【発明の詳細な説明】 （産業上の利用分野） 本発明は、光導電性トナーに関するもので、より詳細
には光感度に優れた光導電性トナーに関する。The present invention relates to a photoconductive toner, and more particularly to a photoconductive toner having excellent photosensitivity.
（従来の技術） 近年感光体ドラム等を用いることなく複写画像を形成
する方法として光導電性トナーの使用が注目されてきて
いる。この光導電性トナーというのは、バインダー樹脂
中に光導電材料及び増感剤等を分散乃至は相溶させたも
のを、粉砕法乃至は噴霧法により粒状化させたトナーで
あり、トナー自体が光導電性を有するというものであ
る。(Prior Art) In recent years, the use of photoconductive toner has attracted attention as a method for forming a copied image without using a photosensitive drum or the like. The photoconductive toner is a toner in which a photoconductive material, a sensitizer, and the like are dispersed or compatible with each other in a binder resin and then granulated by a pulverizing method or a spraying method. It has photoconductivity.
この光導電性トナーを用いた作像（画像形成）方法の
一例としては次の様なものがある。The following is an example of an image forming (image forming) method using this photoconductive toner.
即ち、 （ｉ）帯電した光導電性トナーを導電性基体上に均一に
付着保持させ、トナー層を形成させる。That is, (i) the charged photoconductive toner is uniformly adhered and held on the conductive substrate to form a toner layer.
（ii）画像露光を行う。(Ii) Image exposure is performed.
（iii）トナー層に複写用紙等を重ね合わせ、複写紙の
裏面からコロナ放電を行いトナー像を転写させる。(Iii) Copy paper or the like is superposed on the toner layer, and corona discharge is performed from the back surface of the copy paper to transfer the toner image.
（iv）転写したトナー像を定着する。(Iv) Fix the transferred toner image.
といった工程を順次行う方法である。This is a method of sequentially performing the steps.
しかしながら、上述したプロセスにおいても光導電性
トナーの光感度が一般的に低いということに起因して露
光後に形成された潜像における露光部と比露光部の帯電
量差が小さく、結果として複写画像のコントラストが低
い画像しか得られないという欠点がある。However, even in the above-mentioned process, the photosensitivity of the photoconductive toner is generally low, so that the difference in charge amount between the exposed portion and the specific exposed portion in the latent image formed after exposure is small, resulting in a copy image. However, there is a drawback that only images with low contrast can be obtained.
そこで、トナー層形成後のトナー層にコロナ帯電を行
い、トナー層の表面電位を向上させることで光感度の向
上を目指す試みもなされているが、必ずしも解決できる
にいたっていない。Therefore, attempts have been made to improve the photosensitivity by corona charging the toner layer after forming the toner layer to improve the surface potential of the toner layer, but this has not always been a solution.
また、トナー中の光導電性物質の量を増やして光導電
性を高めることもできるが、逆にトナーが帯電しにくく
なり、かえって光感度が低下してしまい満足な結果が得
られていない。Further, it is possible to increase the photoconductivity by increasing the amount of the photoconductive substance in the toner, but on the contrary, the toner is less likely to be charged and the photosensitivity is rather lowered, so that a satisfactory result is not obtained.
そこで、本発明の目的は、帯電性を阻害することなく
光導電性を向上させ、コントラストの優れた画像が得ら
れる光感度に優れた光導電性トナーを得ることを目的と
する。Therefore, an object of the present invention is to improve the photoconductivity without impairing the charging property, and to obtain a photoconductive toner having excellent photosensitivity, which can provide an image with excellent contrast.
（問題点を解決するための手段） ワックス成分を20乃至80重量％含有する定着用樹脂媒
質と光導電性材料との重量比が、1:1乃至1:3であり、該
ワックス成分が球状粒子の状態で存在している光導電性
トナーを得ることにより本発明の目的が達成される。(Means for Solving the Problems) The weight ratio of the fixing resin medium containing 20 to 80% by weight of the wax component and the photoconductive material is 1: 1 to 1: 3, and the wax component is spherical. The object of the invention is achieved by obtaining a photoconductive toner which is present in the form of particles.
（発明の概要） 本発明者は、鋭意研究を重ねた結果、定着用樹脂媒質
中にワックス成分を球状粒子の形態で分散させることに
よりトナーの帯電性を阻害することなく光導電性が向上
し、コントラストの優れた画像形成が行える光感度に優
れた光電性トナーが得られることを見出した。(Summary of the Invention) As a result of earnest studies, the present inventor has improved the photoconductivity without impairing the charging property of the toner by dispersing the wax component in the form of spherical particles in the fixing resin medium. It was found that a photosensitive toner having excellent photosensitivity capable of forming an image with excellent contrast can be obtained.
本明細書中において光導電性トナーの光感度とは、帯
電されたトナー層の表面電位から露光（光照射）によっ
て、いかに効率良くトナー層の電荷が消失されるかを示
しており、ここでは0.5秒間光照射した後、1.5秒後に消
失した電荷量をトナー層の表面電位の減衰率で表してい
る。In the present specification, the photosensitivity of the photoconductive toner refers to how efficiently the charge of the toner layer is lost by exposure (light irradiation) from the surface potential of the charged toner layer. The amount of charge lost after 1.5 seconds of light irradiation for 1.5 seconds is represented by the decay rate of the surface potential of the toner layer.
上記構成からなる光導電性トナーが光感度を向上さ
せ、コントラストに優れた画像形成が行える点について
本発明者は以下のように考えている。The present inventor believes that the photoconductive toner having the above-mentioned structure improves the photosensitivity and can form an image with excellent contrast.
つまり、定着用樹脂媒質中のワックス成分は球状で乳
白色を示す微粒子として光導電性材料のまわりに分散し
ており、露光時にトナー中の光導電性材料を照射する光
は、直接光導電材料を照射する光の他に、球状ワックス
表面に到着して乱反射することによりトナー中に散乱し
光導電材料を照射する光が加わる。そのために光導電性
材料に入照する光量が増大して効率よくフォトキャリア
を発生するものと考える。That is, the wax component in the fixing resin medium is dispersed around the photoconductive material as fine particles having a spherical and milky white color, and the light irradiating the photoconductive material in the toner at the time of exposure is directly exposed to the photoconductive material. In addition to the irradiation light, light that arrives at the surface of the spherical wax and is diffusely reflected and scattered in the toner to irradiate the photoconductive material is added. Therefore, it is considered that the amount of light incident on the photoconductive material is increased to efficiently generate photocarriers.
また、ワックス粒子はトナー表面や光導電性材料のま
わりに集中せず定着用樹脂媒質中に微粒子状に分散して
存在しているために、摩擦帯電性を大きく支配するスチ
レンアクリル、ポリエステル等の極性基含有定着用樹脂
媒質によるトナー表面の摩擦帯電性や、光導電材料と定
着用樹脂媒質との界面での電荷の授受を妨げられず、ト
ナーの帯電機構や光導性機構の作用関係が一定に保たれ
る。In addition, since the wax particles are not concentrated on the toner surface or around the photoconductive material and are dispersed in the fixing resin medium in the form of fine particles, the wax particles such as styrene acrylic, polyester, etc. The triboelectric chargeability of the toner surface by the polar group-containing fixing resin medium and the transfer of charge at the interface between the photoconductive material and the fixing resin medium are not hindered, and the working relationship between the toner charging mechanism and the light-conducting mechanism is constant. Kept in.
また、本発明のトナーにおいてはワックスの形状及び
存在形態とともに、定着用樹脂媒質中のワックス成分の
含有量及び樹脂分全体と光導電性材料との量比も鮮明な
画像を得る上で重要である。In addition, in the toner of the present invention, the shape and existence form of the wax as well as the content of the wax component in the fixing resin medium and the ratio of the entire resin content to the photoconductive material are important for obtaining a clear image. is there.
つまり、定着用樹脂媒質中のワックス成分が20重量％
以下であると光感度の増大が期待しがたく、80重量％以
上であるとワックス成分が偏在してしまい、得られるト
ナーは正規な帯電量が得られず、光導電材料と定着用樹
脂媒質との電荷の授受を阻害し、逆に感度の低下をまね
きコントラストのきいた鮮明な画像が得られなくなる。That is, the wax component in the fixing resin medium is 20% by weight.
If it is less than the range, it is difficult to expect an increase in photosensitivity, and if it is 80% by weight or more, the wax component is unevenly distributed, and the toner obtained cannot obtain a regular charge amount, and the photoconductive material and the fixing resin medium are not obtained. It hinders the transfer of electric charges to and from the battery, and conversely causes a decrease in sensitivity, making it impossible to obtain a clear image with high contrast.
また、樹脂分全体に対する光導電材料の重量比は1:1
乃至1:3にすることが重要であり、重量比が1:1以下では
光導電性が乏しく充分な感度がえられない。また、重量
比が1:3以上で光導電材料が多く存在するとトナーの帯
電性が悪化し充分なトナー帯電量が得られないととも
に、トナーの定着性を損ない鮮明の画像が得られなくな
る。Also, the weight ratio of the photoconductive material to the total resin content is 1: 1.
It is important to set the ratio to 1: 3, and if the weight ratio is 1: 1 or less, the photoconductivity is poor and sufficient sensitivity cannot be obtained. Further, when the weight ratio is 1: 3 or more and a large amount of photoconductive material is present, the chargeability of the toner is deteriorated, a sufficient toner charge amount cannot be obtained, and the fixability of the toner is impaired, and a clear image cannot be obtained.
（発明の好適態様） 本発明の光導電性トナーに用いる光導電材料として
は、Se、フタロシアニン、ペリレン、スクアリン酸、ア
ゾ顔料、インジコ顔料、CdS、TiO2、PbO、SnO2、ZnO等
の公知の光導電材料が使用できる。(Preferred embodiment of the invention) As the photoconductive material used in the photoconductive toner of the present invention, known are Se, phthalocyanine, perylene, squaric acid, azo pigments, indigo pigments, CdS, TiO2 , PbO, SnO2 , ZnO and the like. Photoconductive materials of
上記光導電材料を分散させる定着用樹脂媒質として
は、スチレン系重合体、アクリル系重合体、スチレン−
アクリル系重合体、、ポリ塩化ビニル、ポリエステル、
ポリアミド、ポリウレタン、エポキシ樹脂、ジアリルフ
タレート樹脂、シリコーン樹脂、フェノール樹脂、ロジ
ン変成フェノール樹脂、キシレン樹脂、ロジン変成マレ
イン酸樹脂、ロジンエステル、石油樹脂等の各種の重合
体が例示できる。As the fixing resin medium in which the photoconductive material is dispersed, a styrene polymer, an acrylic polymer, styrene-
Acrylic polymer, polyvinyl chloride, polyester,
Examples include various polymers such as polyamide, polyurethane, epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, rosin-modified phenol resin, xylene resin, rosin-modified maleic acid resin, rosin ester, and petroleum resin.
これらは、使用する光導電材料と生成されたトナーの
帯電性及び定着性を考慮して１種または２種以上混合し
て用いられる。These are used alone or in combination of two or more in consideration of the photoconductive material to be used and the charging property and fixing property of the generated toner.
本発明に使用されるワックスとしては、ポリエチレン
ワックス、ポリプロピレンワックス、エチレン−プロピ
レンワックス、パラフィンワックス等の各種ワックス、
炭素数４以上のオレフィン単量体等の低分子量オレフィ
ン等が使用される。As the wax used in the present invention, various waxes such as polyethylene wax, polypropylene wax, ethylene-propylene wax and paraffin wax,
A low molecular weight olefin such as an olefin monomer having 4 or more carbon atoms is used.
上記ワックスは、熱トルエン、一般に65℃以上特に80
℃以上のトルエン中に溶解させ、この溶液を撹拌下に室
温乃至それ以下の温度に急冷することにより微細な乳白
色の球状粒子に析出する。The wax is hot toluene, typically above 65 ° C, especially 80
It is dissolved in toluene at a temperature of not lower than 0 ° C., and this solution is rapidly cooled to a temperature of room temperature or lower with stirring to precipitate fine milky white spherical particles.
前記物質を熱時溶解させる溶媒としては、トルエンの
他に、キシレン、エチルベンゼン、クメン、ベンゼン、
混合芳香族溶媒等の芳香族溶媒を挙げることができる。As a solvent for dissolving the above substance when heated, in addition to toluene, xylene, ethylbenzene, cumene, benzene,
Aromatic solvents such as mixed aromatic solvents can be mentioned.
析出するワックス粒子の粒径は、冷却速度、溶液濃度
及び撹拌の程度を変化させることにより調節することが
できる。本発明においては、一般に前記物質の溶液濃度
を１乃至30重量％、特に５乃至20重量％の程度とし、冷
却速度を１℃乃至100℃／分、特に３乃至50℃／分とす
ることが望ましく、粒径は0.01乃至0.1μｍに析出させ
ることが好ましい。The particle size of the precipitated wax particles can be adjusted by changing the cooling rate, the solution concentration and the degree of stirring. In the present invention, the solution concentration of the substance is generally set to 1 to 30% by weight, particularly 5 to 20% by weight, and the cooling rate is set to 1 ° C to 100 ° C / min, particularly 3 to 50 ° C / min. Desirably, the grain size is preferably 0.01 to 0.1 μm.
更に、本発明のトナーの分光感度を可視光域に一致さ
せる為に公知の増感色素を光導電材料と共に含有させる
か、あるいは前もって光導電材料を増感色素で処理する
こともできる。Further, in order to match the spectral sensitivity of the toner of the present invention to the visible light region, a known sensitizing dye may be contained together with the photoconductive material, or the photoconductive material may be previously treated with the sensitizing dye.
これら増感色素は光導電材料100重量部当たり0.01乃
至0.1重量部、特に0.03乃至0.5重量部の量比で配合でき
る。These sensitizing dyes can be added in an amount ratio of 0.01 to 0.1 part by weight, particularly 0.03 to 0.5 part by weight, per 100 parts by weight of the photoconductive material.
たとえば、光導電材料が酸化亜鉛のときはローズベン
ガル、エオシン、フルオレッセン、プリリアントグリー
ン、チオフラビン、アクリジンオレンジ、エリトロシン
等の増感色素が利用される。For example, when the photoconductive material is zinc oxide, sensitizing dyes such as rose bengal, eosin, fluorescein, prilyant green, thioflavin, acridine orange and erythrosine are used.
また、本発明のトナーには、樹脂中に前記ワックスの
他に、必要に応じで公知のトナー用の顔料、染料等の着
色剤を添加することもできる。In addition to the wax described above, a known colorant such as a pigment or dye for toner may be added to the toner of the present invention in the resin, if necessary.
これら着色剤は定着用樹脂100重量部当たり５乃至60
重量部、特に15乃至30重量部使用することが好ましい。These colorants are used in an amount of 5 to 60 per 100 parts by weight of the fixing resin.
It is preferred to use parts by weight, especially 15 to 30 parts by weight.
また、磁性トナーとして用いる時は、磁性体をトナー
中に含有させることも可能であり、磁性体としては磁性
を示すか磁化可能な材料でよく、例えば、フェライト、
マグネタイトをはじめとする鉄、コバルト、ニッケル、
マンガン等の強磁性を示す金属、合金等が使用される。When used as a magnetic toner, a magnetic substance may be contained in the toner, and the magnetic substance may be a material exhibiting magnetism or magnetizability, such as ferrite,
Iron, including magnetite, cobalt, nickel,
A metal, alloy, or the like that exhibits ferromagnetism such as manganese is used.
これら、磁性体は定着用樹脂100重量部当たり50乃至2
00重量部使用することができる。These magnetic materials are 50 to 2 per 100 parts by weight of the fixing resin.
00 parts by weight can be used.
本発明のトナーの製造においては、前述した製法によ
り作成した球状のワックス微細粒子が分散した溶媒を、
定着用樹脂媒質が溶解し光導電材料及び必要に応じて添
加した他の添加剤が分散乃至溶解させた溶液中に前記溶
媒をそのまま投入し、充分に分散させた後にスプレード
ライ法により３μｍ乃至20μｍ、好ましくは７μｍ乃至
10μｍの球状の光導電性トナーを得る。尚、定着用樹脂
を溶解した溶液とワックスが分散した溶媒とを混合し、
トナー化するまでワックス粒子は再溶解したり、粒成長
が生じるものであってはならない。In the production of the toner of the present invention, the solvent in which the spherical wax fine particles prepared by the above-mentioned production method are dispersed,
3 μm to 20 μm by a spray dry method after the above solvent is directly added to a solution in which the fixing resin medium is dissolved and the photoconductive material and other additives added as necessary are dispersed or dissolved. , Preferably 7 μm or more
A 10 μm spherical photoconductive toner is obtained. In addition, by mixing the solution in which the fixing resin is dissolved and the solvent in which the wax is dispersed,
The wax particles should not re-dissolve or cause particle growth until they become toner.
更に、トナーの種々の物性を向上させる目的で、流動
性改質剤としてシリカ、アルミナ、酸化チタン、分散性
改良剤としてシリコンオイル等をトナー組成物100重量
部当たり0.4乃至２重量部の量比で使用することができ
る。Further, for the purpose of improving various physical properties of the toner, silica, alumina, titanium oxide as a fluidity modifier and silicon oil as a dispersibility modifier are used in an amount ratio of 0.4 to 2 parts by weight per 100 parts by weight of the toner composition. Can be used in.
以下に実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
（実施例１） 低分子量ポリエチレンワックス（三洋化成製）50重量部 トリエン 1000重量部 を80℃に加熱して溶解し、ワックスが完全に溶解した後
に撹拌しながら５℃まで急冷して、粒径0.05μｍの球状
のワックス粒子を析出させたエマルジョンを得た。(Example 1) 50 parts by weight of low molecular weight polyethylene wax (manufactured by Sanyo Kasei) 1000 parts by weight of triene were heated to 80 ° C. to be melted, and after the wax was completely dissolved, the wax was rapidly cooled to 5 ° C. with stirring to give a particle size. An emulsion was obtained in which spherical wax particles of 0.05 μm were deposited.
一方トルエン1000重量部中にスチレン−アクリル樹脂
（三井東圧化学社製、PA525）50重量部、光導電材料と
してZnO（正同化学社製、SOX100）300重量部、増感剤と
してブロムフェノールブルー0.3重量部を溶解乃至分散
させた溶液を得た。そして、この溶液に上記得られたエ
マルジョンを投入し、充分に混合分散した後スプレード
ライ法によって中心粒径約９μｍの光導電性トナーを得
た。On the other hand, in 1000 parts by weight of toluene, 50 parts by weight of styrene-acrylic resin (PA525, manufactured by Mitsui Toatsu Chemical Co., Inc.), 300 parts by weight of ZnO (manufactured by Shodo Chemical Co., SOX100) as a photoconductive material, and bromphenol blue as a sensitizer. A solution having 0.3 parts by weight dissolved or dispersed was obtained. Then, the emulsion obtained above was added to this solution, sufficiently mixed and dispersed, and then a photoconductive toner having a central particle diameter of about 9 μm was obtained by a spray drying method.
この光導電性トナーをフェライトキャリアと混合して
摩擦帯電させ、電子写真複写機用の磁気ブラシ現像装置
に投入し、この現像装置を用いてアルミニウム基板上に
光導電性トナーを均一に付着させた。This photoconductive toner was mixed with a ferrite carrier, triboelectrified and charged into a magnetic brush developing device for an electrophotographic copying machine, and this developing device was used to uniformly attach the photoconductive toner onto an aluminum substrate. .
この形成された光導電性トナー層に、モノクロメータ
ーから取り出した単色光（620nm）を0.5秒間照射し、初
期表面電位と照射後1.5秒後の表面電位を測定し、デジ
タルオシロスコープに接続したコンピューターにより表
面電位の減衰率を測定したところ最大表面電位減衰率は
約35％であった。The formed photoconductive toner layer is irradiated with monochromatic light (620 nm) taken out from the monochromator for 0.5 seconds, the initial surface potential and the surface potential 1.5 seconds after the irradiation are measured, and the computer connected to the digital oscilloscope is used. When the decay rate of the surface potential was measured, the maximum decay rate of the surface potential was about 35%.
同様にして一様に付着させた光導電性トナー層に画像
露光を行い、その後転写紙を重ね背面から正極性のコロ
ナ放電を行い転写したところ、コントラストのはっきり
した鮮明な複写画像が得られた。In the same manner, image exposure was performed on the photoconductive toner layer that was evenly adhered, and then transfer paper was overlaid and positive corona discharge was applied from the back side to transfer, and a clear copy image with clear contrast was obtained. .
（実施例２） 実施例１において低分子量ポリエチレンワックスに変
えて低分子量ポリプロピレンワックス（三洋化成製）50
重量部使用する以外は実施例１と同様にして、粒径0.03
μｍの球状のワックス粒子を析出させたエマルジョンを
得た。(Example 2) Instead of the low molecular weight polyethylene wax in Example 1, a low molecular weight polypropylene wax (manufactured by Sanyo Kasei) 50
A particle size of 0.03 was obtained in the same manner as in Example 1 except that the parts by weight were used.
An emulsion was obtained in which spherical wax particles of μm were deposited.
更に、実施例１と同様にしてスプレードライ法によっ
て中心粒径約10μｍの光導電性トナーを得た。Further, in the same manner as in Example 1, a photoconductive toner having a central particle size of about 10 μm was obtained by a spray drying method.
実施例１と同様の操作をして、摩擦帯電、トナー層形
成を行い最大表面電位減衰率を測定したところ約34％で
あった。また、複写画像も実験例１と同様に鮮明な画像
が得られた。The same operation as in Example 1 was carried out to perform triboelectric charging and toner layer formation, and the maximum surface potential decay rate was measured and found to be about 34%. As for the copied image, a clear image was obtained as in Experimental Example 1.
（実施例３） 実施例１においてポリエチレンを35重量部とした以外
は同様にして粒径0.05μｍの球状のワックス粒子を析出
させたエマルジョンを得た。Example 3 An emulsion in which spherical wax particles having a particle size of 0.05 μm were deposited was obtained in the same manner as in Example 1 except that polyethylene was 35 parts by weight.
一方トルエン1000重量部中にスチレン−アクリル樹脂
（三井東圧化学社製、PA525）65重量部、光導電材料と
してZnO（正同化学社製SOX100）250重量部、増感剤とし
てブロムフェノールブルー0.3重量部を溶解乃至分散さ
せた溶液を得た。そして、この溶液に上記得られたエマ
ルジョンを投入し、充分に混合分散した後スプレードラ
イ法によって中心粒径約９μｍの光導電性トナーを得
た。On the other hand, in 1000 parts by weight of toluene, 65 parts by weight of styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemical Co., Inc.), 250 parts by weight of ZnO (SOX100 manufactured by Shodo Chemical Co., Ltd.) as a photoconductive material, and bromphenol blue 0.3 as a sensitizer. A solution in which parts by weight were dissolved or dispersed was obtained. Then, the emulsion obtained above was added to this solution, sufficiently mixed and dispersed, and then a photoconductive toner having a central particle diameter of about 9 μm was obtained by a spray drying method.
この光導電性トナーをフェライトキャリアと混合して
摩擦帯電させ、電子写真複写機用の磁気ブラシ現像装置
に投入し、この現像装置を用いてアルミニウム基板上に
光導電性トナーを均一に付着させた。This photoconductive toner was mixed with a ferrite carrier, triboelectrified and charged into a magnetic brush developing device for an electrophotographic copying machine, and this developing device was used to uniformly attach the photoconductive toner onto an aluminum substrate. .
この光導電性トナーを実施例１と同様にして最大表面
電位減衰率を測定したところ約30％であった。更に、同
様にして画像形成を行ったところ鮮明な画像が得られ
た。When the maximum surface potential decay rate of this photoconductive toner was measured in the same manner as in Example 1, it was about 30%. Further, when an image was formed in the same manner, a clear image was obtained.
（実施例４） 実施例１においてポリエチレンワックスを70重量部と
した以外は同様にして、粒径0.05μｍの析出粒子のが分
散したエマルジョンを得た。Example 4 An emulsion in which precipitated particles having a particle diameter of 0.05 μm were dispersed was obtained in the same manner as in Example 1 except that the polyethylene wax was changed to 70 parts by weight.
一方トルエン1000重量部中にスチレン−アクリル樹脂
（三井東圧化学社製、PA525）30重量部、光導電材料と
してZnO（正同化学社製SOX100）300重量部、増感剤とし
てブロムフェノールブルー0.3重量部を溶解乃至分散さ
せた溶液を得た。そして、この溶液に上記得られたエマ
ルジョンを投入し、充分に混合分散した後スプレードラ
イ法によって中心粒径約10μｍの光導電性トナーを得
た。On the other hand, in 1000 parts by weight of toluene, 30 parts by weight of styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemical Co., Inc.), 300 parts by weight of ZnO (SOX100 manufactured by Shodo Chemical Co., Ltd.) as a photoconductive material, and bromphenol blue 0.3 as a sensitizer. A solution in which parts by weight were dissolved or dispersed was obtained. Then, the emulsion obtained above was added to this solution, sufficiently mixed and dispersed, and then a photoconductive toner having a central particle diameter of about 10 μm was obtained by a spray drying method.
この光導電性トナーを実施例１と同様にして最大表面
電位減衰率を測定したところ約29％であった。更に、同
様にして画像形成を行ったところ鮮明な画像が得られ
た。When the maximum surface potential decay rate of this photoconductive toner was measured in the same manner as in Example 1, it was about 29%. Further, when an image was formed in the same manner, a clear image was obtained.
（比較例１） 実施例１においてポリエチレンワックスを85重量部と
した以外は同様にして、粒径0.03μｍの析出粒子が分散
したエマルジョンを得た。Comparative Example 1 An emulsion in which precipitated particles having a particle size of 0.03 μm were dispersed was obtained in the same manner as in Example 1 except that the polyethylene wax was changed to 85 parts by weight.
一方トルエン1000重量部中にスチレン−アクリル樹脂
（三井東圧化学社製、PA525）15重量部、光導電材料と
してZnO（正同化学社製SOX100）300重量部、増感剤とし
てブロムフェノールブルー0.3重量部を溶解乃至分散さ
せた溶液を得た。そして、この溶液に上記得られたエマ
ルジョンを投入し、充分に混合分散した後スプレードラ
イ法によって中心粒径約10μｍの光導電性トナーを得
た。On the other hand, in 1000 parts by weight of toluene, 15 parts by weight of styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemical Co., Inc.), 300 parts by weight of ZnO (SOX100 manufactured by Shodo Chemical Co., Ltd.) as a photoconductive material, and bromphenol blue 0.3 as a sensitizer. A solution in which parts by weight were dissolved or dispersed was obtained. Then, the emulsion obtained above was added to this solution, sufficiently mixed and dispersed, and then a photoconductive toner having a central particle diameter of about 10 μm was obtained by a spray drying method.
この得られたトナーをフェライトキャイアと混合して
摩擦帯電させたが適性帯電量が得られず、−10μc/g以
下の摩擦帯電量しか示さなかった。更にアルミニウム基
板上にトナー層を形成して、実施例１と同様にして最大
表面電位減衰率を測定したが約16％と低い値を示し、得
られた複写画像もカブリの多い粗悪な画像であった。The toner thus obtained was mixed with a ferrite carrier and triboelectrified, but an appropriate amount of triboelectrification was not obtained and the triboelectrification amount was not more than -10 μc / g. Further, a toner layer was formed on an aluminum substrate, and the maximum surface potential decay rate was measured in the same manner as in Example 1, but it showed a low value of about 16%, and the obtained copied image was also a poor image with many fogs. there were.
（比較例２） 実施例１においてポリエチレンワックスを10重量部と
した以外は同様にして、粒径0.05μｍの析出粒子のが分
散したエマルジョンを得た。Comparative Example 2 An emulsion in which precipitated particles having a particle size of 0.05 μm were dispersed was obtained in the same manner as in Example 1 except that 10 parts by weight of polyethylene wax was used.
一方トルエン1000重量部中にスチレン−アクリル樹脂
（三井東圧化学社製、PA525）90重量部、光導電材料と
してZnO（正同化学社製SOX100）300重量部、増感剤とし
てブロムフェノールブルー0.3重量部を溶解乃至分散さ
せた溶液を得た。そして、この溶液に上記得られたエマ
ルジョンを投入し、充分に混合分散した後スプレードラ
イ法によって中心粒径約10μｍの光導電性トナーを得
た。On the other hand, in 1000 parts by weight of toluene, 90 parts by weight of styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemical Co., Inc.), 300 parts by weight of ZnO (SOX100 manufactured by Shodo Chemical Co., Ltd.) as a photoconductive material, and bromphenol blue 0.3 as a sensitizer. A solution in which parts by weight were dissolved or dispersed was obtained. Then, the emulsion obtained above was added to this solution, sufficiently mixed and dispersed, and then a photoconductive toner having a central particle diameter of about 10 μm was obtained by a spray drying method.
この光導電性トナーを実施例１と同様にして摩擦帯電
させトナー層形成を行い最大表面電位減衰率を測定した
ところ約14％と低い値であった。更に、同様にして画像
形成を行ったところカブリが見られ、コントラストに欠
ける画像であった。This photoconductive toner was triboelectrically charged in the same manner as in Example 1 to form a toner layer, and the maximum surface potential decay rate was measured to be a low value of about 14%. Further, when an image was formed in the same manner, fog was observed and the image lacked in contrast.
（比較例３） スチレン−アクリル樹脂（三井東圧化学社製 PA525）1
00 重量部 ZnO（正同化学社製 SOX100） 300 重量部 ブロムフェノールブルー 0.3重量部 をトルエン2000重量部に溶解分散し、充分に混合した後
にスプレードライ法により中心粒径が10μｍの光導電性
トナーを得た。(Comparative Example 3) Styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemicals, Inc.) 1
00 parts by weight ZnO (SOX100 manufactured by Shodo Kagaku Co., Ltd.) 300 parts by weight Bromphenol blue 0.3 parts by weight is dissolved and dispersed in 2000 parts by weight of toluene, and after thorough mixing, a photoconductive toner having a central particle size of 10 μm by a spray drying method. Got
実施例１と同様にして最大表面電位減衰率を測定した
ところ、約13％であった。そして、得られた複写画像は
カブリが見られ、鮮明さの欠ける画像となった。When the maximum surface potential decay rate was measured in the same manner as in Example 1, it was about 13%. Then, the obtained copied image was fogged and lacked in sharpness.
（比較例４） スチレン−アクリル樹脂（三井東圧化学社製 PA525）5
0 重量部 ポリエチレンワックス（三洋化成社製） 50 重量部 ZnO（正同化学社製 SOX100） 300 重量部 ブロムフェノールブルー 0.3重量部 上記混合物を三本ロールミルで溶融混練して混練物を
得、冷却、粉砕、分級して平均粒計10μｍのトナーを得
た。(Comparative Example 4) Styrene-acrylic resin (PA525 manufactured by Mitsui Toatsu Chemicals, Inc.) 5
0 parts by weight Polyethylene wax (manufactured by Sanyo Kasei Co., Ltd.) 50 parts by weight ZnO (SOX100 manufactured by Shodo Kagaku Co., Ltd.) 300 parts by weight Bromphenol blue 0.3 parts by weight The above mixture is melt-kneaded in a three-roll mill to obtain a kneaded product, which is then cooled, The particles were pulverized and classified to obtain a toner having an average particle size of 10 μm.
この光導電性トナーをフェライトキャリアと混合して
摩擦帯電させ、電子写真複写機用の磁気ブラシ現像装置
に投入し、この現像装置を用いてアルミニウム基板上に
光導電性トナーを均一に付着させた。This photoconductive toner was mixed with a ferrite carrier, triboelectrified and charged into a magnetic brush developing device for an electrophotographic copying machine, and this developing device was used to uniformly attach the photoconductive toner onto an aluminum substrate. .
実施例１と同様にして最大表面電位減衰率を測定した
ところ、約14％であった。そして、得られた複写画像は
カブリが多く、鮮明さの欠ける画像となった。When the maximum surface potential decay rate was measured in the same manner as in Example 1, it was about 14%. Then, the obtained copied image had a lot of fog and lacked sharpness.
上記実施例及び比較例の結果を表−１に記す。 The results of the above Examples and Comparative Examples are shown in Table-1.
表中、○は良、×は不良を表す。帯電特性はブローオ
フ法によって測定し、画像カブリは反射濃度計によって
測定して判断した。In the table, ◯ means good and X means bad. The charging property was measured by the blow-off method, and the image fog was judged by measuring with a reflection densitometer.
（発明の効果） 表−１からも明らかなように、定着用樹脂媒質中に特
定量のワックス成分を球状の微粒子として分散させたト
ナーを得ることにより、摩擦帯電性が良好で光導電性が
増加して、光照射時の電荷の消失が速やかに行われる光
導電性トナーが得られる。そして、転写材上に形成され
る複写画像はコントラストのきいた鮮明の画像が得られ
る。 (Effects of the invention) As is clear from Table 1, by obtaining a toner in which a specific amount of wax component is dispersed as spherical fine particles in a fixing resin medium, good triboelectricity and good photoconductivity can be obtained. As a result, it is possible to obtain a photoconductive toner in which the charge is rapidly lost upon irradiation with light. As a copy image formed on the transfer material, a clear image with high contrast can be obtained.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044688AJP2567019B2 (en) | 1988-02-26 | 1988-02-26 | Photoconductive toner |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044688AJP2567019B2 (en) | 1988-02-26 | 1988-02-26 | Photoconductive toner |
| Publication Number | Publication Date |
|---|---|
| JPH01217467A JPH01217467A (en) | 1989-08-31 |
| JP2567019B2true JP2567019B2 (en) | 1996-12-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63044688AExpired - LifetimeJP2567019B2 (en) | 1988-02-26 | 1988-02-26 | Photoconductive toner |
| Country | Link |
|---|---|
| JP (1) | JP2567019B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3314326B2 (en)* | 1995-05-30 | 2002-08-12 | ミノルタ株式会社 | Toner for developing electrostatic latent images |
| JP3225889B2 (en)* | 1996-06-27 | 2001-11-05 | 富士ゼロックス株式会社 | Toner for electrostatic latent image developer, method for producing the same, electrostatic latent image developer, and image forming method |
| JPH1144969A (en)* | 1997-07-28 | 1999-02-16 | Fuji Xerox Co Ltd | Electrophotographic toner and manufacture thereof, and method for forming image with use of the same toner |
| US6746808B2 (en) | 2001-08-29 | 2004-06-08 | Fuji Xerox Co., Ltd. | Image forming color toner, color image forming method and color image forming apparatus |
| JP2004163879A (en) | 2002-06-13 | 2004-06-10 | Heidelberger Druckmas Ag | Electrophotographic toner in which wax is uniformly dispersed |
| Publication number | Publication date |
|---|---|
| JPH01217467A (en) | 1989-08-31 |
| Publication | Publication Date | Title |
|---|---|---|
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