、例えばポリプロピレンワックス、ポリエチレンワックス、フィッシャートロフィシュワックス、ステアリルビスアミド、酸化ワックス等の合成ワックス類や、カルナバワックス、ライスワックス等の天然ワックス等が挙げられる。
【００９２】
また、帯電制御剤を用いると帯電特性が良好なトナーが得られる。帯電制御剤としては、例えば、ニグロシン系の電子供与性染料、ナフテン酸、高級脂肪酸の金属塩、アルコキシル化アミン、４級アンモニウム塩、アルキルアミド、金属錯体、顔料、フッ素処理活性剤等のプラス帯電制御剤や、電子受容性の有機錯体、塩素化パラフィン、塩素化ポリエステル、銅フタロシアニンのスルホニルアミン等のマイナス帯電制御剤等が挙げられる。
【００９３】
帯電制御剤を使用する際には、これらの帯電制御剤を有機溶剤（Ｓ）に予め溶解しておいてからポリエステル樹脂（Ｐ）に加えると良い。コア粒子とシェル層からなるトナーを製造する際には、シェル層を製造する際に帯電制御剤を用いれば、帯電制御剤を前記シェル層に配置したトナーを製造することもできる。
【００９４】
本発明において、ポリエステル樹脂微粒子水性分散体中の不揮発分の割合は、前記水性分散体を真空乾燥器中に１００℃、０．１ＫＰａ、３時間の条件で放置し、前記水性分散体の重量変化から求めた。また、微粒子の体積平均粒子径は、０．００１〜２μｍの粒子径測定はＬｅｅｄｓ＋Ｎｏｒｔｈｒｕｐ社製のＭＩＣＲＯＴＲＡＣ ＵＰＡ１５０を用いて測定し、１〜４０μｍの粒子測定はベックマンコールター社製マルチサイザーＴＭ３を用いて測定した。
【００９５】
粒子径が０．００１〜２μｍである粒子の粒度分布の値の評価は、前記ＭＩＣＲＯＴＲＡＣ ＵＰＡ１５０を用いて粒子径の小さい側から積算した場合に体積が１０％となるところの粒子径（Ｄ１０）と粒子経の小さい側から積算した場合に体積が９０％となるところの粒子径（Ｄ９０）とを測定し、この比（Ｄ９０／Ｄ１０）を求めることにより行った。
粒子径が１〜４０μｍである粒子の粒度分布の値の評価は、前記コ−ルターマルチサイザーＴＭ３を用いて粒子径の小さい側から積算した場合に累積重量が１６％となるところの粒子経（Ｄ１６）と粒子径の小さい側から積算した場合に累積重量が８４％（Ｄ８４）となるところの粒子経とを測定し、この比（Ｄ８４／Ｄ１６）の平方根を求めることにより行った。粒度分布の値は小さい程粒度分布の幅が狭いことを表す。
【００９６】
また、ポリエステル樹脂微粒子水性分散体中の残留溶剤の定量は、下記条件でガスクロマトグラフィ法で測定した。
測定機；島津ＧＣ−１７Ａ
カラム；ＵＬＢＯＮ ＨＲ−２０Ｍ（ＰＰＧ）
カラム温度；８０〜１５０℃
昇温速度；１０℃／分
【００９７】
【実施例】
以下に本発明を、合成例、実施例および比較例を挙げて具体的に説明する。例中の部および％は、特に断らない限り重量基準である。
【００９８】
合成例１〔ポリエステル樹脂（Ｐ）の調製〕
攪拌機、窒素ガス導入口、温度計および精留塔を備えた３Ｌステンレスフラスコに、エチレングリコ−ル３２４部、ネオペンチルグリコ−ル５４５部およびトリメチロ−ルプロパン１１２部を仕込み、温度を１４０℃まで上げ、ジブチル錫オキサイド２．４部を投入し、系内が均一に攪拌できることを確認後、テレフタル酸１，８０８部を徐々に投入した。次いで、攪拌を継続しながら、３時間を要して温度を１９５℃まで上げ、その後１０時間を要して温度を２４０℃まで上げた。さらに同温度で５時間反応させ、酸価が１０．０ｍｇＫＯＨ／ｇになった時に温度を２２０℃まで下げた後、ドデセニル無水コハク酸１００部を投入し、同温度で３０分間ドデセニル無水コハク酸とポリエステル樹脂の水酸基末端との開環付加反応を行ない、酸価が１６．０、環球法による軟化点が１１３℃、示差走査熱量測定（ＤＳＣ）法によるガラス転移温度（Ｔｇ）が５８℃、ＧＰＣ法による数平均分子量（Ｍｎ）が３，５００、重量平均分子量（Ｍｗ）が２０，０００であるポリエステル樹脂を得た。これをポリエステル樹脂（Ｐ−１）と略記する。
【００９９】
合成例２（同上）
攪拌機、窒素ガス導入口、温度計および精留塔を備えた３Ｌステンレスフラスコに、ビスフェノ−ルＡのエチレンオキサイド付加物（平均付加モル数２．２）１，４２８部およびシクロヘキサンジメタノ−ル１３７部を仕込み、温度を１４０℃まで上げ、ジブチル錫オキサイド１．４部を投入し、系が均一に攪拌されていることを確認後、テレフタル酸９３６部を徐々に投入した。次いで、攪拌を継続しながら、３時間を要して温度を２２０℃まで上げ、その後３時間を要して温度を２４５℃まで上げた。さらに同温度で８時間反応させ、酸価が２０．０になった時に温度を２３０℃まで下げた後、カ−ジュラ−Ｅ１０（シェルケミカル社製分岐脂肪酸のグリシジルエステル）１０１部を投入し、同温度で３０分間カ−ジュラ−Ｅ１０のエポキシ基とポリエステル樹脂の末端カルボキシル基との開環付加反応を行い、酸価が９．９、環球法による軟化点が１１４℃、ＤＳＣによるＴｇが６３℃、ＧＰＣ法によるＭｎが４，０００、Ｍｗが１６，０００であるポリエステル樹脂を得た。これをポリエステル樹脂（Ｐ−２）と略記する。
【０１００】
合成例３（比較対照用ポリエステル樹脂の調製）
攪拌機、窒素ガス導入口、温度計および精留塔を備えた３Ｌステンレスフラスコに、ビスフェノ−ルＡのエチレンオキサイド付加物（平均付加モル数２．２）１６９８部およびシクロヘキサンジメタノール１６３部を仕込み、温度を１４０℃まで上げ、ジブチル錫オキサイド１．４部を投入し、系内が均一に攪拌できることを確認後、テレフタル酸９４３部およびイソフタル酸１１１部を徐々に投入した。次いで、攪拌を継続しながら、３時間を要して温度を２２０℃まで上げ、その後３時間を要して温度を２４５℃まで上げた。さらに同温度で８時間反応させ、酸価が１６．０、環球法による軟化点が１１５℃、ＤＳＣによるＴｇが６５℃、ＧＰＣ法によるＭｎが４，２００、Ｍｗが１８，０００であるポリエステル樹脂を得た。これを比較対照用ポリエステル樹脂（Ｐ′−１）と略記する。
【０１０１】
実施例１
樹脂の濃度が１０％となる条件でアセトンに対するポリエステル樹脂（Ｐ−１）の溶解性の判定をＡＳＴＭ Ｄ３１３２−８４（Ｒｅａｐｐｒｏｖｅｄ １９９６）の７．２．１．１〜７．２．１．３に記載された判定法を用いて行ったところ、前記判定法の判定区分で「境界線上の溶液」であった。
【０１０２】
ポリエステル樹脂（Ｐ−１）の粗粉砕物１００部およびアセトン１００部をプロペラ翼付きの２Ｌガラスオ−トクレ−ブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し、１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、９００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌しながら粗粉砕物にアセトンを吸収させることにより半透明なのり状の膨潤体を得た。その後、２５％アンモニア水２．９部とイオン交換水３９７．１部からなる９０℃に予備加熱した水性媒体４００部を５分間かけて加圧注入し、水中に膨潤体を微粒子状に分散させた乳濁色の初期水性分散体を得た。この時の中和率〔水性媒体中のアンモニアのモル数（Ｍａ）のポリエステル樹脂（Ｐ−１）中のカルボキシル基のモル数（Ｍｃ）に対する比［（Ｍａ）／（Ｍｃ）］を百分率で表したもの。以下同様。〕は１５０モル％であった。攪拌を続けながら得られた初期水性分散体を３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でアセトンを留去してポリエステル樹脂微粒子水性分散体１を得た。
【０１０３】
得られたポリエステル樹脂微粒子水性分散体１の不揮発分、体積平均粒子径、粒度分布、残留溶剤量の測定と、保存安定性試験を行った。不揮発分、体積平均粒子径、粒度分布、残留溶剤量の測定は前記した方法を用いて測定し、保存安定性試験は下記に示す方法に従った。結果を第１表に示す。
【０１０４】
保存安定性試験の方法：ポリエステル樹脂微粒子水性分散体１を容器に入れ密閉し、２５℃で６ヶ月間静置保存し、性状を目視で観察し以下の通り評価した。
×：容器の底部に沈降物がある。
○：均一な分散体であり、容器の底に沈殿物が認められない。
【０１０５】
実施例２
実施例１と同様にしてポリエステル樹脂（Ｐ−２）の溶解性の判定を行ったところ、判定区分で「境界線上の溶液」であった。
【０１０６】
ポリエステル樹脂（Ｐ−１）１００部の代わりにポリエステル樹脂（Ｐ−２）１００部を使用した以外は実施例１と同様にして、ポリエステル樹脂微粒子水性分散体２を得た。実施例１と同様にして評価を行い、その結果を第１表に示す。
【０１０７】
実施例３
ポリエステル樹脂（Ｐ−１）４９部、リ−ガル３３０（キャボット社製のカーボンブラック）３０部、ビスコ−ル５５０Ｐ（株式会社三洋化成製のポリプロピレンワックス）９部及びボントロンＥ−８０（オリエント化学工業株式会社製の帯電制御剤）１２部を混合し、ヘンシェルミキサーにてミキシングを行い、加圧ニーダーで混練し混練物を調製した。この混練物の粗粉砕物１００部およびアセトン１００部をプロペラ翼付の２Ｌのオ−トクレ−ブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、９００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌しながら粗粉砕物にアセトンを吸収させることにより黒色のり状の膨潤体を得た。その後、２５％アンモニア水２．９部とイオン交換水３９７．１部からなる９０℃に予備加熱した水性媒体４００部を５分間かけて加圧注入し、水中に膨潤体を微粒子状に分散させた黒色の初期水性分散体を得た。この時の中和率は１５０モル％であった。得られた初期水性分散体を攪拌を続けながら３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でアセトンを留去してポリエステル樹脂微粒子水性分散体３を得た。実施例１と同様にして評価を行い、その結果を第１表に示す。
【０１０８】
実施例４
ポリエステル樹脂（Ｐ−１）１００部およびリーガルＲ３３０ １００部とを混合し、ヘンシェルミキサーにてミキシングを行い、加圧ニーダーを用いて溶融混練し混練物を調製した。この混練物の粗粉砕物１００部およびアセトン１００部とをプロペラ翼付の２Ｌのオートクレーブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し、１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、９００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌しながら粗粉砕物にアセトンを吸収させることにより黒色のり状の膨潤体を得た。その後、２５％アンモニア水５部とイオン交換水４００部からなる９０℃に予備加熱した水性媒体４０５部を５分間かけて加圧注入し、水中に膨潤体を微粒子状に分散させた黒色の初期水性分散体を得た。この時の中和率は２５９モル％であった。攪拌を続けながら得られた初期水性分散体を３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でアセトンを留去してポリエステル樹脂微粒子水性分散体４を得た。実施例１と同様にして評価を行い、その結果を第１表に示す。
【０１０９】
実施例５
リーガルＲ３３０ １００部の代わりにビスコール５５０Ｐ １００部を用いた以外は実施例４と同様にしてポリエステル樹脂微粒子水性分散体５を得た。実施例１と同様にして評価を行い、その結果を第１表に示す。
【０１１０】
実施例６
リーガルＲ３３０ １００部の代わりにボントロンＥ−８０ １００部を用いた以外は実施例４と同様にしてポリエステル樹脂微粒子水性分散体６を得た。実施例１と同様にして評価を行い、その結果を第１表に示す。
【０１１１】
比較例１
樹脂の濃度を１０％から１５％に変更し、かつ、アセトンの代わりにテトラヒドロフラン（ＴＨＦ）を用いた以外は実施例１と同様にして、ポリエステル樹脂（Ｐ′−１）の溶解性の判定を行ったところ、判定区分は共に「完全な溶液」であった。
【０１１２】
ポリエステル樹脂（Ｐ′−１）の粗粉砕物１００部およびＴＨＦ１００部をプロペラ翼付きの２Ｌガラスオ−トクレ−ブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し、１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、９００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌して樹脂溶液を得た。その後、２５％アンモニア水２．９部とイオン交換水３９７．１部からなる９０℃に予備加熱した水性媒体４００部を５分間かけて加圧注入し、水中にポリエステル樹脂を微粒子状に分散させた乳濁色の初期水性分散体を得た。この時の中和率は１５０モル％であった。攪拌を続けながら得られた初期水性分散体を３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でＴＨＦを留去して比較対照用ポリエステル樹脂微粒子水性分散体１′を得た。実施例１と同様にして評価を行い、その結果を第２表に示す。
【０１１３】
比較例２
ポリエステル樹脂（Ｐ′−１）４９部、リ−ガル３３０ ３０部、ビスコ−ル５５０Ｐ ９部およびボントロンＥ−８０ １２部を混合し、ヘンシェルミキサーにてミキシングを行い、加圧ニーダーで混練し混練物を調製した。この混練物の粗粉砕物１００部およびＴＨＦ１００部をプロペラ翼付の２Ｌのオ−トクレ−ブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、９００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌して樹脂溶液を得た。その後、２５％アンモニア水２．９部とイオン交換水３９７．１部からなる９０℃に予備加熱した水性媒体４００部を５分間かけて加圧注入し、水中に前記混練物を微粒子状に分散させた黒色の初期水性分散体を得た。この時の中和率は１５０モル％であった。得られた初期水性分散体を攪拌を続けながら３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でＴＨＦを留去して比較対照用ポリエステル樹脂微粒子水性分散体２′を得た。実施例１と同様にして評価を行い、その結果を第２表に示す。
【０１１４】
【表１】
【表２】
実施例７
アンカ−翼、コンデンサ−、窒素ガス導入口、温度計を装備したガラス製２Ｌオ−トクレ−ブに、ポリエステル樹脂微粒子水性分散体１ ３００部、ポリエステル樹脂微粒子水性分散体３ １００部及びアセトン４０部を仕込み室温で５０ｒｐｍでアンカー翼を回転させながら１％希塩酸２０部と１％塩化カルシウム水溶液２０部と１％ドデシルベンゼンスルフォン酸ナトリウム水溶液２０部との混合物を３０分間を要して滴下した。その後、系内の温度を８０℃まで１時間を要して上昇させ、同温度でさらに５時間会合を行い、球形の着色粒子を含むポリエステル樹脂微粒子水性分散体を得た。ロータリーエバポレーターを使用して４７℃、６０分間の条件でアセトンを留去し、イオン交換水で分散体を３回洗浄し、水と分離後乾燥し、ポリエステル樹脂微粒子を得た。このポリエステル樹脂粒子の残留溶剤量、体積平均粒子径および粒度分布を測定を測定したところ、残留溶剤量は２０ｐｐｍ（検出限界）以下であり、体積平均粒子径は５．９μｍ、粒度分布は１．３であった。このポリエステル樹脂微粒子とこの樹脂微粒子の重量に対して０．３％のアエロジルＲ−９７４（日本アエロジル製シリカ）とヘンシェルミキサ−で混合してトナー１を調製した。このトナーを用いて得られる画像の評価を下記に示す方法で行った。結果を第３表に示す。
【０１１７】
画像評価方法：トナー１を市販のフルカラ−複写機に装填し、テストチャートとして電子写真学会発行のＡ４カラ−用（番号５−１）を用いて１２００ｄｐｉの画像を形成したときの１ｄｏｔ ｌｉｎｅの解像性を下記判定に従い評価した。
◎：完全な１ｄｏｔ ｌｉｎｅを形成している。
○：ほぼ完全な１ｄｏｔ ｌｉｎｅを形成している。
×：不完全な１ｄｏｔ ｌｉｎｅを形成している。
××：１ｄｏｔ ｌｉｎｅを形成していない。
【０１１８】
実施例８
アンカー翼、コンデンサーを備えたオートクレーブに、ポリエステル樹脂微粒子水性分散体１ ２８０部、ポリエステル樹脂微粒子水性分散体４ ５６部、ポリエステル樹脂微粒子水性分散体５ ４０部およびポリエステル樹脂微粒子水性分散体６ ２４部を仕込み、５０ｒｐｍでアンカー翼を回転させながら１％希塩酸２０部と１％塩化カルシウム２０部と１％ドデシルベンゼンスルフォン酸ナトリウム水溶液２０部との混合物を３０分間を要して滴下した。その後、系内の温度を８０℃まで１時間を要して上昇させ、同温度でさらに５時間会合を行い、球形の着色粒子を含むポリエステル樹脂微粒子水性分散体を得た。イオン交換水で分散体を３回洗浄し、水と分離後乾燥し、ポリエステル樹脂微粒子を得た。このポリエステル樹脂粒子の残留溶剤量、体積平均粒子径および粒度分布を測定を測定したところ、残留溶剤量は２０ｐｐｍ（検出限界）以下であり、体積平均粒子径は６．０μｍ、粒度分布は２．１であった。このポリエステル樹脂微粒子とこの樹脂微粒子の重量に対して０．３％のアエロジルＲ−９７４（日本アエロジル製シリカ）とヘンシェルミキサ−で混合してトナー２を調製した。実施例７と同様に評価を行いその結果を第３表に示す。
【０１１９】
実施例９
アンカー翼、コンデンサーを備えたオートクレーブに、ポリエステル樹脂微粒子水性分散体１ ２８０部、リーガルＲ３３０ ５部に界面活性剤０．０５部とイオン交換水１０部を加えてホモジナイザー処理した着色剤、ビスコール５５０Ｐを乳化した乳化液を固形分換算で２部、および、Ｔ−７７（保土ヶ谷化学工業株式会社製の帯電制御剤）１．５部をアセトン３５部に溶解したものを仕込み、５０ｒｐｍでアンカー翼を回転させながら１％希塩酸２０部と１％塩化カルシウム２０部と１％ドデシルベンゼンスルフォン酸ナトリウム水溶液２０部との混合物を３０分間を要して滴下した。その後、系内の温度を８０℃まで１時間を要して上昇させ、同温度でさらに５時間会合を行い、球形の着色粒子を含むポリエステル樹脂微粒子水性分散体を得た。ロータリーエバポレーターを使用して４７℃、６０分間の条件でアセトンを留去しイオン交換水で分散体を３回洗浄を繰り返した後、水と分離後乾燥し、ポリエステル樹脂微粒子を得た。このポリエステル樹脂粒子の残留溶剤量、体積平均粒子径および粒度分布を測定を測定したところ、残留溶剤量は２０ｐｐｍ（検出限界）以下であり、体積平均粒子径は６．１μｍ、粒度分布は２．３であった。このポリエステル樹脂微粒子とこの樹脂微粒子の重量に対して０．３％のアエロジルＲ−９７４（日本アエロジル製シリカ）とヘンシェルミキサ−で混合してトナー３を調製した。実施例７と同様に評価を行いその結果を第３表に示す。
【０１２０】
比較例３
ポリエステル樹脂微粒子水性分散体１ ３００部およびポリエステル樹脂微粒子水性分散体３ １００部を用いる代わりに比較対照用ポリエステル樹脂微粒子水性分散体１′ ３００部および比較対照用ポリエステル樹脂微粒子水性分散体２′ １００部を用いる以外は実施例７と同様にしてポリエステル樹脂微粒子を得た。このポリエステル樹脂粒子の残留溶剤量、体積平均粒子径および粒度分布を測定を測定したところ、残留溶剤量は６００ｐｐｍ、体積平均粒子径は６．５μｍ、粒度分布は３．３であった。このポリエステル樹脂微粒子とこの樹脂微粒子の重量に対して０．３％のアエロジルＲ−９７４（日本アエロジル製シリカ）とヘンシェルミキサ−で混合して比較対象用トナー１′を調製した。実施例７と同様に評価を行いその結果を第３表に示す。
【０１２１】
比較例４
ポリエステル樹脂（Ｐ′−１）４９部、リ−ガル３３０ ３０部、ビスコ−ル５５０Ｐ ９部およびボントロンＥ−８０ １２部を混合し、ヘンシェルミキサーにてミキシングを行い、加圧ニーダーで混練し混練物を調製した。この混練物の粗粉砕物１００部およびＴＨＦ１００部をプロペラ翼付の２Ｌのオ−トクレ−ブに仕込み、窒素ガスで０．２ＭＰａに予備加圧し１００ｒｐｍでプロペラ翼を回転させながら系内が９０℃になるまで加熱した。この時のオートクレーブ内の圧力は０．４５ＭＰａに増加していた。系内が９０℃になった後、５００ｒｐｍにプロペラ翼の回転数を上げて１０分間攪拌して樹脂溶液を得た。その後、２５％アンモニア水１．４部とイオン交換水３９８．６部からなる９０℃に予備加熱した水性媒体４００部を５分間かけて加圧注入し、水中に膨潤体を微粒子状に分散させた黒色の初期水性分散体を得た。この時の中和率は７０モル％であった。得られた初期水性分散体を攪拌を続けながら３０℃まで水冷して取り出し、ロータリーエバポレーターを使用して４７℃、３０分間の条件でＴＨＦを留去して後、得られた分散体をイオン交換水で３回洗浄を繰り返した後、水と分離後乾燥し、ポリエステル樹脂微粒子を得た。このポリエステル樹脂粒子の残留溶剤量、体積平均粒子径および粒度分布を測定を測定したところ、残留溶剤量は６５０ｐｐｍであり、体積平均粒子径は６．６μｍ、粒度分布は３．８であった。このポリエステル樹脂微粒子とこの樹脂微粒子の重量に対して０．３％のアエロジルＲ−９７４（日本アエロジル製シリカ）とヘンシェルミキサ−で混合して比較対照用トナー２′を調製した。実施例７と同様に評価を行いその結果を第３表に示す。
【０１２２】
【表３】
【発明の効果】
本発明の製造方法は、ポリエステル樹脂としてアルキル基および／またはアルケニル基とカルボキシル基とを含有するポリエステル樹脂（Ｐ）を溶解しないが膨潤させることができる沸点１００℃未満の有機溶剤（Ｓ）、好ましくは水と相溶する有機溶剤を用い、前記ポリエステル樹脂（Ｐ）に前記有機溶剤（Ｓ）で吸収させて膨潤体とした後、転相乳化して前記膨潤体を微粒子状で水性媒体中に分散させ、次いで得られた分散体から前記有機溶剤の除去を行うため、有機溶剤の除去が容易で、樹脂微粒子内に残存する残存溶剤が極めて少ない熱可塑性樹脂微粒子水性分散体が得られる。
前記アルキル基／およびアルケニル基とカルボキシル基とを含有するポリエステル樹脂を用いることにより、アルキル基およびアルケニル基とを含有しないポリエステル樹脂を用いた時と比べてポリエステル樹脂微粒子水性分散体中のポリエステル樹脂微粒子の安定性が格段に向上し、かつ、ポリエステル樹脂微粒子の形状も不定形の少ない球形である。
前記本発明の製造方法で得られるポリエステル樹脂微粒子水性分散から樹脂微粒子を分離し、乾燥して得られる微粒子を含有する本発明の電子写真用トナーは、前記アルキル基／およびアルケニル基とカルボキシル基とを含有するポリエステル樹脂を用いることにより不定形の少ない球形のトナーであり、耐久性と流動性が良好である。
また、前記本発明の製造方法で得られる電子写真用トナーは、残存溶剤が極めて少ない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an aqueous dispersion of polyester resin fine particles used in the fields of electrophotographic toner, printing materials such as inks, paints, adhesives, pressure-sensitive adhesives, fiber processing, papermaking / paper processing, civil engineering, and the like. The present invention relates to an electrophotographic toner containing polyester resin fine particles obtained by a production method.
[0002]
[Prior art]
Examples of a method for producing the aqueous dispersion of polyester resin fine particles include a dispersion granulation method in which the polyester resin is finely divided. Phase inversion emulsification is one of such dispersion granulation methods.For example, phase inversion is performed by adding an aqueous medium to a resin solution obtained by dissolving a polyester resin having a neutralized salt structure in a water-miscible organic solvent. There is known a method for producing a toner for developing an electrostatic image, in which emulsification is performed, followed by removal of an organic solvent and drying. In this production method, a polyester resin having a neutralized salt structure, which is a self-water dispersible polyester resin, is used, so that an aqueous dispersion of polyester resin fine particles is produced without using auxiliary materials such as an emulsifier and a suspension stabilizer. (For example, see Patent Document 1). Further, an aqueous dispersion obtained by mixing a neutralized acid group-containing polyester resin, a water-soluble organic compound having a boiling point of 60 to 200 ° C., and water at a specific mixing ratio is also known (for example, Patent Document 2 and See Patent Document 3.).
[0003]
Since the phase inversion emulsification method disclosed in Patent Document 1 is considered to prepare an organic solvent solution of a self-water-dispersible polyester resin, the self-water-dispersible polyester resin and the polyester resin can be dissolved. Only a study on a combination with an organic solvent (good solvent) has been proposed. Therefore, it has not been applied to a combination of a self-water dispersible polyester resin and an organic solvent that does not dissolve the polyester resin. Further, since the transfer emulsification method is a combination of a self-water-dispersible polyester resin and an organic solvent (good solvent) capable of dissolving the polyester resin, even after the self-water-dispersible polyester resin is dispersed in an aqueous medium. High affinity between the self-water-dispersible polyester resin and the organic solvent. As a result, even after the step of removing the organic solvent, the organic solvent remains in the resin particles at a high concentration, and there is an environmental health problem. .
[0004]
Patent Documents 2 and 3 disclose, as a water-soluble organic compound having a boiling point of 60 to 200 ° C., an organic solvent having a boiling point of 100 ° C. or higher that dissolves the polyester resin and an organic solvent having a boiling point of less than 100 ° C. that does not dissolve the polyester resin. Although exemplified, the description and suggestion regarding removing the organic solvent from the obtained aqueous dispersion and using the polyester resin in combination with an organic solvent having a boiling point of less than 100 ° C. that does not dissolve the polyester resin are disclosed in US Pat. In Examples, an aqueous dispersion was produced using any of organic solvents including organic solvents (good solvents) having a boiling point of 100 ° C. or higher that dissolve the polyester resin, and then the coating agent was removed without removing the organic solvent. And so on. In the aqueous dispersions obtained in these examples, even when the organic solvent is removed, the organic solvent remains in the resin particles at a high concentration, and thus there is a problem of environmental hygiene.
[0005]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 08-211165 (page 2, pages 4 to 6)
[Patent Document 2]
JP-A-56-088454 (pages 2, 4 and 7)
[Patent Document 3]
JP-A-56-125432 (page 2, page 4, page 7)
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing an aqueous dispersion of polyester resin fine particles in which the amount of residual solvent remaining in resin particles is extremely small, and an electrophotographic toner in which the amount of residual solvent is extremely small.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found the following findings (a) to (h), and have completed the present invention.
[0008]
(A) a polyester resin (P) containing an alkyl group and / or an alkenyl group and a carboxyl group as a polyester resin, and a boiling point of 100 ° C. which does not dissolve the polyester resin (P) but swells as an organic solvent. The swelled body obtained by absorbing the organic solvent (S) into the polyester resin (P) using less than the organic solvent (S) is transferred to and emulsified in an aqueous medium containing a basic compound. It is easy to obtain a self-water-dispersible polyester resin fine particle aqueous dispersion dispersed in the form of fine particles in a medium.
[0009]
(B) Since the polyester resin containing the alkyl group and / or the alkenyl group and the carboxyl group is used as the polyester resin, the polyester resin is compared with the case where the carboxyl group-containing polyester resin not containing the alkyl group and the alkenyl group is used. The stability of the fine polyester resin particles in the aqueous resin fine particle dispersion is remarkably improved, and the obtained fine polyester resin particles are spherical with few irregular shapes and have a narrow particle size distribution.
[0010]
(C) Since the organic solvent (S) having a boiling point of less than 100 ° C. that does not dissolve the polyester resin (P) is used as the organic solvent, the organic solvent in the obtained aqueous dispersion can be easily removed, and the residual organic solvent can be easily removed. Aqueous dispersion of polyester resin fine particle can be produced very little.
[0011]
(D) In the method for producing an aqueous dispersion of polyester resin fine particles, by using the colorant (C) in combination with the polyester resin (P), the fine particles of the polyester resin (P) colored with the colorant (C) become aqueous. Obtaining a dispersion dispersed in a medium.
[0012]
(E) Separating the colored fine particles of the aqueous polyester resin fine particle dispersion obtained by the above-mentioned method for producing an aqueous dispersion of polyester resin fine particles, and adding the fine particles obtained by drying, the residual solvent is extremely small for electrophotography. Toner can be obtained.
[0013]
(F) The electrophotographic toner obtained by associating the colored fine particles with each other and separating and drying the resulting fine particles has a very small amount of residual solvent and an improved image quality.
[0014]
(G) mixing the aqueous dispersion of polyester resin fine particles obtained by the above production method with the aqueous medium of the colorant (C) or the aqueous medium of the colored resin particles, and mixing the fine particles of the polyester resin with the colorant particles or the colored resin particles. The toner for electrophotography obtained by associating, separating and drying is extremely low in residual solvent and has improved image quality.
[0015]
(H) The toner for electrophotography is a spherical toner having a small amount of irregular shape and a narrow particle size distribution because the polyester resin containing the alkyl group and / or alkenyl group and the carboxyl group is used. An image obtained using the toner has excellent color tone and resolution.
[0016]
That is, the present invention relates to an organic solvent having a boiling point of less than 100 ° C., which does not dissolve the polyester resin (P) but swells the polyester resin (P) containing an alkyl group and / or an alkenyl group and a carboxyl group. A first step of producing a swelled body by swelling in (S); and mixing the swelled body in an aqueous medium containing a basic compound to form part or all of the carboxyl groups in the polyester resin (P). A second step of producing an initial aqueous dispersion by performing neutralization with a basic compound of the above and dispersing the swelled body in the form of fine particles in an aqueous medium; A third step of producing a dispersion in which the fine particles of the polyester resin (P) are dispersed in the aqueous medium by removing S). There is provided a method for producing a fat particle aqueous dispersion.
[0017]
The present invention also provides a method for separating fine particles of a polyester resin (P) from a thermoplastic resin fine particle aqueous dispersion obtained by using a colorant (C) together with a polyester resin (P) in the above production method, followed by drying. An object of the present invention is to provide an electrophotographic toner containing the obtained fine particles.
[0018]
Furthermore, the present invention relates to a method for producing a thermoplastic resin fine particle aqueous dispersion obtained by using a colorant (C) in combination with a polyester resin (P) in the above-mentioned production method. And an electrophotographic toner obtained by drying.
[0019]
Further, the present invention provides a method of mixing and dispersing an aqueous dispersion of polyester resin fine particles obtained by the above production method with an aqueous dispersion of the colorant (C) or an aqueous dispersion of colored resin particles. The present invention provides an electrophotographic toner characterized by being obtained by associating fine particles with colorant particles or colored resin fine particles, separating and drying the fine particles.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The method for preparing the polyester resin (P) containing an alkyl group and / or an alkenyl group and a carboxyl group used in the present invention includes, for example,
(1) A dibasic acid having an alkyl group or an alkenyl group and a dihydric alcohol are essential, and if necessary, other dibasic acids or anhydrides thereof, trifunctional or higher polybasic acids or anhydrides, Preparation method of mixing monobasic acid, trifunctional or higher alcohol, monohydric alcohol, etc., and dehydrating and condensing while measuring the acid value under heating in a nitrogen atmosphere,
{Circle around (2)} A polyester resin having a hydroxyl group at the terminal (which may have a carboxyl group in the main chain) prepared by essentially including a dibasic acid or its anhydride and a dihydric alcohol is heated and dissolved therein. A preparation method in which an acid anhydride having an alkyl group or an alkenyl group is charged into the resin, and ring-opening addition is performed to a terminal hydroxyl group of the polyester resin,
{Circle around (3)} A polyester resin having a carboxyl group at the terminal (which may contain a carboxyl group in the main chain) prepared by essentially including a dibasic acid or its anhydride and a dihydric alcohol, is heated and melted. There may be mentioned a preparation method in which an aliphatic monoepoxy compound having an alkyl group or an alkenyl group is added thereto, and ring opening is added to a part of the terminal carboxyl group of the polyester resin.
[0021]
As the apparatus used in the above-described preparation method, a batch-type production apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, a rectification tower, and the like can be preferably used, and a deaeration port is provided. Extruders, continuous reaction devices, kneaders and the like can also be used. In the dehydration condensation, the esterification reaction can be promoted by reducing the pressure of the reaction system as required. Further, various catalysts can be added to promote the esterification reaction.
[0022]
Examples of the alkyl group and alkenyl group of the polyester resin (P) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Octyl group, nonyl group, isononyl group, dodecyl group, dodecenyl group and the like.
[0023]
Examples of the dibasic acid having an alkyl group or an alkenyl group used in the preparation method (1) include dibasic acids such as n-butylsuccinic acid, n-octylsuccinic acid, n-dodecylsuccinic acid, and n-dodecenylsuccinic acid. Acids and their anhydrides.
[0024]
Examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, Aliphatic diols such as neopentyl glycol; bisphenols such as bisphenol A and bisphenol F; bisphenol A alkylene oxide adducts such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct; xylylene diglycol, cyclohexanedicyclohexane Examples include aralkylene glycols such as methanol and hydrogenated bisphenol A, and alicyclic diols.
[0025]
Other dibasic acids and anhydrides thereof include, for example, maleic acid, fumaric acid, itaconic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid and the like. Aliphatic dibasic acid; phthalic acid, tetrahydrophthalic acid and its anhydride, hexahydrophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, tetrachlorophthalic acid and its anhydride, hetic acid and its anhydride And aromatic or alicyclic dibasic acids such as highmic acid and anhydride thereof, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.
[0026]
Examples of the trifunctional or higher polybasic acid and its anhydride include trimellitic acid, trimellitic anhydride, methylcyclohexentricarboxylic acid, methylcyclohexentricarboxylic anhydride, pyromellitic acid, pyromellitic anhydride and the like.
[0027]
Examples of the monobasic acid include benzoic acid and p-tert-butylbenzoic acid.
[0028]
Examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, -Methylpropanetriol, 1,3,5-trihydroxybenzene, tris (2-hydroxyethyl) isocyanurate and the like.
[0029]
Examples of the monohydric alcohol include higher alcohols such as stearyl alcohol.
[0030]
Examples of the dibasic acid or its anhydride and the dihydric alcohol used for preparing the hydroxyl group-containing polyester resin of the preparation method (2) or the carboxyl group-containing polyester resin of the preparation method (3) include, for example, the preparation method Other dibasic acids and their anhydrides, dihydric alcohols and the like used in 1) can be used. Also, for example, trifunctional or higher polybasic acids and their anhydrides, monobasic acids, trifunctional or higher polyhydric alcohols, monohydric alcohols and the like used in the preparation method (1) may be prepared as necessary. good.
[0031]
Examples of the acid anhydride having an alkyl group or an alkenyl group used in the preparation method (2) include, for example, n-butyl succinic anhydride, n-pentyl succinic anhydride, neopentyl succinic anhydride, n-hexyl succinic anhydride, n-heptyl succinic anhydride, n-octyl succinic anhydride, isooctyl succinic anhydride, 2-ethylhexyl succinic anhydride, n-dodecyl succinic anhydride, isododecyl succinic anhydride, n-dodecenyl succinic anhydride, isododecenyl succinic anhydride, 6-butyl-1,2,4-benzenetricarboxylic anhydride, 6-n-octyl-1,2,4-benzenetricarboxylic anhydride and the like. The acid anhydride having an alkyl group or an alkenyl group may be used alone or in combination of two or more.
[0032]
Examples of the aliphatic monoepoxy compound having an alkyl group or an alkenyl group used in the preparation method (3) include, for example, those of saturated or unsaturated fatty acids such as castor oil fatty acid, coconut oil fatty acid, soybean oil fatty acid and tung oil fatty acid. Examples include glycidyl esters and monoglycidyl esters of branched fatty acids such as isononanoic acid and vasatic acid. Commercial products of the above-mentioned monoglycidyl esters of branched fatty acids include Kadura E10 (manufactured by Shell Chemical Company). The aliphatic monoepoxy compounds may be used alone or in combination of two or more.
[0033]
Dibasic acids and anhydrides, trifunctional or higher polybasic acids and anhydrides, and monobasic acids used in the above-mentioned preparation methods (1) to (3) may be used alone, Two or more kinds may be used in combination. Further, those in which part or all of the carboxyl group is an alkyl ester, alkenyl ester or aryl ester can also be used.
[0034]
The dihydric alcohol, trihydric or higher alcohol, and monohydric alcohol used in the above-mentioned preparation methods (1) to (3) may be used alone or in combination of two or more. May be.
[0035]
In addition, for example, compounds having both a hydroxyl group and a carboxyl group in one molecule such as dimethylolpropionic acid, dimethylolbutanoic acid, and 6-hydroxyhexanoic acid, or reactive derivatives thereof are also prepared according to the above-mentioned preparation methods (1) to (3). Can be used with ▼.
[0036]
The polyester resin (P) may be, for example, a polyester resin (P1) containing an alkyl group and / or an alkenyl group and a carboxyl group obtained by the above-mentioned preparation method (1). Polyester resin (P2) having a terminal structure produced by ring-opening addition of an acid anhydride having an alkyl group or an alkenyl group to the terminal hydroxyl group of the carboxyl group-containing polyester resin having a hydroxyl group at the terminal obtained in ▼, and a preparation method The polyester resin (P3) having a terminal structure formed by ring-opening addition of an aliphatic monoepoxy compound having an alkyl group or an alkenyl group to a terminal carboxyl group of the polyester resin having a carboxyl group at the terminal obtained in (3). If present, when the polyester resin is dispersed in an aqueous medium in the form of fine particles, It preferred that the particles be dispersed more stably. In this case, the polyester resin having a hydroxyl group at the terminal or the polyester resin having a carboxyl group at the terminal may or may not already contain an alkyl group or an alkenyl group.
[0037]
The polyester resin (P) may contain the terminal structure of the polyester resin (P2) or the terminal structure of the polyester resin (P3) independently in one molecule of the polyester resin, or may have both of these terminal structures. You may have.
[0038]
The polyester resin (P) includes, among others, a terminal structure represented by the general formula (1) obtained by the preparation method (2) and a terminal structure represented by the general formula (2) or (3) obtained by the preparation method (3). Particularly preferred is a polyester resin having a terminal structure to be obtained.
Embedded image
[0039]
R in the general formulas (1), (2) and (3) 1 ~ R 4 The alkyl group having 4 to 20 carbon atoms or the alkenyl group having 4 to 20 carbon atoms may be linear or branched, for example, butyl, isobutyl, pentyl, neopentyl, hexyl , Peptyl group, octyl group, isooctyl group, dodecyl group, dodecenyl group and the like.
[0040]
Next, the properties of the polyester resin (P) will be described.
Since the polyester resin (P) has good stability of the polyester resin fine particles in an aqueous medium, the weight average molecular weight by gel permeation chromatography (GPC) may be in the range of 5,000 to 300,000. Preferably, it is particularly preferably in the range of 7,000 to 100,000.
[0041]
The acid value of the polyester resin (P) is preferably in the range of 1 to 100 mgKOH / g, and more preferably in the range of 5 to 40 mgKOH / g.
[0042]
The organic solvent (S) used in the present invention does not dissolve the polyester resin (P) but is capable of swelling [the boiling point at normal pressure (101.3 KPa). The same applies hereinafter. Any organic solvent having a temperature of less than 100 ° C. may be used. When an organic solvent that dissolves the polyester resin (P) and / or an organic solvent having a boiling point of 100 ° C. or higher is used, it is difficult to remove the organic solvent in the third step, and swell the polyester resin (P). When an organic solvent that cannot be used is used, it is difficult to disperse the polyester resin (P) in the aqueous medium in the second step.
[0043]
Note that the organic solvent (S) that does not dissolve the polyester resin (P) used in the present invention refers to the above-mentioned polyester resin (P) at 25 ° C. when the organic solvent and the polyester resin (P) are used in combination. It means an organic solvent having a solubility in an organic solvent of 15% by weight or less, and does not mean an organic solvent in which the solubility of the polyester resin (P) in the organic solvent is 0% by weight.
[0044]
In the present invention, whether or not the organic solvent corresponds to the organic solvent (S) that does not dissolve the polyester resin (P) is determined, for example, in 7.2 of the 7.2 result of ASTM D3132-84 (Reapproved 1996). The determination can be performed using the determination method described in 2.1.1 to 7.2.1.3.
[0045]
To determine whether or not the organic solvent (S) is applicable, specifically, 15 parts by weight of the particulate polyester resin (P) and 85 parts by weight of the organic solvent are sealed in a flask, and shaken at 25 ° C. for 16 hours. After dissolution, the dissolution state was observed, and according to the following determination categories described in ASTM D3132-84, 7.2.1.1-7.2.1.3. "Perfect solution" or 2. "Boundary solution" or 3. The determination can be made by determining which category of “insoluble” belongs.
1. "Complete solution"; a single clear phase without distinct solids or gel particles.
2. "Boundary solution"; clear or cloudy phase without clear phase separation.
3. "Insoluble"; separated into two phases: a liquid containing a separated gel solid phase or a liquid separated into two phases.
In the present invention, as the particulate polyester resin (P), a coarsely pulverized polyester resin (P) passed through a screen having a hole diameter of 3 mm was used for the determination.
[0046]
In the production method of the present invention, in the determination of whether or not the polyester resin (P) and the organic solvent (S) correspond to the organic solvent (S), 2. "borderline solution", or This is a method used in a combination of “insoluble”, and by using the polyester resin (P) and the organic solvent (S) in this combination, the solvent can be easily removed in the third step.
[0047]
As the organic solvent (S) used in the present invention, the solubility of the polyester resin (P) in the organic solvent at 25 ° C. is 10% by weight or less because the solvent can be more easily removed in the third step. Organic solvent, more preferably 7% by weight or less. The determination of the solubility at this time is not made by determining whether the organic solvent corresponds to the organic solvent (S) at the resin concentration of 15% by weight, but by determining whether the resin concentration is 10% by weight or 7% by weight. It is possible by doing.
[0048]
Further, as the organic solvent (S), it is easy to remove from the particulate swollen body dispersed in the aqueous medium, and it is possible to easily, efficiently and economically produce resin particles having a very small amount of residual solvent. The organic solvent (S1) compatible with is preferred. However, as the organic solvent (S1), it is not necessary that water and the organic solvent form a uniform phase at all mixing ratios, and the swelled body obtained by swelling the polyester resin (P) with the organic solvent (S) is not necessary. It is sufficient that they are compatible with each other at the temperature at the time of dispersion in the aqueous medium and the composition range of water and the organic solvent. The organic solvent (S1) may be either a single solvent or a mixed solvent as long as it satisfies this condition, but it is compatible with water at the temperature at which the organic solvent (S1) is removed in the third step. Those which are compatible with water at 25 ° C. are more preferable. Among them, as the organic solvent (S1), the solubility in water at 25 ° C. is preferably 50% by weight or more, and it is particularly preferable that the organic solvent (S1) is compatible with water at 25 ° C. in all proportions. Further, when the organic solvent (S1) is a mixed solvent, it is preferable that the boiling point of each of the organic solvents used is less than 100 ° C. Further, the boiling point of the organic solvent (S1) is more preferably 40 to 90 ° C. The temperature is more preferably from 40 to 85 ° C, and most preferably from 40 to 60 ° C.
[0049]
Examples of the organic solvent (S1) include ketones such as acetone (solubility: compatible with water in all proportions; boiling point: 56.1 ° C.); methanol (solubility: compatible with water in all proportions). , Boiling point: 64.7 ° C), ethanol (solubility: compatible with water in all proportions, boiling point: 78.3 ° C), isopropyl alcohol (solubility: compatible with water in all proportions, boiling point: 82 And 26.degree. C.); esters such as methyl acetate (solubility: 24% by weight, boiling point: 56.9.degree. C.). These organic solvents (S1) may be used alone or as a mixture of two or more. Preferred as the organic solvent (S1) are ketones and alcohols, more preferred are acetone and isopropyl alcohol, and most preferred is acetone.
[0050]
The amount of the organic solvent (S) used depends on the particle size of the resin fine particles in the aqueous dispersion of the target polyester resin fine particles. However, in the first step, the polyester resin (P) can sufficiently use the organic solvent (S). To be swollen into a paste-like swollen body which is easy to disperse in the form of fine particles, that the swollen body is easily dispersed in an aqueous medium in the second step, and that the dispersion is completed. Since the amount of the aqueous medium to be used can be suppressed, and the content of the organic solvent in the aqueous dispersion of the fine polyester resin particles is not increased and the production efficiency is improved, the amount is 5 to 100 parts by weight of the polyester resin (P). It is preferably 300 parts by weight, more preferably 10 to 200 parts by weight, most preferably 20 to 150 parts by weight.
[0051]
Further, the amount of water used is preferably 70 to 400 parts by weight, more preferably 100 to 250 parts by weight, based on 100 parts by weight of the total of the polyester resin (P) and the organic solvent (S).
[0052]
Examples of the basic compound used for neutralizing a part or all of the carboxyl group in the polyester resin (P) include alkali compounds such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium, potassium, and lithium. Carbonates of alkali metals such as the above; acetates of the above alkali metals; aqueous ammonia; alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine; and alkanolamines such as diethanolamine. Among them, aqueous ammonia is preferable.
[0053]
The amount of the basic compound to be used is preferably 0.9 to 5.0 times the equivalent of the carboxyl group in the polyester resin (P), and more preferably 1.0 to 3.0 times. More preferably, the amount is equivalent.
[0054]
The method for producing the swelled body in the first step of the production method of the present invention is not particularly limited, but the swelled body can be obtained in a short time, and then the swelled body is introduced into the aqueous medium in the second step. It is preferable to produce the swelled body by heating the polyester resin (P) and the organic solvent (S) together, since the dispersion is also facilitated. More preferred. At this time, the heating temperature of the polyester resin (P) and the organic solvent (S) is preferably equal to or higher than the boiling point of the organic solvent (S), more preferably the boiling point of the organic solvent (S) to 180 ° C. The boiling point of the organic solvent (S) + 10 ° C to 120 ° C is particularly preferred. Further, the pressurizing pressure in this system is preferably 0.1 to 2.0 MPa in gauge pressure, more preferably 0.2 to 1.5 MPa in gauge pressure, and still more preferably 0.3 to 1 in gauge pressure. 0.0 MPa. As a method for pressurizing the inside of the system, for example, a method of evaporating the organic solvent (S) by heating to obtain the above-mentioned swollen body and pressurizing the inside of the system, or a method of introducing an inert gas into the system in advance and pre-pressurizing the system. After the pressure is applied, heating may be performed to further pressurize by evaporating the organic solvent (S). The aqueous dispersion of polyester resin fine particles having a narrow particle size distribution can be suppressed while the reflux and boiling of the organic solvent (S) can be suppressed. The method of pre-pressurizing is preferable because it can obtain. The pre-pressurization is preferably 0.05 to 0.5 MPa.
[0055]
After obtaining the swelled body in the first step, the swelled body obtained in the second step is mixed in an aqueous medium containing a basic compound to form a part or all of the carboxyl groups in the polyester resin (P). The method for producing an initial aqueous dispersion by performing neutralization with a basic compound and dispersing the swollen body in the form of fine particles in an aqueous medium is not particularly limited. In the first step, the swelled body obtained by heating the organic solvent (S) to a temperature equal to or higher than the boiling point of the organic solvent (S) in the first step is used, and the swelled body is subjected to the organic treatment under pressure. It is preferable to disperse the fine particles in the aqueous medium containing the basic compound by a mechanical shearing force at a temperature not lower than the boiling point of the solvent (S) and not higher than 120 ° C. to obtain an initial aqueous dispersion. The temperature of the system at this time is preferably from the boiling point of the organic solvent (S) to 180 ° C., particularly preferably from the boiling point of the organic solvent (S) + 10 ° C. to 120 ° C. Further, the pressure of this system is preferably 0.1 to 2.0 MPa in gauge pressure, more preferably 0.2 to 1.5 MPa in gauge pressure, and still more preferably 0.3 to 1.0 MPa in gauge pressure. is there. When the preparation of the swelling body and the preparation of the dispersion are performed in the same container, the heating and pressurizing conditions of the system at the start of the preparation of the dispersion are the same as the temperature and pressure at the end of the preparation of the swelling body. Preferably, there is. The temperature of the aqueous medium containing a basic compound used here is preferably from the boiling point of the organic solvent (S) to 120 ° C., and more preferably from the boiling point of the organic solvent (S) to less than 100 ° C. Further, it is more preferable that the temperature be in the range of −20 ° C. of the system at the start of the second step to the temperature of the system at the start of the second step.
[0056]
Furthermore, the temperature at the time of producing the swollen body in the first step and the temperature at the time of producing the initial aqueous dispersion in the second step are both lower than the melting point and softening point of the polyester resin (P). It is preferable that the temperature is not higher than the glass transition temperature (Tg) of the polyester resin (P), but is preferably not lower than the boiling point of the organic solvent (S) and the glass transition temperature (Tg). The temperature is preferably 10 to 50 ° C. higher than Tg). In addition, the temperature at the time of producing the swollen body in the first step and the temperature at the time of producing the initial aqueous dispersion in the second step may be the same or different.
[0057]
As a method for producing the aqueous dispersion of polyester resin fine particles of the present invention, for example, the following methods (1) to (3) are mentioned as typical production methods.
{Circle around (1)} As a first step, a polyester resin (P) and an organic solvent (S) are charged into a closed container, and the polyester resin (P) is mixed with the organic solvent (S) under heating, preferably under heat and pressure, with stirring. After swelling to produce a swelled body, as a second step, the obtained swelled body is mixed with an aqueous medium containing a basic compound, and is preferably heated and heated by mechanical shearing force such as stirring. Under pressure, disperse in the form of fine particles in an aqueous medium containing a basic compound to obtain an initial aqueous dispersion, and then, as a third step, removing the organic solvent (S) from the obtained initial aqueous dispersion. To produce a dispersion in which the fine particles of the polyester resin (P) are dispersed in an aqueous medium.
[0058]
(2) After obtaining the swelled body in the same manner as in the first step of (1), as a second step, the obtained swelled body and an aqueous medium containing a basic compound are continuously fed to a continuous emulsifying and dispersing machine. Neutralization of the polyester resin (P) in the swelling body with some or all of the basic compounds while supplying the swelling body, and the swelling body in the form of fine particles in the aqueous medium by mechanical shearing force due to mechanical shearing force. And dispersing the mixture to form an initial aqueous dispersion. Then, as a third step, the organic solvent (S) is removed from the obtained initial aqueous dispersion, whereby the fine particles of the polyester resin (P) are dispersed in an aqueous medium. A method for producing a dispersed dispersion.
[0059]
(3) In the first step, the organic solvent (S) is injected into the polyester resin (P) melted by a melt kneader such as an extruder or the synthesized polyester resin (P) by a method such as press-fitting. A swelled body is manufactured by swelling the polyester resin (P) with an organic solvent (S) under continuous supply and mixing, and the obtained swelled body has a melting point or a softening point lower than the melting point or softening point of the polyester resin (P). After the temperature has been lowered to a temperature, as a second step, the polyester resin (P) in the swelled body is continuously supplied to the continuous emulsifying and dispersing machine while continuously supplying the obtained swelled body and the aqueous medium containing a basic compound. Neutralization of a part or all of the carboxyl groups with a basic compound and dispersion of the swollen body in the form of fine particles in the aqueous medium by mechanical shearing force to form an initial aqueous dispersion, and then the third step As Method for producing a dispersion in which fine particles are dispersed in an aqueous medium of the polyester resin (P) from the resulting initial aqueous dispersion by removing the organic solvent (S).
[0060]
Among these methods, the above method (1) or (2) is preferable because an aqueous dispersion of fine particles of polyester resin can be obtained relatively easily. The shape of the polyester resin (P) used in the above methods (1) and (2) is preferably in the form of particles because it can be formed into a swollen body in a relatively short time. Examples include a 7 mm pellet, a coarsely pulverized product passed through a screen having a pore size of 2 to 7 mm, and a powder having an average particle size of 800 μm or less.
[0061]
Hereinafter, more specific production examples of the method for producing an aqueous dispersion of polyester resin fine particles by the methods (1) and (2) will be described.
First, a glass 2L autoclave with propeller blades was used, and the particulate matter obtained by pulverizing the polyester resin (P) and the organic solvent (S) were charged into the autoclave, and an inert gas was introduced into the autoclave. Is pre-pressurized to 0.05 to 0.5 MPa, and then heated to a temperature equal to or higher than the boiling point of the organic solvent (S) under stirring at 10 to 300 rpm to partially vaporize the organic solvent (S). After the inside is pressurized to 0.1 to 2.0 MPa (gauge pressure), the mixture is stirred at 50 to 700 rpm for 3 to 60 minutes to swell the polyester resin (P) with the organic solvent (S) to obtain a swelled body ( First step).
[0062]
Examples of the inert gas used for the preliminary pressurization include a nitrogen gas, a helium gas, a neon gas, an argon gas and the like, and a nitrogen gas is preferable.
[0063]
The swelled body obtained in this step is a mixture of the polyester resin (P) that has absorbed the organic solvent (S) and the organic solvent (S) remaining without being absorbed by the polyester resin (P). Those which are observed as a transparent to cloudy glue-like mixture are preferred. For example, in a system using isopropyl alcohol as the organic solvent (S), when the stirring speed is reduced to about 50 rpm, it is observed that the isopropyl alcohol separates from the resin phase to form two phases, but this may be used. .
[0064]
After the swelled body is thus obtained, in the method (1), an aqueous medium containing a basic compound, for example, ammonia water, which has been heated in advance while stirring at 300 to 1500 rpm, is applied for 2 to 30 minutes. And pressurized and injected to cause phase inversion emulsification to obtain an initial aqueous dispersion in which the swelled body is dispersed in fine particles (second step). At this time, the organic solvent (S) in the swelled body undergoes local boiling and reflux, and molecules of the organic solvent (S) having low affinity with the polyester resin (P) are separated from the polyester resin (P). It is considered that an environment that facilitates phase inversion emulsification is formed.
[0065]
In the method (2), after the swelled body is obtained, a continuous emulsifying and dispersing machine, for example, a ring-shaped stator having a slit and a ring-shaped rotating member having a slit described in JP-A-9-311502 are disclosed. Using a high-speed rotation type continuous emulsifying disperser or the like provided coaxially with the particles, the swelled body is continuously dispersed in fine particles in an aqueous medium containing a basic compound to obtain an initial aqueous dispersion ( 2nd process). In this case, the swollen body and the aqueous medium may be fed to a continuous emulsifying and dispersing machine under predetermined temperature and pressure conditions, and the rotor may be rotated at 300 to 10,000 rpm.
[0066]
After obtaining a dispersion in which the swelled body is dispersed in the form of fine particles, the organic solvent (S) is removed from the obtained dispersion, whereby the polyester resin in which the fine particles of the polyester resin (P) are dispersed in an aqueous medium. An aqueous fine particle dispersion is obtained (third step). Examples of the method of removing the organic solvent (S) include a method of spraying into a decompression chamber, a method of forming a thin film on the inner surface of a desolvation can wall, and a method of passing through a desolvation can containing a filler for solvent absorption. No. As an example of a method for removing the organic solvent (S), a removal method using a rotary evaporator will be described below.
Sample volume: 500ml
Container: 2L eggplant type flask
Rotation speed: 60 rpm
Bath temperature; 47 ° C
Decompression degree: Increase the decompression degree from 13.3 KPa to 1.33 KPa over 20 minutes, and then remove the solvent at 1.33 KPa for 10 minutes.
[0067]
In addition, when the resin fine particles in the polyester resin fine particle aqueous dispersion are used as a powder coating or a hot melt adhesive, or when the generated particles are taken out as a powder such as a toner, the dispersion of the resin fine particles is dispersed. The removal of the organic solvent (S) is preferably performed immediately after the production of the dispersion. This is because if the dispersion is stored for a long time while the organic solvent (S) is contained, the resin fine particles in the dispersion tend to naturally aggregate.
[0068]
In the production method of the present invention, an aqueous medium of polyester resin fine particles having a very small amount of residual solvent can be prepared by using a carboxyl group-containing polyester resin containing no alkyl group and alkenyl group and the organic solvent (S). As compared with the above, the polyester resin fine particles in the aqueous dispersion contain irregular shaped particles and have a wide particle size distribution. Further, the storage stability is not sufficient, and the resin particles tend to increase with time.
[0069]
In the method for producing an aqueous dispersion of polyester resin fine particles of the present invention, the average particle diameter of the resin fine particles in the aqueous dispersion of polyester resin fine particles can be freely controlled within a range of about 0.01 to 50 μm by changing the production conditions in various ways. It is possible to do.
[0070]
In the method for producing an aqueous dispersion of polyester resin fine particles of the present invention, in order to control the average particle diameter of the resin fine particles in the obtained dispersion to be small, for example, the following means may be employed.
{Circle around (1)} Increase the concentration of hydrophilic segments such as carboxyl groups in the polyester resin (P).
{Circle around (2)} The amount of the basic compound used relative to the polyester resin (P) is increased.
{Circle around (3)} Increase the amount of the organic solvent (S) used relative to the polyester resin (P).
{Circle around (4)} Increase the temperature during dispersion production.
{Circle around (5)} Increase the stirring speed during dispersion production.
[0071]
Conversely, in the method for producing an aqueous dispersion of polyester resin fine particles of the present invention, in order to increase the average particle diameter of the resin fine particles in the obtained dispersion, these conditions may be reversed. The dispersion can also be obtained by using other components such as a colorant (C) such as carbon black, magnetic powder, wax, and a charge controlling agent together with the polyester resin (P) and the organic solvent (S). The average particle size of the resin fine particles therein becomes large.
[0072]
The resin fine particles in the aqueous dispersion of polyester resin fine particles obtained by the production method of the present invention are resin fine particles dispersed by controlling conditions such as temperature, pH, and electrolyte concentration of the obtained dispersion. Can be associated to grow into larger particles.
[0073]
The organic solvent (S) used in the present invention also plays a role as an adhesive between the resin fine particles in a later-described process of associating the resin fine particles in the dispersion. Usually, the solvent removal in the third step is performed after the completion of the association step. However, the solvent is once removed and stored before the association step, and the necessary amount of the same or similar organic solvent is used in the association step. After re-addition, association may be performed, and then solvent may be removed.
[0074]
Next, the electrophotographic toner of the present invention will be described.
The electrophotographic toner of the present invention is an electrophotographic toner containing fine particles obtained by separating fine particles of the polyester resin (P) from the dispersion obtained by the method for producing an aqueous dispersion of polyester resin fine particles of the present invention and drying the dispersion. (T1) an electrophotographic toner using the aqueous resin dispersion of polyester resin fine particles obtained by the method of the present invention as it is, separating the resin fine particles from the dispersion, and drying the resin fine particles. Alternatively, after obtaining an aqueous dispersion of polyester resin fine particles in which resin fine particles having a particle size smaller than the toner size are dispersed by the method of the present invention, a dispersion in which resin fine particles having a particle size smaller than the toner size, which is separately manufactured as required, is dispersed. Of the resulting dispersion, and by appropriately controlling the conditions such as temperature, pH, and electrolyte concentration of the obtained dispersion, the resin fine particles in the dispersion are associated with each other to form a toner particle. After the fine particles, the particles were separated, electrophotographic toner obtained by using the fine resin particles obtained by drying (T2), and the like. The electrophotographic toner of the present invention is preferably the electrophotographic toner (T2) because the image quality is improved.
[0075]
Examples of the electrophotographic toner of the present invention include, for example, the following toner (T1) as the electrophotographic toner (T1) and the following (2) to (4) as the electrophotographic toner (T2). Examples include toner.
[0076]
(1) In the method for producing an aqueous dispersion of fine polyester resin particles of the present invention, a colorant (C) is used together with the polyester resin (P) in the first step of swelling the polyester resin (P) with the organic solvent (S). Is obtained by obtaining a dispersion in which the colored resin fine particles obtained by the above are dispersed in an aqueous medium, separating the fine particles of the polyester resin (P) from the obtained dispersion, and using the fine particles obtained by drying. toner. In addition, additives such as wax, magnetic powder, charge control agent and the like can be used together with the coloring agent (C). In this case, the average particle size of the colored resin fine particles in the dispersion is preferably a toner size, for example, 1 to 10 μm.
[0077]
(2) After obtaining a dispersion in which the colored resin fine particles are dispersed in the aqueous medium in the same manner as in the above (1), the surface potential of the resin fine particles is reduced and dispersed by a method such as addition of a reverse neutralizing agent. Resin particles are associated with each other to form a dispersion of colored resin particles having a larger average particle diameter, and then the organic solvent (S) is removed. Electrophotographic toner. The removal of the organic solvent (S) may be performed before the association of the resin fine particles. Further, additives such as wax, magnetic powder, charge control agent and the like can be used together with the coloring agent (C). In this case, the average particle size of the colored resin fine particles in the dispersion before association is preferably 0.01 to 1 μm, and the average particle size of the colored resin fine particles after association is preferably the toner size.
[0078]
(3) After obtaining a dispersion in which the colored resin fine particles are dispersed in the aqueous medium in the same manner as in the above (1), the resin fine particles are associated with each other in the same manner as in the above (2) to have a larger average particle diameter. A dispersion of colored resin particles (core particles) is then mixed with an aqueous dispersion of resin fine particles for the shell layer, which is separately manufactured, and dispersed in the same manner as in (2) above. The resin fine particles for the shell layer are associated with each other to form a dispersion of colored resin particles having a core / shell structure. Then, the organic solvent (S) is removed, the fine particles are separated, and the fine particles obtained by drying are used. Electrophotographic toner. The removal of the organic solvent (S) may be performed before the association of the resin fine particles. In this case, the average particle size of the colored resin fine particles in the dispersion before association is preferably 0.01 to 1 μm, and the average particle size of the colored resin fine particles after completion of association is preferably the toner size.
[0079]
The resin fine particles for the shell layer used in the above (3) may be resin fine particles made of a polyester resin (P) having a Tg higher by 1 to 40 ° C. than the glass transition temperature (Tg) of the resin particles for the core, or charge control described later. When resin fine particles are prepared using an agent, resin fine particles prepared using a large amount of the charge control agent are preferable.
[0080]
(4) After swelling the polyester resin (P) with the organic solvent (S) to obtain a swelled body, the swelled body is dispersed in an aqueous medium in the form of fine particles to obtain a dispersion, and then the obtained dispersion is obtained. To obtain a dispersion in which the fine particles of the polyester resin (P) are dispersed in an aqueous medium by removing the organic solvent (S) from an aqueous dispersion of the colorant (C) or a separately prepared aqueous dispersion of the colorant (C). By mixing with the aqueous dispersion of the colored resin fine particles, reducing the surface potential of the resin fine particles by a method such as addition of a reverse neutralizing agent to associate the dispersed resin fine particles with the colorant particles or the colored resin fine particles, An electrophotographic toner comprising fine particles obtained by forming a dispersion of colored resin particles having a large average particle diameter, separating the fine particles, and then drying. In this case, an additive such as a wax, a magnetic powder, a charge control agent, and the like can be used in combination with the colorant (C), or an aqueous dispersion of resin fine particles containing the additive, the magnetic powder, the charge control agent, and the like. Can be used in combination. The removal of the organic solvent (S) may be performed after association of the resin fine particles with the colorant particles or the colored resin fine particles. The average particle size of the fine particles in each dispersion used here is preferably 0.01 to 1 μm, and the average particle size of the colored resin fine particles after association is preferably the toner size.
[0081]
As the aqueous dispersion of the colorant (C) manufactured separately or the aqueous dispersion of the colorant resin particles separately manufactured used in the above (4), the colorant (C) or the colorant resin fine particles are dispersed in an aqueous medium in the form of fine particles. There is no particular limitation as long as the colorant (C) is emulsified with a surfactant or the like, and the colorant (C) and the resin are heated and melted, and then dispersed. An aqueous dispersion obtained by dissolving an aqueous dispersion containing a coloring agent and a polyester resin having a colorant (C) dispersed therein in an organic solvent, and then adding water to carry out phase inversion emulsification. Aqueous dispersions obtained by using a colorant (C) in combination when the polyester resin (P) is swollen with an organic solvent (S) are exemplified. Among them, aqueous dispersions obtained by the production method of the present invention are exemplified. preferable. The concentration of the colorant (C) in these aqueous dispersions is preferably 5 to 10 times the colorant concentration of the target toner.
[0082]
Examples of the colorant (C) include carbon black, red iron oxide, navy blue, titanium oxide, nigrosine dye (CI No. 50415B), aniline blue (CI No. 50405), and calco oil blue (C). No. azoic Blue 3), chrome yellow (CI. No. 14090), ultramarine blue (CI. No. 77103), Dupont oil red (CI. No. 26105), quinoline yellow ( CI No. 47005), methylene blue chloride (CI. No. 52015), phthalocyanine blue (CI. No. 74160), malachite green oxalate (CI. No. 74160), malachite green oxa Rate (C.I. No. 42000), lamp black (C.I. No. 77266) and Rose Bengal (CI No. 45435).
[0083]
It is preferable to use the coloring agent (C) in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyester resin (P). These colorants can be used alone or in combination of two or more.
[0084]
The process and phenomenon referred to as “association” in the production method of the present invention will be described below.
Generally, the resin fine particles in the aqueous dispersion of polyester resin fine particles as obtained by the production method of the present invention are stably present in the aqueous medium without aggregating due to electrostatic repulsion derived from the surface charge, but at the same time, Attraction is exerted between resin particles by Van der Waals force. Therefore, if the surface charge of the resin particles is appropriately reduced by some action, the attractive force becomes larger than the electrostatic repulsion, and the resin fine particles start to aggregate to form a dispersion of the resin particles grown to a larger particle diameter. This is called a meeting in the present invention. The temperature of this association is preferably from the glass transition temperature (Tg) of the polyester resin (P) to the glass transition temperature + 50 ° C., and depends on the relationship with the boiling point of the organic solvent (S) present in the system during the association step. It is more preferable to heat under a pressure of 0.1 to 1.0 MPa (gauge pressure). The time required for the association is usually 2 to 12 hours, preferably 4 to 10 hours. The association is preferably performed under gentle stirring, for example, under stirring at a rotation speed of about 10 to 100 rpm with the anchor blade.
[0085]
Examples of a method for reducing or losing the surface charge of the resin particles include a method of adding an acid such as dilute hydrochloric acid, dilute sulfuric acid, acetic acid, formic acid, or carbonic acid as a so-called reverse neutralizer. At this time, metal salts such as sodium chloride, potassium chloride, aluminum sulfate, ferric sulfate, and calcium chloride, and metal complexes such as calcium, aluminum, magnesium, and iron may be added as needed. . In addition, a surfactant may be used, if necessary, for the purpose of dispersing the colorant or the like in the association step or controlling the progress of the association.
[0086]
Examples of the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and sodium alkyldiphenyldisulfonate; cationic surfactants such as trimethylstearylammonium chloride; and alkylphenoxypoly (ethyleneoxy). Examples include nonionic surfactants such as ethanol, which can be appropriately selected and used.
[0087]
The method for producing an electrophotographic toner of the present invention is particularly preferable for producing an electrophotographic toner having a particle size of 1 to 10 μm.
[0088]
According to the production method of the present invention, it is possible to produce an aqueous dispersion of polyester resin fine particles composed of spherical resin particles having no sharp cusp portion in the shape thereof, and an electrophotographic toner. Here, the term “spherical” refers to a wide concept including a true spherical shape, an elliptical shape, a distorted spherical shape (potato shape), and the like.
[0089]
In the method for producing an aqueous dispersion of polyester resin fine particles of the present invention and the toner for electrophotography of the present invention, additives such as magnetic powder and wax may be used as necessary. These are preferably kneaded with the polyester resin (P) in advance to form a kneaded material. These additives may be used alone or in combination of two or more.
[0090]
Examples of the magnetic powder include simple metals such as magnetite, ferrite, cobalt, iron and nickel, and alloys thereof.
[0091]
Waxes can be used as offset inhibitors for electrophotographic toners. Examples of the wax include, for example, synthetic waxes such as polypropylene wax, polyethylene wax, Fischer-Tropsch wax, stearylbisamide, and oxidized wax, and natural waxes such as carnauba wax and rice wax.
[0092]
When a charge control agent is used, a toner having good charge characteristics can be obtained. As the charge control agent, for example, positive charge of nigrosine-based electron donating dye, naphthenic acid, metal salt of higher fatty acid, alkoxylated amine, quaternary ammonium salt, alkylamide, metal complex, pigment, fluorinated activator, etc. Control agents, electron-accepting organic complexes, chlorinated paraffins, chlorinated polyesters, and negative charge control agents such as sulfonylamine of copper phthalocyanine, and the like.
[0093]
When using the charge control agent, it is preferable to dissolve the charge control agent in the organic solvent (S) before adding it to the polyester resin (P). When a toner composed of core particles and a shell layer is produced, if a charge control agent is used in producing the shell layer, a toner in which the charge control agent is disposed in the shell layer can be produced.
[0094]
In the present invention, the ratio of non-volatile content in the aqueous dispersion of polyester resin fine particles is determined by allowing the aqueous dispersion to stand in a vacuum drier at 100 ° C. and 0.1 KPa for 3 hours to change the weight of the aqueous dispersion. Asked from. The volume average particle diameter of the fine particles is 0.001-2 μm, the particle diameter is measured using MICROTRAC UPA150 manufactured by Leeds + Northrup, and the particle diameter of 1-40 μm is measured by Beckman Coulter Multisizer. TM 3 was used.
[0095]
Evaluation of the value of the particle size distribution of particles having a particle diameter of 0.001 to 2 μm is based on the particle diameter (D10) at which the volume becomes 10% when integrated from the smaller particle diameter using the MICROTRAC UPA150. The measurement was performed by measuring the particle diameter (D90) at which the volume becomes 90% when integrated from the smaller particle diameter side, and calculating the ratio (D90 / D10).
Evaluation of the value of the particle size distribution of particles having a particle diameter of 1 to 40 μm is based on the aforementioned Coulter Multisizer. TM 3, the particle diameter (D16) where the cumulative weight becomes 16% when integrated from the smaller particle diameter side, and the cumulative weight becomes 84% (D84) when integrated from the smaller particle diameter side And the square root of this ratio (D84 / D16) was determined. The smaller the value of the particle size distribution, the narrower the width of the particle size distribution.
[0096]
Further, the quantitative determination of the residual solvent in the aqueous dispersion of polyester resin fine particles was measured by gas chromatography under the following conditions.
Measuring machine: Shimadzu GC-17A
Column; ULBON HR-20M (PPG)
Column temperature: 80 to 150 ° C
Heating rate: 10 ° C / min
[0097]
【Example】
Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples. Parts and percentages in the examples are by weight unless otherwise specified.
[0098]
Synthesis Example 1 [Preparation of polyester resin (P)]
In a 3L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, a thermometer and a rectification tower, 324 parts of ethylene glycol, 545 parts of neopentyl glycol and 112 parts of trimethylolpropane were charged, and the temperature was raised to 140 ° C. Then, 2.4 parts of dibutyltin oxide were added, and after confirming that the inside of the system could be uniformly stirred, 1,808 parts of terephthalic acid was gradually added. Next, the temperature was raised to 195 ° C. over 3 hours while continuing the stirring, and then raised to 240 ° C. over 10 hours. The reaction was further continued at the same temperature for 5 hours. When the acid value reached 10.0 mgKOH / g, the temperature was lowered to 220 ° C., and then 100 parts of dodecenyl succinic anhydride was added, and the mixture was treated with dodecenyl succinic anhydride at the same temperature for 30 minutes. A ring-opening addition reaction with a hydroxyl group terminal of the polyester resin is carried out, the acid value is 16.0, the softening point is 113 ° C by the ring and ball method, the glass transition temperature (Tg) is 58 ° C by the differential scanning calorimetry (DSC) method, and the GPC A polyester resin having a number average molecular weight (Mn) of 3,500 and a weight average molecular weight (Mw) of 20,000 by a method was obtained. This is abbreviated as polyester resin (P-1).
[0099]
Synthesis Example 2 (same as above)
In a 3 L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, a thermometer and a rectification tower, 1,428 parts of an ethylene oxide adduct of bisphenol A (average number of moles added: 2.2) and 137 parts of cyclohexanedimethanol were added. Then, the temperature was raised to 140 ° C., and 1.4 parts of dibutyltin oxide was added. After confirming that the system was uniformly stirred, 936 parts of terephthalic acid were gradually added. Next, the temperature was raised to 220 ° C. over 3 hours while continuing the stirring, and then raised to 245 ° C. over 3 hours. The reaction was further continued at the same temperature for 8 hours. When the acid value reached 20.0, the temperature was lowered to 230 ° C., and 101 parts of Kadura-E10 (glycidyl ester of a branched fatty acid manufactured by Shell Chemical Company) was added. A ring-opening addition reaction between the epoxy group of Cadulla-E10 and the terminal carboxyl group of the polyester resin was carried out at the same temperature for 30 minutes, the acid value was 9.9, the softening point by the ring and ball method was 114 ° C., and the Tg by DSC was 63. A polyester resin having an Mn of 4,000 and a Mw of 16,000 as determined by a GPC method at ℃ was obtained. This is abbreviated as polyester resin (P-2).
[0100]
Synthesis Example 3 (Preparation of comparative polyester resin)
A 3L stainless steel flask equipped with a stirrer, a nitrogen gas inlet, a thermometer and a rectification tower was charged with 1698 parts of an ethylene oxide adduct of bisphenol A (average addition mole number: 2.2) and 163 parts of cyclohexanedimethanol. The temperature was raised to 140 ° C., and 1.4 parts of dibutyltin oxide was added. After confirming that the inside of the system could be uniformly stirred, 943 parts of terephthalic acid and 111 parts of isophthalic acid were gradually added. Next, the temperature was raised to 220 ° C. over 3 hours while continuing the stirring, and then raised to 245 ° C. over 3 hours. A polyester resin having an acid value of 16.0, a softening point of 115 ° C. by a ring and ball method, a Tg of 65 ° C. by a DSC, a Mn of 4,200, and a Mw of 18,000 by a GPC method is further reacted at the same temperature for 8 hours. Got. This is abbreviated as a comparative polyester resin (P′-1).
[0101]
Example 1
The determination of the solubility of the polyester resin (P-1) in acetone under the condition that the concentration of the resin is 10% was determined in accordance with 7.2.1-1.7.2.1.3 of ASTM D3132-84 (Reapproved 1996). When the determination was performed using the described determination method, it was "solution on the boundary line" in the determination category of the determination method.
[0102]
100 parts of the coarsely pulverized polyester resin (P-1) and 100 parts of acetone are charged into a 2 L glass autoclave with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and while rotating the propeller blade at 100 rpm. The system was heated to 90 ° C. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotational speed of the propeller blade was increased to 900 rpm, and acetone was absorbed into the coarsely pulverized product while stirring for 10 minutes to obtain a translucent paste-like swollen body. Thereafter, 400 parts of an aqueous medium preheated to 90 ° C., consisting of 2.9 parts of 25% aqueous ammonia and 397.1 parts of ion-exchanged water, is injected under pressure over 5 minutes to disperse the swelled material in water into fine particles. A milky initial aqueous dispersion was obtained. At this time, the neutralization ratio [the ratio of the number of moles of ammonia in the aqueous medium (Ma) to the number of moles of carboxyl groups in the polyester resin (P-1) (Mc) [(Ma) / (Mc)] is expressed as a percentage. Representation. The same applies hereinafter. ] Was 150 mol%. The obtained initial aqueous dispersion was cooled with water to 30 ° C. while stirring was taken out, and acetone was distilled off at 47 ° C. for 30 minutes using a rotary evaporator to obtain an aqueous dispersion 1 of polyester resin fine particles. .
[0103]
The non-volatile content, volume average particle size, particle size distribution, residual solvent amount of the obtained polyester resin fine particle aqueous dispersion 1 were measured, and a storage stability test was performed. The measurement of the nonvolatile content, the volume average particle size, the particle size distribution, and the amount of the residual solvent were measured by the above-described methods, and the storage stability test was performed according to the method described below. The results are shown in Table 1.
[0104]
Method of storage stability test: The polyester resin fine particle aqueous dispersion 1 was put in a container, sealed, stored at 25 ° C. for 6 months, and visually observed for properties, and evaluated as follows.
×: There is sediment at the bottom of the container.
：: A uniform dispersion, and no precipitate is observed at the bottom of the container.
[0105]
Example 2
When the solubility of the polyester resin (P-2) was determined in the same manner as in Example 1, the result was "solution on the boundary line" in the determination category.
[0106]
A polyester resin fine particle aqueous dispersion 2 was obtained in the same manner as in Example 1 except that 100 parts of the polyester resin (P-2) was used instead of 100 parts of the polyester resin (P-1). Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[0107]
Example 3
49 parts of polyester resin (P-1), 30 parts of legal 330 (carbon black manufactured by Cabot Corporation), 9 parts of Biscol 550P (polypropylene wax manufactured by Sanyo Chemical Co., Ltd.) and Bontron E-80 (Orient Chemical Industries, Ltd.) 12 parts of a charge control agent (manufactured by Co., Ltd.) were mixed, mixed with a Henschel mixer, and kneaded with a pressure kneader to prepare a kneaded material. 100 parts of the coarsely pulverized material of this kneaded material and 100 parts of acetone are charged into a 2 L autoclave equipped with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and the inside of the system is rotated at 90 rpm while rotating the propeller blade at 100 rpm. Heated to ° C. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotational speed of the propeller blade was increased to 900 rpm, and acetone was absorbed into the coarsely pulverized product while stirring for 10 minutes to obtain a black paste-like swollen product. Thereafter, 400 parts of an aqueous medium preheated to 90 ° C., consisting of 2.9 parts of 25% aqueous ammonia and 397.1 parts of ion-exchanged water, is injected under pressure over 5 minutes to disperse the swelled material in water into fine particles. A black initial aqueous dispersion was obtained. The neutralization ratio at this time was 150 mol%. The obtained initial aqueous dispersion was water-cooled to 30 ° C. while stirring and taken out, and acetone was distilled off at 47 ° C. for 30 minutes using a rotary evaporator to obtain an aqueous dispersion 3 of polyester resin fine particles. . Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[0108]
Example 4
100 parts of the polyester resin (P-1) and 100 parts of Regal R330 were mixed, mixed by a Henschel mixer, and melt-kneaded using a pressure kneader to prepare a kneaded product. 100 parts of the coarsely pulverized product of this kneaded material and 100 parts of acetone are charged into a 2 L autoclave equipped with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and the inside of the system is heated to 90 ° C. while rotating the propeller blade at 100 rpm. Heat until complete. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotational speed of the propeller blade was increased to 900 rpm, and acetone was absorbed into the coarsely pulverized product while stirring for 10 minutes to obtain a black paste-like swollen product. Thereafter, 405 parts of an aqueous medium preheated to 90 ° C. consisting of 5 parts of 25% ammonia water and 400 parts of ion-exchanged water was pressurized and injected over 5 minutes, and a black initial dispersion in which the swelled body was dispersed in water in the form of fine particles. An aqueous dispersion was obtained. The neutralization rate at this time was 259 mol%. The obtained initial aqueous dispersion was cooled with water to 30 ° C. while stirring was taken out, and acetone was distilled off at 47 ° C. for 30 minutes using a rotary evaporator to obtain an aqueous polyester resin fine particle dispersion 4. . Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[0109]
Example 5
An aqueous dispersion of polyester resin fine particles 5 was obtained in the same manner as in Example 4, except that 100 parts of Viscol 550P was used instead of 100 parts of Regal R330. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[0110]
Example 6
Aqueous dispersion 6 of polyester resin fine particles was obtained in the same manner as in Example 4 except that 100 parts of Bontron E-80 was used instead of 100 parts of Regal R330. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[0111]
Comparative Example 1
The solubility of the polyester resin (P'-1) was determined in the same manner as in Example 1 except that the concentration of the resin was changed from 10% to 15%, and tetrahydrofuran (THF) was used instead of acetone. As a result, the judgment category was "complete solution".
[0112]
100 parts of coarsely crushed polyester resin (P'-1) and 100 parts of THF are charged into a 2 L glass autoclave with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and while rotating the propeller blade at 100 rpm. The system was heated to 90 ° C. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotation speed of the propeller blade was increased to 900 rpm, and the mixture was stirred for 10 minutes to obtain a resin solution. Thereafter, 400 parts of an aqueous medium preheated to 90 ° C., consisting of 2.9 parts of 25% aqueous ammonia and 397.1 parts of ion-exchanged water, is injected under pressure over 5 minutes to disperse the polyester resin into fine particles in water. A milky initial aqueous dispersion was obtained. The neutralization ratio at this time was 150 mol%. The obtained initial aqueous dispersion was cooled with water to 30 ° C. while stirring was taken out, and THF was distilled off at 47 ° C. for 30 minutes using a rotary evaporator, and the aqueous dispersion of polyester resin fine particles for comparison 1 was removed. '. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.
[0113]
Comparative Example 2
49 parts of polyester resin (P'-1), 30 parts of legal 330, 9 parts of Biscol 550P and 12 parts of Bontron E-80 were mixed, mixed with a Henschel mixer, and kneaded with a pressure kneader. Was prepared. 100 parts of the coarsely pulverized product of this kneaded material and 100 parts of THF are charged into a 2 L autoclave equipped with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and the inside of the system is heated to 90 ° C. while rotating the propeller blade at 100 rpm. Until heated. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotation speed of the propeller blade was increased to 900 rpm, and the mixture was stirred for 10 minutes to obtain a resin solution. Thereafter, 400 parts of an aqueous medium preheated to 90 ° C., consisting of 2.9 parts of 25% aqueous ammonia and 397.1 parts of ion-exchanged water, are injected under pressure over 5 minutes, and the kneaded material is dispersed in water in the form of fine particles. A black initial aqueous dispersion was obtained. The neutralization ratio at this time was 150 mol%. The obtained initial aqueous dispersion was cooled with water to 30 ° C. while stirring, and was taken out. THF was distilled off at 47 ° C. for 30 minutes using a rotary evaporator to obtain a comparative polyester resin fine particle aqueous dispersion 2 for comparison. '. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.
[0114]
[Table 1]
[Table 2]
Example 7
A glass 2L autoclave equipped with anchor blades, a condenser, a nitrogen gas inlet, and a thermometer, 300 parts of an aqueous dispersion of polyester resin fine particles 1, 100 parts of an aqueous dispersion of polyester resin fine particles 3, and 40 parts of acetone And a mixture of 20 parts of a 1% diluted hydrochloric acid, 20 parts of a 1% aqueous solution of calcium chloride, and 20 parts of a 1% aqueous solution of sodium dodecylbenzenesulfonate was dropped over 30 minutes while rotating the anchor blade at 50 rpm at room temperature. Thereafter, the temperature in the system was raised to 80 ° C. over 1 hour, and the association was carried out at the same temperature for another 5 hours to obtain an aqueous dispersion of polyester resin fine particles containing spherical colored particles. Acetone was distilled off at 47 ° C. for 60 minutes using a rotary evaporator, and the dispersion was washed three times with ion-exchanged water, separated from water and dried to obtain polyester resin fine particles. When the residual solvent amount, volume average particle size and particle size distribution of the polyester resin particles were measured, the residual solvent amount was 20 ppm (detection limit) or less, the volume average particle size was 5.9 μm, and the particle size distribution was 1. It was 3. Toner 1 was prepared by mixing the polyester resin fine particles with 0.3% of Aerosil R-974 (silica manufactured by Nippon Aerosil) based on the weight of the resin fine particles using a Henschel mixer. An image obtained using this toner was evaluated by the following method. The results are shown in Table 3.
[0117]
Image evaluation method: 1 dot line solution when toner 1 was loaded in a commercially available full-color copying machine and an image of 1200 dpi was formed using an A4 color (No. 5-1) issued by the Institute of Electrophotography as a test chart. The image quality was evaluated according to the following judgment.
A: A complete 1 dot line is formed.
：: An almost complete 1 dot line is formed.
×: Incomplete 1 dot line is formed.
XX: 1 dot line is not formed.
[0118]
Example 8
An autoclave equipped with anchor wings and a condenser was charged with 280 parts of an aqueous dispersion of polyester resin fine particles 1, 456 parts of an aqueous dispersion of polyester resin fine particles, 40 parts of an aqueous dispersion of polyester resin fine particles 5 and 24 parts of an aqueous dispersion of polyester resin fine particles 624. A mixture of 20 parts of 1% diluted hydrochloric acid, 20 parts of 1% calcium chloride and 20 parts of a 1% aqueous solution of sodium dodecylbenzenesulfonate was dropped over 30 minutes while charging and rotating the anchor blade at 50 rpm. Thereafter, the temperature in the system was raised to 80 ° C. over 1 hour, and the association was carried out at the same temperature for another 5 hours to obtain an aqueous dispersion of polyester resin fine particles containing spherical colored particles. The dispersion was washed three times with ion-exchanged water, separated from water and dried to obtain polyester resin fine particles. When the residual solvent amount, volume average particle size and particle size distribution of the polyester resin particles were measured, the residual solvent amount was 20 ppm (detection limit) or less, the volume average particle size was 6.0 μm, and the particle size distribution was 2. It was one. Toner 2 was prepared by mixing the polyester resin fine particles with 0.3% of Aerosil R-974 (silica manufactured by Nippon Aerosil) based on the weight of the resin fine particles using a Henschel mixer. Evaluation was performed in the same manner as in Example 7, and the results are shown in Table 3.
[0119]
Example 9
To an autoclave equipped with anchor wings and a condenser, 280 parts of a polyester resin fine particle aqueous dispersion 1 and 5 parts of Regal R330 were added with 0.05 part of a surfactant and 10 parts of ion-exchanged water, and a colorant, Viscol 550P, homogenized and added thereto. A solution prepared by dissolving 2 parts of the emulsified emulsion in terms of solid content and 1.5 parts of T-77 (charge control agent manufactured by Hodogaya Chemical Industry Co., Ltd.) in 35 parts of acetone, and rotating the anchor blade at 50 rpm. While stirring, a mixture of 20 parts of 1% diluted hydrochloric acid, 20 parts of 1% calcium chloride, and 20 parts of 1% aqueous solution of sodium dodecylbenzenesulfonate was dropped over 30 minutes. Thereafter, the temperature in the system was raised to 80 ° C. over 1 hour, and the association was carried out at the same temperature for another 5 hours to obtain an aqueous dispersion of polyester resin fine particles containing spherical colored particles. Acetone was distilled off at 47 ° C. for 60 minutes using a rotary evaporator, and the dispersion was washed three times with ion-exchanged water, separated from water and dried to obtain polyester resin fine particles. When the residual solvent amount, volume average particle size, and particle size distribution of the polyester resin particles were measured, the residual solvent amount was 20 ppm (detection limit) or less, the volume average particle size was 6.1 μm, and the particle size distribution was 2. It was 3. Toner 3 was prepared by mixing the polyester resin fine particles, Aerosil R-974 (silica manufactured by Nippon Aerosil) of 0.3% by weight of the resin fine particles with a Henschel mixer. Evaluation was performed in the same manner as in Example 7, and the results are shown in Table 3.
[0120]
Comparative Example 3
Instead of using 300 parts of polyester resin fine particle aqueous dispersion 1 and 100 parts of polyester resin fine particle aqueous dispersion 3, 300 parts of comparative polyester resin fine particle aqueous dispersion 1 'and 300 parts of comparative polyester resin fine particle aqueous dispersion 2' 100 parts Polyester resin fine particles were obtained in the same manner as in Example 7 except for using. When the residual solvent amount, volume average particle size and particle size distribution of the polyester resin particles were measured, the residual solvent amount was 600 ppm, the volume average particle size was 6.5 μm, and the particle size distribution was 3.3. The polyester resin fine particles were mixed with Aerosil R-974 (silica manufactured by Nippon Aerosil Co., Ltd.) of 0.3% by weight of the resin fine particles using a Henschel mixer to prepare a comparative toner 1 '. Evaluation was performed in the same manner as in Example 7, and the results are shown in Table 3.
[0121]
Comparative Example 4
49 parts of polyester resin (P'-1), 30 parts of legal 330, 9 parts of Biscol 550P and 12 parts of Bontron E-80 were mixed, mixed with a Henschel mixer, and kneaded with a pressure kneader. Was prepared. 100 parts of the coarsely pulverized product of this kneaded material and 100 parts of THF are charged into a 2 L autoclave with a propeller blade, pre-pressurized to 0.2 MPa with nitrogen gas, and the inside of the system is heated to 90 ° C. while rotating the propeller blade at 100 rpm. Until heated. At this time, the pressure in the autoclave had increased to 0.45 MPa. After the temperature in the system reached 90 ° C., the rotation speed of the propeller blade was increased to 500 rpm, and the mixture was stirred for 10 minutes to obtain a resin solution. Thereafter, 400 parts of an aqueous medium preheated to 90 ° C., consisting of 1.4 parts of 25% aqueous ammonia and 398.6 parts of ion-exchanged water, is injected under pressure over 5 minutes to disperse the swollen body in water into fine particles. A black initial aqueous dispersion was obtained. The neutralization ratio at this time was 70 mol%. The obtained initial aqueous dispersion was cooled with water to 30 ° C. while stirring, taken out, and THF was distilled off at 47 ° C. for 30 minutes using a rotary evaporator, and the obtained dispersion was subjected to ion exchange. After repeating washing with water three times, the resultant was separated from water and dried to obtain polyester resin fine particles. When the residual solvent amount, volume average particle size, and particle size distribution of the polyester resin particles were measured, the residual solvent amount was 650 ppm, the volume average particle size was 6.6 μm, and the particle size distribution was 3.8. Comparative polyester toner 2 ′ and Aerosil R-974 (silica made by Nippon Aerosil Co., Ltd.) of 0.3% by weight of the resin microparticles were mixed with a Henschel mixer to prepare comparative toner 2 ′. Evaluation was performed in the same manner as in Example 7, and the results are shown in Table 3.
[0122]
[Table 3]
【The invention's effect】
The production method of the present invention provides an organic solvent (S) having a boiling point of less than 100 ° C., which does not dissolve but swells a polyester resin (P) containing an alkyl group and / or an alkenyl group and a carboxyl group as a polyester resin. Is an organic solvent that is compatible with water, and is absorbed into the polyester resin (P) with the organic solvent (S) to form a swelled body. Since the organic solvent is removed from the dispersion obtained after the dispersion, the organic solvent is easily removed, and an aqueous dispersion of thermoplastic resin fine particles with very little residual solvent remaining in the resin fine particles is obtained.
The use of the polyester resin containing the alkyl group and / or the alkenyl group and the carboxyl group makes the polyester resin fine particles in the aqueous dispersion of the polyester resin fine particles smaller than the case where the polyester resin containing no alkyl group and the alkenyl group is used. Is significantly improved, and the shape of the fine particles of the polyester resin is spherical with little irregularity.
The toner for electrophotography of the present invention containing fine particles obtained by separating and drying resin fine particles from the aqueous dispersion of polyester resin fine particles obtained by the production method of the present invention contains the alkyl group and / or alkenyl group and carboxyl group. Is a spherical toner with less irregularity and good durability and fluidity by using a polyester resin containing.
Further, the electrophotographic toner obtained by the production method of the present invention has an extremely small residual solvent.
Claims (13)
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204032A (en) * | 2002-12-25 | 2004-07-22 | Dainippon Ink & Chem Inc | Method for manufacturing aqueous dispersion of fine thermoplastic resin particle, and toner for electrophotography |
| JP2004204033A (en) * | 2002-12-25 | 2004-07-22 | Dainippon Ink & Chem Inc | Method for manufacturing aqueous dispersion of minute thermoplastic resin particle and toner for electrophotography |
| JP2006274138A (en) * | 2005-03-30 | 2006-10-12 | Toyobo Co Ltd | Aqueous dispersion of hyperbranched polyester |
| JP2007106906A (en) * | 2005-10-14 | 2007-04-26 | Kao Corp | Method for producing resin emulsion |
| JP2007178630A (en) * | 2005-12-27 | 2007-07-12 | Toyobo Co Ltd | Electrophotographic toner and method for manufacturing the same |
| JP2007241161A (en) * | 2006-03-13 | 2007-09-20 | Seiko Epson Corp | Method for manufacturing negative charging toner |
| JP2007241160A (en) * | 2006-03-13 | 2007-09-20 | Seiko Epson Corp | Method for manufacturing negative charging toner |
| JP2007322831A (en) * | 2006-06-01 | 2007-12-13 | Toyobo Co Ltd | Toner for electrostatic image developer and its manufacturing method |
| JP2008115333A (en) * | 2006-11-07 | 2008-05-22 | Kao Corp | Resin emulsion |
| WO2009041275A1 (en) | 2007-09-28 | 2009-04-02 | M.Technique Co., Ltd. | Method for production of aqueous resin microparticle dispersion, and aqueous resin microparticle dispersion and resin microparticle produced by the method |
| JP2009144156A (en) * | 2007-12-13 | 2009-07-02 | Xerox Corp | Method for producing emulsion containing curable polyester |
| JP2010059266A (en) * | 2008-09-02 | 2010-03-18 | Unitika Ltd | Method for producing aqueous dispersion of polyester resin |
| US7887983B2 (en) | 2004-09-09 | 2011-02-15 | Kao Corporation | Process for preparing toner for electrophotography |
| WO2012043510A1 (en) * | 2010-09-29 | 2012-04-05 | 東レ株式会社 | Aqueous dispersion of fine resin particles |
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| JPH05117402A (en) * | 1991-10-28 | 1993-05-14 | Minolta Camera Co Ltd | Production of fine polymer particle |
| JPH09296100A (en) * | 1996-03-08 | 1997-11-18 | Unitika Ltd | Aqueous polyester resin dispersion and production thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05117402A (en) * | 1991-10-28 | 1993-05-14 | Minolta Camera Co Ltd | Production of fine polymer particle |
| JPH09296100A (en) * | 1996-03-08 | 1997-11-18 | Unitika Ltd | Aqueous polyester resin dispersion and production thereof |
Cited By (20)
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| JP2004204033A (en) * | 2002-12-25 | 2004-07-22 | Dainippon Ink & Chem Inc | Method for manufacturing aqueous dispersion of minute thermoplastic resin particle and toner for electrophotography |
| JP2004204032A (en) * | 2002-12-25 | 2004-07-22 | Dainippon Ink & Chem Inc | Method for manufacturing aqueous dispersion of fine thermoplastic resin particle, and toner for electrophotography |
| US7887983B2 (en) | 2004-09-09 | 2011-02-15 | Kao Corporation | Process for preparing toner for electrophotography |
| JP2006274138A (en) * | 2005-03-30 | 2006-10-12 | Toyobo Co Ltd | Aqueous dispersion of hyperbranched polyester |
| US7811739B2 (en) * | 2005-10-14 | 2010-10-12 | Kao Corporation | Process for producing a resin emulsion and toner |
| JP2007106906A (en) * | 2005-10-14 | 2007-04-26 | Kao Corp | Method for producing resin emulsion |
| JP4634273B2 (en) * | 2005-10-14 | 2011-02-16 | 花王株式会社 | Method for producing resin emulsion |
| JP2007178630A (en) * | 2005-12-27 | 2007-07-12 | Toyobo Co Ltd | Electrophotographic toner and method for manufacturing the same |
| JP2007241161A (en) * | 2006-03-13 | 2007-09-20 | Seiko Epson Corp | Method for manufacturing negative charging toner |
| JP2007241160A (en) * | 2006-03-13 | 2007-09-20 | Seiko Epson Corp | Method for manufacturing negative charging toner |
| JP4662058B2 (en) * | 2006-03-13 | 2011-03-30 | セイコーエプソン株式会社 | Method for producing negatively chargeable toner |
| JP4716021B2 (en) * | 2006-03-13 | 2011-07-06 | セイコーエプソン株式会社 | Method for producing negatively chargeable toner |
| JP2007322831A (en) * | 2006-06-01 | 2007-12-13 | Toyobo Co Ltd | Toner for electrostatic image developer and its manufacturing method |
| JP2008115333A (en) * | 2006-11-07 | 2008-05-22 | Kao Corp | Resin emulsion |
| WO2009041275A1 (en) | 2007-09-28 | 2009-04-02 | M.Technique Co., Ltd. | Method for production of aqueous resin microparticle dispersion, and aqueous resin microparticle dispersion and resin microparticle produced by the method |
| EP2194087A1 (en) * | 2007-09-28 | 2010-06-09 | M Technique Co., Ltd. | Method for production of aqueous resin microparticle dispersion, and aqueous resin microparticle dispersion and resin microparticle produced by the method |
| EP2194087A4 (en) * | 2007-09-28 | 2012-11-07 | M Tech Co Ltd | Method for production of aqueous resin microparticle dispersion, and aqueous resin microparticle dispersion and resin microparticle produced by the method |
| JP2009144156A (en) * | 2007-12-13 | 2009-07-02 | Xerox Corp | Method for producing emulsion containing curable polyester |
| JP2010059266A (en) * | 2008-09-02 | 2010-03-18 | Unitika Ltd | Method for producing aqueous dispersion of polyester resin |
| WO2012043510A1 (en) * | 2010-09-29 | 2012-04-05 | 東レ株式会社 | Aqueous dispersion of fine resin particles |
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