JPH1195478A - Electrophotographic toner and its production - Google Patents
Electrophotographic toner and its productionInfo
- Publication number
- JPH1195478A JPH1195478A JP25664197A JP25664197A JPH1195478A JP H1195478 A JPH1195478 A JP H1195478A JP 25664197 A JP25664197 A JP 25664197A JP 25664197 A JP25664197 A JP 25664197A JP H1195478 A JPH1195478 A JP H1195478A
- Authority
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- Prior art keywords
- particles
- toner
- resin particles
- equation
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【0001】[0001]
【発明の属する技術分野】本発明は、電子写真用トナ
ー、および、その製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner and a method for producing the same.
【0002】[0002]
【従来の技術】電子写真は、一般に光導電性部材上に静
電潜像を構成し、そこに正または負の電荷を持ったトナ
ーを静電的に付着させた後、転写紙上にトナー画像を転
写し、定着させることによって画像形成が行われる。こ
こで用いられるトナーとは、主成分としてバインダー樹
脂および着色剤からなる平均粒径5〜20μmの粒子
で、キャリアもしくは帯電ブレードなどの摩擦帯電部材
により適当な帯電量に制御される。ここで、トナーの帯
電量が適性値より大きくなると、画像濃度が小さくな
り、逆にトナーの帯電量が適性値より小さくなると、ト
ナー飛散や地肌カブリなどが起こり、画像品質の劣化を
きたす。2. Description of the Related Art In electrophotography, generally, an electrostatic latent image is formed on a photoconductive member, a toner having a positive or negative charge is electrostatically attached thereto, and then a toner image is formed on a transfer paper. Is transferred and fixed to form an image. The toner used here is a particle having an average particle diameter of 5 to 20 μm comprising a binder resin and a colorant as main components, and is controlled to an appropriate charge amount by a frictional charging member such as a carrier or a charging blade. Here, if the charge amount of the toner is larger than the appropriate value, the image density is reduced. Conversely, if the charge amount of the toner is smaller than the appropriate value, toner scattering or background fogging occurs, resulting in deterioration of image quality.
【0003】通常、これらの問題を防ぐためにトナー中
には荷電制御剤が添加される。正帯電性トナーに添加さ
れる荷電制御剤としては、従来よりニグロシン系染料、
ピリジニウム塩、アンモニウム塩、およびそのレーキ化
合物等が用いられている。Usually, a charge control agent is added to a toner to prevent these problems. As a charge control agent added to a positively chargeable toner, a nigrosine dye,
Pyridinium salts, ammonium salts, and lake compounds thereof have been used.
【0004】しかしながら、これら化合物は微細な粉体
とはいえ粒度分布が広いうえに一定の形状を有しておら
ず、ゆえにバインダー樹脂の中の荷電制御剤の分散状態
を制御することは難しい。荷電制御剤の分散粒径が大き
くなり過ぎると、連続コピー時に荷電制御剤が離脱しや
すくなり、キャリア等の帯電部材の汚染を引き起こし、
逆に荷電制御剤の分散粒径が小さくなり過ぎると、トナ
ーを安定に帯電させる作用が弱まる。その結果、補給ト
ナーの帯電量の立ち上がりがそれまでに比べて遅くな
り、地肌カブリやトナー飛散などの不具合が生じるとい
う欠点がある。また、荷電制御剤は生産時の分散条件に
よりトナー表面に露出する割合が変化するため帯電量が
安定しにくいといった欠点もある。[0004] However, although these compounds are fine powders, they have a wide particle size distribution and do not have a fixed shape, and therefore it is difficult to control the dispersion state of the charge control agent in the binder resin. If the dispersion particle size of the charge control agent is too large, the charge control agent tends to separate during continuous copying, causing contamination of a charging member such as a carrier,
Conversely, if the dispersion particle size of the charge control agent is too small, the effect of stably charging the toner is weakened. As a result, the rise of the charge amount of the replenishment toner becomes slower than before, and there is a disadvantage that a problem such as background fog or toner scattering occurs. Further, the charge control agent has a disadvantage that the charge amount is difficult to stabilize because the ratio of exposure to the toner surface changes depending on the dispersion conditions at the time of production.
【0005】上記問題を解決するために、トナー表面に
帯電性微粒子を固着させることによりトナーの帯電を制
御する方法が知られている。例えば、特開昭63−24
4056号公報には、シランカップリング剤やシリコン
オイルなどにより表面処理されたシリカやアルミナ、も
しくは酸化チタンなどの無機系外添剤を、あるいは、荷
電制御剤等により帯電性を付与した樹脂微粒子などを、
粉体表面改質装置により機械的な衝撃力を加えて、トナ
ー表面に固着させる方法が開示されている。[0005] In order to solve the above-mentioned problem, there is known a method of controlling charging of toner by fixing chargeable fine particles on the surface of toner. For example, JP-A-63-24
Japanese Patent No. 4056 discloses an inorganic external additive such as silica or alumina surface-treated with a silane coupling agent or silicon oil, or titanium oxide, or resin fine particles provided with a chargeability by a charge control agent or the like. To
A method is disclosed in which a mechanical impact force is applied by a powder surface modification device to fix the toner to the toner surface.
【0006】しかし、無機系外添剤あるいは樹脂微粒子
がトナー表面全体に固着すると、無機系外添剤は定着性
が弱いため、また、樹脂微粒子は一般にトナー粒子と比
較して溶融粘度が高いため、その結果、トナーの主成分
であるバインダー樹脂のもつ定着性が損なわれ、トナー
全体の定着性に悪影響を及ぼす。However, if the inorganic external additive or resin fine particles adhere to the entire surface of the toner, the inorganic external additive has poor fixability, and the resin fine particles generally have a higher melt viscosity than the toner particles. As a result, the fixability of the binder resin, which is the main component of the toner, is impaired, which adversely affects the fixability of the entire toner.
【0007】さらに、この問題を解決するための方法と
して、前記特開昭63−244056号公報には、無機
系外添剤あるいは樹脂微粒子をトナー表面に部分的に固
着させる方法が、合わせて開示されている。Further, as a method for solving this problem, Japanese Patent Application Laid-Open No. 63-244056 discloses a method of partially fixing an inorganic external additive or resin fine particles to the toner surface. Have been.
【0008】[0008]
【発明が解決しようとする課題】無機系外添剤あるいは
樹脂微粒子をトナー表面に部分的に固着させる方法にお
いても、通常は部分的に存在する無機系外添剤あるいは
樹脂微粒子の大きさや形状および分散状態が異なるた
め、トナー全体としての長期使用における帯電量の経時
変化を安定させることは非常に難しい。In the method of partially fixing the inorganic external additive or the resin fine particles to the toner surface, the size and shape of the inorganic external additive or the resin fine particles which are usually partially present, and Since the dispersion state is different, it is very difficult to stabilize the change over time in the charge amount during long-term use of the toner as a whole.
【0009】さらに、使用する無機系外添剤あるいは樹
脂微粒子の粒径により下記のような不具合も生ずる。粒
径が大きい場合、トナー表面への付着力は非常に弱く、
キャリアなどの摩擦帯電部材との接触において、これら
がトナー表面より容易に離脱し帯電量が安定しない現象
が生ずる。逆に粒径が小さい場合、これらの粒子はトナ
ー表面の凹部に集中して付着、もしくはトナー中に埋没
しやすくなるため、トナー全体の帯電量は上昇しにくい
といった不具合も生ずる。Further, the following disadvantages also occur depending on the particle size of the inorganic external additive or resin fine particles used. If the particle size is large, the adhesion to the toner surface is very weak,
Upon contact with a frictional charging member such as a carrier, a phenomenon occurs in which these are easily separated from the toner surface and the charge amount is unstable. Conversely, if the particle size is small, these particles are likely to adhere to the concave portions on the toner surface or to be easily buried in the toner, so that there is a problem that the charge amount of the entire toner is hard to increase.
【0010】本発明の目的は長期間の使用時において、
現像剤の帯電安定性に優れ、定着性、および保存性に優
れた電子写真用トナーを提供することにある。An object of the present invention is to provide a long-term use
An object of the present invention is to provide an electrophotographic toner which is excellent in charge stability of a developer and excellent in fixability and storage stability.
【0011】[0011]
【課題を解決するための手段】本発明の電子写真用トナ
ーは、少なくとも着色剤およびバインダー樹脂からなる
着色粒子(A)の表面に、樹脂粒子(B)が凝集物とし
て部分的に固着されていることを特徴とする。In the electrophotographic toner of the present invention, the resin particles (B) are partially fixed as aggregates on the surface of the colored particles (A) comprising at least a colorant and a binder resin. It is characterized by being.
【0012】前記樹脂粒子(B)の平均粒径が0.3μ
m以下であり、樹脂粒子(B)の凝集物の平均粒径が直
径0.5μm以上1.0μm以下であり、さらに、着色
粒子(A)の平均粒径をaμm、樹脂粒子(B)の凝集
物の平均粒径をbμmとすると、これらが下記の(式
1)を満足することが好ましい。The average particle size of the resin particles (B) is 0.3 μm.
m or less, the average particle diameter of the aggregate of the resin particles (B) is 0.5 μm or more and 1.0 μm or less, the average particle diameter of the colored particles (A) is a μm, and the average particle diameter of the resin particles (B) is Assuming that the average particle size of the aggregates is b μm, it is preferable that these satisfy the following (formula 1).
【0013】b≦(a/10) ・・・(式1) また、前記樹脂粒子(B)の凝集物が、着色粒子(A)
の表面に、被覆率50%以上80%以下の範囲で部分的
に固着していることが好ましい。B ≦ (a / 10) (Equation 1) The aggregate of the resin particles (B) is colored particles (A)
Is preferably partially adhered to the surface of the substrate in a range of 50% or more and 80% or less.
【0014】また、前記樹脂粒子(B)がトナー中に含
有される量は、2重量%以上6重量%以下であることが
好ましい。The amount of the resin particles (B) contained in the toner is preferably 2% by weight or more and 6% by weight or less.
【0015】また、前記樹脂粒子(B)の140℃にお
ける粘度η(Pa・sec)は、下記の(式2)を満足
する範囲内にあることが好ましい。The viscosity η (Pa · sec) at 140 ° C. of the resin particles (B) is preferably in a range satisfying the following (formula 2).
【0016】104<η<106 ・・・(式2) さらに、前記着色粒子(A)のガラス転移温度をTgA
(℃)、前記樹脂粒子(B)のガラス転移温度をTgB
(℃)とすると、これらが下記の(式3)を満足するこ
とが好ましい。10 4 <η <10 6 (Equation 2) Further, the glass transition temperature of the colored particles (A) is defined as Tg A
(° C.), the glass transition temperature of the resin particles (B) is determined by Tg B
(° C.), it is preferable that these satisfy the following (Equation 3).
【0017】 TgA≦TgB≦(TgA+15) ・・・(式3) 本発明の電子写真用トナーの製造方法は、円筒状の外壁
と撹拌羽根を有する気流混合機を用いて、着色粒子
(A)の表面に樹脂粒子(B)を固着処理する工程にお
いて、着色粒子(A)のガラス転移温度をTg
A(℃)、樹脂粒子(B)のガラス転移温度をTg
B(℃)、撹拌羽根の先端周速をS(m/sec)、気
流混合機内の温度をH(℃)とすると、これらが下記の
(式4)および(式5)を満足することを特徴とする。Tg A ≦ Tg B ≦ (Tg A +15) (Equation 3) In the method for producing an electrophotographic toner of the present invention, coloring is performed using an airflow mixer having a cylindrical outer wall and a stirring blade. In the step of fixing the resin particles (B) to the surface of the particles (A), the glass transition temperature of the colored particles (A) is set to Tg.
A (° C.), the glass transition temperature of the resin particles (B) is Tg
Assuming that B (° C.), the peripheral speed of the tip of the stirring blade is S (m / sec), and the temperature inside the airflow mixer is H (° C.), they satisfy the following (Equation 4) and (Equation 5). Features.
【0018】 5≦S≦15 ・・・(式4) (TgA−10)≦H≦(TgA+5) ・・・(式5) また、本発明の電子写真用トナーの製造方法は、前記樹
脂粒子(B)を、水溶性重合開始剤の存在下において、
水中で重合性単量体を反応させた後、乾燥して製造する
ことを特徴とする。5 ≦ S ≦ 15 (Equation 4) (Tg A −10) ≦ H ≦ (Tg A +5) (Equation 5) The method for producing the electrophotographic toner of the present invention is as follows. The resin particles (B), in the presence of a water-soluble polymerization initiator,
It is characterized in that it is produced by reacting a polymerizable monomer in water and then drying.
【0019】また、前記樹脂粒子(B)の凝集物は、ス
プレードライ法で乾燥することにより得られた、直径
0.5μm以上1.0μm以下の凝集物であることが好
ましい。The aggregate of the resin particles (B) is preferably an aggregate having a diameter of 0.5 μm or more and 1.0 μm or less, obtained by drying by a spray drying method.
【0020】本発明で得られる電子写真用トナーは、着
色粒子(A)の表面に樹脂粒子(B)が島状に部分的に
存在するため、トナーの定着性を損なうことなく、帯電
特性、流動性、および高温環境下における保存性に優れ
ているため、長期間の使用においても優れた画像品質を
維持することができる。In the electrophotographic toner obtained in the present invention, the resin particles (B) are partially present in the form of islands on the surface of the colored particles (A). Since it is excellent in fluidity and preservability in a high-temperature environment, it is possible to maintain excellent image quality even in long-term use.
【0021】本発明の電子写真用トナーの製造方法にお
いて、上記(式1)、(式2)、(式3)、(式4)、
および(式5)を満足させることにより、着色粒子
(A)の表面に樹脂粒子(B)の凝集物を50〜80%
の被覆率となるよう島状に部分的に固着させることがで
きる。こうして得られた電子写真用トナーは、長期の使
用においても樹脂粒子(B)の被覆率が変化しにくく、
安定した帯電量を維持することができる。In the method for producing an electrophotographic toner according to the present invention, the above (Equation 1), (Equation 2), (Equation 3), (Equation 4)
By satisfying (Equation 5), the aggregate of the resin particles (B) is 50 to 80% on the surface of the colored particles (A).
Can be partially fixed in an island shape so as to have a coverage of In the electrophotographic toner thus obtained, the coverage of the resin particles (B) hardly changes even after long-term use,
A stable charge amount can be maintained.
【0022】[0022]
【発明の実施の形態】以下、本発明をさらに詳細に説明
する。まず、着色粒子(A)について述べる。本発明を
構成する着色粒子(A)としては、主成分としてバイン
ダー樹脂および着色剤からなる粒径5μm〜10μmの
無定型の粒子が使用できる。一般には、バインダー樹脂
が70〜95重量%に対して、着色剤が30〜5重量%
の割合で混合されるが、その他必要に応じてワックスな
どの定着助剤等を使用することも可能である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. First, the colored particles (A) will be described. As the colored particles (A) constituting the present invention, amorphous particles having a particle size of 5 μm to 10 μm and comprising a binder resin and a colorant as main components can be used. Generally, the colorant is 30 to 5% by weight based on 70 to 95% by weight of the binder resin.
However, it is also possible to use a fixing aid such as wax if necessary.
【0023】着色粒子(A)を製造する方法としては、
重合法および混練粉砕法がある。前者の重合法では、懸
濁重合法および分散重合法をはじめとする各種重合法を
利用することにより、下記の重合体を合成し、必要に応
じて得られた粒子を分級することにより着色粒子(A)
が得られる。後者の混練粉砕法では、着色剤およびバイ
ンダー樹脂からなる混合物を2軸混練機などの加熱混合
処理が可能な装置により溶融混練し、次いで冷却固化し
たものをジェットミルなどの粉砕機により5〜10μm
程度の粒径に粉砕することにより、着色粒子(A)が得
られる。The method for producing the colored particles (A) includes:
There are a polymerization method and a kneading and pulverizing method. In the former polymerization method, the following polymers are synthesized by using various polymerization methods including a suspension polymerization method and a dispersion polymerization method, and if necessary, the obtained particles are classified to obtain colored particles. (A)
Is obtained. In the latter kneading and pulverizing method, a mixture comprising a colorant and a binder resin is melt-kneaded by a device capable of heating and mixing such as a twin-screw kneader, and then cooled and solidified by a pulverizer such as a jet mill to 5 to 10 μm.
By crushing to a particle size of the order, colored particles (A) are obtained.
【0024】上記着色粒子(A)に含まれるバインダー
樹脂の例としては、ポリスチレン、スチレン−アクリル
共重合体、スチレン−アクリロニトリル共重合体、アク
リル樹脂、スチレン−無水マレイン酸共重合体、スチレ
ン−アクリル−無水マレイン酸共重合体、ポリ塩化ビニ
ル、ポリ酢酸ビニル、ポリオレフィン樹脂、ポリエステ
ル樹脂、ポリウレタン樹脂、ウレタン変成ポリエステル
樹脂、およびエポキシ樹脂などが単独、または混合物と
して使用できるほか、ブロック重合体、あるいはグラフ
ト重合体として使用することも可能である。Examples of the binder resin contained in the colored particles (A) include polystyrene, styrene-acrylic copolymer, styrene-acrylonitrile copolymer, acrylic resin, styrene-maleic anhydride copolymer, styrene-acrylic -Maleic anhydride copolymer, polyvinyl chloride, polyvinyl acetate, polyolefin resin, polyester resin, polyurethane resin, urethane modified polyester resin, epoxy resin, etc. can be used alone or as a mixture, as well as a block polymer or graft. It is also possible to use it as a polymer.
【0025】また、上記着色粒子(A)に含まれる着色
剤の例としては、カーボンブラック、磁性粉、あるいは
ニトロ系、アゾ系、スチルベンアゾ系、ジフェニルメタ
ン系、トリフェニルメタン系、メチン系、チアゾール
系、アントラキノン系、インダミン系、アジン系、オキ
サアジン系、チアジン系、硫化染料系、インジゴイド
系、およびフタロシアニン系などの有機染料や顔料等が
挙げられる。Examples of the coloring agent contained in the colored particles (A) include carbon black, magnetic powder, nitro, azo, stilbene azo, diphenylmethane, triphenylmethane, methine, and thiazole. And organic dyes and pigments of anthraquinone type, indamine type, azine type, oxaazine type, thiazine type, sulfur dye type, indigoid type and phthalocyanine type.
【0026】次に、樹脂粒子(B)について述べる。本
発明に用いられる樹脂粒子(B)は、正または負の帯電
性を有している。Next, the resin particles (B) will be described. The resin particles (B) used in the present invention have positive or negative chargeability.
【0027】樹脂粒子(B)の製法としては、水溶性重
合開始剤を用いて乳化重合法やソープフリー乳化重合法
などの重合法により製造することが好ましい。水溶性重
合開始剤としては、過硫酸カリウム、過硫酸ナトリウ
ム、過硫酸アンモニウム、アゾビス(アミジノプロパ
ン)2塩酸塩、等を用いることができる。The resin particles (B) are preferably produced by a polymerization method such as an emulsion polymerization method or a soap-free emulsion polymerization method using a water-soluble polymerization initiator. As the water-soluble polymerization initiator, potassium persulfate, sodium persulfate, ammonium persulfate, azobis (amidinopropane) dihydrochloride and the like can be used.
【0028】他の製法として、アミノ基、アミド基、カ
ルボン酸、スルホン酸などの極性基を持つモノマーを用
いて重合することもできる。As another production method, polymerization can be carried out using a monomer having a polar group such as an amino group, an amide group, a carboxylic acid or a sulfonic acid.
【0029】以上の重合開始剤を使用する重合におい
て、使用できるモノマーとしては、スチレン、p−メチ
ルスチレン、スチレンスルホン酸ナトリウム、ビニルベ
ンジルクロリド、アクリル酸、メチルアクリレート、エ
チルアクリレート、ブチルアクリレート、ジメチルアミ
ノエチルアクリレート、メタクリル酸、メチルメタクリ
レート、エチルメタクリレート、ブチルメタクリレー
ト、およびジメチルアミノエチルメタクリレートなどが
挙げられるが、これらに限定されるものではなく、これ
らを単独で重合、あるいは共重合して使用される。In the polymerization using the above-mentioned polymerization initiator, usable monomers include styrene, p-methylstyrene, sodium styrenesulfonate, vinylbenzyl chloride, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and dimethylamino. Examples include, but are not limited to, ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and dimethylaminoethyl methacrylate. These may be used alone or in a copolymerized form.
【0030】次に、着色粒子(A)と樹脂粒子(B)の
関係について述べる。樹脂粒子(B)の平均粒径は、
0.3μm以下であり、これらは互いに凝集して塊を形
成しており、その凝集物の平均粒径は0.5μm以上
1.0μm以下であることが望ましく、さらに、樹脂粒
子(B)の凝集物の平均粒径は、着色粒子(A)の平均
粒径に対して10分の1以下であることが望ましい。Next, the relationship between the colored particles (A) and the resin particles (B) will be described. The average particle size of the resin particles (B) is
0.3 μm or less, these are aggregated with each other to form a lump, and the average particle size of the aggregate is desirably 0.5 μm or more and 1.0 μm or less. Furthermore, the resin particles (B) The average particle size of the aggregate is preferably 1/10 or less of the average particle size of the colored particles (A).
【0031】その理由は、以下のとおりである。樹脂粒
子(B)の平均粒径が小さいほど、表面積の総和が大き
くなりトナーの帯電性は高くなり好ましいが、重合で製
造する際には、0.1以上0.3μm以下の粒子が製造
容易である。したがって、樹脂粒子(B)の凝集物はこ
れより大きくなり、凝集物の平均粒径bは、少なくとも
0.5μm以上になる。The reason is as follows. The smaller the average particle size of the resin particles (B), the larger the total surface area and the higher the chargeability of the toner, which is preferable. However, when produced by polymerization, particles having a size of 0.1 to 0.3 μm are easily produced. It is. Therefore, the aggregate of the resin particles (B) is larger than this, and the average particle size b of the aggregate is at least 0.5 μm or more.
【0032】一方、樹脂粒子(B)の凝集物の平均粒径
bが、着色粒子(A)の平均粒径aの10分の1より大
きくなると、気流混合機で固着処理する際に、樹脂粒子
(B)の凝集物の着色粒子(A)への固着力が非常に弱
くなる。通常、着色粒子(A)の平均粒径aは5〜10
μm程度であるので、樹脂粒子(B)の凝集物の平均粒
径bとしては、その10分の1以下、すなわち、1.0
μm以下の大きさであることが必要である。On the other hand, if the average particle size b of the aggregate of the resin particles (B) is larger than one-tenth of the average particle size a of the colored particles (A), the resin particles may be hardened by a gas flow mixer. The fixing force of the aggregate of the particles (B) to the colored particles (A) becomes very weak. Usually, the average particle diameter a of the colored particles (A) is 5 to 10
Therefore, the average particle size b of the aggregate of the resin particles (B) is 1/10 or less thereof, that is, 1.0 μm.
It is necessary that the size be not more than μm.
【0033】また、これら凝集した樹脂粒子(B)が、
着色粒子(A)の表面を完全に覆うとトナーとしての定
着性が低下するため、被覆率が50〜80%の範囲で部
分的に固着していることが望ましい。これにより、得ら
れたトナーの帯電特性はほぼ樹脂粒子(B)によって支
配されているといえる。すなわち、樹脂粒子(B)の種
類を変えることによって、容易にトナー粒子の帯電特性
を、正帯電や負帯電に、あるいは帯電量などを自由にコ
ントロールすることも可能である。Further, these aggregated resin particles (B) are
If the surface of the colored particles (A) is completely covered, the fixability as a toner is reduced. Therefore, it is desirable that the colored particles (A) be partially fixed in a coverage of 50 to 80%. Thus, it can be said that the charging characteristics of the obtained toner are substantially controlled by the resin particles (B). That is, by changing the type of the resin particles (B), the charging characteristics of the toner particles can be easily controlled to be positively charged or negatively charged, or the amount of charge can be freely controlled.
【0034】さらに、樹脂粒子(B)の溶融粘度は高す
ぎると定着性が悪化し、逆に低いとトナー凝集が起こり
やすくなるため、ある一定範囲内での粘性が必要であ
る。具体的には、140℃における樹脂粒子(B)の粘
度η(Pa・sec)は下記(式2)を満足する範囲内
にあることが望ましい。Furthermore, if the melt viscosity of the resin particles (B) is too high, the fixability deteriorates. On the other hand, if the melt viscosity is low, toner aggregation is apt to occur, so that the viscosity within a certain range is required. Specifically, the viscosity η (Pa · sec) of the resin particles (B) at 140 ° C. is desirably within a range satisfying the following (Equation 2).
【0035】104<η<106 ・・・(式2) 樹脂粒子(B)の凝集物は、樹脂粒子(B)の重合後に
スプレードライヤーなどにより造粒・乾燥させて、必要
に応じて分級することにより得られる。乾燥方法には様
々な方法があるが、スプレードライ法が、凝集物を得る
ことができる最も簡便な方法である。10 4 <η <10 6 (Formula 2) The aggregate of the resin particles (B) is granulated and dried by a spray drier or the like after polymerization of the resin particles (B), and if necessary, Obtained by classification. Although there are various drying methods, a spray drying method is the simplest method by which aggregates can be obtained.
【0036】本発明において使用される着色粒子(A)
のガラス転移温度TgA(℃)、および樹脂粒子(B)
のガラス転移温度TgB(℃)については、下記(式
3)を満足することが好ましい。Colored particles (A) used in the present invention
Glass transition temperature Tg A (° C.) and resin particles (B)
The glass transition temperature Tg B (° C.) preferably satisfies the following (Equation 3).
【0037】 TgA≦TgB≦(TgA+15) ・・・(式3) その理由は、以下のとおりである。樹脂粒子(B)のガ
ラス転移温度TgBが着色粒子(A)のガラス転移温度
TgAに対して低い場合、樹脂粒子(B)はトナーの表
面に存在するので、複数のトナー粒子の凝集が起こりや
すくなり、トナーの保存性が悪化する。また逆に(Tg
A+15)より高い場合、固着処理する工程において樹
脂粒子(B)の固着力が極端に弱くなる。したがって、
(式3)の範囲が好ましい。Tg A ≦ Tg B ≦ (Tg A +15) (Equation 3) The reason is as follows. If the glass transition temperature Tg B of the resin particles (B) is lower than the glass transition temperature Tg A of the colored particles (A), the resin particles (B) present on the surface of the toner, agglomeration of the plurality of toner particles This easily occurs, and the storage stability of the toner deteriorates. Conversely, (Tg
If it is higher than ( A + 15), the fixing force of the resin particles (B) becomes extremely weak in the fixing treatment step. Therefore,
The range of (Equation 3) is preferable.
【0038】本発明においては、(式3)に示すように
樹脂粒子(B)のガラス転移温度TgBが着色粒子
(A)のガラス転移温度TgAよりも高いので、トナー
中における樹脂粒子(B)の含有率が多すぎると、トナ
ーの定着性が悪化し、逆に、樹脂粒子(B)の含有率が
少なすぎると、高温環境下における保存性が低下する。
このため、トナー中における樹脂粒子(B)の含有量は
2〜6重量%の範囲にあることが好ましい。In the present invention, since the glass transition temperature Tg B of the resin particles (B) is higher than the glass transition temperature Tg A of the colored particles (A) as shown in (Formula 3), the resin particles ( If the content of B) is too high, the fixability of the toner deteriorates. On the other hand, if the content of the resin particles (B) is too low, the storability in a high-temperature environment decreases.
For this reason, the content of the resin particles (B) in the toner is preferably in the range of 2 to 6% by weight.
【0039】次に、着色粒子(A)の表面に、樹脂粒子
(B)を凝集物として部分的に固着させる方法について
述べる。Next, a method of partially fixing the resin particles (B) as aggregates to the surface of the colored particles (A) will be described.
【0040】着色粒子(A)の表面に、樹脂粒子(B)
を凝集物として部分的に固着するための装置としては、
温度制御可能な外壁と撹拌羽根を最低限の構成要素とす
る気流混合機、例えば、ヘンシェルミキサー、スーパー
ミキサー、およびメカノミルなどを用いることができ
る。その際、撹拌羽根の先端周速をS(m/sec)、
気流混合機内の温度をH(℃)とすると、これらが、下
記(式4)および(式5)を満足するような条件下で、
無定型の着色粒子(A)と樹脂粒子(B)を混合撹拌す
ることにより得られる。On the surface of the colored particles (A), resin particles (B)
As a device for partially fixing as an aggregate,
An air flow mixer having a temperature-controllable outer wall and a stirring blade as minimum components, such as a Henschel mixer, a super mixer, and a mechano mill, can be used. At this time, the peripheral speed of the tip of the stirring blade is set to S (m / sec),
Assuming that the temperature in the airflow mixer is H (° C.), under the conditions that satisfy the following (Equation 4) and (Equation 5),
It is obtained by mixing and stirring the amorphous colored particles (A) and the resin particles (B).
【0041】 5≦S≦15 ・・・(式4) (TgA−10)≦H≦(TgA+5) ・・・(式5) 上記(式4)について、気流混合機の撹拌羽根の先端周
速Sが5m/secより小さい場合、着色粒子(A)と
樹脂粒子(B)の衝突力が弱くなり、互いに固着しにく
くなる。また逆に15m/secより大きい場合、互い
の粒子の衝突力が強くなり、樹脂粒子(B)が着色粒子
(A)に埋没する。5 ≦ S ≦ 15 (Equation 4) (Tg A −10) ≦ H ≦ (Tg A +5) (Equation 5) Regarding the above (Equation 4), the stirring blade of the air-flow mixer is used. When the tip peripheral speed S is smaller than 5 m / sec, the collision force between the colored particles (A) and the resin particles (B) is weakened, and it is difficult for the colored particles (A) and the resin particles (B) to adhere to each other. On the other hand, when it is larger than 15 m / sec, the collision force of the particles becomes stronger, and the resin particles (B) are buried in the colored particles (A).
【0042】撹拌羽根の回転から受ける機械的エネルギ
ーおよび粒子間の衝突エネルギーが着色粒子(A)と樹
脂粒子(B)の固着を進行させる。このエネルギーが、
小さいと固着は十分に起こりにくく、逆に大きすぎると
島状に付着しない。The mechanical energy received from the rotation of the stirring blade and the collision energy between the particles promote the fixation of the colored particles (A) and the resin particles (B). This energy,
If it is too small, sticking is unlikely to occur sufficiently, and if it is too large, it does not adhere in an island shape.
【0043】上記(式5)について、気流混合機内の温
度Hが着色粒子(A)のガラス転移点TgAに対して
(TgA−10)より低い場合、着色粒子(A)と樹脂
粒子(B)の固着力が不十分となり、逆に(TgA+
5)より高い場合、樹脂粒子(B)の着色粒子(A)へ
の埋没、複数のトナー粒子の融着、あるいはトナー粒子
の球形化がおこる。Regarding the above (Equation 5), when the temperature H in the airflow mixer is lower than (Tg A -10) with respect to the glass transition point Tg A of the colored particles (A), the colored particles (A) and the resin particles ( B) becomes insufficient in fixing force, and conversely (Tg A +
If it is higher than 5), the resin particles (B) are buried in the colored particles (A), a plurality of toner particles are fused, or the toner particles are made spherical.
【0044】また、本発明の電子写真用トナーの製造方
法において、前記固着処理をする前に、気流混合機など
により室温雰囲気下で混合し、着色粒子(A)と樹脂粒
子(B)を分散処理させてもよい。In the method for producing an electrophotographic toner according to the present invention, before performing the fixing treatment, the colored particles (A) and the resin particles (B) are dispersed by mixing with an airflow mixer at room temperature. It may be processed.
【0045】本発明に使用される着色粒子(A)のガラ
ス転移温度TgAは、低すぎるとトナーの保存性が悪化
し、逆に高すぎると定着性が悪化する傾向にあるため、
ガラス転移温度は50〜60℃の範囲内にあることが好
ましい。If the glass transition temperature Tg A of the colored particles (A) used in the present invention is too low, the storability of the toner tends to deteriorate, and if it is too high, the fixability tends to deteriorate.
Preferably, the glass transition temperature is in the range of 50-60C.
【0046】本発明においては、着色粒子(A)の表面
に部分的に固着させる樹脂粒子(B)が、凝集物の形と
なって固着していることが特徴である。従来、粒径の大
きい粒子をトナー表面に付着させる場合、付着力が弱い
ため非常に大きな熱エネルギーと機械的衝撃力を必要と
し、非常に困難であった。しかし、本発明における樹脂
粒子(B)の凝集物は、着色粒子(A)の表面に付着し
た状態で、少量の熱あるいは機械的衝撃力により容易に
固着させることが可能である。これは、本発明の凝集物
が熱や機械的エネルギーによって容易に変形、溶融する
ことができるためである。また、従来では困難であった
凸部への固着も、本発明の凝集物を用いると容易に固着
させることが可能である。The present invention is characterized in that the resin particles (B) partially fixed to the surface of the colored particles (A) are fixed in the form of aggregates. Heretofore, it has been very difficult to attach particles having a large particle diameter to the toner surface, which requires very large thermal energy and mechanical impact force due to weak adhesion. However, the aggregates of the resin particles (B) in the present invention can be easily fixed by a small amount of heat or mechanical impact while being attached to the surface of the colored particles (A). This is because the aggregate of the present invention can be easily deformed and melted by heat or mechanical energy. In addition, the use of the aggregates of the present invention makes it possible to easily fix to the projections, which was difficult in the past.
【0047】また、本発明において凝集物を固着させる
ことは、トナー全体としての定着性にも有利である。従
来では、粒径の大きい粒子がトナー表面に存在していた
ため、その定着性には非常に不利であった。しかし、本
発明においては、粒径の小さな樹脂粒子(B)の凝集物
を用いることにより、定着時に樹脂粒子(B)の凝集物
が変形もしくは着色粒子(A)の内部に埋没されるた
め、着色粒子(A)のもつ定着性が損なわれる現象を大
幅に抑制させることができる。In the present invention, fixing the aggregates is also advantageous for the fixability of the toner as a whole. Conventionally, particles having a large particle size are present on the toner surface, which is extremely disadvantageous for the fixing property. However, in the present invention, by using an aggregate of the resin particles (B) having a small particle size, the aggregate of the resin particles (B) is deformed or embedded in the colored particles (A) at the time of fixing. The phenomenon that the fixability of the colored particles (A) is impaired can be significantly suppressed.
【0048】本発明で得られるトナーは、流動性や研磨
性の付与などを目的にシリカ、酸化チタン、およびアル
ミナ微粒子など既知の外添剤を併用することもでき、磁
性粉キャリアと混合し2成分磁気ブラシ現像剤として使
用できるほか、1成分系現像剤としても使用することが
可能である。The toner obtained in the present invention may be used in combination with known external additives such as silica, titanium oxide, and fine alumina particles for the purpose of imparting fluidity and abrasiveness. It can be used as a component magnetic brush developer, and can also be used as a one-component developer.
【0049】(実施例)以下、実施例により本発明を詳
細に説明するが、本発明はこれらのみに限定されるもの
ではない。なお、実施例中では「重量部」をすべて
「部」と略す。 〈実施例1〉 スチレン−アクリル共重合体樹脂 100部 Tg=55℃,Mn=3×103,Mw=2×105 (ただし、Mnは数平均分子量、Mwは重量平均分子量を表す。) カーボンブラック MA−100(三菱化成社製) 6部 ポリプロピレンワックス ビスコール550P(三洋化成社製) 2部 上記材料をスーパーミキサーで2分間撹拌後、二軸混練
機で溶融混練した後、ハンマーミルおよびジェットミル
で粉砕し、気流分級することにより非球形の平均粒径約
10μmの着色粒子(A1)を得た。EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, "parts by weight" are all abbreviated as "parts". <Example 1> Styrene-acrylic copolymer resin 100 parts Tg = 55 ° C, Mn = 3 × 10 3 , Mw = 2 × 10 5 (where Mn represents the number average molecular weight and Mw represents the weight average molecular weight) Carbon black MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.) 6 parts Polypropylene wax Viscole 550P (manufactured by Sanyo Chemical Co., Ltd.) 2 parts The resulting mixture was pulverized with a mill and subjected to air classification to obtain non-spherical colored particles (A1) having an average particle diameter of about 10 μm.
【0050】これとは別に、スチレンおよびメタクリル
酸n−ブチルをモノマーとして用い、開始剤として2,
2−アゾビス(2−アミジノプロパン)二塩酸塩(以下
ABAHと称す)を使用して、ソープフリー乳化重合法
により共重合を行い、スプレードライヤーで造粒・乾燥
させ分級することにより、正帯電性を示すスチレン−ブ
チルメタクリレート共重合体樹脂粒子(B1)を得た。Separately, styrene and n-butyl methacrylate were used as monomers and 2,2
Positive chargeability is obtained by performing copolymerization by soap-free emulsion polymerization using 2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as ABAH), granulating and drying with a spray drier, and classifying. The styrene-butyl methacrylate copolymer resin particles (B1) shown below were obtained.
【0051】スチレン−ブチルメタクリレート共重合体
樹脂粒子(B1) Tg=65℃、粒径0.15μm、凝集物の粒径0.9
1μm、 140℃の溶融粘度3×105Pa・sec 次に、上記着色粒子(A1)100部に対して上記スチ
レン−ブチルメタクリレート共重合体樹脂粒子(B1)
を6部加え、混合物をスーパーミキサーを用い下記条件
にて固着処理を行った。Styrene-butyl methacrylate copolymer resin particles (B1) Tg = 65 ° C., particle size 0.15 μm, particle size of aggregate 0.9
1 μm, 140 ° C. melt viscosity 3 × 10 5 Pa · sec Next, the styrene-butyl methacrylate copolymer resin particles (B1) are used for 100 parts of the colored particles (A1).
Was added and the mixture was fixed using a supermixer under the following conditions.
【0052】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 50℃ 混合時間 30分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されて
おり、かつ、非球形状で曲率半径が1μm以下の角のあ
る粒子が70%以上であった。Peripheral speed of the tip of the stirring blade 10 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 30 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 60 to 70% of the toner surface was fixed by agglomerates, and more than 70% of non-spherical and angular particles having a radius of curvature of 1 μm or less were formed.
【0053】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0054】表1に示すように、画像濃度、カブリ、帯
電量、定着性、クリーニング性、耐凝集性のすべてにつ
いて良好であった。As shown in Table 1, all of the image density, fog, charge amount, fixing property, cleaning property and aggregation resistance were good.
【0055】〈実施例2〉スチレンおよびメタクリル酸
n−ブチルをモノマーとして用い、開始剤としてABA
Hを使用して、ソープフリー乳化重合法により共重合を
行い、スプレードライヤーで造粒・乾燥させ分級するこ
とにより、正帯電性を示すスチレン−ブチルメタクリレ
ート共重合体樹脂粒子(B2)を得た。Example 2 Styrene and n-butyl methacrylate were used as monomers, and ABA was used as an initiator.
Using H, copolymerization was carried out by a soap-free emulsion polymerization method, and the mixture was granulated, dried and classified by a spray drier to obtain styrene-butyl methacrylate copolymer resin particles (B2) having positive chargeability. .
【0056】スチレン−ブチルメタクリレート共重合体
樹脂粒子(B2) Tg=70℃,粒径0.15μm、凝集物の粒径0.8
8μm、 140℃の溶融粘度8×105Pa・sec 実施例1で用いた着色粒子(A1)100部に対して、
上記スチレン−ブチルメタクリレート共重合体樹脂粒子
(B2)を5部加え、混合物をスーパーミキサーを用い
下記条件にて固着処理を行った。Styrene-butyl methacrylate copolymer resin particles (B2) Tg = 70 ° C., particle size 0.15 μm, particle size of aggregate 0.8
8 μm, melt viscosity at 140 ° C. 8 × 10 5 Pa · sec With respect to 100 parts of the colored particles (A1) used in Example 1,
Five parts of the styrene-butyl methacrylate copolymer resin particles (B2) were added, and the mixture was subjected to a fixing treatment using a super mixer under the following conditions.
【0057】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 50℃ 混合時間 30分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されて
おり、かつ、非球形状で曲率半径が1μm以下の角のあ
る粒子が70%以上であった。Peripheral speed of the tip of the stirring blade 10 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 30 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 60 to 70% of the toner surface was fixed by agglomerates, and more than 70% of non-spherical and angular particles having a radius of curvature of 1 μm or less were formed.
【0058】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0059】表1に示すように、画像濃度、カブリ、帯
電量、定着性、クリーニング性、耐凝集性のすべてにつ
いて良好であった。As shown in Table 1, all of the image density, fog, charge amount, fixability, cleaning property and aggregation resistance were good.
【0060】〈実施例3〉スチレンおよびメタクリル酸
n−ブチルをモノマーとして用い、開始剤としてABA
Hを使用して、ソープフリー乳化重合法により共重合を
行い、スプレードライヤーで造粒・乾燥させ分級するこ
とにより、正帯電性を示すスチレン−ブチルメタクリレ
ート共重合体樹脂粒子(B3)を得た。Example 3 Styrene and n-butyl methacrylate were used as monomers, and ABA was used as an initiator.
Using H, copolymerization was performed by a soap-free emulsion polymerization method, and the mixture was granulated and dried with a spray drier and classified to obtain styrene-butyl methacrylate copolymer resin particles (B3) exhibiting positive chargeability. .
【0061】スチレン−ブチルメタクリレート共重合体
樹脂粒子(B3) Tg=70℃、粒径0.15μm、凝集物の粒径0.9
0μm、 140℃の溶融粘度8×105Pa・sec 実施例1で用いた着色粒子(A1)100部に対して、
上記スチレン−ブチルメタクリレート共重合体樹脂粒子
(B3)を4部加え、混合物をスーパーミキサーを用い
下記条件にて固着処理を行った。Styrene-butyl methacrylate copolymer resin particles (B3) Tg = 70 ° C., particle size 0.15 μm, particle size of aggregate 0.9
0 μm, melt viscosity at 140 ° C. 8 × 10 5 Pa · sec With respect to 100 parts of the colored particles (A1) used in Example 1,
4 parts of the above styrene-butyl methacrylate copolymer resin particles (B3) were added, and the mixture was fixed using a super mixer under the following conditions.
【0062】撹拌羽根の先端周速 15m/sec 気流混合機内の温度 50℃ 混合時間 20分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されて
おり、かつ、非球形状で曲率半径が1μm以下の角のあ
る粒子が70%以上であった。Peripheral speed of the tip of the stirring blade 15 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 20 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 60 to 70% of the toner surface was fixed by agglomerates, and more than 70% of non-spherical and angular particles having a radius of curvature of 1 μm or less were formed.
【0063】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0064】表1に示すように、画像濃度、カブリ、帯
電量、定着性、クリーニング性、耐凝集性のすべてにつ
いて良好であった。As shown in Table 1, all of the image density, fog, charge amount, fixability, cleaning properties, and aggregation resistance were good.
【0065】〈実施例4〉実施例1で用いた着色粒子
(A1)100部に対して、正帯電性を示すスチレン−
ブチルメタクリレート共重合体樹脂粒子(B1)を3部
加え、混合物をスーパーミキサーを用い下記条件にて固
着処理を行った。Example 4 100 parts of the colored particles (A1) used in Example 1 were charged with styrene-
3 parts of butyl methacrylate copolymer resin particles (B1) were added, and the mixture was fixed using a super mixer under the following conditions.
【0066】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 50℃ 混合時間 20分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されて
おり、かつ、非球形状で曲率半径が1μm以下の角のあ
る粒子が70%以上であった。Peripheral speed of the tip of the stirring blade 10 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 20 minutes 100 parts of the obtained composite particles were mixed with hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 60 to 70% of the toner surface was fixed by agglomerates, and more than 70% of non-spherical and angular particles having a radius of curvature of 1 μm or less were formed.
【0067】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0068】表1に示すように、画像濃度、カブリ、帯
電量、定着性、クリーニング性、耐凝集性のすべてにつ
いて良好であった。As shown in Table 1, all of the image density, fog, charge amount, fixability, cleaning properties, and aggregation resistance were good.
【0069】〈実施例5〉実施例1で用いた着色粒子
(A1)100部に対して、正帯電性を示すスチレン−
ブチルメタクリレート共重合体樹脂粒子(B1)を2部
加え、混合物をスーパーミキサーを用い下記条件にて固
着処理を行った。Example 5 100 parts of the colored particles (A1) used in Example 1 were charged with styrene-
Two parts of butyl methacrylate copolymer resin particles (B1) were added, and the mixture was fixed using a super mixer under the following conditions.
【0070】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 50℃ 混合時間 20分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されて
おり、かつ、非球形状で曲率半径が1μm以下の角のあ
る粒子が70%以上であった。The peripheral speed of the tip of the stirring blade is 10 m / sec. The temperature inside the airflow mixer is 50 ° C., the mixing time is 20 minutes.
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 60 to 70% of the toner surface was fixed by agglomerates, and more than 70% of non-spherical and angular particles having a radius of curvature of 1 μm or less were formed.
【0071】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0072】表1に示すように、画像濃度、カブリ、帯
電量、定着性、クリーニング性、耐凝集性のすべてにつ
いて良好であった。As shown in Table 1, all of the image density, fog, charge amount, fixability, cleaning properties, and aggregation resistance were good.
【0073】〈比較例1〉実施例2で用いた着色粒子
(A1)100部に対してスチレン−ブチルメタクリレ
ート共重合体樹脂粒子(B2)を10部加え、混合物を
スーパーミキサーを用い下記条件にて固着処理を行っ
た。Comparative Example 1 10 parts of styrene-butyl methacrylate copolymer resin particles (B2) were added to 100 parts of the colored particles (A1) used in Example 2, and the mixture was mixed under the following conditions using a super mixer. To perform a fixing process.
【0074】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 40℃ 混合時間 30分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、非球形状で曲率半径が1μm以下の角のある粒子
が70%以上であったが、トナー表面全域が樹脂粒子で
覆われており、樹脂粒子単独で存在するものも多数確認
された。Peripheral speed of the tip of the stirring blade 10 m / sec Temperature in the airflow mixer 40 ° C. Mixing time 30 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. Observation of this toner with a SEM revealed that 70% or more of the particles were non-spherical and had a radius of curvature of 1 μm or less, but the entire surface of the toner was covered with resin particles. Many were also confirmed.
【0075】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0076】帯電量、クリーニング性、耐凝集性につい
ては良好であったが、画像濃度が低下し、1万枚複写後
にカブリが発生した。また、トナー表面全域が樹脂粒子
で覆われているため定着性が悪かった。Although the charge amount, the cleaning property and the aggregation resistance were good, the image density was lowered and fog occurred after copying 10,000 sheets. Further, since the entire surface of the toner was covered with the resin particles, the fixability was poor.
【0077】〈比較例2〉実施例2で用いた着色粒子
(A1)100部に対してスチレン−ブチルメタクリレ
ート共重合体樹脂粒子(B2)を5部加え、混合物をス
ーパーミキサーを用い下記条件にて固着処理を行った。Comparative Example 2 Five parts of styrene-butyl methacrylate copolymer resin particles (B2) were added to 100 parts of the colored particles (A1) used in Example 2, and the mixture was mixed under the following conditions using a super mixer. To perform a fixing process.
【0078】撹拌羽根の先端周速 20m/sec 気流混合機内の温度 50℃ 混合時間 30分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の60〜70%が凝集物で固着されい
たが、撹拌羽根の先端周速が大きいため、着色粒子の表
面で樹脂粒子Bが一部固着、一部埋没した状態であり、
また、非球形状の曲率半径が1μm以下の角のある粒子
はほとんどなく、形状はほぼ球形であった。Peripheral speed of the tip of the stirring blade 20 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 30 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed with an SEM, 60 to 70% of the toner surface was fixed by agglomerates, but because the peripheral speed of the tip of the stirring blade was large, the resin particles B partially fixed and partially buried on the surface of the colored particles. State
In addition, there were almost no non-spherical particles having a corner having a radius of curvature of 1 μm or less and the shape was almost spherical.
【0079】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0080】表1に示すように、画像濃度、定着性、耐
凝集性については良好であったが、帯電量が低下して、
カブリが発生した。また、球形であるためクリーニング
性が悪かった。As shown in Table 1, the image density, fixability, and aggregation resistance were good, but the charge amount was reduced.
Fog occurred. In addition, cleaning properties were poor due to the spherical shape.
【0081】〈比較例3〉実施例2で用いた着色粒子
(A1)100部に対してスチレン−ブチルメタクリレ
ート共重合体樹脂粒子(B2)を1部加え、混合物をス
ーパーミキサーを用い下記条件にて固着処理を行った。Comparative Example 3 One part of styrene-butyl methacrylate copolymer resin particles (B2) was added to 100 parts of the colored particles (A1) used in Example 2, and the mixture was mixed under the following conditions using a super mixer. To perform a fixing process.
【0082】撹拌羽根の先端周速 10m/sec 気流混合機内の温度 50℃ 混合時間 30分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、非球形状で曲率半径が1μm以下の角のある粒子
が70%以上であったが、トナー表面の20〜30%し
か樹脂粒子が固着していなかった。The peripheral speed of the tip of the stirring blade is 10 m / sec. The temperature in the airflow mixer is 50 ° C., the mixing time is 30 minutes.
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. When this toner was observed by SEM, 70% or more of non-spherical particles having a radius of curvature of 1 μm or less were found to be 70% or more, but only 20 to 30% of the toner surface had resin particles adhered thereto.
【0083】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0084】樹脂粒子の被覆率が少ないため、帯電量が
低く、複写すると初期よりカブリが発生した。また、耐
凝集性が悪く凝集が発生した。Since the coverage of the resin particles was small, the charge amount was low, and fogging occurred from the beginning when copying. In addition, aggregation resistance was poor and aggregation occurred.
【0085】〈比較例4〉スチレンおよびメタクリル酸
n−ブチルをモノマーとして用い、開始剤としてABA
Hを使用して、ソープフリー乳化重合法により共重合を
行い、乾燥させた粒子を解砕・分級することにより、正
帯電性を示すスチレン−ブチルメタクリレート共重合体
樹脂粒子(B4)を得た。Comparative Example 4 Styrene and n-butyl methacrylate were used as monomers, and ABA was used as an initiator.
Using H, copolymerization was performed by a soap-free emulsion polymerization method, and the dried particles were crushed and classified to obtain styrene-butyl methacrylate copolymer resin particles (B4) exhibiting positive chargeability. .
【0086】スチレン−ブチルメタクリレート共重合体
樹脂粒子(B4) Tg=70℃、粒径0.15μm、 140℃の溶融粘度8×105Pa・sec 実施例1で用いた着色粒子(A1)100部に対して、
上記スチレン−ブチルメタクリレート共重合体樹脂粒子
(B4)を4部加え、混合物をスーパーミキサーを用い
下記条件にて固着処理を行った。Styrene-butyl methacrylate copolymer resin particles (B4) Tg = 70 ° C., particle size 0.15 μm, melt viscosity at 140 ° C. 8 × 10 5 Pa · sec Colored particles (A1) 100 used in Example 1 For the department
4 parts of the above styrene-butyl methacrylate copolymer resin particles (B4) were added, and the mixture was fixed using a super mixer under the following conditions.
【0087】撹拌羽根の先端周速 15m/sec 気流混合機内の温度 50℃ 混合時間 20分 得られた複合粒子100部に対して、疎水性シリカR−
972(日本アエロジル社製)を0.3部外添して正帯
電性を示すトナーを得た。このトナーをSEMで観察す
ると、トナー表面の100%が凝集物で固着されてお
り、かつ、非球形状で曲率半径が1μm以下の角のある
粒子が70%以上であった。Peripheral speed of the tip of the stirring blade 15 m / sec Temperature in the airflow mixer 50 ° C. Mixing time 20 minutes To 100 parts of the obtained composite particles, hydrophobic silica R-
0.32 of 972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to obtain a toner having positive chargeability. Observation of this toner with an SEM revealed that 100% of the toner surface was fixed by agglomerates, and that non-spherical particles having a radius of curvature of 1 μm or less having corners were 70% or more.
【0088】得られたトナー4部をフッ素樹脂をコート
したフェライトキャリア100部と混合し現像剤を作成
した。この現像剤を用いて複写機SF−8300(シャ
ープ社製)にて1万枚の連続複写試験を行った。その結
果を表1に示す。4 parts of the obtained toner was mixed with 100 parts of a ferrite carrier coated with a fluororesin to prepare a developer. Using this developer, a continuous copying test of 10,000 sheets was performed with a copying machine SF-8300 (manufactured by Sharp Corporation). Table 1 shows the results.
【0089】画像濃度、カブリ、クリーニング性、耐凝
集性については良好であったが、樹脂粒子の被覆率が1
00%であるため、定着性が悪かった。The image density, fog, cleaning properties, and coagulation resistance were good, but the resin particle coverage was 1%.
Since it was 00%, the fixability was poor.
【0090】[0090]
【表1】 [Table 1]
【0091】[0091]
【発明の効果】本発明による電子写真用トナーは、帯電
性樹脂粒子の凝集物が着色粒子の表面に部分的に固着さ
れているので、定着性に優れ、帯電特性および耐凝集性
が高いため、長期間の使用においても優れた画像品質を
維持することができる。The toner for electrophotography according to the present invention is excellent in fixability, and has high charging characteristics and agglomeration resistance because the aggregates of the chargeable resin particles are partially fixed to the surface of the colored particles. In addition, excellent image quality can be maintained even during long-term use.
Claims (9)
からなる着色粒子(A)の表面に、樹脂粒子(B)が凝
集物として部分的に固着されていることを特徴とする電
子写真用トナー。1. An electrophotographic toner, wherein resin particles (B) are partially fixed as aggregates on the surface of colored particles (A) comprising at least a colorant and a binder resin.
以下であり、樹脂粒子(B)の凝集物の平均粒径が直径
0.5μm以上1.0μm以下であり、さらに、着色粒
子(A)の平均粒径をaμm、樹脂粒子(B)の凝集物
の平均粒径をbμmとすると、これらが下記の(式1)
を満足することを特徴とする請求項1記載の電子写真用
トナー。 b≦(a/10) ・・・(式1)2. An average particle size of the resin particles (B) is 0.3 μm.
The average particle diameter of the aggregate of the resin particles (B) is 0.5 μm or more and 1.0 μm or less, the average particle diameter of the colored particles (A) is a μm, and the aggregation of the resin particles (B) is Assuming that the average particle size of the product is b μm, these are represented by the following (formula 1)
2. The electrophotographic toner according to claim 1, wherein the toner satisfies the following. b ≦ (a / 10) (formula 1)
(A)の表面に、被覆率50%以上80%以下の範囲で
部分的に固着していることを特徴とする請求項1、また
は請求項2記載の電子写真用トナー。3. The method according to claim 1, wherein the resin particles (B) are partially fixed as aggregates on the surface of the colored particles (A) in a range of 50% or more and 80% or less. Or the toner for electrophotography according to claim 2.
上6重量%以下含有されていることを特徴とする請求項
1、または請求項2記載の電子写真用トナー。4. The electrophotographic toner according to claim 1, wherein the toner contains the resin particles (B) in an amount of 2% by weight or more and 6% by weight or less.
η(Pa・sec)が、下記の(式2)を満足する範囲
内にあることを特徴とする請求項1記載の電子写真用ト
ナー。 104<η<106 ・・・(式2)5. The toner for electrophotography according to claim 1, wherein the viscosity η (Pa · sec) of the resin particles (B) at 140 ° C. is within a range satisfying the following (Equation 2). . 10 4 <η <10 6 (Equation 2)
A(℃)、樹脂粒子(B)のガラス転移温度をTg
B(℃)とすると、これらが下記の(式3)を満足する
ことを特徴とする請求項1記載の電子写真用トナー。 TgA≦TgB≦(TgA+15) ・・・(式3)6. The glass transition temperature of the colored particles (A) is defined as Tg.
A (° C.), the glass transition temperature of the resin particles (B) is Tg
2. The electrophotographic toner according to claim 1, wherein when B (° C.), these satisfy the following (Equation 3). Tg A ≦ Tg B ≦ (Tg A +15) (Equation 3)
合機を用いて、着色粒子(A)の表面に樹脂粒子(B)
を固着処理する工程において、着色粒子(A)のガラス
転移温度をTgA(℃)、樹脂粒子(B)のガラス転移
温度をTgB(℃)、撹拌羽根の先端周速をS(m/s
ec)、気流混合機内の温度をH(℃)とすると、これ
らが下記の(式4)および(式5)を満足することを特
徴とする電子写真用トナーの製造方法。 5≦S≦15 ・・・(式4) (TgA−10)≦H≦(TgA+5) ・・・(式5)7. Using a gas mixer having a cylindrical outer wall and stirring blades, apply resin particles (B) to the surface of the colored particles (A).
In the step of fixing treatment, the glass transition temperature of the colored particles (A) is Tg A (° C.), the glass transition temperature of the resin particles (B) is Tg B (° C.), and the peripheral speed of the tip of the stirring blade is S (m / s
ec) a method for producing a toner for electrophotography, wherein when the temperature in the airflow mixer is H (° C.), these satisfy the following (Equation 4) and (Equation 5). 5 ≦ S ≦ 15 (Equation 4) (Tg A −10) ≦ H ≦ (Tg A +5) (Equation 5)
存在下において、水中で重合性単量体を反応させ、乾燥
することにより得られた樹脂粒子であることを特徴とす
る、請求項7記載の電子写真用トナーの製造方法。8. The method according to claim 1, wherein the resin particles (B) are resin particles obtained by reacting a polymerizable monomer in water in the presence of a water-soluble polymerization initiator and drying. A method for producing an electrophotographic toner according to claim 7.
ライ法で乾燥することにより得られた、直径0.5μm
以上1.0μm以下の凝集物であることを特徴とする請
求項7、または請求項8記載の電子写真用トナーの製造
方法。9. An aggregate of the resin particles (B) having a diameter of 0.5 μm obtained by drying by a spray drying method.
The method for producing an electrophotographic toner according to claim 7, wherein the aggregate is an aggregate of not less than 1.0 μm or less.
Priority Applications (1)
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JP25664197A JP3457857B2 (en) | 1997-09-22 | 1997-09-22 | Electrophotographic toner |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25664197A JP3457857B2 (en) | 1997-09-22 | 1997-09-22 | Electrophotographic toner |
Publications (2)
Publication Number | Publication Date |
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JPH1195478A true JPH1195478A (en) | 1999-04-09 |
JP3457857B2 JP3457857B2 (en) | 2003-10-20 |
Family
ID=17295433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP25664197A Expired - Fee Related JP3457857B2 (en) | 1997-09-22 | 1997-09-22 | Electrophotographic toner |
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JP (1) | JP3457857B2 (en) |
Cited By (9)
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---|---|---|---|---|
JP2002287597A (en) * | 2001-03-28 | 2002-10-03 | Ricoh Co Ltd | Cleaning device and image forming apparatus having the same |
US6987944B2 (en) | 2001-03-28 | 2006-01-17 | Ricoh Company, Ltd. | Cleaning device and image forming apparatus using the cleaning device |
JP2006161018A (en) * | 2004-11-15 | 2006-06-22 | Sanyo Chem Ind Ltd | Aqueous dispersion of resin particle |
JP2008191639A (en) * | 2007-01-09 | 2008-08-21 | Sharp Corp | Toner and method of manufacturing the same, two-component developer, developing apparatus, and image forming apparatus |
JP2011033916A (en) * | 2009-08-04 | 2011-02-17 | Canon Inc | Toner |
JP2012048191A (en) * | 2010-08-26 | 2012-03-08 | Trend Tone Imaging Inc | Nonmagnetic developer and method of spherizing the same |
US8216758B2 (en) | 2008-05-29 | 2012-07-10 | Sharp Kabushiki Kaisha | Toner, developer, developing device, and image forming apparatus |
JP2015141220A (en) * | 2014-01-27 | 2015-08-03 | 京セラドキュメントソリューションズ株式会社 | Toner and method of manufacturing the same |
JP2015141221A (en) * | 2014-01-27 | 2015-08-03 | 京セラドキュメントソリューションズ株式会社 | Toner and method of manufacturing the same |
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1997
- 1997-09-22 JP JP25664197A patent/JP3457857B2/en not_active Expired - Fee Related
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002287597A (en) * | 2001-03-28 | 2002-10-03 | Ricoh Co Ltd | Cleaning device and image forming apparatus having the same |
US6987944B2 (en) | 2001-03-28 | 2006-01-17 | Ricoh Company, Ltd. | Cleaning device and image forming apparatus using the cleaning device |
JP2006161018A (en) * | 2004-11-15 | 2006-06-22 | Sanyo Chem Ind Ltd | Aqueous dispersion of resin particle |
JP2008191639A (en) * | 2007-01-09 | 2008-08-21 | Sharp Corp | Toner and method of manufacturing the same, two-component developer, developing apparatus, and image forming apparatus |
US8216758B2 (en) | 2008-05-29 | 2012-07-10 | Sharp Kabushiki Kaisha | Toner, developer, developing device, and image forming apparatus |
JP2011033916A (en) * | 2009-08-04 | 2011-02-17 | Canon Inc | Toner |
JP2012048191A (en) * | 2010-08-26 | 2012-03-08 | Trend Tone Imaging Inc | Nonmagnetic developer and method of spherizing the same |
JP2015141220A (en) * | 2014-01-27 | 2015-08-03 | 京セラドキュメントソリューションズ株式会社 | Toner and method of manufacturing the same |
JP2015141221A (en) * | 2014-01-27 | 2015-08-03 | 京セラドキュメントソリューションズ株式会社 | Toner and method of manufacturing the same |
US9690223B2 (en) | 2014-01-27 | 2017-06-27 | Kyocera Document Solutions Inc. | Toner and method of manufacturing the same |
US9772573B2 (en) | 2014-01-27 | 2017-09-26 | Kyocera Document Solutions Inc. | Toner and method of manufacturing the same |
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