JP3582033B2 - Toner for electrostatic charge development, method for producing the same, and developer - Google Patents

Description

【００２２】
以下本発明のトナーの好ましい製造方法の詳細を説明する。
【００２３】
〔トナーを作製するための重合性単量体〕
本発明のトナーを作製するためには、重合性単量体、特に疎水性単量体を使用する。この重合性単量体に対して必要に応じて親水性単量体、架橋性単量体を加えても使用してもよい。
【００２４】
（１）疎水性単量体
単量体成分を構成する疎水性単量体としては、特に限定されるものではなく従来公知の単量体を用いることができる。また、要求される特性を満たすように、１種または２種以上のものを組み合わせて用いることができる。
【００２５】
具体的には、ビニル芳香族系単量体、α−メチレン樹脂族カルボン酸及びエステル系単量体、ビニルエステル系単量体、ビニルエーテル系単量体、モノオレフィン系単量体、ジオレフィン系単量体、ハロゲン化オレフィン系単量体等を用いることができる。
【００２６】
ビニル芳香族系単量体としては、例えば、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ｐ−メトキシスチレン、ｐ−フェニルスチレン、ｐ−クロロスチレン、ｐ−エチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、２，４−ジメチルスチレン、３，４−ジクロロスチレン等のスチレン系単量体およびその誘導体が挙げられる。
【００２７】
α−メチレン脂肪族カルボン酸及びそのエステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸−２−エチルヘキシル、アクリル酸シクロヘキシル、アクリル酸フェニル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸−２−エチルヘキシル、β−ヒドロキシアクリル酸エチル、γ−アミノアクリル酸プロピル、メタクリル酸ステアリル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチル等のアクリル酸エステル、メタクリル酸エステルが挙げられる。
【００２８】
ビニルエステル系単量体としては、酢酸ビニル、プロピオン酸ビニル、ベンゾエ酸ビニル等が挙げられる。
【００２９】
ビニルエーテル系単量体としては、ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテル、ビニルフェニルエーテル等が挙げられる。
【００３０】
モノオレフィン系単量体としては、エチレン、プロピレン、イソブチレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン等が挙げられる。
【００３１】
ジオレフィン系単量体としては、ブタジエン、イソプレン、クロロプレン等が挙げられる。
【００３２】
（２）親水性単量体
単量体成分を構成する親水性単量体としては、特に限定されるものではなく従来公知の単量体を用いることができる。また、要求される特性を満たすように、１種または２種以上のものを組み合わせて用いることができる。
【００３３】
例えば、カルボキシル基含有単量体、スルホン酸基含有単量体、第１級アミン、第２級アミン、第３級アミン、第４級アンモニウム塩等のアミン系の化合物を用いることができる。
【００３４】
カルボキシル基含有単量体としては、アクリル酸、メタクリル酸、フマール酸、マレイン酸、イタコン酸、ケイ皮酸、マレイン酸モノブチルエステル、マレイン酸モノオクチルエステル等が挙げられる。
【００３５】
スルホン酸基含有単量体としては、スルホン酸スチレン、アリルスルホコハク酸、アリルスルホコハク酸オクチル等が挙げられる。
【００３６】
アミン系の化合物としては、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタアクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタアクリレート、３−ジメチルアミノフェニルアクリレート、２−ヒドロキシ−３−メタクリルオキシプロピルトリメチルアンモニウム塩等が挙げられる。
【００３７】
（３）架橋性単量体
重合粒子の特性を改良するために架橋性単量体を添加しても良い。架橋性単量体としては、ジビニルベンゼン、ジビニルナフタレン、ジビニルエーテル、ジエチレングリコールメタクリレート、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、フタル酸ジアリル等の不飽和結合を２個以上有するものが挙げられる。
【００３８】
本発明に係る単量体は、疎水性単量体が８５乃至９９．５重量パーセントで且つ親水性単量体が０．１乃至１５重量パーセントの範囲で適宜選択される。
【００３９】
〔重合開始剤〕
本発明に用いられるラジカル重合開始剤は水溶性であれば適宜使用が可能である。例えば過硫酸塩（過硫酸カリウム、過硫酸アンモニウム等）、アゾ系化合物（４，４′−アゾビス４−シアノ吉草酸及びその塩、２，２′−アゾビス（２−アミジノプロパン）塩等）、パーオキサイド化合物等が挙げられる。
【００４０】
更に上記ラジカル性重合開始剤は、必要に応じて還元剤と組み合わせレドックス系開始剤とする事が可能である。レドックス系開始剤を用いる事で、重合活性が上昇し重合温度の低下が図れ、更に重合時間の短縮が期待できる。
【００４１】
重合温度は、重合開始剤の最低ラジカル生成温度以上であればどの温度を選択しても良いが例えば５０℃から８０℃の範囲が用いられる。但し、常温開始の重合開始剤例えば過酸化水素−還元剤（アスコルビン酸等）の組み合わせを用いる事で室温またはそれに近い温度で重合する事も可能である。
【００４２】
〔界面活性剤〕
界面活性剤は、スルホン酸塩（ドデシルベンゼンスルホン酸ナトリウム、アリールアルキルポリエーテルスルホン酸ナトリウム、３，３−ジスルホンジフェニル尿素−４，４−ジアゾ−ビス−アミノ−８−ナフトール−６−スルホン酸ナトリウム、オルト−カルボキシベンゼン−アゾ−ジメチアニリン、２，２，５，５−テトラメチル−トリフェニルメタン−４，４−ジアゾ−ビス−β−ナフトール−６−スルホン酸ナトリウムなど）、硫酸エステル塩（テトラデシル硫酸ナトリウム、ペンタデシル硫酸ナトリウム、オクチル硫酸ナトリウムなど）、脂肪酸塩（オレイン酸ナトリウム、ラウリン酸ナトリウム、カプリン酸ナトリウム、カプリル酸ナトリウム、カプロン酸ナトリウム、ステアリン酸カリウム、オレイン酸カルシウムなど）などが挙げられる。
【００４３】
〔着色剤〕
着色剤としては特に限定されず、一般的に使用される無機顔料、有機顔料を用いることができる。
【００４４】
（１）無機顔料
無機顔料としては、従来公知のものを用いることができる。どのような顔料でも使用することができるが、具体的な無機顔料を以下に例示する。
【００４５】
黒色の顔料としては、例えば、ファーネスブラック、チャンネルブラック、アセチレンブラック、サーマルブラック、ランプブラック等のカーボンブラック、更にマグネタイト、フェライト等の磁性粉も用いられる。
【００４６】
これらの無機顔料は必要に応じて単独または複数を選択併用する事が可能である。また顔料の添加量は重合体に対して約２〜２０重量部であり、好ましくは約３〜１５重量部が選択される。
【００４７】
（２）有機顔料
有機顔料としては、従来公知のものを用いることができる。どのような顔料でも使用することができるが、望ましい具体的な有機顔料を以下に例示する。
【００４８】
マゼンタまたはレッド用の顔料としては、Ｃ．Ｉ．ピグメントレッド２、Ｃ．Ｉ．ピグメントレッド３、Ｃ．Ｉ．ピグメントレッド５、Ｃ．Ｉ．ピグメントレッド６、Ｃ．Ｉ．ピグメントレッド７、Ｃ．Ｉ．ピグメントレッド１５、Ｃ．Ｉ．ピグメントレッド１６、Ｃ．Ｉ．ピグメントレッド４８：１、Ｃ．Ｉ．ピグメントレッド５３：１、Ｃ．Ｉ．ピグメントレッド５７：１、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド１２３、Ｃ．Ｉ．ピグメントレッド１３９、Ｃ．Ｉ．ピグメントレッド１４４、Ｃ．Ｉ．ピグメントレッド１４９、Ｃ．Ｉ．ピグメントレッド１６６、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド１７８、Ｃ．Ｉ．ピグメントレッド２２２等が挙げられる。
【００４９】
オレンジまたはイエロー用の顔料としては、Ｃ．Ｉ．ピグメントオレンジ３１、Ｃ．Ｉ．ピグメントオレンジ４３、Ｃ．Ｉ．ピグメントイエロー１２、Ｃ．Ｉ．ピグメントイエロー１３、Ｃ．Ｉ．ピグメントイエロー１４、Ｃ．Ｉ．ピグメントイエロー１５、Ｃ．Ｉ．ピグメントイエロー１７、Ｃ．Ｉ．ピグメントイエロー９３、Ｃ．Ｉ．ピグメントイエロー９４、Ｃ．Ｉ．ピグメントイエロー１３８、等が挙げられる。
【００５０】
グリーンまたはシアン用の顔料としては、Ｃ．Ｉ．ピグメントブルー１５、Ｃ．Ｉ．ピグメントブルー１５：２、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１６、Ｃ．Ｉ．ピグメントブルー６０、Ｃ．Ｉ．ピグメントグリーン７等が挙げられる。
【００５１】
これらの有機顔料は所望に応じて単独または複数を選択併用する事が可能である。また顔料の添加量は重合体に対して約２から約２０部であり、好ましくは約３から１５部が選択される。
【００５２】
〔表面改質剤〕
着色剤の表面改質剤としては、従来公知のものを使用することができる。具体的には、シラン化合物、チタン化合物、アルミニウム化合物等が好ましく用いることができる。
【００５３】
シラン化合物としては、メチルトリメトキシシラン、フェニルトリメトキシシラン、メチルフェニルジメトキシシタン、ジフェニルジメトキシシラン、等のアルコキシシラン、ヘキサメチルジシロザン等のシリザン、γ−クロロプロピルトリメトキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−ウレイドプロピルトリエトキシシラン等が挙げられる。
【００５４】
チタン化合物としては、例えば、味の素社製の「プレンアクト」と称する商品名で市販されているＴＴＳ、９Ｓ、３８Ｓ、４１Ｂ、４６Ｂ、５５、１３８Ｓ、２３８Ｓ等、日本曹達社製の市販品Ａ−１、Ｂ−１、ＴＯＴ、ＴＳＴ、ＴＡＡ、ＴＡＴ、ＴＬＡ、ＴＯＧ、ＴＢＳＴＡ、Ａ−１０、ＴＢＴ、Ｂ−２、Ｂ−４、Ｂ−７、Ｂ−１０、ＴＢＳＴＡ−４００、ＴＴＳ、ＴＯＡ−３０、ＴＳＤＭＡ、ＴＴＡＢ、ＴＴＯＰ等が挙げられる。
【００５５】
アルミニウム化合物としては、例えば、味の素社製の「プレンアクトＡＬ−Ｍ」等が挙げられる。
【００５６】
これらの表面改質剤濃度は着色剤に対して０．０１〜２０ｗｔ％であり、好ましくは１〜１５ｗｔ％が選択される。
【００５７】
〔無機微粒子〕
無機微粒子としては、従来公知のものを使用することができる。具体的には、シリカ、チタン、アルミナ微粒子等が好ましく用いることができる。
【００５８】
シリカ微粒子としては、例えば、日本アエロジル（株）製の市販品Ｒ−８０５、Ｒ−９７６、Ｒ−９７４、Ｒ−９７２、Ｒ−８１２、Ｒ−８０９、ヘキスト（株）製のＨＶＫ−２１５０、Ｈ−２００、キャボット（株）製の市販品ＴＳ−７２０、ＴＳ−５３０、ＴＳ−６１０、Ｈ−５、ＭＳ−５等が挙げられる。
【００５９】
チタン微粒子としては、例えば、日本アエロジル（株）製の市販品Ｔ−８０５、Ｔ−６０４、テイカ（株）製の市販品ＭＴ−１００Ｓ、ＭＴ−１００Ｂ、ＭＴ−５００ＢＳ、ＭＴ−６００、ＭＴ−６００ＳＳ、ＪＡ−１、富士チタン（株）製の市販品ＴＡ−３００ＳＩ、ＴＡ−５００、ＴＡＦ−１３０、ＴＡＦ−５１０、ＴＡＦ−５１０Ｔ、出光興産（株）製の市販品ＩＴ−Ｓ、ＩＴ−ＯＡ、ＩＴ−ＯＢ、ＩＴ−ＯＣ等が挙げられる。
【００６０】
アルミナ微粒子としては、例えば、日本アエロジル（株）製の市販品ＲＦＹ−Ｃ、Ｃ−６０４、石原産業（株）製の市販品ＴＴＯ−５５等が挙げられる。
【００６１】
〔静電荷像現像剤用トナーのその他添加剤〕
本発明の着色重合体粒子（着色粒子ということもある）を静電荷像現像剤用トナーとして用いる場合、重合体内に添加されるべきトナー成分を含有させる必要がある。上記成分として、荷電制御剤、定着向上剤等が挙げられる。これらの成分は、重合性単量体中に所望の含量を添加する事で導入する事が可能である。
【００６２】
また、本発明の着色重合体粒子を静電荷像現像剤トナーとして使用する際に、流動性や帯電性を改良するための後添加剤（外添剤とも称する）を配合して用いる事ができる。
【００６３】
（１）定着改良剤
定着改良剤としては、公知のものが用いられる。一般的には、ポリオレフィン系が用いられる。例えば低分子量ポリエチレン、低分子量ポリプロピレン、酸化処理されたポリエチレン及びポリプロピレン、酸変成処理されたポリエチレン及びポリプロピレン等が用いられる。
【００６４】
（２）荷電制御剤
荷電制御剤も同様に公知のものが用いられる。但し、重合体粒子表面に極性基を有するモノマーを共重合させた場合には、必要がない場合もある。ここで言う極性基とはカルボキシル基、スルホン酸基、アミノ基、アンモニウム塩基等、正負に問わず電荷を有する基を表す。
【００６５】
荷電制御剤としては、プラス帯電性としてニグロシン系の電子供与性染料、ナフテン酸または高級脂肪酸の金属塩、アルコキシル化アミン、第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、マイナス帯電性として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が挙げられる。
【００６６】
（３）外添剤
外添剤には、例えば流動化剤、帯電制御剤及び滑剤等の微粒子がある。流動化剤としては、無機微粉末、例えば疎水性シリカ、酸化チタン、アルミナ及びこれらの硫化物、窒化物及び炭化ケイ素等が挙げられる。帯電制御剤としては、ポリフッ化ビニリデン、ポリスチレン粉末、ポリメチルメタクリレート粉末及びポリエチレン微粒子等が挙げられる。
【００６７】
（４）滑剤
滑剤には、例えばステアリン酸のカドミウム、バリウム、ニッケル、コバルト、ストロンチウム、銅、マグネシウム、カルシウム塩等、オレイン酸亜鉛、マンガン、鉄、コバルト、銅、鉛、マグネシウム塩、パルミチン酸の亜鉛、コバルト、銅、マグネシウム、ケイ素、カルシウム塩、リノール酸の亜鉛、コバルト、カルシウム塩、リシノール酸の亜鉛、カドミウム塩、カプリル酸の鉛塩、カプロン酸の鉛塩等の高級脂肪酸の金属塩が挙げられる。これらは必要に応じて添加される。
【００６８】
〔着色剤の表面処理方法〕
着色剤の表面改質法は、溶媒中に着色剤を分散し、その中に表面改質剤を添加した後昇温し反応を行う。反応終了後、ろ過し同一の溶媒で洗浄ろ過を繰り返し乾燥させ表面改質剤で処理された顔料を得る。
【００６９】
〔着色剤の分散〕
着色剤の分散は、水相中で界面活性剤濃度をＣＭＣ以上で行われる。分散方法は、機械的撹拌、例えば、サンドグラインダー、音波処理、例えば、超音波分散、加圧分散、例えば、マントンゴーリン等が用いられる。
【００７０】
〔着色重合体粒子の製造方法〕
本発明の顔料含有重合体粒子の製造方法は、表面改質剤で処理された着色剤を界面活性剤分散濃度をＣＭＣ以上にした水溶液中で分散した分散液を界面活性剤濃度がＣＭＣ以下になるまで希釈する。その分散液に水溶性ラジカル重合開始剤を溶解し、エチレン性不飽和単量体を添加し水系析出重合を行い顔料含有重合体粒子を得る方法であって、前記着色剤を重合粒子中に含有させるものである。
【００７１】
〔会合融着工程〕
重合工程によって生成された着色剤含有複合重合体粒子（着色剤含有粒子ともいう）を用いて会合、融着を行い非球形状トナーを生成する。
【００７２】
会合融着方法としては、様々な方法、例えば特開昭６０−２２０３５８号、特開平４−２８４４６１号等がある。しかし、これらの方法では、所望の粒径、粒径分布を制御することがかなり困難である。そこで本発明者等は、特開平５−１１５５７２号の方法、すなわち、重合体微粒子分散液の臨界凝集濃度以上の凝集剤及び水に対して無限溶解する有機溶媒を添加する方法で非球状粒子を生成した。
【００７３】
【実施例】
以下、実施例を挙げて本発明を詳細に説明するが、本発明の態様はこれに限定されない。
【００７４】
トナー製造例１
カーボンブラック（リーガル３３０Ｒ：キャボット社製）をアルミニウムカップリング剤（プレンアクトＡｌ−Ｍ：味の素社製）で処理したもの１０．６７ｇをドデシル硫酸ナトリウム４．９２ｇを１２０ｍｌの純水に溶解した溶液に添加し、撹拌しつつ超音波を付与することによりカーボンブラックの水分散液を調整した。また、低分子量ポリプロピレン（数平均分子量＝３２００）を熱を加えながら水中に界面活性剤により乳化させた固形分濃度＝２０重量％の乳化分散液を調整した。上記カーボンブラックの分散液に低分子量ポリプロピレン乳化分散液４３ｇを混合し、さらに、スチレンモノマー９８．１ｇ、ｎ−ブチルアクリレートモノマー１８．４ｇ、メタクリル酸モノマー６．１ｇ、連鎖移動定数が３．０であるｔ−ドデシルメルカプタン３．３ｇ、脱気済み純水８５０ｍｌを添加した後に、窒素気流下撹拌を行いながら７０℃まで昇温した。ついで、過硫酸カリウム４．１ｇを溶解した純水２００ｍｌを加え、７０℃にて６時間反応させた。得られたカーボンブラック含有着色粒子分散液を「分散液１」とする。なお、このものの重量平均一次粒子径（光散乱電気永動粒径測定装置 ＥＬＳ−８００：大塚電子工業社製）及び分子量分布を下記に示す条件にて測定した。
【００７５】
装置：東ソーＨＬＣ−８０２０
カラム：ＧＭＨＸＬｘ２，Ｇ２０００ＨＸＬｘ１
検出器：ＲＩ
溶出液流速：１．０ミリリットル／分
試料濃度：０．０１ｇ／２０ミリリットル
試料量：１００マイクロリットル
検量線：標準ポリスチレンにて作成
結果を下記表１に示す。この「分散液１」６００ｍｌに対して２．７モル／ｌの塩化カリウム水溶液を１６０ｍｌ添加し、さらにイソプロピルアルコール９４ｍｌ及びポリオキシエチレンオクチルフェニルエーテル（エチレンオキサイド平均重合度は１０である）５．４ｇを溶解した純水４０ｍｌを添加した。その後、８５℃まで昇温し、６時間反応させた。ついで反応終了後、反応液を濾過、水洗を行い、さらに、本発明の化合物を除去するために、メタノールにて洗浄した。ついで、乾燥しすることで本発明に係る着色粒子を得た。このものを「着色粒子１」とし、この粒子の体積平均粒子径（島津製ＳＡＬＤ−１１００使用）を下記表１に示す。この着色粒子１に疎水性シリカ（数平均一次粒子径＝１２ｎｍ）を１．０部添加して本発明のトナー「トナー１」を得た。得られたトナー中の各本発明の化合物の含有量は下記に示す条件にて測定し、その結果を表２に併記した。
【００７６】
装置：島津ＧＣ−８Ａ
分離カラム：ステンレス製充填カラム 内径 ３ｍｍ 全長 ２ｍ
充填剤：ＧＬサイエンス ＰＥＧ−２０Ｍ １０％ Ｃｈｒｏｍｏｓｏｒｂ
ＷＡＷ ＤＭＣＳ ６０／８０ｍｅｓｈ
移動相：Ｈｅ
検出器：ＦＩＤ
注入量：０．５μｌ（尚、試料は濃縮導入装置により濃縮したものを使用）
トナー製造例２
トナー製造例１において、ｔ−ドデシルメルカプタン３．５ｇを連鎖移動定数が０．２１であるα−メチルスチレンダイマー３．８３ｇにした他は同様にして「着色粒子２」「トナー２」を得た。
【００７７】
トナー製造例３
着色粒子製造例１において、ｔ−ドデシルメルカプタン３．５ｇを連鎖移動定数が１９．３であるオクチルメルカプタン１．０２ｇと連鎖移動定数が１４．８であるドデシルメルカプタン１．４０ｇの混合物にした他は同様にして「着色粒子３」「トナー３」を得た。
【００７８】
比較用トナー製造例１
着色粒子製造例１において、ｔ−ドデシルメルカプタンを使用せず、反応温度条件を制御することのみによって調整した他は同様にして「比較用着色粒子１」及び「比較用トナー１」を得た。
【００７９】
比較用トナー製造例２
着色粒子製造例１において、メタノール洗浄をしない他は同様にして「比較用着色粒子２」及び「比較用トナー２」を得た。
【００８０】
【表１】

【００８１】
評価
（１）テープ剥離試験
上記着色粒子１〜３および比較用着色粒子１を用いて、定着温度を自由に変えることの可能な複写機を使用して、定着速度を８０ｍｍ／ｓｅｃとして、初期濃度を１．０〜１．２のベタ画像を画出しした後、メンディングテープ（住友３Ｍ製）を画像部上へ貼りつけた後、剥した部分の画像濃度を測定し初期濃度との比率を算出したものをテープ剥離による定着率とし、定着温度１７０℃における定着率で評価した。
【００８２】
（２）画像汚れの評価
画像汚れは、各トナーを用いて３３℃／８０％ＲＨの条件で２万枚印字を行い、１０００枚単位で白紙を印字し、その時の白紙に対する汚れの有無により評価した。目視で汚れが見える状態の枚数を表２に記載した。
【００８３】
【表２】

【００８４】
なお、比較用トナー２では、定着時にメルカプタンの臭気が感じられた。
【００８５】
以上の結果が示すように本発明のトナーは、テープ剥離による定着率が定着温度１７０℃において８０％以上と高く、紙への吸着性に優れている。また、画像汚れについても本発明のトナーは、比較用トナーに比べ発生のしにくいものとなった。
【００８６】
【発明の効果】
本発明により、定着性が安定して確保することのできる静電荷現像用トナー及び現像剤を提供することが出来る。
【００８７】
さらに、本発明の化合物を用いて、安定した定着性を確保したトナーであって、且つ、臭気が無く、環境に影響を与えないトナーを提供することが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrostatic charge developing toner used in a copying machine, a printer, and the like, a method for manufacturing the same, and a developer.
[0002]
[Prior art]
Conventionally, as a means for adjusting a toner, a resin is adjusted by various polymerization methods and used. In this polymerization reaction, it is necessary to adjust the molecular weight at the polymerization stage, and as a method for adjusting the molecular weight, it is often carried out by adjusting the kind and the amount of the so-called polymerization initiator.
[0003]
However, this method only suppresses the polymerization reaction itself, and is insufficient as a method for controlling the length of the molecular chain due to non-uniformity of heat transfer and the like. As a result, it becomes difficult to control the molecular weight distribution, and it is not possible to sufficiently control the fixing property and the like. For this reason, when the toner for electrostatic charge development is used for a long period, a problem of contamination of the fixing roller is likely to occur.
[0004]
When a chain transfer agent is used, it reacts uniformly with the monomer, so that the molecular weight distribution in the resin can be controlled uniformly. However, when used as the chain transfer agent, particularly when a mercaptan-based material is used, a stable reaction inhibition is exhibited due to the adverse effect of the odor and the variation in the reaction inhibition due to the structure, and It was difficult to adjust the residual mercaptan and keep it low.
[0005]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for electrostatic charge development capable of stably securing the fixing property.
[0006]
Still another object of the present invention is to provide a toner and a developer which are stable in fixing property using a chain transfer agent, have no odor, and do not affect the environment.
[0007]
[Means for Solving the Problems]
The object of the present invention is achieved by adopting one of the following constitutions.
[0008]
(1) An electrostatic charge developing toner containing a tertiary alkyl mercaptan in a weight ratio of 2 to 100 ppm.
(2) An electrostatic charge developing toner comprising α-methylstyrene dimer in a weight ratio of 2 to 100 ppm.
(3) A toner for electrostatic charge development, comprising a mixture of alkyl mercaptans having different carbon numbers in a weight ratio of 2 to 100 ppm.
In addition, the mixture of the above-mentioned tertiary alkyl mercaptan, α-methylstyrene dimer and alkyl mercaptan having different carbon numbers is hereinafter also referred to as the compound of the present invention.
[0009]
(4) is characterized by using a polymerizable monomer the tertiary alkyl mercaptan polymerization allowed to the polymer obtained in the presence of, (1) static charge developing toner according, the method of manufacturing.
(5) is characterized by using a polymerizable monomer and α- methyl styrene polymerization allowed to the polymer obtained in the presence of dimers, (2) electrostatic developing toner according, the method of manufacturing.
(6) a polymerizable monomer which comprises using the polymerization allowed to the polymer obtained in the presence of a mixture of different alkyl mercaptan carbon number, (3) an electrostatic developing toner according, preparation of Method.
[0010]
(7) The electrostatic charge developing toner according to (1), wherein the tertiary alkyl mercaptan has a chain transfer constant of 0.2 to 20.
(8) The electrostatic charge developing toner according to ( 2 ), wherein the α-methylstyrene dimer has a chain transfer constant of 0.2 to 20.
(9) The electrostatic charge developing toner according to ( 3 ), wherein the mixture of alkyl mercaptans having different carbon numbers has a chain transfer constant of 0.2 to 20.
[0011]
(10) An electrostatic charge developer comprising a toner and a carrier, wherein the toner contains a tertiary alkyl mercaptan in a weight ratio of 2 to 100 ppm.
(11) An electrostatic charge developer having a toner and a carrier, wherein the toner contains 2 to 100 ppm by weight of α-methylstyrene dimer.
(12) An electrostatic developer having a toner and a carrier, wherein the toner contains a mixture of alkyl mercaptans having different carbon numbers in a weight ratio of 2 to 100 ppm.
[0012]
The present invention can achieve the object of the present invention by using the above-mentioned compound of the present invention. That is, by containing the compound of the present invention in a specific amount, the fixing property can be stably secured over a long period of time. In addition, the above-mentioned compound of the present invention is generally a compound having an odor, but since it is used in a very small amount, there is no odor, and no odor problem occurs during use.
[0013]
Since the content of the compound of the present invention is very small, the content is generally measured by gas chromatography (GC-8A manufactured by Shimadzu Corporation), and the content is 100 ppm or less by weight of the toner. It is necessary that the lower limit of the content be too small to achieve the object of the present invention.
[0014]
As a means of adjusting the content, a method of preparing a resin by incorporating the compound of the present invention, followed by washing with a solvent that dissolves the compound of the present invention without dissolving the resin, or removing by a heat treatment or the like Can be adjusted. In addition, by using these compounds of the present invention, the molecular weight can be easily adjusted to be uniform.
[0015]
As the tertiary alkyl mercaptan, those in which the carbon atom adjacent to the mercapto group is a tertiary carbon atom are preferable, and the number of carbon atoms is preferably 6 or more. For example, t-dodecyl mercaptan, 1,1,3, Examples include 3-tetramethylbutyl mercaptan, 1,1,3,3,5,5-hexamethylhexyl mercaptan, 1,1,3,3,5,5,7,7-octamethyloctyl mercaptan, and the like. The number of these carbon atoms is preferably 20 or less from a practical viewpoint. The alkyl mercaptan to be used as a mixture is not particularly limited, and includes, for example, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, dodecyl mercaptan, tetradecyl mercaptan, octadecyl mercaptan, and two or more of these. A mixture of the above alkylmercaptans is used. These alkyl mercaptans may have a primary, secondary, or tertiary alkyl group, or may be linear or branched, but the alkyl group has 5 or more carbon atoms. It is preferable to use a mixture of mercaptans, and the upper limit is preferably 20 or less carbon atoms from a practical viewpoint. In addition, when using a mixture of alkyl mercaptans, the mixture can be used in an arbitrary ratio, but the mixture is preferably in a ratio of 1: 0.3 to 1.8 (molar ratio). It is preferable to achieve the object of the invention, and it is particularly preferable to use a mixture in a ratio of 1: 0.8 to 1.3 (molar ratio).
[0016]
The α-methylstyrene dimer may be a dimer of an α-methylstyrene monomer, or may contain a small amount of the monomer itself or a trimer or higher polymer depending on the production method.
[0017]
The toner of the present invention may be produced by any known method, for example, a method of kneading, pulverizing, and separating the compound of the present invention and various additives necessary for the toner into a resin, but is produced by the method described below. Is preferred. Hereinafter, a method for producing the toner of the present invention will be described based on a so-called polymerization method in a dispersion, which is a preferable production method in the present invention.
[0018]
That is, a preferred method for producing the toner of the present invention is to polymerize a polymerizable monomer in the presence of a mixture of the compounds of the present invention to obtain a toner, and is prepared by a suspension polymerization method. It is prepared by a method or a method of associating a plurality of colorant-containing particles prepared by an emulsion polymerization method. In this case, in addition to the above-described compound of the present invention, a toner additive such as a coloring agent, a charge control agent, and a fixing improver, a polymerization initiator for controlling polymerization and obtaining desired particles, a surfactant, and the like. May be optionally added. In particular, in the present invention, a method of using an emulsion polymerization method and preparing the obtained fine particles by associating them thereafter is preferable.
[0019]
The chain transfer constant of the compound of the present invention during this preparation is preferably from 0.2 to 20.
[0020]
The definition of the chain transfer constant is shown below.
[0021]
(Equation 1)

[0022]
Hereinafter, a preferred method for producing the toner of the present invention will be described in detail.
[0023]
(Polymerizable monomer for producing toner)
In order to prepare the toner of the present invention, a polymerizable monomer, particularly, a hydrophobic monomer is used. If necessary, a hydrophilic monomer or a crosslinkable monomer may be added to the polymerizable monomer.
[0024]
(1) Hydrophobic monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and a conventionally known monomer can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics.
[0025]
Specifically, vinyl aromatic monomers, α-methylene resin carboxylic acid and ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers Monomers, halogenated olefin monomers and the like can be used.
[0026]
Examples of the vinyl aromatic monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and p-methylstyrene. -Ethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn- Styrene-based monomers such as dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof.
[0027]
Examples of α-methylene aliphatic carboxylic acids and esters thereof include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Acrylic esters and methacrylic esters such as butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate Is mentioned.
[0028]
Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl benzoate.
[0029]
Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.
[0030]
Examples of the monoolefin-based monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and the like.
[0031]
Examples of the diolefin-based monomer include butadiene, isoprene, and chloroprene.
[0032]
(2) Hydrophilic monomer The hydrophilic monomer constituting the monomer component is not particularly limited, and a conventionally known monomer can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics.
[0033]
For example, amine compounds such as carboxyl group-containing monomers, sulfonic acid group-containing monomers, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts can be used.
[0034]
Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monobutyl maleate, and monooctyl maleate.
[0035]
Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and the like.
[0036]
Examples of the amine compound include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 3-dimethylaminophenyl acrylate, and 2-hydroxy-3-methacryloxypropyltrimethylammonium salt. .
[0037]
(3) A crosslinkable monomer may be added in order to improve the properties of the crosslinked monomer polymer particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.
[0038]
The monomer according to the present invention is appropriately selected such that the hydrophobic monomer is in the range of 85 to 99.5% by weight and the hydrophilic monomer is in the range of 0.1 to 15% by weight.
[0039]
(Polymerization initiator)
The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4'-azobis-4-cyanovaleric acid and its salts, 2,2'-azobis (2-amidinopropane) salts, etc.), Oxide compounds and the like.
[0040]
Further, the radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. By using the redox initiator, the polymerization activity is increased, the polymerization temperature is lowered, and the polymerization time can be further reduced.
[0041]
As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. However, it is also possible to polymerize at room temperature or a temperature close thereto by using a combination of a polymerization initiator started at room temperature, for example, a hydrogen peroxide-reducing agent (such as ascorbic acid).
[0042]
(Surfactant)
The surfactant is a sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, sodium 3,3-disulfondiphenylurea-4,4-diazo-bis-amino-8-naphthol-6-sulfonate) , Sodium ortho-carboxybenzene-azo-dimethaniline, sodium 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate), sulfate salts ( Sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc., fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) And the like.
[0043]
(Colorant)
The colorant is not particularly limited, and commonly used inorganic pigments and organic pigments can be used.
[0044]
(1) Inorganic Pigment As the inorganic pigment, conventionally known ones can be used. Although any pigment can be used, specific inorganic pigments are exemplified below.
[0045]
As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.
[0046]
These inorganic pigments can be used alone or in combination as needed. The amount of the pigment added is about 2 to 20 parts by weight, preferably about 3 to 15 parts by weight, based on the polymer.
[0047]
(2) Organic Pigment As the organic pigment, a conventionally known organic pigment can be used. Although any pigment can be used, preferred specific organic pigments are exemplified below.
[0048]
Pigments for magenta or red include C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.
[0049]
Examples of orange or yellow pigments include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138, and the like.
[0050]
Examples of green or cyan pigments include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.
[0051]
These organic pigments can be used alone or in combination of two or more as desired. The addition amount of the pigment is about 2 to about 20 parts, preferably about 3 to 15 parts, based on the polymer.
[0052]
(Surface modifier)
As the surface modifier for the colorant, a conventionally known one can be used. Specifically, silane compounds, titanium compounds, aluminum compounds and the like can be preferably used.
[0053]
Examples of the silane compound include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxycytane, and diphenyldimethoxysilane; silizane such as hexamethyldisilozane; γ-chloropropyltrimethoxysilane; vinyltrichlorosilane; and vinyl. Trimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxy Silane and the like.
[0054]
Examples of the titanium compound include commercial products A-1 manufactured by Nippon Soda Co., Ltd. such as TTS, 9S, 38S, 41B, 46B, 55, 138S, and 238S, which are commercially available under the trade name "Plenact" manufactured by Ajinomoto Co. , B-1, TOT, TST, TAA, TAT, TLA, TOG, TBSTA, A-10, TBT, B-2, B-4, B-7, B-10, TBSTA-400, TTS, TOA-30 , TSDMA, TTAB, TTOP and the like.
[0055]
As the aluminum compound, for example, "Plenact AL-M" manufactured by Ajinomoto Co., Inc., and the like are listed.
[0056]
The concentration of these surface modifiers is 0.01 to 20% by weight, preferably 1 to 15% by weight, based on the colorant.
[0057]
(Inorganic fine particles)
Conventionally known inorganic fine particles can be used. Specifically, silica, titanium, alumina fine particles and the like can be preferably used.
[0058]
Examples of the silica fine particles include commercial products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., and HVK-2150 manufactured by Hoechst Co., Ltd. H-200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5, etc., manufactured by Cabot Corporation.
[0059]
As the titanium fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., and commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600 manufactured by Teika Co., Ltd. 600SS, JA-1, commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd., commercial products IT-S, IT- manufactured by Idemitsu Kosan Co., Ltd. OA, IT-OB, IT-OC and the like.
[0060]
Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.
[0061]
(Other additives of toner for electrostatic image developer)
When the colored polymer particles (sometimes referred to as colored particles) of the present invention are used as a toner for an electrostatic image developer, it is necessary to include a toner component to be added to the polymer. Examples of the above components include a charge control agent and a fixing improver. These components can be introduced by adding a desired content to the polymerizable monomer.
[0062]
When the colored polymer particles of the present invention are used as an electrostatic image developer toner, a post-additive (also referred to as an external additive) for improving fluidity and chargeability can be blended and used. .
[0063]
(1) Fixing improver Known fixing improvers are used. Generally, a polyolefin type is used. For example, low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene and polypropylene, acid modified polyethylene and polypropylene, and the like are used.
[0064]
(2) Charge control agent A known charge control agent is also used. However, when a monomer having a polar group on the surface of the polymer particles is copolymerized, it may not be necessary in some cases. As used herein, the polar group refers to a carboxyl group, a sulfonic acid group, an amino group, an ammonium base, or the like, having a positive or negative charge.
[0065]
Examples of the charge control agent include a nigrosine-based electron-donating dye having a positive charge, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt, an alkylamide, a metal complex, a pigment, a fluorinated activator, and the like. And organic complexes having an electron accepting property as negative charge, chlorinated paraffin, chlorinated polyester, sulfonylamine of copper phthalocyanine, and the like.
[0066]
(3) External additives The external additives include, for example, fine particles such as a fluidizing agent, a charge controlling agent, and a lubricant. Examples of the fluidizing agent include inorganic fine powders such as hydrophobic silica, titanium oxide, and alumina, and sulfides, nitrides, and silicon carbide thereof. Examples of the charge control agent include polyvinylidene fluoride, polystyrene powder, polymethyl methacrylate powder, and polyethylene fine particles.
[0067]
(4) Lubricants Lubricants include, for example, cadmium, barium, nickel, cobalt, strontium, copper, magnesium and calcium salts of stearic acid, zinc oleate, manganese, iron, cobalt, copper, lead, magnesium salts, and palmitic acid. Metal salts of higher fatty acids such as zinc, cobalt, copper, magnesium, silicon, calcium salts, zinc linoleic acid, cobalt, calcium salts, zinc ricinoleic acid, cadmium salts, lead salts of caprylic acid, and lead salts of caproic acid. No. These are added as needed.
[0068]
(Surface treatment method of colorant)
In the method for modifying the surface of a colorant, the colorant is dispersed in a solvent, the surface modifier is added thereto, and then the temperature is raised to cause a reaction. After completion of the reaction, the mixture is filtered, washed and filtered repeatedly with the same solvent, and dried to obtain a pigment treated with a surface modifier.
[0069]
(Dispersion of colorant)
The dispersion of the colorant is performed in the aqueous phase at a surfactant concentration of CMC or higher. As a dispersion method, mechanical stirring, for example, a sand grinder, sonication, for example, ultrasonic dispersion, pressure dispersion, for example, Menton-Gaulin or the like is used.
[0070]
(Production method of colored polymer particles)
The method for producing the pigment-containing polymer particles of the present invention is a method of dispersing a dispersion obtained by dispersing a colorant treated with a surface modifier in an aqueous solution having a surfactant dispersion concentration of not less than CMC so that the surfactant concentration is not more than CMC. Dilute until completely. A method of dissolving a water-soluble radical polymerization initiator in the dispersion, adding an ethylenically unsaturated monomer and performing aqueous precipitation polymerization to obtain pigment-containing polymer particles, wherein the colorant is contained in the polymer particles. It is to let.
[0071]
(Association fusing step)
Using a colorant-containing composite polymer particle (also referred to as a colorant-containing particle) generated in the polymerization step, association and fusion are performed to produce a non-spherical toner.
[0072]
There are various methods for associative fusion, for example, JP-A-60-220358 and JP-A-4-284461. However, with these methods, it is quite difficult to control the desired particle size and particle size distribution. Therefore, the present inventors have proposed the method of JP-A-5-115572, that is, a method of adding a coagulant having a critical coagulation concentration of the polymer fine particle dispersion or higher and an organic solvent that is infinitely soluble in water to add non-spherical particles. Generated.
[0073]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.
[0074]
Toner production example 1
Carbon black (REGAL 330R: manufactured by Cabot) treated with an aluminum coupling agent (preneact Al-M: manufactured by Ajinomoto Co.) was added to a solution obtained by dissolving 10.67 g of sodium dodecyl sulfate (4.92 g) in 120 ml of pure water. An aqueous dispersion of carbon black was prepared by applying ultrasonic waves with stirring. In addition, an emulsified dispersion having a solid content of 20% by weight was prepared by emulsifying low molecular weight polypropylene (number average molecular weight = 3200) in water while adding heat to the surfactant. 43 g of a low molecular weight polypropylene emulsified dispersion was mixed with the carbon black dispersion, and further, 98.1 g of a styrene monomer, 18.4 g of an n-butyl acrylate monomer, 6.1 g of a methacrylic acid monomer, and a chain transfer constant of 3.0. After adding 3.3 g of a certain t-dodecyl mercaptan and 850 ml of deaerated pure water, the temperature was raised to 70 ° C. while stirring under a nitrogen stream. Then, 200 ml of pure water in which 4.1 g of potassium persulfate was dissolved was added, and the mixture was reacted at 70 ° C. for 6 hours. The resulting carbon black-containing colored particle dispersion is referred to as “dispersion 1”. The weight-average primary particle size (light scattering electric permanent particle size analyzer ELS-800: manufactured by Otsuka Electronics Co., Ltd.) and molecular weight distribution of the product were measured under the following conditions.
[0075]
Equipment: Tosoh HLC-8020
Column: GMHXLx2, G2000HXLx1
Detector: RI
Eluent flow rate: 1.0 ml / min Sample concentration: 0.01 g / 20 ml Sample amount: 100 microliter Calibration curve: Prepared with standard polystyrene The results are shown in Table 1 below. 160 ml of a 2.7 mol / l aqueous potassium chloride solution was added to 600 ml of the “dispersion 1”, and 94 ml of isopropyl alcohol and 5.4 g of polyoxyethylene octylphenyl ether (the average degree of polymerization of ethylene oxide was 10). Was dissolved in 40 ml of pure water. Thereafter, the temperature was raised to 85 ° C., and the reaction was performed for 6 hours. After the completion of the reaction, the reaction solution was filtered and washed with water, and further washed with methanol to remove the compound of the present invention. Subsequently, by drying, the colored particles according to the present invention were obtained. This was designated as “colored particle 1”, and the volume average particle diameter of the particle (using SALD-1100 manufactured by Shimadzu) is shown in Table 1 below. 1.0 part of hydrophobic silica (number average primary particle size = 12 nm) was added to the colored particles 1 to obtain a toner “Toner 1” of the present invention. The content of each compound of the present invention in the obtained toner was measured under the following conditions, and the results are shown in Table 2.
[0076]
Equipment: Shimadzu GC-8A
Separation column: packed column made of stainless steel Inner diameter 3 mm Total length 2 m
Filler: GL Science PEG-20M 10% Chromosorb
WAW DMCS 60/80 mesh
Mobile phase: He
Detector: FID
Injection volume: 0.5 μl (Note that the sample used was concentrated by a concentration introducing device.)
Toner production example 2
"Colored particle 2" and "Toner 2" were obtained in the same manner as in Toner Production Example 1, except that 3.5 g of t-dodecyl mercaptan was changed to 3.83 g of α-methylstyrene dimer having a chain transfer constant of 0.21. .
[0077]
Toner Production Example 3
In Colored Particle Production Example 1, except that 3.5 g of t-dodecyl mercaptan was used as a mixture of 1.02 g of octyl mercaptan having a chain transfer constant of 19.3 and 1.40 g of dodecyl mercaptan having a chain transfer constant of 14.8. Similarly, “colored particles 3” and “toner 3” were obtained.
[0078]
Comparative toner production example 1
"Comparative colored particles 1" and "Comparative toner 1" were obtained in the same manner as in Colored Particle Production Example 1, except that t-dodecyl mercaptan was not used and the reaction temperature was adjusted only by controlling the reaction temperature conditions.
[0079]
Comparative toner production example 2
"Comparative colored particles 2" and "Comparative toner 2" were obtained in the same manner as in Colored Particle Production Example 1 except that methanol washing was not performed.
[0080]
[Table 1]

[0081]
Evaluation (1) Tape Peeling Test Using the above colored particles 1 to 3 and comparative colored particles 1, using a copying machine capable of freely changing the fixing temperature, setting the fixing speed to 80 mm / sec, and setting the initial density After a solid image of 1.0 to 1.2 was formed, a mending tape (manufactured by Sumitomo 3M) was applied to the image area, and the image density of the stripped portion was measured and the ratio to the initial density was measured. Was calculated as the fixing rate by tape peeling, and the fixing rate at a fixing temperature of 170 ° C. was evaluated.
[0082]
(2) Evaluation of image stains Image stains are evaluated by printing 20,000 sheets at 33 ° C./80% RH using each toner, printing a blank sheet in units of 1000 sheets, and determining whether there is stain on the blank sheet at that time. did. Table 2 shows the number of sheets in which dirt can be visually observed.
[0083]
[Table 2]

[0084]
In the comparative toner 2, the odor of mercaptan was felt at the time of fixing.
[0085]
As shown by the above results, the toner of the present invention has a high fixing rate by tape peeling of 80% or more at a fixing temperature of 170 ° C., and is excellent in adsorbability to paper. Also, the toner of the present invention is less likely to cause image stains than the comparative toner.
[0086]
【The invention's effect】
According to the present invention, it is possible to provide an electrostatic charge developing toner and a developer that can stably secure the fixing property.
[0087]
Further, it is possible to provide a toner which uses the compound of the present invention to secure stable fixability, has no odor, and does not affect the environment.

Claims (12)

An electrostatic charge developing toner containing a tertiary alkyl mercaptan in a weight ratio of 2 to 100 ppm. An electrostatic charge developing toner comprising 2 to 100 ppm by weight of an α-methylstyrene dimer. A toner for electrostatic charge development, comprising a mixture of alkyl mercaptans having different carbon numbers in a weight ratio of 2 to 100 ppm. Characterized by using the obtained polymer polymerizable monomers by polymerizing in the presence of a tertiary alkyl mercaptan, an electrostatic developing toner according to claim 1, the method of manufacturing. Characterized by using a polymer obtained by the polymerizable monomer by polymerizing in the presence of α- methyl styrene dimer, toner for electrostatic charge development of claim 2, the method of manufacturing. Characterized by using the obtained polymer polymerizable monomers by polymerizing in the presence of a mixture of different alkyl mercaptan carbon number, an electrostatic developing toner according to claim 3, the method of manufacturing. The electrostatic charge developing toner according to claim 1, wherein the tertiary alkyl mercaptan has a chain transfer constant of 0.2 to 20. 3. The toner according to claim 2, wherein the α-methylstyrene dimer has a chain transfer constant of 0.2 to 20. 4. The electrostatic charge developing toner according to claim 3, wherein the mixture of alkyl mercaptans having different carbon numbers has a chain transfer constant of 0.2 to 20. An electrostatic charge developer having a toner and a carrier, wherein the toner contains a tertiary alkyl mercaptan in a weight ratio of 2 to 100 ppm. An electrostatic charge developer having a toner and a carrier, wherein the toner contains 2 to 100 ppm by weight of α-methylstyrene dimer. An electrostatic developer having a toner and a carrier, wherein the toner contains a mixture of alkyl mercaptans having different carbon atoms in a weight ratio of 2 to 100 ppm.