JP3748505B2 - Toner production method - Google Patents

Description

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ₁及びＲ₂は炭素数が１〜４０の有機基を示し、且つＲ₁とＲ₂との炭素数差が１０以上である基を示し、ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）
【００３８】
【化２】

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ₁は炭素数が１〜４０の有機基を示し、ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）
【００３９】
【化３】

（式中、ａ及びｂは０〜３の整数を示し、ａ＋ｂは３以下であり、Ｒ₁及びＲ₂は炭素数が１〜４０の有機基を示し、且つＲ₁とＲ₂との炭素数差が１０以上である基を示し、Ｒ₃は炭素数が１以上の有機基を示し、ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０になることはない。）
【００４０】
本発明で好ましく用いられるエステルワックスは、硬度０．５〜５．０を有するものが好ましい。エステルワックスの硬度は、直径２０ｍｍφで厚さが５ｍｍの円筒形状のサンプルを作製した後、例えば島津製作所製ダイナミック超微小硬度計（ＤＵＨ−２００）を用いビッカース硬度を測定した値である。測定条件は、０．５ｇの荷重で負荷速度が９．６７ｍｍ／秒の条件で１０μｍ変位させた後１５秒間保持し、得られた打痕形状を測定しビッカース硬度を求める。硬度が０．５未満の低軟化点物質では定着器の圧力依存性及びプロセススピード依存性が大きくなり、耐高温オフセット効果の発現が不十分となりやすく、他方５．０を超える場合ではトナーの保存安定性に乏しく、離型剤自身の自己凝集力も小さいため同様に耐高温オフセットが不十分となりやすい。具体的化合物としては、下記化合物が挙げられる。
【００４１】
【化４】

【００４２】
近年フルカラー両面画像の必要性も増してきており、両面画像を形成せしめる際においては、最初に表面に形成された転写紙上のトナー像が次に裏面に画像を形成する時にも定着器の加熱部を再度通過する可能性があり、よりトナーの耐高温オフセット性を十分に考慮する必要がある。その為に本発明においては、多量の低軟化点物質の添加が望ましい。具体的には、低軟化点物質をトナー中に５〜４０質量％添加することが好ましい。５質量％未満の添加では、十分な耐高温オフセット性を示さず、更に両面画像の定着時において裏面の画像がオフセット現象を示す傾向がある。また４０質量％を超える場合は、造粒時にトナー粒子同士の合一が起きやすく、粒度分布の広いものが生成しやすく、本発明には不適当であった。
【００４３】
本発明のトナー粒子を製造する方法としては、特公昭３６−１０２３１号公報、特開昭５９−５３８５６号公報、特開昭５９−６１８４２号公報に述べられている懸濁重合方法を用いて直接トナーを生成する方法を用いトナーを製造することが可能である。
【００４４】
本発明においては、一旦得られた重合粒子に更に単量体を吸着せしめた後、重合開始剤を用い重合せしめる所謂シード重合方法も本発明に好適に利用することができる。
【００４５】
また、本発明において、定着性の観点から多量の低軟化点物質をトナーに含有せしめることを考えると、必然的に低軟化点物質を外殻樹脂中に内包化せしめる必要がある。低軟化点物質を内包化せしめる具体的方法としては、水系媒体中での材料の極性を主要単量体より低軟化点物質の方を小さく設定し、更に少量の極性の大きな樹脂又は単量体を添加せしめることで低軟化点物質を外殻樹脂で被覆した所謂コア−シェル構造を有するトナーを得ることができる。トナーの粒度分布制御や粒径の制御は、難水溶性の無機塩や保護コロイド作用をする分散安定剤の種類や添加量を変える方法や機械的装置条件、例えばローターの周速，パス回数，撹拌羽根形状等の撹拌条件や容器形状又は、水溶液中での固形分濃度等を制御することにより所定の本発明のトナーを得ることができる。
【００４６】
本発明においてトナーの断層面を測定する具体的方法としては、常温硬化性のエポキシ樹脂中にトナーを十分分散させた後、温度４０℃の雰囲気中で２日間硬化させ、得られた硬化物を四三酸化ルテニウム、必要により四三酸化オスミウムを併用し染色を施した後、ダイヤモンド歯を備えたミクロトームを用い薄片状のサンプルを切り出し透過電子顕微鏡（ＴＥＭ）を用いトナーの断層形態を測定した。本発明においては、用いる低軟化点物質と外殻を構成する樹脂との若干の結晶化度の違いを利用して材料間のコントラストを付けるため、四三酸化ルテニウム染色法を用いることが好ましい。
【００４７】
上記重合トナーに使用できる重合性単量体としては、スチレン，ｏ（ｍ−，ｐ−）−メチルスチレン，ｍ（ｐ−）−エチルスチレン等のスチレン系単量体；（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸プロピル，（メタ）アクリル酸ブチル，（メタ）アクリル酸オクチル，（メタ）アクリル酸ドデシル，（メタ）アクリル酸ステアリル，（メタ）アクリル酸ベヘニル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸ジメチルアミノエチル，（メタ）アクリル酸ジエチルアミノエチル等の（メタ）アクリル酸エステル系単量体；ブタジエン，イソプレン，シクロヘキセン，（メタ）アクリロニトリル，アクリル酸アミド等のビニル系単量体が好ましく用いられる。これらは、単独または一般的には出版物ポリマーハンドブック第２版ＩＩＩ−Ｐ１３９〜１９２（Ｊｏｈｎ Ｗｉｌｅｙ＆Ｓｏｎｓ社製）に記載の理論ガラス転移温度（Ｔｇ）が、４０〜７５℃を示すように単量体を適宜混合し用いられる。理論ガラス転移温度が４０℃未満の場合には、トナーの保存安定性や現像剤の耐久安定性の面から問題が生じ、一方７５℃を超える場合は定着点の上昇をもたらし、特にフルカラートナーの場合においては各色トナーの混色が不十分となり色再現性に乏しく、更にＯＨＰ画像の透明性を著しく低下させ高画質の面から好ましくない。
【００４８】
本発明において、外殻樹脂中に低軟化点物質を内包化せしめる場合、外殻樹脂の他に更に極性樹脂を添加せしめることが特に好ましい。本発明に用いられる極性樹脂としては、スチレンと（メタ）アクリル酸の共重合体，マレイン酸共重合体，飽和ポリエステル樹脂，エポキシ樹脂が好ましく用いられる。該極性樹脂は、外殻樹脂又は単量体と反応しうる不飽和基を分子中に含まないものが特に好ましい。不飽和基を有する極性樹脂を含む場合においては、外殻樹脂層を形成する単量体と架橋反応が起きフルカラー用トナーとしては、極めて高分子量になり四色トナーの混色には不利となり好ましくない。
【００４９】
本発明に用いられる着色剤は、黒色着色剤としてカーボンブラック，磁性体，以下に示すイエロー／マゼンタ／シアン着色剤を用い黒色に調色されたものが利用される。
【００５０】
イエロー着色剤としては、縮合アゾ化合物，イソインドリノン化合物，アンスラキノン化合物，アゾ金属錯体，メチン化合物，アリルアミド化合物に代表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントイエロー１２、１３、１４、１５、１７、６２、７４、８３、９３、９４、９５、１０９、１１０、１１１、１２８、１２９、１４７、１６８等が好適に用いられる。
【００５１】
マゼンタ着色剤としては、縮合アゾ化合物，ジケトピロロピロール化合物，アンスラキノン，キナクリドン化合物，塩基染料レーキ化合物，ナフトール化合物，ベンズイミダゾロン化合物，チオインジゴ化合物，ペリレン化合物が用いられる。具体的には、Ｃ．Ｉ．ピグメントレッド２、３、５、６、７、２３、４８：２、４８：３、４８：４、５７：１、８１：１、１２２、１４４、１４６、１６６、１６９、１７７、１８４、１８５、２０２、２０６、２２０、２２１、２５４が特に好ましい。
【００５２】
シアン着色剤としては、銅フタロシアニン化合物及びその誘導体，アンスラキノン化合物，塩基染料レーキ化合物等が利用できる。具体的には、Ｃ．Ｉ．ピグメントブルー１、７、１５、１５：１、１５：２、１５：３、１５：４、６０、６２、６６等が特に好適に利用できる。
【００５３】
これらの着色剤は、単独又は混合し更には固溶体の状態で用いることができる。本発明の着色剤は、色相角，彩度，明度，耐候性，ＯＨＰ透明性，トナー中への分散性の点から選択される。該着色剤の添加量は、樹脂１００質量部に対し１〜２０質量部添加して用いられる。
【００５４】
黒色着色剤として磁性体を用いた場合には、他の着色剤と異なり、樹脂１００質量部に対し４０〜１５０質量部添加して用いられる。
【００５５】
本発明に用いられる荷電制御剤としては、公知のものが利用できるが、フルカラー画像用のトナーに用いる荷電制御剤としては、カルボキシル基を含有する化合物が良く、重合トナーの場合、重合性単量体中に分散させて用いられる。色の影響を考慮すると、無色または、白色または淡色の結晶状態のものが好ましく、特に、アルキルサリチル酸の金属化合物がカラートナー用として好ましく、金属化合物としては、金属錯体または、金属錯塩または、金属錯体と金属錯塩の混合物が挙げられ、低結晶性又は非結晶性のものが好ましく用いられる。
【００５６】
本発明に係る重合トナーに使用できる重合開始剤としては、例えば、２，２’−アゾビス−（２，４−ジメチルバレロニトリル）、２，２’−アゾビスイソブチロニトリル、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス−４−メトキシ−２，４−ジメチルバレロニトリル、アゾビスイソブチロニトリル等のアゾ系又はジアゾ系重合開始剤；ベンゾイルペルオキシド、メチルエチルケトンペルオキシド、ジイソプロピルペルオキシカーボネート、クメンヒドロペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルペルオキシド等の過酸化物系重合開始剤が用いられる。該重合開始剤の添加量は、目的とする重合度により変化するが一般的には単量体に対し０．５〜２０質量％添加され用いられる。重合開始剤の種類は、重合方法により若干異なるが、１０時間半減期温度を参考に、単独又は混合し利用される。
【００５７】
重合度を制御するため公知の架橋剤，連鎖移動剤，重合禁止剤等を更に添加し用いることも可能である。
【００５８】
また、外添剤が添加され、乾燥されたトナー粒子は、更に機械的衝撃力を付与し、トナー粒子への外添剤の付着状態を調整することが好ましい。即ち、ヘンシェルミキサーの如き乾式混合機により、機械的衝撃力を付与してトナー粒子への外添剤の付着状態を調整することが好ましい。より具体的には、ヘンシェルミキサーの高速回転羽根の周速及び処理時間を調整して、トナー粒子への外添剤の付着状態を調整する。
【００５９】
またこのとき、必要に応じ、帯電性付与剤、研磨剤等の他の外添剤を加え、同時に処理することが好ましい。
【００６０】
【実施例】
以下、本発明の実施例及び比較例を挙げて本発明を更に具体的に説明する。
【００６１】
用いた各水のアルカリ金属及びアルカリ土類金属イオン（Ｎａ⁺，Ｋ⁺，Ｍｇ²⁺及びＣａ²⁺）含有量を表１に示す。
【００６２】
【表１】

【００６３】
＜実施例１＞
まず、イオン交換水（水Ａ）７１０質量部に０．１モル／リットル−Ｎａ₃ＰＯ₄（米山化学社製）水溶液４５０質量部を投入し６０℃に加温した後、クリアミキサー（エム・テクニック社製）を用いて３，５００回転／分にて撹拌した。これに１．０モル／リットル−ＣａＣｌ₂水溶液６８質量部を添加し、Ｃａ₃（ＰＯ₄）₂を含むｐＨ６．０のりん酸とカルシウムの化合物の水系媒体を得た。
【００６４】
一方、分散質としては、まず、下記処方のうち、Ｃ．Ｉ．ピグメントブルー１５：３、ジアルキルサリチル酸アルミニウム化合物とスチレン単量体１００質量部をアトライター（三井三池化工機製）を用い３時間分散し、着色剤分散液を得た。次に、着色剤分散液に下記処方の残りすべてを添加し、６０℃に加温し３０分間溶解混合した。これに、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）８質量部を溶解し、重合性単量体組成物を調製した。
・スチレン単量体 １６５質量部
・ｎ−ブチルアクリレート ３５質量部
・Ｃ．Ｉ．ピグメントブルー１５：３ １０質量部
・飽和ポリエステル １０質量部
・ジアルキルサリチル酸アルミニウム化合物 ２質量部
・化合物（１）のワックス ２５質量部
（ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）
【００６５】
上記重合性単量体組成物を前記水系分散媒中に投入し、回転数を維持しつつ１５分間造粒した。その後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変え、内温を６０℃に昇温させ５０回転／分で重合を５時間継続させた後、内温を８０℃に昇温させ８時間重合を継続させた。重合終了後、スラリーを３０℃まで冷却した。
【００６６】
着色重合体粒子スラリーを洗浄容器に移し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐＨ１．５で２時間撹拌し、Ｃａ₃（ＰＯ₄）₂を含むりん酸とカルシウムの化合物を溶解させた後、加圧ろ過方式の装置ＫＦフィルター（三進製作所製）で固液分離を行った。
【００６７】
次に、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の４倍量注水した。この時点での排水中の分散安定剤由来の金属イオンの濃度は、０．１ｍｇ／リットル未満であった（Ｎａ⁺＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ²⁺＝０．０ｍｇ／リットル）。その後、水Ｃを、導入したスラリー量の０．２倍量注水した。さらに脱水した後、解砕し、乾燥を行った。
【００６８】
乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度を以下のようにして求めた。着色重合体粒子１．０ｇを０．１規定の水酸化ナトリウム水溶液５０ｇ中に投入し、３時間撹拌させた後、ろ過によって得られた濾液を吸光度測定法により所定の検量線を用い測定した。その結果、１５００ｐｐｍであった。
【００６９】
また、着色重合体粒子の重量平均粒径は６．９μｍであった。
【００７０】
得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００７１】
また、他に、得られた着色重合体粒子を３０℃／８０％ＲＨの環境下に２日間放置した後、上記と同様に、平均粒径０．０３μｍの疎水性シリカと平均粒径０．０５μｍの酸化チタンを添加してヘンシェルミキサーで混合しトナーとした。
【００７２】
これらいずれのトナーに、トナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。
【００７３】
これらの現像剤を用いて、キヤノン製カラー複写機ＣＬＣ５００改造機を用いて２３℃／６５％ＲＨの環境下で画出し試験を行ったところ、いずれも、１万枚耐久においても、初期と耐久後の画像濃度に変化がなく、中抜けのない高画質の画が得られた。また、有機半導体である感光体に、トナー融着やメモリーゴーストのような問題を生じなかった。さらに両面画像を形成させたが、転写材の表裏面共にオフセットの発生は認められなかった。
【００７４】
また、下記の方法により求めた転写効率は、いずれも９８％であった。
【００７５】
［転写効率］
１０ｃｍ²のベタ画像を感光体上に形成し、感光体上のトナーの量（Ｗ１）と、転写後の紙上のトナーの量（Ｗ２）を用い、両者の比：Ｗ２／Ｗ１×１００（％）より算出した。
【００７６】
また、３０℃／８０％ＲＨの環境下で同様な画出し試験を行ったところ、同様な結果が得られた。
【００７７】
＜実施例２＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の４倍量注水した後、水Ｄを、導入したスラリー量の０．３倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は１５５０ｐｐｍであった。
【００７８】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００７９】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。
【００８０】
＜比較例１＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の４．５倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１５００ｐｐｍであった。
【００８１】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００８２】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、２３℃／６５％ＲＨの環境下では、実施例１と同様に良好な画像が得られたが、３０℃／８０％ＲＨの環境下では、次第に画像濃度が低くなり、カブリが顕著になった。また、３０℃／８０％ＲＨの環境下に２日間放置した後に、トナーとしたものは、初期より画像濃度が低く、カブリがみられた。
【００８３】
＜比較例２＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｃを、導入したスラリー量の４倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、７００ｐｐｍであった。
【００８４】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００８５】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。
【００８６】
さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様な画像濃度の画像は得られたが、初期より、カブリが多く、また現像器からの現像剤の飛散が激しい。
【００８７】
＜実施例３＞
酸洗浄後の固液分離をフィルタープレス（則武鉄工所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した（この時点での排水中の分散安定剤由来の金属イオンの濃度は、０．１ｍｇ／リットル未満であった（Ｎａ⁺＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ²⁺＝０．０ｍｇ／リットル））後、水Ｄを、導入したスラリー量の０．２倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１８００ｐｐｍであった。
【００８８】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００８９】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。
【００９０】
＜実施例４＞
酸洗浄後の固液分離をフィルタープレス（則武鉄工所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｅを、導入したスラリー量の０．３倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び、分解物の濃度は、１７８０ｐｐｍであった。
【００９１】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００９２】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。
【００９３】
＜参考例１＞
酸洗浄後の固液分離をフィルタープレス（則武鉄工所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｆを、導入したスラリー量の１．０倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１８１０ｐｐｍであった。
【００９４】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００９５】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、３０℃／８０％ＲＨの環境下に２日間放置した後にトナーとしたものは、若干カブリがあるものの、実施例１と同様に良好な画像が得られた。
【００９６】
＜参考例２＞
酸洗浄後の固液分離をフィルタープレス（則武鉄工所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｇを、導入したスラリー量の１．０倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１８２０ｐｐｍであった。
【００９７】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【００９８】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、３０℃／８０％ＲＨの環境下に２日間放置した後にトナーとしたものは、若干のカブリがあり、現像器からの現像剤の飛散がわずかにみられるものの、実施例１と同様に良好な画像が得られた。
【００９９】
＜比較例３＞
酸洗浄後の固液分離をフィルタープレス（則武鉄鋼所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ａを、導入したスラリー量の５倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１８００ｐｐｍであった。
【０１００】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．８質量部と平均粒径０．０５μｍの酸化チタン０．３質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１０１】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、２３℃／６５％ＲＨの環境下では、実施例１と同様に良好な画像が得られたが、３０℃／８０％ＲＨの環境下では、次第に画像濃度が低くなり、カブリが顕著になった。また、３０℃／８０％ＲＨの環境下に２日間放置した後に、トナーとしたものは、初期より画像濃度が低く、カブリがみられた。
【０１０２】
＜比較例４＞
酸洗浄後の固液分離を加圧ろ過方式の装置ＫＦフィルターで行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｄを、導入したスラリー量の５倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１２００ｐｐｍであった。
【０１０３】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．８質量部と平均粒径０．０５μｍの酸化チタン０．３質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１０４】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様な画像濃度の画像は得られたが、初期より、カブリが多く、また現像器からの現像剤の飛散が激しい。
【０１０５】
＜比較例５＞
酸洗浄後の固液分離をフィルタープレス（則武鉄工所製）で行い、フィルタープレス中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｄを、導入したスラリー量の３倍量注水した以外は実施例１と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１４５０ｐｐｍであった。
【０１０６】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．８質量部と平均粒径０．０５μｍの酸化チタン０．３質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１０７】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、初期は実施例１と同様な画像が得られたが、次第にカブリが多くなり、また現像器からの現像剤の飛散が目立つようになった。
【０１０８】
上記実施例１〜４，参考例１及び２並びに比較例１〜５の結果を表２にまとめて示す。
【０１０９】
【表２】

【０１１０】
＜実施例５＞
まず、イオン交換水（水Ａ）７１０質量部に０．１モル／リットル−Ｎａ₃ＰＯ₄（ラサ工業社製）水溶液４５０質量部を投入し６０℃に加温した後、クリアミキサーを用いて３，５００回転／分にて撹拌した。これに１．０モル／リットル−ＣａＣｌ₂水溶液６８質量部を添加し、Ｃａ₃（ＰＯ₄）₂を含むｐＨ５．８のりん酸とカルシウムの化合物の水系媒体を得た。
【０１１１】
一方、分散質としては、まず、下記処方のうち、ピグメントレッド顔料、ジアルキルサリチル酸アルミニウム化合物とスチレン単量体１００質量部をアトライター（三井三池化工機製）を用い３時間分散し、着色剤分散液を得た。次に、着色剤分散液に下記処方の残りすべてを添加し、６０℃に加温し３０分間溶解混合した。これに、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）８質量部を溶解し、重合性単量体組成物を調製した。
・スチレン単量体 １６５質量部
・ｎ−ブチルアクリレート ３５質量部
・ピグメントレッド１２２ ２０質量部
・飽和ポリエステル ２０質量部
・ジアルキルサリチル酸アルミニウム化合物 ２質量部
・化合物（１）のワックス ２５質量部
（ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）
【０１１２】
上記重合性単量体組成物を前記水系分散媒中に投入し、回転数を維持しつつ１５分間造粒した。その後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変え、内温を６０℃に昇温させ５０回転／分で重合を５時間継続させた後、内温を８０℃に昇温させ１０時間重合を継続させた。重合終了後、スラリーを３０℃まで冷却した。
【０１１３】
着色重合体粒子スラリーを洗浄容器に移し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐＨ１．８で、２時間撹拌し、Ｃａ₃（ＰＯ₄）₂を含むりん酸とカルシウムの化合物を溶解させた後、加圧ろ過方式の装置ＫＦフィルター（三進製作所製）で固液分離を行った。
【０１１４】
次に、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した。この時点での排水中の分散安定剤由来の金属イオンの濃度は、０．１ｍｇ／リットル未満であった（Ｎａ⁺＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ²⁺＝０．０ｍｇ／リットル）。その後、水Ｈを、導入したスラリー量の０．４倍量注水した。さらに脱水した後、解砕し、乾燥を行った。
【０１１５】
乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１７２０ｐｐｍであった。
【０１１６】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１１７】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例１と同様に良好な画像が得られた。
【０１１８】
＜実施例６＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｉを、導入したスラリー量の０．４倍量注水した以外は実施例５と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は１６７０ｐｐｍであった。
【０１１９】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１２０】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、実施例５と同様に良好な画像が得られた。
【０１２１】
＜参考例３＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｊを、導入したスラリー量の１．０倍量注水した以外は実施例５と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は１７４０ｐｐｍであった。
【０１２２】
実施例１と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．７質量部と平均粒径０．０５μｍの酸化チタン０．７質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１２３】
これらのトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、３０℃／８０％ＲＨの環境下に２日間放置した後にトナーとしたものは、若干カブリがあり、若干現像器からの現像剤の飛散があるものの、実施例５と同様な画像が得られた。
【０１２４】
＜比較例６＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｋを、導入したスラリー量の０．４倍量注水した以外は実施例５と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１５３０ｐｐｍであった。
【０１２５】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．８質量部と平均粒径０．０５μｍの酸化チタン０．３質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１２６】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、初期は、実施例５と同様な画像が得られたが、次第にカブリが多くなり、また現像器からの現像剤の飛散が目立つようになった。
【０１２７】
＜比較例７＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量注水した後、水Ｌを、導入したスラリー量の０．４倍量注水した以外は実施例５と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１０２０ｐｐｍであった。
【０１２８】
実施例１と同様に、得られた着色重合体粒子１００質量部に対し、平均粒径０．０３μｍの疎水性シリカ０．８質量部と平均粒径０．０５μｍの酸化チタン０．３質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１２９】
このトナー５質量部に対し、磁性体分散型樹脂キャリア９５質量部を混合し、現像剤とした。さらに、この現像剤を用いて、実施例１と同様の画出し評価を行ったところ、カブリが多く、また現像器からの現像剤の飛散が目立った。
【０１３０】
上記実施例５及び６、参考例３並びに比較例６〜７の結果を表３にまとめて示す。
【０１３１】
【表３】

【０１３２】
＜実施例７＞
まず、イオン交換水（水Ａ）７１０質量部に０．１モル／リットル−Ｎａ₃ＰＯ₄（ラサ工業社製）水溶液４５０質量部を投入し６０℃に加温した後、クリアミキサーを用いて３，５００回転／分にて撹拌した。これに１．０モル／リットル−ＣａＣｌ₂水溶液６８質量部を添加し、Ｃａ₃（ＰＯ₄）₂を含むｐＨ１０．５のりん酸とカルシウムの化合物の水系媒体を得た。
【０１３３】
一方、分散質としては、まず、下記処方のうち、ピグメントイエロー顔料、結晶性ジアルキルサリチル酸の亜鉛錯体とスチレン単量体１００質量部をアトライター（三井三池化工機製）を用い３時間分散し、着色剤分散液を得た。次に、着色剤分散液に下記処方の残りすべてを添加し、６０℃に加温し３０分間溶解混合した。これに、重合開始剤である２，２’−アゾビス（２，４−ジメチルバレロニトリル）８質量部を溶解し、重合性単量体組成物を調製した。
・スチレン単量体 １６０質量部
・ｎ−ブチルアクリレート ４０質量部
・ピグメントイエロー９３ １５質量部
・飽和ポリエステル ２０質量部
・結晶性ジアルキルサリチル酸の亜鉛錯体 ３質量部
・化合物（１）のワックス ２５質量部
（ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）
【０１３４】
上記重合性単量体組成物を前記水系分散媒中に投入し、回転数を維持しつつ１５分間造粒した。その後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変え、内温を６０℃に昇温させ５０回転／分で重合を５時間継続させた後、内温を８０℃に昇温させ８時間重合を継続させた。重合終了後、スラリーを３０℃まで冷却した。
【０１３５】
着色重合体粒子スラリーを洗浄容器に移し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐＨ１．６で、２時間撹拌し、Ｃａ₃（ＰＯ₄）₂を含むりん酸とカルシウムの化合物を溶解させた後、加圧ろ過方式の装置ＫＦフィルター（三進製作所製）で固液分離を行った。
【０１３６】
次に、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の４倍量注水した。この時点での排水中の分散安定剤由来の金属イオンの濃度は、０．１ｍｇ／リットル未満であった（Ｎａ⁺＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ²⁺＝０．０ｍｇ／リットル）。その後、水Ｄを、導入したスラリー量の０．２倍量注水した。さらに脱水した後、解砕し、乾燥を行った。
【０１３７】
乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１６３０ｐｐｍであった。
【０１３８】
得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．００５μｍの疎水性シリカ１．５質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１３９】
このトナーを用いて、中間転写体を備えたキヤノン製カラーレーザージェットプリンターカラーレーザーショット−２０３０改造機を用いて２３℃／６５％ＲＨの環境下で画出し試験を行ったところ、５，０００枚耐久においても、初期と耐久後の画像濃度に変化がなく、中抜けのない高画質の画像が得られた。
【０１４０】
また、３０℃／８０％ＲＨの環境下で同様な画出し試験を行ったところ、同様な結果が得られた。
【０１４１】
＜比較例８＞
酸洗浄後、ＫＦフィルター中に残った着色重合体粒子ケーキに、水Ｂを、導入したスラリー量の４．５倍量注水した以外は実施例７と同様に行った。乾燥後の着色重合体粒子表面に付着残存している荷電制御剤の不純物及び分解物の濃度は、１５００ｐｐｍであった。
【０１４２】
実施例７と同様に、得られた着色重合体粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置した後の前記着色重合体粒子を、それぞれ１００質量部に対し、平均粒径０．００５μｍの疎水性シリカ１．５質量部を添加してヘンシェルミキサーで混合しトナーとした。
【０１４３】
さらに、この現像剤を用いて、実施例７と同様の画出し評価を行ったところ、２３℃／６５％ＲＨの環境下では、実施例７と同様に良好な画像が得られたが、３０℃／８０％ＲＨの環境下では、次第に画像濃度が低くなり、カブリが顕著になった。また、３０℃／８０％ＲＨの環境下に２日間放置した後に、トナーとしたものは、初期より画像濃度が低く、カブリがみられ、また、現像器からのトナーの飛散が発生した。
【０１４４】
【発明の効果】
上述したように本発明によれば、懸濁重合法によって得られた着色重合体粒子から、無機化合物の安定化剤を効率良く除去を行い、荷電制御剤であるアルキルサリチル酸の金属錯体または、錯塩または、錯体と錯塩の混合物の分解生成物や他の添加剤の水中への溶解物に起因する水中への溶解物の乾燥後のトナー表面への存在状態を制御し、帯電性の環境安定性が良く、画像濃度変化及びカブリのないトナー得るトナーの製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electronic printing or a toner manufacturing method for forming a toner fixed image in a toner jet type image forming method. The present invention relates to a method for producing toner used in a fixing method in which an image is heated and fixed on a print sheet such as a transfer material.
[0002]
[Prior art]
As described in U.S. Pat. No. 2,297,691, etc., a number of methods are known for electrophotography. Generally, a photoconductive material is used on a photoreceptor by various means. After forming an electrical latent image and then developing the latent image with fine particles made of a colored resin composition called toner, the toner image is transferred from a photoreceptor to a transfer material such as paper as necessary. It is fixed on the transfer material by heating, pressure, solvent vapor or the like to obtain a copy or a print. Further, in the above method, various methods have been proposed as a method for developing a latent image using toner or a method for fixing a toner image on a transfer material, which is suitable for each image forming process. The method is adopted.
[0003]
Further, a toner used for developing an electric latent image has conventionally been generally melt-mixed with a colorant such as a dye and a pigment in a thermoplastic resin, and after these materials are uniformly dispersed, It is manufactured by a so-called pulverization method in which a finely pulverized product is obtained with a fine pulverizer and then the finely pulverized product is classified using a classifier to obtain a toner (resin colorant dispersion) having a desired particle size.
[0004]
According to the method for producing toner by the above pulverization method, a considerably excellent toner can be produced, but there are certain limitations, that is, the selection range of the toner material. For example, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized with economically possible production equipment. However, if the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at high speed tends to be widened. It is included in the problem. Further, such a highly brittle material is likely to be further pulverized or powdered when used for development in a copying machine or the like. Also, with this method, it is difficult to completely disperse solid fine particles such as a colorant in the resin, and depending on the degree of dispersion, the increase in fog, the decrease in image density, and the color mixing / transparency may be difficult. Care must be taken to disperse as it will cause defects. Further, exposure of the colorant to the fracture surface may cause a change in development characteristics.
[0005]
On the other hand, in order to overcome these problems of the toner by the pulverization method, a suspension polymerization method toner and a method for producing the same are proposed in Japanese Patent Publication Nos. 36-10231, 43-10799, and 51-14895. Has been. For example, in the suspension polymerization method, a polymerizable monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives. After preparing the product, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, such as an aqueous phase, using a suitable stirrer, and simultaneously subjected to a polymerization reaction to obtain a desired particle size. Toner particles are obtained.
[0006]
Since the toner manufacturing method using such a polymerization method does not include a pulverization step, the toner forming material is not required to be brittle as in the case of manufacturing by a pulverization method. Can be used. In addition, since the classification process can be omitted, the cost reduction effect such as saving energy, shortening the manufacturing time, and improving the process yield is great.
[0007]
In recent years, there has been a demand for multifunctional toners such as high image quality, full color, and energy saving in recent copying machines and printers. For example, the toner particles have a small particle size to cope with high-resolution, digital methods with a finer particle size, improved transparency of OHP images with full color, and low-temperature fixing with energy saving. There is a demand for the inclusion of a softening point substance and the formation of toner particles that are effective in improving the transfer efficiency to a transfer material. As a means for realizing these requirements, a toner by a polymerization method is exemplified.
[0008]
As the charge control agent used in the toner for full-color images, a compound containing a carboxyl group is preferable, and in the case of a polymerized toner, it is used by being dispersed in a polymerizable monomer. In consideration of the influence of color, a colorless, white or light crystalline state is preferable. In particular, a metal complex of alkyl salicylic acid or a complex salt or a mixture of a complex and a complex salt is preferably used for a color toner.
[0009]
However, in the polymerization method, a granulation / polymerization step in water is required, and in this case, the substance dispersed or dissolved in the polymerizable monomer has solubility in water or is unstable. In this case, the substance dissolves in water and the dissolved decomposition impurities adhere to the toner surface, which may cause changes in the charging characteristics and environmental characteristics of the toner depending on the conditions of the manufacturing process, particularly the cleaning process after completion of polymerization. Became clear.
[0010]
Water that is generally used industrially includes water from which impurities have been removed by a distillation method, ion exchange method, reverse osmosis method, filtration method, and the like. The same applies to water used in the water washing step in toner synthesis.
[0011]
However, as a result of investigation by the present inventor, Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ It was revealed that the toner after drying when washed with water having a total content of less than 5 mg / liter is left in a high-temperature and high-humidity environment, the chargeability is lowered.
[0012]
On the other hand, Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ In the case of washing with water having a total content of 10 mg / liter or more, the amount of compounds derived from metal complexes or complex salts of alkyl salicylic acid remaining on the toner surface after drying or a mixture of complexes and complex salts is reduced. From the beginning, a phenomenon in which the chargeability of the toner is reduced has been clarified. In this case, the degree of reduction in the amount of the compound derived from the metal complex or complex salt of the alkyl salicylic acid remaining on the toner surface after drying or a mixture of the complex and the complex salt may vary depending on the ion content and the water temperature. all right.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to provide a toner manufacturing method that solves the above-described problems.
[0014]
Specifically, the object of the present invention is to control the state of the toner dissolved in water caused by additives such as a charge control agent on the surface of the toner after drying in the production of toner by suspension polymerization. Another object of the present invention is to provide a method for producing a toner excellent in the above.
[0015]
[Means for Solving the Problems]
Therefore, as a result of intensive studies, the inventor paid attention to the ionic components contained in the water in the washing step after the acid washing step after the completion of polymerization, and changed the water washing step after the acid washing step to the metal positive step. After washing with water having a total ion content of less than 5 mg / liter and the total content of metal cations derived from the dispersion stabilizer in the washing wastewater being less than 5 mg / liter, a certain amount of alkali metal and alkaline earth Metal ions (Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ The toner after drying the metal complex of alkylsalicylic acid as a charge control agent, or a decomposition product of a complex salt or a mixture of the complex and complex salt, or a solution of other additives in water. The present inventors have found that the present invention provides a method for producing a toner having excellent chargeability in which the state of existence on the surface is controlled.
[0016]
That is, the present invention comprises at least a polymerizable monomer and a colorant. Alkyl salicylic acid metal compounds and A polymerizable monomer composition containing , Minutes dissolved with acid Powder stabilizer Aqueous dispersion medium containing Suspended in water to produce colored polymer particles, acid washed, dehydrated, washed with water with a total metal cation content of less than 5 mg / liter, dispersed in washed waste water After the total content of metal cations from the stabilizer is less than 5 mg / liter, Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ The total content of 70 Thru 120 mg / liter of water 0.1 to 1.0 part by mass with respect to 1 part by mass of the suspension to be washed The toner production method is characterized by pouring water, dehydrating, and drying the obtained wet colored polymer particles.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the toner production method of the present invention.
[0018]
In the toner manufacturing method of the present invention, the toner can be specifically manufactured by the following manufacturing method.
[0019]
That is, a release agent composed of a low softening point substance, a colorant, a charge control agent, a polymerization initiator and other additives are added to the polymerizable monomer, and the mixture is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser or the like. The monomer system is dispersed in an aqueous phase containing a dispersion stabilizer by a normal stirrer, clear mixer, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is preferably carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing, the latter half of the reaction, or the completion of the reaction. A part of the aqueous medium may be distilled off later. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.
[0020]
In the polymerized toner according to the present invention, the dispersion stabilizer used particularly in the case of utilizing suspension polymerization using a dispersion stabilizer includes tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, carbonic acid. Examples thereof include inorganic compounds such as magnesium, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
[0021]
When using these inorganic compound dispersion stabilizers, commercially available ones may be used as they are, but in order to obtain fine particles, the inorganic compounds may be produced in a dispersion medium. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.
[0022]
Further, for fine dispersion of these dispersion stabilizers, 0.001 to 0.1 parts by mass of a surfactant may be used. This is to promote the initial action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate. , Potassium stearate, calcium oleate and the like.
[0023]
In the present invention, after the polymerization is completed, an acid is added to the cooled colored polymer particle slurry, and the mixture is stirred to dissolve the inorganic compound dispersion stabilizer, followed by solid-liquid separation. Remove.
[0024]
Acids used include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, chromic acid, hydroiodic acid, sulfurous acid, citric acid, acetic acid, boric acid, carbonic acid, hydrofluoric acid, phosphoric acid, nitrous acid, etc. Sulfuric acid, nitric acid and the like are preferable in terms of price and handling.
[0025]
Further, the pH after addition of acid is preferably 3 or less, more preferably 2 or less because the effect of removing the inorganic compound dispersion stabilizer is high.
[0026]
The acid washing time is preferably several tens of minutes to 3 hours, and if it is 10 minutes or less, the removal effect of the inorganic compound dispersion stabilizer is low, and even if it is carried out for 3 hours or more, no further removal effect is obtained.
[0027]
Solid-liquid separation can be performed with a commercially available solid-liquid separation device, but the pressure filtration system device that can wash the post-process by pouring water into the cake and easily discharge the cake that can be supplied to the drying device, For example, SP filters (manufactured by Nissen Co., Ltd.), KF filters (manufactured by Sanshin Seisakusho), filter presses (each company) and the like are preferably used.
[0028]
Further, the colored polymer particle cake remaining in the solid-liquid separator is washed by pouring water having a total metal cation content of less than 5 mg / liter, and the metal cation derived from the dispersion stabilizer in the washing waste water. After total content of less than 5 mg / liter, alkali metal and alkaline earth metal ions (Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ Water with a total content of 20 to 150 mg / liter is poured. By such water injection / washing, the dispersion stabilizer of the inorganic compound adhering to the colored polymer particle cake is removed, and at the same time, it is caused by the metal complex or the complex salt of the alkylsalicylic acid as the charge control agent or the mixture of the complex and the complex salt. Controls the state of the dissolved matter in water on the toner surface after drying.
[0029]
If water is added to the colored polymer particle cake, the mixture is stirred, reslurried, and then solid-liquid separation is performed again using a solid-liquid separation device, the removal effect is high, but the process becomes complicated and the cost becomes difficult. It is desirable to inject water into the colored polymer particle cake remaining in the liquid separator and dehydrate it.
[0030]
The amount of washing water is necessary until the metal ions derived from the dispersion stabilizer are present in the toner after drying to 100 mg / kg or less, and the total content of metal cations to be poured and washed in the initial stage is less than 5 mg / liter. Is necessary until the total content of metal cations derived from the dispersion stabilizer in the washing wastewater is less than 5 mg / liter, and is 1 to 5 parts by mass with respect to 1 part by mass of the slurry subjected to solid-liquid separation. Equivalent to.
[0031]
In addition, additional cleaning is performed, Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ The amount of water having a total content of 20 to 150 mg / liter (more preferably 70 to 120 mg / liter) is preferably 0.1 to 1.0 part by mass with respect to 1 part by mass of the solid-liquid separated slurry.
[0032]
When the amount is less than 0.1 parts by mass, the effect of additional cleaning is hardly exhibited. When the amount is more than 1.0 parts by mass, the metal complex or complex salt or complex of the alkylsalicylic acid that is the charge control agent is again used. As a result, the decomposition product of the mixture of the complex salt and the dissolved product of other additives in water are removed, and the amount is excessively reduced.
[0033]
The toner according to the present invention has a finer particle diameter, more specifically a weight average diameter of 4 to 10 μm as measured by a Coulter counter, in order to faithfully develop finer latent image dots for higher image quality. And a toner having a number variation coefficient of 35% or less is most preferable. When the toner has a weight average diameter of less than 4 μm, a large amount of untransferred toner is generated on the photosensitive member or the intermediate transfer member due to poor transfer efficiency, which causes undesirable image unevenness due to fogging or transfer failure. Further, when the weight average diameter of the toner exceeds 10 μm, fusion to the member is likely to occur, and when the number variation coefficient of the toner exceeds 35%, the tendency further increases and becomes a problem.
[0034]
As the low softening point substance used in the toner according to the present invention, a compound having a main maximum peak value measured according to ASTM D3418-8 of 40 to 90 ° C. is preferable. When the maximum peak is less than 40 ° C., the self-cohesion force of the low softening point substance becomes weak, and as a result, the high temperature offset resistance becomes weak, which is not preferable for a full color toner. On the other hand, when the maximum peak exceeds 90 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the surface of the fixed image, which is not preferable from the viewpoint of color mixing. Furthermore, in the case of obtaining a toner by a direct polymerization method, granulation and polymerization are carried out in an aqueous system, so if the temperature at the maximum peak value is high, a low softening point substance mainly precipitates during granulation and inhibits the suspension system. Therefore, it is not preferable.
[0035]
For example, DSC-7 manufactured by Perkin Elmer is used to measure the temperature of the maximum peak value. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. For the sample, an aluminum pan is used, an empty pan is set for control, and the measurement is performed at a heating rate of 10 ° C./min.
[0036]
Specifically, paraffin wax, polyolefin wax, Fischer tropish wax, amide wax, higher fatty acid, ester wax and derivatives thereof, or graft / block compounds thereof can be used. Preferably, the ester wax having one or more long-chain ester moieties having 10 or more carbon atoms represented by the following general structural formula has an effect on high-temperature offset resistance without impairing the transparency of OHP. preferable. Specific structural formulas of typical ester wax compounds preferable for the present invention are shown as general structural formula (1), general structural formula (2), and general structural formula (3) below.
[0037]
[Chemical 1]

(In the formula, a and b represent an integer of 0 to 4, a + b is 4, and R ₁ And R ₂ Represents an organic group having 1 to 40 carbon atoms, and R ₁ And R ₂ And n and m are integers of 0 to 15, and n and m are not 0 at the same time. )
[0038]
[Chemical 2]

(In the formula, a and b represent an integer of 0 to 4, a + b is 4, and R ₁ Represents an organic group having 1 to 40 carbon atoms, n and m represent integers of 0 to 15, and n and m are not 0 at the same time. )
[0039]
[Chemical 3]

(Wherein, a and b represent an integer of 0 to 3, a + b is 3 or less, R ₁ And R ₂ Represents an organic group having 1 to 40 carbon atoms, and R ₁ And R ₂ And a group having a carbon number difference of 10 or more, and R _Three Represents an organic group having 1 or more carbon atoms, n and m represent an integer of 0 to 15, and n and m are not 0 at the same time. )
[0040]
The ester wax preferably used in the present invention preferably has a hardness of 0.5 to 5.0. The hardness of the ester wax is a value obtained by measuring a Vickers hardness using, for example, a dynamic ultra-micro hardness meter (DUH-200) manufactured by Shimadzu Corporation after preparing a cylindrical sample having a diameter of 20 mmφ and a thickness of 5 mm. The measurement conditions are as follows: a load of 0.5 g and a load speed of 9.67 mm / second are displaced by 10 μm and held for 15 seconds, and the resulting dent shape is measured to determine the Vickers hardness. A low softening point material having a hardness of less than 0.5 increases the pressure dependency and process speed dependency of the fixing device, and the high temperature offset effect tends to be insufficient. Since the stability is poor and the self-cohesive force of the release agent itself is small, the high-temperature offset resistance tends to be insufficient. Specific compounds include the following compounds.
[0041]
[Formula 4]

[0042]
In recent years, the need for full-color double-sided images has increased, and when a double-sided image is formed, the heating part of the fixing unit is also used when the toner image on the transfer paper first formed on the front side forms the next image on the back side. It is necessary to sufficiently consider the high-temperature offset resistance of the toner. Therefore, in the present invention, it is desirable to add a large amount of a low softening point substance. Specifically, it is preferable to add 5 to 40% by mass of a low softening point substance in the toner. When the amount is less than 5% by mass, sufficient high-temperature offset resistance is not exhibited, and the image on the back side tends to exhibit an offset phenomenon at the time of fixing a double-sided image. On the other hand, when the amount exceeds 40% by mass, coalescence of toner particles is likely to occur during granulation, and a product having a wide particle size distribution is likely to be generated, which is inappropriate for the present invention.
[0043]
As the method for producing the toner particles of the present invention, the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842 is directly used. It is possible to produce toner using a method of producing toner.
[0044]
In the present invention, a so-called seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can be suitably used in the present invention.
[0045]
Further, in the present invention, considering that a large amount of a low softening point substance is contained in the toner from the viewpoint of fixability, it is inevitably necessary to encapsulate the low softening point substance in the outer shell resin. As a specific method for embedding the low softening point substance, the polarity of the material in the aqueous medium is set to be smaller for the low softening point substance than the main monomer, and a small amount of a resin or monomer having a large polarity. Is added to obtain a toner having a so-called core-shell structure in which a low softening point substance is coated with an outer shell resin. Toner particle size distribution control and particle size control can be achieved by changing the type and amount of dispersion-inhibiting inorganic salts and protective colloids and mechanical equipment conditions such as rotor speed, number of passes, A predetermined toner of the present invention can be obtained by controlling the stirring conditions such as the shape of the stirring blades, the container shape, or the solid content concentration in the aqueous solution.
[0046]
In the present invention, as a specific method for measuring the tomographic plane of the toner, the toner is sufficiently dispersed in a room temperature curable epoxy resin, and then cured in an atmosphere at a temperature of 40 ° C. for 2 days. After staining with ruthenium tetroxide and, if necessary, osmium tetroxide, a flaky sample was cut out using a microtome equipped with diamond teeth, and the tomographic morphology of the toner was measured using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.
[0047]
Examples of the polymerizable monomer that can be used in the polymerized toner include styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (Meth) acrylic acid ester monomers such as (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid dimethylaminoethyl, (meth) acrylic acid diethylaminoethyl; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, acrylic Vinyl monomers such as acid amides are preferably used. These are monomers alone or generally such that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-P139-192 (John Wiley & Sons) shows 40-75 ° C. Are appropriately mixed and used. When the theoretical glass transition temperature is less than 40 ° C., there are problems in terms of storage stability of the toner and durability of the developer. On the other hand, when it exceeds 75 ° C., the fixing point is increased. In some cases, the color toners are not sufficiently mixed, resulting in poor color reproducibility. Further, the transparency of the OHP image is remarkably lowered, which is not preferable from the viewpoint of high image quality.
[0048]
In the present invention, when the low softening point substance is encapsulated in the outer shell resin, it is particularly preferable to add a polar resin in addition to the outer shell resin. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the outer shell resin or the monomer. In the case of containing a polar resin having an unsaturated group, a cross-linking reaction occurs with the monomer forming the outer shell resin layer, and as a full color toner, it becomes extremely high molecular weight, which is disadvantageous for the color mixture of four color toners. .
[0049]
As the colorant used in the present invention, a black colorant that is toned in black using carbon black, a magnetic material, and the following yellow / magenta / cyan colorant is used.
[0050]
As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, etc. are preferably used.
[0051]
As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.
[0052]
As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.
[0053]
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.
[0054]
When a magnetic material is used as the black colorant, 40 to 150 parts by mass are added to 100 parts by mass of the resin, unlike other colorants.
[0055]
As the charge control agent used in the present invention, known ones can be used. However, as the charge control agent used for the toner for full-color images, a compound containing a carboxyl group is preferable. Used by dispersing in the body. In consideration of the influence of color, a colorless, white or light crystalline state is preferable. Particularly, a metal compound of alkyl salicylic acid is preferable for a color toner. As the metal compound, a metal complex, a metal complex salt, or a metal complex is preferable. And a mixture of a metal complex salt, and a low crystalline or non-crystalline one is preferably used.
[0056]
Examples of the polymerization initiator that can be used in the polymerized toner according to the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 ′. -Azo or diazo polymerization initiators such as azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide; Peroxide polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally 0.5 to 20% by mass is added to the monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but can be used alone or in combination with reference to the 10-hour half-life temperature.
[0057]
In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.
[0058]
In addition, it is preferable that the toner particles to which the external additive has been added and dried are further imparted with a mechanical impact force to adjust the adhesion state of the external additive to the toner particles. That is, it is preferable to adjust the adhesion state of the external additive to the toner particles by applying a mechanical impact force with a dry mixer such as a Henschel mixer. More specifically, the peripheral speed of the high-speed rotary blade of the Henschel mixer and the processing time are adjusted to adjust the adhesion state of the external additive to the toner particles.
[0059]
At this time, if necessary, it is preferable to add other external additives such as a charge imparting agent and an abrasive and simultaneously perform the treatment.
[0060]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.
[0061]
Alkaline metal and alkaline earth metal ions (Na ⁺ , K ⁺ , Mg ²⁺ And Ca ²⁺ ) Content is shown in Table 1.
[0062]
[Table 1]

[0063]
<Example 1>
First, 0.1 mol / liter-Na is added to 710 parts by mass of ion-exchanged water (water A). _Three PO _Four (Made by Yoneyama Chemical Co., Ltd.) 450 parts by mass of an aqueous solution was added and heated to 60 ° C., and then stirred at 3,500 rpm using a clear mixer (manufactured by M Technique). To this, 1.0 mol / liter-CaCl ₂ Add 68 parts by mass of aqueous solution and add Ca. _Three (PO _Four ) ₂ An aqueous medium of a phosphoric acid-calcium compound having a pH of 6.0 was obtained.
[0064]
On the other hand, as the dispersoid, first, among the following prescriptions, C.I. I. Pigment Blue 15: 3, an aluminum dialkyl salicylate compound and 100 parts by mass of a styrene monomer were dispersed for 3 hours using an attritor (manufactured by Mitsui Miike Chemical Industries) to obtain a colorant dispersion. Next, the rest of the following formulation was added to the colorant dispersion, heated to 60 ° C., and dissolved and mixed for 30 minutes. In this, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.
・ 165 parts by mass of styrene monomer
・ 35 parts by mass of n-butyl acrylate
・ C. I. Pigment Blue 15: 3 10 parts by mass
・ 10 parts by weight of saturated polyester
-Aluminum dialkyl salicylate compound 2 parts by mass
-25 parts by weight of compound (1) wax
(Peak temperature 5DSC in DSC, Vickers hardness 1.5)
[0065]
The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer is changed from a high-speed stirrer to a propeller stirring blade, the internal temperature is raised to 60 ° C., polymerization is continued at 50 rpm for 5 hours, and then the internal temperature is raised to 80 ° C. for 8 hours. Was continued. After completion of the polymerization, the slurry was cooled to 30 ° C.
[0066]
Transfer the colored polymer particle slurry to a washing vessel, add dilute hydrochloric acid for acid washing while stirring, stir at pH 1.5 for 2 hours, _Three (PO _Four ) ₂ After dissolving the phosphoric acid and calcium compound containing, solid-liquid separation was performed with a pressure filtration type apparatus KF filter (manufactured by Sanshin Seisakusho).
[0067]
Next, water B was poured into the colored polymer particle cake remaining in the KF filter in an amount 4 times the amount of the introduced slurry. At this time, the concentration of metal ions derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na ⁺ = 1.5 mg / liter ... concentration in water B, Ca ²⁺ = 0.0 mg / liter). Thereafter, water C was injected by 0.2 times the amount of the introduced slurry. Furthermore, after dehydrating, it was crushed and dried.
[0068]
The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was determined as follows. 1.0 g of colored polymer particles was put into 50 g of a 0.1 N sodium hydroxide aqueous solution and stirred for 3 hours, and then the filtrate obtained by filtration was measured by a spectrophotometric method using a predetermined calibration curve. As a result, it was 1500 ppm.
[0069]
The weight average particle diameter of the colored polymer particles was 6.9 μm.
[0070]
To 100 parts by mass of the obtained colored polymer particles, 0.7 part by mass of hydrophobic silica having an average particle diameter of 0.03 μm and 0.7 part by mass of titanium oxide having an average particle diameter of 0.05 μm were added. The toner was mixed.
[0071]
In addition, after leaving the colored polymer particles obtained in an environment of 30 ° C./80% RH for 2 days, hydrophobic silica having an average particle size of 0.03 μm and an average particle size of 0. Toner was added by adding 05 μm of titanium oxide and mixing with a Henschel mixer.
[0072]
In any of these toners, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of toner to obtain a developer.
[0073]
Using these developers, an image printing test was performed in a 23 ° C./65% RH environment using a Canon color copier CLC500 remodeling machine. There was no change in the image density after endurance, and a high-quality image with no voids was obtained. Further, problems such as toner fusion and memory ghost did not occur on the photoconductor which is an organic semiconductor. Further, double-sided images were formed, but no occurrence of offset was observed on the front and back surfaces of the transfer material.
[0074]
The transfer efficiency obtained by the following method was 98% in all cases.
[0075]
[Transfer efficiency]
10cm ² A solid image is formed on the photoreceptor, and the amount of toner on the photoreceptor (W1) and the amount of toner on the paper after transfer (W2) are used. From the ratio of the two: W2 / W1 × 100 (%) Calculated.
[0076]
Further, the same image output test was performed in an environment of 30 ° C./80% RH, and similar results were obtained.
[0077]
<Example 2>
After acid washing, water B was poured into the colored polymer particle cake remaining in the KF filter 4 times the amount of the introduced slurry, and then water D was poured 0.3 times the amount of the introduced slurry. Was carried out in the same manner as in Example 1. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1550 ppm.
[0078]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0079]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer. Furthermore, when this developer was used for image output evaluation in the same manner as in Example 1, a good image was obtained as in Example 1.
[0080]
<Comparative Example 1>
After the acid cleaning, the same procedure as in Example 1 was performed except that water B was poured 4.5 times the amount of the introduced slurry into the colored polymer particle cake remaining in the KF filter. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1500 ppm.
[0081]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0082]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer. Furthermore, using this developer, the same image formation evaluation as in Example 1 was performed. Under the environment of 23 ° C./65% RH, a good image was obtained as in Example 1. Under an environment of 30 ° C./80% RH, the image density gradually decreased and fogging became prominent. In addition, the toner used after being allowed to stand in an environment of 30 ° C./80% RH for 2 days had a lower image density from the initial stage and fogging was observed.
[0083]
<Comparative Example 2>
After the acid cleaning, the same procedure as in Example 1 was performed except that water C was injected into the colored polymer particle cake remaining in the KF filter in an amount four times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 700 ppm.
[0084]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0085]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer.
[0086]
Further, using this developer, an image formation evaluation similar to that in Example 1 was carried out. As a result, an image having the same image density as that in Example 1 was obtained. The developer splashes from.
[0087]
<Example 3>
Solid-liquid separation after acid washing was performed with a filter press (manufactured by Noritake Iron Works), and water B was poured into the colored polymer particle cake remaining in the filter press in an amount three times the amount of the introduced slurry (at this point). The concentration of metal ions derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na ⁺ = 1.5 mg / liter ... concentration in water B, Ca ²⁺ = 0.0 mg / liter))) Thereafter, water D was carried out in the same manner as in Example 1 except that 0.2 times of the introduced slurry was injected. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1800 ppm.
[0088]
Similarly to Example 1, for 100 parts by mass of the obtained colored polymer particles, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0089]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Furthermore, when this developer was used for image output evaluation in the same manner as in Example 1, a good image was obtained as in Example 1.
[0090]
<Example 4>
Solid-liquid separation after acid washing is performed with a filter press (manufactured by Noritake Iron Works), water B is poured into the colored polymer particle cake remaining in the filter press in an amount three times the amount of the introduced slurry, and then water E Was carried out in the same manner as in Example 1 except that water was injected in an amount 0.3 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1780 ppm.
[0091]
Similarly to Example 1, for 100 parts by mass of the obtained colored polymer particles, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0092]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Furthermore, when this developer was used for image output evaluation in the same manner as in Example 1, a good image was obtained as in Example 1.
[0093]
< Reference example 1 >
Solid-liquid separation after acid cleaning is performed with a filter press (manufactured by Noritake Iron Works), water B is poured into the colored polymer particle cake remaining in the filter press in an amount three times the amount of the introduced slurry, and then water F Was carried out in the same manner as in Example 1 except that water was injected 1.0 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1810 ppm.
[0094]
Similarly to Example 1, for 100 parts by mass of the obtained colored polymer particles, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0095]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Further, using this developer, the same image formation evaluation as in Example 1 was performed, and the toner that was left in an environment of 30 ° C./80% RH for 2 days was slightly fogged. As with Example 1, good images were obtained.
[0096]
< Reference example 2 >
Solid-liquid separation after acid washing is performed with a filter press (manufactured by Noritake Iron Works), water B is poured into the colored polymer particle cake remaining in the filter press in an amount three times the amount of the introduced slurry, and then water G Was carried out in the same manner as in Example 1 except that water was injected 1.0 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1820 ppm.
[0097]
Similarly to Example 1, for 100 parts by mass of the obtained colored polymer particles, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0098]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Further, using this developer, the same image formation evaluation as in Example 1 was carried out. As a result, the toner that had been allowed to stand in an environment of 30 ° C./80% RH for 2 days had some fog. Although a slight scattering of the developer from the developing device was observed, a good image was obtained as in Example 1.
[0099]
<Comparative Example 3>
Example, except that solid-liquid separation after acid cleaning was performed with a filter press (manufactured by Noritake Steel Works), and water A was poured into the colored polymer particle cake remaining in the filter press in an amount 5 times the amount of the introduced slurry. 1 was performed. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1800 ppm.
[0100]
Similarly to Example 1, with respect to 100 parts by mass of the obtained colored polymer particles, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.3 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0101]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Furthermore, using this developer, the same image formation evaluation as in Example 1 was performed. Under the environment of 23 ° C./65% RH, a good image was obtained as in Example 1. Under an environment of 30 ° C./80% RH, the image density gradually decreased and fogging became prominent. In addition, the toner used after being allowed to stand in an environment of 30 ° C./80% RH for 2 days had a lower image density from the initial stage and fogging was observed.
[0102]
<Comparative Example 4>
Example, except that solid-liquid separation after acid cleaning is performed with a pressure filtration apparatus KF filter, and water D is poured into the colored polymer particle cake remaining in the filter press in an amount 5 times the amount of the introduced slurry. 1 was performed. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1200 ppm.
[0103]
Similarly to Example 1, with respect to 100 parts by mass of the obtained colored polymer particles, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.3 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0104]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Further, using this developer, an image formation evaluation similar to that in Example 1 was carried out. As a result, an image having the same image density as that in Example 1 was obtained. The developer splashes from.
[0105]
<Comparative Example 5>
Solid-liquid separation after acid washing is performed with a filter press (manufactured by Noritake Iron Works), water B is poured into the colored polymer particle cake remaining in the filter press in an amount three times the amount of the introduced slurry, and then water D Was carried out in the same manner as in Example 1 except that water was injected in an amount three times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining adhering to the surface of the colored polymer particles after drying was 1450 ppm.
[0106]
Similarly to Example 1, with respect to 100 parts by mass of the obtained colored polymer particles, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.3 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0107]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Furthermore, when the same image output evaluation as in Example 1 was performed using this developer, an image similar to that in Example 1 was initially obtained. However, the fog gradually increased, and the image from the developing unit was gradually increased. The scattering of the developer became conspicuous.
[0108]
Example 1 to above 4, Reference examples 1 and 2 And the result of Comparative Examples 1-5 is put together in Table 2, and is shown.
[0109]
[Table 2]

[0110]
<Example 5 >
First, 0.1 mol / liter-Na is added to 710 parts by mass of ion-exchanged water (water A). _Three PO _Four 450 parts by mass of an aqueous solution (manufactured by Lhasa Kogyo Co., Ltd.) was added and heated to 60 ° C., and then stirred at 3,500 rpm with a clear mixer. To this, 1.0 mol / liter-CaCl ₂ Add 68 parts by mass of aqueous solution and add Ca. _Three (PO _Four ) ₂ An aqueous medium of a phosphoric acid and calcium compound having a pH of 5.8 was obtained.
[0111]
On the other hand, as a dispersoid, first, among the following formulations, pigment red pigment, aluminum dialkyl salicylate compound and 100 parts by mass of a styrene monomer are dispersed for 3 hours using an attritor (Mitsui Miike Chemical Co., Ltd.), and a colorant dispersion Got. Next, the rest of the following formulation was added to the colorant dispersion, heated to 60 ° C., and dissolved and mixed for 30 minutes. In this, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.
・ 165 parts by mass of styrene monomer
・ 35 parts by mass of n-butyl acrylate
・ Pigment Red 122 20 parts by mass
・ 20 parts by weight of saturated polyester
-Aluminum dialkyl salicylate compound 2 parts by mass
-25 parts by weight of compound (1) wax
(Peak temperature 5DSC in DSC, Vickers hardness 1.5)
[0112]
The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer is changed from a high-speed stirrer to a propeller stirring blade, the internal temperature is raised to 60 ° C., polymerization is continued at 50 rpm for 5 hours, and then the internal temperature is raised to 80 ° C. for 10 hours. Was continued. After completion of the polymerization, the slurry was cooled to 30 ° C.
[0113]
The colored polymer particle slurry is transferred to a washing vessel, and while stirring, dilute hydrochloric acid is added for acid washing, and the mixture is stirred at pH 1.8 for 2 hours. _Three (PO _Four ) ₂ After dissolving the phosphoric acid and calcium compound containing, solid-liquid separation was performed with a pressure filtration type apparatus KF filter (manufactured by Sanshin Seisakusho).
[0114]
Next, water B was poured into the colored polymer particle cake remaining in the KF filter in an amount three times the amount of the introduced slurry. At this time, the concentration of metal ions derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na ⁺ = 1.5 mg / liter ... concentration in water B, Ca ²⁺ = 0.0 mg / liter). Thereafter, water H was injected 0.4 times the amount of the introduced slurry. Furthermore, after dehydrating, it was crushed and dried.
[0115]
The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1720 ppm.
[0116]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0117]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer. Furthermore, when this developer was used for image output evaluation in the same manner as in Example 1, a good image was obtained as in Example 1.
[0118]
<Example 6 >
After acid washing, water B was injected into the colored polymer particle cake remaining in the KF filter by 3 times the amount of the introduced slurry, and then water I was injected 0.4 times the amount of the introduced slurry. Example 5 As well as. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1670 ppm.
[0119]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0120]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer. Further, using this developer, the same image output evaluation as in Example 1 was performed. 5 A good image was obtained in the same manner as above.
[0121]
< Reference example 3 >
After acid cleaning, water B was injected into the colored polymer particle cake remaining in the KF filter by 3 times the amount of the introduced slurry, and then water J was injected 1.0 times the amount of the introduced slurry. Example 5 As well as. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1740 ppm.
[0122]
In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size with respect to 100 parts by mass, respectively. A toner was prepared by adding 0.7 parts by mass of 0.03 μm hydrophobic silica and 0.7 parts by mass of titanium oxide having an average particle diameter of 0.05 μm and mixing with a Henschel mixer.
[0123]
95 parts by mass of a magnetic material-dispersed resin carrier was mixed with 5 parts by mass of these toners to obtain a developer. Further, using this developer, the same image formation evaluation as in Example 1 was carried out. As a result, the toner left after standing in an environment of 30 ° C./80% RH for 2 days had a slight fog. Although there is a slight scattering of developer from the developing device, the example 5 A similar image was obtained.
[0124]
<Comparative Example 6>
After acid washing, water B was added to the colored polymer particle cake remaining in the KF filter by 3 times the amount of the introduced slurry, and then water K was added 0.4 times the amount of the introduced slurry. Example 5 As well as. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1530 ppm.
[0125]
Similarly to Example 1, with respect to 100 parts by mass of the obtained colored polymer particles, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.3 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0126]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Further, using this developer, the same image output evaluation as in Example 1 was performed. 5 Although the same image was obtained, the fog gradually increased and the scattering of the developer from the developing device became conspicuous.
[0127]
<Comparative Example 7>
After acid washing, water B was added to the colored polymer particle cake remaining in the KF filter by 3 times the amount of the introduced slurry, and then water L was injected 0.4 times the amount of the introduced slurry. Example 5 As well as. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1020 ppm.
[0128]
Similarly to Example 1, with respect to 100 parts by mass of the obtained colored polymer particles, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.3 parts by mass of titanium oxide having an average particle size of 0.05 μm Was added and mixed with a Henschel mixer to obtain a toner.
[0129]
To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier was mixed to obtain a developer. Furthermore, when this developer was used for image output evaluation in the same manner as in Example 1, there was a lot of fogging and the scattering of the developer from the developing device was conspicuous.
[0130]
Example above 5 and 6, Reference Example 3 And the result of Comparative Examples 6-7 is put together in Table 3, and is shown.
[0131]
[Table 3]

[0132]
<Example 7 >
First, 0.1 mol / liter-Na is added to 710 parts by mass of ion-exchanged water (water A). _Three PO _Four 450 parts by mass of an aqueous solution (manufactured by Lhasa Kogyo Co., Ltd.) was added and heated to 60 ° C., and then stirred at 3,500 rpm with a clear mixer. To this, 1.0 mol / liter-CaCl ₂ Add 68 parts by mass of aqueous solution and add Ca. _Three (PO _Four ) ₂ An aqueous medium of a phosphoric acid and calcium compound having a pH of 10.5 and containing 1 was obtained.
[0133]
On the other hand, as a dispersoid, first, pigment yellow pigment, a zinc complex of crystalline dialkyl salicylic acid and 100 parts by mass of a styrene monomer are dispersed for 3 hours using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) and colored. An agent dispersion was obtained. Next, the rest of the following formulation was added to the colorant dispersion, heated to 60 ° C., and dissolved and mixed for 30 minutes. In this, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.
・ 160 parts by mass of styrene monomer
・ 40 parts by mass of n-butyl acrylate
・ Pigment Yellow 93 15 parts by mass
・ 20 parts by weight of saturated polyester
・ 3 parts by mass of crystalline dialkyl salicylic acid zinc complex
-25 parts by weight of compound (1) wax
(Peak temperature 5DSC in DSC, Vickers hardness 1.5)
[0134]
The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer is changed from a high-speed stirrer to a propeller stirring blade, the internal temperature is raised to 60 ° C., polymerization is continued at 50 rpm for 5 hours, and then the internal temperature is raised to 80 ° C. for 8 hours. Was continued. After completion of the polymerization, the slurry was cooled to 30 ° C.
[0135]
The colored polymer particle slurry is transferred to a washing container, and while stirring, dilute hydrochloric acid is added for acid washing, and the mixture is stirred at pH 1.6 for 2 hours. _Three (PO _Four ) ₂ After dissolving the phosphoric acid and calcium compound containing, solid-liquid separation was performed with a pressure filtration type apparatus KF filter (manufactured by Sanshin Seisakusho).
[0136]
Next, water B was poured into the colored polymer particle cake remaining in the KF filter in an amount 4 times the amount of the introduced slurry. At this time, the concentration of metal ions derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na ⁺ = 1.5 mg / liter ... concentration in water B, Ca ²⁺ = 0.0 mg / liter). Thereafter, water D was injected in an amount 0.2 times the amount of the introduced slurry. Furthermore, after dehydrating, it was crushed and dried.
[0137]
The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1630 ppm.
[0138]
Hydrophobic silica having an average particle diameter of 0.005 μm with respect to 100 parts by mass of the obtained colored polymer particles and the colored polymer particles after standing for 2 days in an environment of 30 ° C./80% RH. 1.5 parts by mass was added and mixed with a Henschel mixer to obtain a toner.
[0139]
Using this toner, an image-printing test was conducted in an environment of 23 ° C./65% RH using a Canon color laser jet printer color laser shot-2030 modified with an intermediate transfer member. Even in sheet durability, there was no change in the image density between the initial stage and after endurance, and a high-quality image with no voids was obtained.
[0140]
Further, the same image output test was performed in an environment of 30 ° C./80% RH, and similar results were obtained.
[0141]
<Comparative Example 8>
Example except that water B was added 4.5 times the amount of the introduced slurry to the colored polymer particle cake remaining in the KF filter after the acid washing. 7 As well as. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1500 ppm.
[0142]
Example 7 In the same manner as described above, the obtained colored polymer particles and the colored polymer particles after being allowed to stand in an environment of 30 ° C./80% RH for 2 days were average particle size of 0.005 μm with respect to 100 parts by mass, respectively. 1.5 parts by mass of hydrophobic silica was added and mixed with a Henschel mixer to obtain a toner.
[0143]
In addition, using this developer, 7 In the same manner as in Example 1, the image was evaluated under the environment of 23 ° C./65% RH. 7 A good image was obtained in the same manner as in Example 1, but in an environment of 30 ° C./80% RH, the image density gradually decreased and fogging became remarkable. Further, the toner used after being allowed to stand in an environment of 30 ° C./80% RH for 2 days had a lower image density from the beginning, fogging was observed, and toner scattering from the developing unit occurred.
[0144]
【The invention's effect】
As described above, according to the present invention, an inorganic compound stabilizer is efficiently removed from the colored polymer particles obtained by the suspension polymerization method, and a metal complex or complex salt of an alkylsalicylic acid that is a charge control agent. Or, control the state of presence of the dissolved product in water after drying the decomposition products of the mixture of complex and complex salt and other additives in water, and control the state of chargeability on the surface of the toner. Therefore, it is possible to provide a method for producing a toner which can obtain a toner having good image density change and no fogging.

Claims (3)

At least a polymerizable monomer composition containing a polymerizable monomer and a metal compound colorant and alkyl salicylic acids, the polymerization is suspended in an aqueous dispersion medium containing distributed stabilizer which dissolves in acid The colored polymer particles are produced, washed with acid, dehydrated, washed with water having a total metal cation content of less than 5 mg / liter, and the metal cation derived from the dispersion stabilizer in the washing waste water. After the total content is less than 5 mg / liter, water having a total content of Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ of 70 to 120 mg / liter is added to 1 part by mass of the suspension to be washed. A method for producing a toner, wherein 0.1 to 1.0 part by mass of water is injected, dehydrated, and the resulting wet colored polymer particles are dried. 2. The toner production according to claim 1 , wherein the metal compound of the alkyl salicylic acid is a low-crystalline or non-crystalline metal complex salt of an alkyl salicylic acid, a metal complex, or a mixture of the metal complex and the metal complex. Method. Washing after acid washing method for producing a toner according to claim 1 or 2, characterized by being performed by the water injection dewatering Kekihe.