JP3972763B2 - Toner, toner manufacturing method, and image forming apparatus - Google Patents

Description

【０１４１】
【表２】

【０１４２】
【表３】

【０１４３】
【表４】

【０１４４】
(表５)に図１の電子写真装置により、画像出しを行った結果を示す。(表６)ではトナーが３色重なったフルカラー画像における文字部での転写不良の状態、及び定着での定着ベルトへの紙の巻付き性を評価した。
【０１４５】
【表５】

【０１４６】
【表６】

【０１４７】
図１に示す画像形成装置により、前記のように製造したトナーを用いて画像出しを行ったところ、横線の乱れやトナーの飛び散り、文字の中抜けなどがなくベタ黒画像が均一で、１６本／ｍｍの画線をも再現した極めて高解像度高画質の画像が得られ、画像濃度１．３以上の高濃度の画像が得られた。また、非画像部の地かぶりも発生していなかった。更に、Ａ４用紙1万枚の長期耐久テストにおいても、流動性、画像濃度とも変化が少なく安定した特性を示した。また現像時の全面ベタ画像を取ったときの均一性も良好であった。現像メモリも発生していない。連続使用時においても、縦筋の異常画像は発生しなかった。また転写においても中抜けは実用上問題ないレベルであり、転写効率は９８％程度を示した。また、感光体、転写ベルトへのトナーのフィルミングも実用上問題ないレベルであった。転写ベルトのクリーニング不良も未発生であった。また定着時のトナーの乱れやトナー飛びもほとんど生じていない。またクリーニングブレード８を使用せずに転写時の残トナーをこのまま現像での回収を行うクリーナプロセスにおいても、回収がスムーズに行え、前画像の履歴が残ることがなかった。また３色の重なったフルカラー画像においても、転写不良は発生せず、定着時において、定着ベルトへの紙の巻付きは発生しなかった。
【０１４８】
しかし、ｔｍ６、ｔｙ６、ｔｃ６、ｔｂ６のトナーは感光体のフィルミングがやや発生し、転写不良や、転写時の文字の飛び散りも他のトナーに比べて多めになっている。カブリも多く発生した。現像時の全面ベタ画像を取ったときに後半部にかすれが生じた。連続使用時に現像ブレードに異物の融着による縦筋の異常画像が発生した。３色重ねの画像出力時には定着ベルトへの紙の巻付きが発生した。
【０１４９】
次に、ＯＨＰ用紙に付着量１．２ｇ／ｃｍ²以上のベタ画像を形成し、プロセス速度１００ｍｍ／ｓで、オイルを塗布しないベルトを用いた定着装置にて耐オフセット性試験を行った。その結果、定着ニップ部におけるＯＨＰのジャムは発生しなかった。また、普通紙の全面ベタグリーン画像では、オフセットは１２２０００枚目まで全く発生しなかった。さらに、シリコーン又はフッ素系の定着ベルトを用い、オイルを塗布しない構成においても、ベルト表面の劣化現象はみられなかった。
【０１５０】
また、透過率と、高温での耐オフセット性を評価した。プロセス速度は１００ｍｍ／ｓ、定着温度１８０℃で透過率は分光光度計Ｕ−３２００（日立製作所）で、７００ｎｍの光の透過率を測定した。ＯＨＰ透過率、及び耐オフセット性の結果を（表７）に示す。
【０１５１】
【表７】

【０１５２】
ＯＨＰ透過率が８０％以上を示しており、また高温オフセット発生温度２００℃以上であり、オイルを使用しない定着ローラにおいても良好な定着性を示した。また６０℃、５時間の保存安定性においても凝集はほとんど見られなかった。
【０１５３】
しかし、ｔｍ６のトナーは貯蔵安定性テストで固まりが生じ、また高温オフセット発生温度も低いという結果となった。
【０１５４】
【発明の効果】
以上のように、重合性単量体に、少なくともワックスと着色剤とを添加して、水系媒体中で懸濁重合させるトナーの製造方法であって、ワックスを重合性単量体の一部に溶解して水系媒体中で懸濁重合させる第１工程と、第１工程により得られる溶液に、着色剤の水溶性有機溶剤分散液と重合性単量体の残りとを添加して懸濁重合させる第２工程とを有するトナーの製造方法により、製造方法を簡素化し、かつ懸濁粒子の重合時に該粒子中の着色剤の再凝集を防ぎ、着色力の大きいトナーを得ることができる。
【図面の簡単な説明】
【図１】本発明の実施例で使用した画像形成装置の構成を示す断面図
【図２】本発明の実施例で使用した定着ユニットの構成を示す断面図
【符号の説明】
１ 感光体
４ 現像ローラ
５ ブレード
７ トナー
１０ 第１転写ローラ
１２ 転写ベルト
１４ 第２転写ローラ
１８ 像形成ユニット
２０１ 定着ローラ
２０２ 加圧ローラ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner by a suspension polymerization method used in a copying machine, a laser printer, plain paper FAX, a color PPC, a color laser printer and a color FAX, a toner manufacturing method, and an image forming apparatus.
[0002]
[Prior art]
As described in U.S. Pat. No. 2,297,691, etc., many methods are known for electrophotography. Generally, a photoconductive material is used and a photoconductor is used by various means. An electrical latent image is formed on the surface, the latent image is developed with toner, and the toner image is transferred onto a transfer medium such as paper as necessary. It is a way to get things. As methods for developing or fixing, many methods have been conventionally proposed, and methods suitable for the respective image forming processes are employed.
[0003]
In recent years, the electrophotographic apparatus is shifting from the purpose of office use to personal use, and there is a demand for technology that realizes miniaturization, high speed, high image quality, maintenance-free, and the like. Therefore, it is highly glossy without using a cleaner-less process that collects residual toner in the developer without cleaning it, a tandem color process that enables high-speed output of color images, or no fixing oil to prevent offset during fixing. Oil-free fixing that achieves both a clear color image with high transparency and high translucency and anti-offset properties is required along with conditions such as maintenance and low ozone exhaust. These functions need to be compatible at the same time. For that purpose, not only the process but also the improvement of toner characteristics is an important factor.
[0004]
In a color printer, an image carrier (hereinafter referred to as a photoconductor) is charged by corona discharge using a charging charger, and then an image pattern of each color is irradiated onto the photoconductor as an optical signal to form an electrostatic latent image. The latent image is developed by developing with color, for example, yellow toner. Thereafter, a transfer member charged with a polarity opposite to that of the yellow toner is brought into contact with the photosensitive member to transfer the yellow toner image formed on the photosensitive member. The photosensitive member is neutralized after cleaning the toner remaining at the time of transfer, and the development and transfer of the first color toner are completed. Thereafter, the same operation as that of the yellow toner is repeated for toners such as magenta and cyan, and a color toner image is formed by superimposing the toner images of the respective colors on the transfer body. Then, a four-pass color process for transferring these superimposed color toner images onto paper charged with a polarity opposite to that of the toner has been put into practical use.
[0005]
In addition, a plurality of image forming stations having a charger, a photosensitive member, a developing device, and the like are arranged side by side, and an endless belt-like transfer member is brought into contact with the photosensitive member to successively transfer toner of each color sequentially to the transfer member. A secondary transfer process in which a multi-color toner image is formed on a transfer body by executing a transfer process, and then the color toner images formed on the transfer body are collectively transferred to a transfer medium such as paper or OHP. A tandem color process configured to perform the above and a tandem color process for continuously transferring directly onto a transfer medium such as paper or OHP without using a transfer body have been put into practical use.
[0006]
This tandem method has the feature that a color image can be output at high speed, but the toner layer becomes thicker because the four color toner images are superimposed on the transfer body or the transfer medium, and the toner layer is absent or thin. A pressure difference is easily generated between the toner layer and the thick toner layer. For this reason, due to the aggregation of toner, a part of the image is not transferred, and a “collapse” phenomenon that becomes a hole easily occurs. Further, if a material having a high toner releasability is used on the surface of the transfer body in order to surely clean the toner remaining after the transfer, the voids appear remarkably and the quality of the image is remarkably lowered. Furthermore, in a fine line image such as a character or a line, more toner adheres due to the edge effect, so that the toner tends to agglomerate due to pressurization, and the void is more noticeable. In particular, it tends to become more prominent in a low temperature and low temperature environment.
[0007]
Furthermore, in order to reduce the size and increase the speed of the machine, it is required that the distance between image forming stations (corresponding to the distance between the photoconductors) is shortened and printing is performed at a higher speed. As a result, for example, since the time from when the yellow toner is transferred to when the next magenta toner is transferred is extremely short, the charge of the transfer medium or transfer medium is alleviated and the charge of the transferred toner is alleviated. I will not. For this reason, when the magenta toner is transferred onto the yellow toner, the magenta toner is repelled by the electric charge of the yellow toner, causing problems such as image disturbance due to the scattering of the toner image, a decrease in transfer efficiency, and an omission. In addition, there arises a problem of reverse transfer in which the yellow toner transferred onto the transfer body or the transfer medium moves to the magenta toner photoconductor when the magenta toner is transferred.
[0008]
Further, in the configuration using the transfer body, the toner image is repelled by the mutual charge of the toner when the last toner of the fourth color is transferred (primary transfer) and then collectively transferred (secondary transfer) to paper or the like. Disturbance occurs.
[0009]
Further, if the resistance of the transfer body is set to a high resistance in order to improve the dot reproducibility in transfer, these toner image disturbances and the tendency of transfer failure are more prominent.
[0010]
Further, as will be described later, in order to enable oilless fixing without using oil at the time of fixing, the toner composition in which a release agent such as wax is added to the sharp melt resin has a strong toner charge retaining property, and the toner It has the property of being highly cohesive. For this reason, the toner image is disturbed and the transfer tends to be defective, and it is difficult to achieve both transfer and fixing. In addition, when a wax having a polar group is added in order to enhance the dispersibility in the polyester resin, the cohesiveness becomes stronger and it becomes more difficult to achieve both oilless fixing and transferability.
[0011]
Further, in a color image, it is necessary to melt and mix color toners in the fixing process to increase translucency. In particular, light transmission on OHP paper has become more important due to the increase in presentation opportunities in color. When the toner is poorly melted, light scattering occurs on the surface or inside of the toner image, and the original color tone of the toner coloring matter is impaired. In addition, in the overlapped portion, light does not enter the lower layer and color reproducibility is lowered. Therefore, it is a necessary condition that the toner has a complete melting characteristic and a translucency that does not disturb the color tone.
[0012]
However, if the resin structure has a sharp melt melting characteristic for improving light transmittance, the offset resistance is lowered, and the offset adheres to the surface of the fixing roller. For this reason, it is necessary to apply a large amount of oil or the like to the fixing roller, which complicates the handling and configuration of the device. Therefore, an oilless color fixing configuration that does not require oil is required.
[0013]
In addition, a fluorine-based material is generally used to improve the releasability and durability of the fixing roller and the fixing belt. However, the fluorine-based material is easily charged, and there is a problem that the unfixed toner image is electrostatically affected before entering the fixing unit, and the toner image is likely to be disturbed. Further, before entering the fixing nip portion, the toner may fly to the fixing roller or the fixing belt to cause an offset in the halftone image. In particular, in the configuration in which oil is not applied, the influence of the charging property of the fluorine-based material as described above tends to occur. In addition, in a toner to which a release agent is added for the purpose of improving the offset property, the fixing roller is liable to be damaged due to poor dispersion of the internal additive, which causes generation of vertical stripes in the image.
[0014]
As is well known, a toner for electrostatic charge development used in an electrophotographic method is generally a resin component which is a binder resin, a coloring component consisting of a pigment or a dye, a plasticizer, a charge control agent, It is comprised by additional components, such as a mold release agent, as needed. As the resin component, natural or synthetic resins may be used alone or mixed in a timely manner.
[0015]
Then, the above additives are premixed at an appropriate ratio, heated and kneaded by heat melting, finely pulverized by an airflow type impact plate method, and finely classified to complete a toner base. Thereafter, an external additive such as hydrophobic silica is externally added to the toner base to complete the toner. For one-component development, only toner is used, but for two-component development, a toner and a carrier made of magnetic particles are mixed and used.
[0016]
As a release agent to be added for the purpose of improving the fixing property, JP-A-2-266372 discloses a desorbed fatty acid type carnauba wax and / or a montan ester wax, an oxidized rice wax having an acid value of 10 to 30, and a special one. No. 9-281748 discloses a vinyl copolymer polymerized in the presence of a natural gas Fischer-Tropsch wax, and a polyhydric alcohol component and a dicarboxylic acid in JP-A-10-327196. And a polycarboxylic acid compound having a valence of 3 or more are added, and an average dispersed particle size of the release agent is 0.1 to 3 μm, and a particle size of the external additive is 4 to 200 nm and 1 to 5 parts by weight are added Is disclosed. Japanese Patent Application Laid-Open No. 5-333584 discloses a content in which the fixability is improved by a constitution containing a fluorine-modified polyolefin resin such as polypropylene modified with an organic fluorine compound such as perfluorooctyl methacrylate. . In JP-A-5-188632, the softening point is 80 to 140 ° C., and a low molecular weight polyolefin containing fluorine, and a melt mixture of a low molecular weight olefin and polytetrafluoroethylene is blended to improve offset resistance during fixing. The content to be improved is disclosed, and it is described that there is an effect in improving the fixing property.
[0017]
In JP-A-59-148067, a softening point is specified by using an unsaturated ethylene polymer having a low molecular weight and a high molecular weight portion in the resin and defining a low molecular weight peak value and Mw / Mn. Toners containing such polyolefins are disclosed. As a result, fixing property and offset resistance are ensured. Japanese Patent Application Laid-Open No. 56-158340 discloses a toner mainly composed of a resin comprising a specific low molecular weight polymer component and a high molecular weight polymer component. The purpose is to secure the fixing property by the low molecular weight component and to secure the offset resistance by the high molecular weight component. Japanese Patent Application Laid-Open No. 58-223155 discloses a resin composed of an unsaturated ethylene polymer having a maximum value in a molecular weight region of 1000 to 10,000 and 200,000 to 1,000,000 and Mw / Mn of 10 to 40 and a specific one. A toner containing a polyolefin having a softening point is disclosed. It is used for the purpose of securing fixability with a low molecular weight component and ensuring offset resistance with a high molecular weight component and polyolefin.
[0018]
JP-A-63-56659 and JP-A-2000-98661 disclose toners relating to polyester resins, and disclose that good fixability can be obtained.
[0019]
Examples of charge control agents that impart chargeability to the toner include benzylic acid derivatives disclosed in JP-A-2-221967, JP-A-7-84409, JP-A-5-72812, and JP-A-5-165257. Toners using these metal salts are disclosed. JP-A-53-127726, JP-A-55-42752, JP-A-7-221797 and the like disclose toners using metal salts of salicylic acid derivatives.
[0020]
However, when the melt viscosity of the binder resin is lowered or the resin having a low molecular weight is used in order to increase the fixing strength, so-called spent occurs in which the toner adheres to the carrier during two-time development during long-term use. It becomes easy to do. Further, the stress resistance of the developer is lowered. Furthermore, an offset in which toner adheres to the heat roller during fixing is likely to occur. Furthermore, blocking occurs in which toners are fused to each other during long-term storage.
[0021]
A composition in which a release agent having a low melting point, such as polyethylene or polypropylene wax, is added to a resin obtained by blending or copolymerizing a high molecular weight component and a low molecular weight component, improves the releasability from the heat roller during fixing. Therefore, it is made for the purpose of enhancing the offset resistance. However, it is difficult for these release agents to improve the dispersibility in the binder resin, reverse polarity toner due to poor dispersion is likely to occur, and fogging to non-image areas occurs. In addition, image defects such as those scraped off with a brush at the rear end portion of the solid black image portion occur, and the image quality is deteriorated. Another problem is that the carrier, the photoconductor, and the developing sleeve are contaminated by filming. Further, in the contact type one-component development method in which an elastic blade that regulates the toner layer is used in contact with a developing roller such as silicone or urethane, and a supply roller such as urethane that supplies toner to the developing roller is used, the low melting point is low. In a toner to which a release agent is added, the rising property of charge is deteriorated, or the charge maintenance property is deteriorated during continuous use for a long time. In addition, the use of toner to which a low melting point release agent is added causes vertical streaks to gradually develop on the developing roller with the use of several thousand sheets, causing image defects such as white spots and black streaks. This is thought to be due to the occurrence of scratches on the developing roller due to poor dispersion of the release agent, fusion to the blade, and aggregation due to friction between the supply roller and the developing roller.
[0022]
Furthermore, it is important to realize a cleanerless process without a cleaning process from the viewpoint of downsizing of equipment and resource saving. After the toner that has visualized the electrostatic latent image formed on the photoconductor is transferred to a transfer body or paper by a transfer unit, the toner remaining on the photoconductor is usually collected by a cleaning unit such as a blade or a fur brush. To do. The collected toner becomes waste toner. On the other hand, a cleanerless process is a process in which the next charging, exposure, and development processes are performed without cleaning. In order to realize this cleaner-less process, it is essential to realize high transferability in transfer. Even if the transfer residual toner remains on the photoconductor to some extent, if the transfer residual toner in the non-image area is collected in the development area in the next development process, no image problem will occur. In the case of color image output, in the transfer step of superimposing the color toner images, the previously transferred toner may be reversely transferred to the photoconductor when the next toner is transferred, thereby generating an abnormal image. Therefore, countermeasures against this untransferred toner and reverse transfer toner are important points.
[0023]
In addition, in a toner to which a release agent such as a low melting point wax is added in order to satisfy the offset resistance at the time of fixing described above, the compatibility between the resin and the wax is poor, and the wax particles in the toner become coarse. Therefore, the fluidity tends to decrease, the transferability is not good, and the toner cohesion is strong. Therefore, in the cleanerless process, it is difficult to collect the transfer residual toner in the development, and the non-image area is Image pattern memory remains. Furthermore, when the toner is subjected to spheroidization by applying heat or impact force to improve the transferability, the transferability is improved, but the coarsened wax bleeds to the toner surface, which is the photoreceptor. There is a problem in that the carrier, the developing roller, and the transfer body are contaminated, and the uniformity of charging and the life are deteriorated.
[0024]
In addition, the toner obtained by the above-described pulverization method has a wide particle size distribution of toner particles, and there is a limit to reducing the particle size of the toner from the technical and productivity viewpoints. On the other hand, it is possible to cope with the reduction in particle size, and as an advantageous method over the grinding method in terms of productivity, Suspension A method for producing a polymerized toner by a polymerization method has been proposed.
[0025]
[Problems to be solved by the invention]
This method involves adding a polymerizable monomer, a colorant, and other additives to remove the toner. Suspension It is a method of manufacturing in a state and granulating. This polymerized toner has several advantages over the pulverized toner, but has been found to have problems to be solved in terms of manufacturing and the like.
[0026]
In general, a polymerized toner is obtained by uniformly dissolving or dispersing a polymerizable monomer, a wax, a colorant, a polymerization initiator, and, if necessary, a charge control agent and other additives to obtain a monomer composition. This monomer composition can be obtained by dispersing in a water phase containing a dispersion stabilizer using a suitable stirrer and carrying out a polymerization reaction.
[0027]
For this reason, a special ball mill such as a special attritor capable of controlling the temperature is required in order to efficiently dissolve the wax requiring heating and disperse the colorant at the same time.
[0028]
In the initial stage of the polymerization reaction, the viscosity of the monomer composition is very low, so that the colorant once dispersed in the particles may cause reaggregation.
[0029]
As a result, the chargeability of the toner is lowered, and the image is liable to deteriorate during long-term durability use, and the character dropout or reverse transfer is likely to occur during multi-layer transfer of toner during color image formation. Further, in oilless fixing in which no oil is used during fixing, the glossiness and translucency of the image tend to be deteriorated.
[0030]
In JP-A-4-188156, a monomer composition containing a wax to prevent aggregation of a colorant is first heated to dissolve the wax and dispersed in a dispersion medium. Up to below the temperature at which wax precipitates Suspension A method for initiating polymerization by lowering the liquid temperature is disclosed. Specifically, the wax was dissolved and dispersed at 70 ° C. Suspension In starting the polymerization of the liquid, the temperature is lowered to 20 ° C., and the temperature control is extremely inefficient.
[0031]
[Means for Solving the Problems]
In order to solve the above-described problems, a toner production method according to the present invention is a toner production method in which at least a wax and a colorant are added to a polymerizable monomer and suspension polymerization is performed in an aqueous medium. And dissolve the wax in a part of the polymerizable monomer in an aqueous medium. Suspension A first step of polymerizing, and a second step of adding a water-soluble organic solvent dispersion of a colorant and the remainder of the polymerizable monomer to the solution obtained by the first step to perform suspension polymerization. Features.
[0032]
In the first step, an organic material having an acid value of 5 or more having a carboxyl group is added in the aqueous medium. Suspension It is preferable to polymerize.
[0033]
In the first step, the amount of the polymerizable monomer to be subjected to suspension polymerization is preferably 30 to 60% of the total amount of the polymerizable monomer.
[0034]
Further, in the second step, it is preferable that suspension polymerization is performed by further adding an organic material having an acid value of 5 or more having a carboxyl group.
[0035]
The water-soluble organic solvent in which the colorant is dispersed is preferably selected from ethyl alcohol, tetrahydrofuran, and dimethylformamide.
[0036]
The wax has a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) in the molecular weight distribution in gel permeation chromatography (GPC). ) Is 1.01 to 8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, molecular weight 5 × 10 ² ~ 1x10 ^Four It is preferable to have at least one molecular weight maximum peak in this region.
[0037]
The wax is preferably an ester wax having an iodine value of 25 or less and a saponification value of 30 to 300.
[0038]
The toner according to the present invention is manufactured by the above-described toner manufacturing method.
[0039]
An image forming apparatus according to the present invention includes a plurality of toner image forming stations having an image carrier and a developing unit that visualizes the electrostatic latent image formed on the image carrier with the above-described toner; Transfer means for transferring the toner images visualized by the means onto the transfer medium successively in succession.
[0040]
In addition, an image forming apparatus according to the present invention includes a plurality of toner image forming stations having an image carrier and a developing unit that visualizes the electrostatic latent image formed on the image carrier with the above-described toner. A primary transfer means for bringing the endless belt-like transfer body into contact with the image carrier and successively transferring the toner images developed by the developing means onto the transfer body, and a toner image transferred onto the transfer body And a secondary transfer unit that collectively transfers the image onto a transfer medium.
[0041]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0042]
As a result of intensive studies, the present inventors have dissolved wax in a part of the polymerizable monomer and dissolved it in an aqueous medium. Suspension A toner comprising: a first step of polymerizing; and a second step of adding a water-soluble organic solvent dispersion of a colorant and the remainder of the polymerizable monomer to the solution obtained by the first step to perform suspension polymerization. It has been found that the production method is simplified, and the re-aggregation of the colorant in the particles is prevented, and a polymerized toner having excellent coloring power can be obtained.
[0043]
That is, in general, a polymerized toner has a monomer composition obtained by uniformly dissolving or dispersing various additives such as a polymerizable monomer, a wax, and a colorant because of its production characteristics. Dispersing the body composition in an aqueous medium; Suspension In order to make particles and perform the polymerization reaction, it is necessary to simultaneously dissolve the wax and disperse the colorant. It should be noted that a special ball mill such as a special attritor with temperature control is required since the wax requires heating. On the other hand, in the present invention, since the dispersion of the colorant and the dissolution of the wax are performed separately, a special apparatus as described above is not required, and the manufacturing method can be simplified. Further, in the present invention, when the colorant is added, polymerization proceeds in advance and the viscosity of the particles is high, so that reaggregation of the colorant dispersed in the particles hardly occurs. Therefore, the dispersion state of the colorant is maintained even during the polymerization reaction, and a toner having a high coloring power can be obtained.
[0044]
Also conventional Suspension In the production method of the polymerized toner by the method, since the colorant is dispersed in the polymerizable monomer in advance, there is a limit to the amount of the colorant added, and if it is used too much, the fluidity of the dispersion is lost. Handling becomes difficult. On the other hand, in the present invention, since a water-soluble organic solvent is used for dispersing the colorant, there is no limit to the amount of the colorant used, and therefore it is easy to increase the coloring power by increasing the amount of the colorant. Become.
[0045]
Next, a method for producing the polymerized toner used in the present invention will be described below. That is, a wax is added to a part of the polymerizable monomer and heated until the wax is dissolved or melted, and this monomer system is placed in an aqueous phase at the same temperature as the monomer system containing the dispersion stabilizer. Disperse with a homomixer or the like. Preferably, the stirring speed and the stirring time are adjusted so that the particles of the monomer composition have a particle size of 10 μm or less, and then a polymerization initiator is added under stirring to such an extent that the particles do not settle. To start. Then, the stirring speed is increased again during the polymerization, and the remaining polymerizable monomer and a dispersion obtained by dispersing a colorant, a charge control agent and the like in a water-soluble organic solvent with a ball mill or the like are added. At this time, the stirring speed and the stirring time are adjusted so that the monomer-based particles have a particle size of 30 μm or less, and thereafter, a polymerization initiator is added under stirring to such an extent that the particles do not settle. Continue to do. After completion of the reaction, the produced toner particles are washed, separated by filtration, and dried.
[0046]
In the above production method, the monomer is dispersed and polymerized in two stages. The amount of monomer used in the first stage is preferably 30 to 60 wt% of the total amount of monomers. If it is less than 30 wt%, the monomer concentration becomes too low and the polymerization tends to be inhibited, making it meaningless to carry out in two steps. On the other hand, if it exceeds 60 wt%, the amount of monomer used in the second stage becomes too small, and the colorant is not smoothly dispersed in the particles.
[0047]
Moreover, it is preferable that the polymerization time of the polymerizable monomer initially added is between 30 minutes and 1 hour. If it is shorter than 30 minutes, the colorant added in the second stage is likely to aggregate in the particles, and if it is longer than 1 hour, dispersion of the colorant into the particles during polymerization is difficult to occur. Moreover, it is preferable to use 300-1200 weight part of water as a dispersion medium with respect to 100 weight part of total monomers.
[0048]
Further, as the water-soluble organic solvent in which the colorant is dispersed with a ball mill or the like, it is more preferable to use ethyl alcohol, tetrahydrofuran, or dimethylformamide. The amount used is preferably 15 to 30 times the amount of colorant by weight. When the amount is less than 15 times, the viscosity of the dispersant becomes high and handling becomes difficult. On the other hand, when the amount is more than 30 times, problems such as deterioration of the polymerization yield due to shortening of the life of the polymerization initiator and partial dissolution of the wax into the dispersion medium arise.
[0049]
Examples of the polymerizable monomer that can be used in the polymerized toner include vinyl aromatic monomers, (meth) acrylic ester monomers, (meth) acrylic acid monomers, vinyl ether monomers, and the like. . Specific examples include, for example, styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o, m, p-chlorostyrene, p-ethylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl. Acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, ethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, acrylic acid, methacrylic acid, anhydrous Maleic acid, vinyl n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like can be mentioned.
[0050]
These monomers can be used alone or in combination. Among these monomers, it is preferable to use a styrene monomer or a (meth) acrylic acid ester monomer.
[0051]
The aqueous medium used in the present invention preferably contains a water-soluble polymer such as polyvinyl alcohol or a dispersion stabilizer such as calcium phosphate or aluminum hydroxide in water. In particular, calcium phosphate is more preferable as a dispersion stabilizer because it can be easily dissolved and removed by an acid after the polymerization reaction. In the case of calcium phosphate, it is preferable to use 1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer.
[0052]
In particular, when calcium phosphate is used as the dispersion stabilizer, it is more preferable to polymerize by adding an anionic polymer having reverse charge to the monomer system. That is, the anionic polymer contained in the monomer system is electrostatically attracted to the reversely charged cationic dispersant such as calcium phosphate dispersed in the aqueous phase on the particle surface to disperse the particle surface. This is because the covering of the agent prevents the particles from being united and is stabilized.
[0053]
Examples of the anionic polymer include a copolymer of acrylic acid, methacrylic acid and a styrene monomer, or a polyester polymer having a carboxyl group at the molecular terminal and having an acid value of 5 or more.
[0054]
Examples of the styrene monomer used for a copolymer of acrylic acid and a styrene monomer or a copolymer of methacrylic acid and a styrene monomer include styrene, O-methylstyrene, m- Methyl styrene, p-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, p- Examples thereof include styrene such as n-hexylstyrene and P-chlorostyrene, and derivatives thereof, and styrene is particularly preferable.
[0055]
As the polyester resin, a polyester resin obtained by polycondensation of a dihydric alcohol component with a divalent carboxylic acid component such as a divalent carboxylic acid, a divalent carboxylic acid ester, and a carboxylic acid anhydride is preferably used.
[0056]
As divalent carboxylic acid or lower alkyl ester of divalent carboxylic acid, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, Examples thereof include aliphatic unsaturated dibasic acids such as itaconic acid and citraconic acid, and aromatic dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid and isophthalic acid, and methyl esters and ethyl esters thereof. I can do it. Of these, aromatic dibasic acids such as succinic acid, phthalic acid, terephthalic acid, and isophthalic acid, and lower alkyl esters thereof are preferred. It is preferable to use a combination of succinic acid and terephthalic acid, or phthalic acid and terephthalic acid.
[0057]
Examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Examples thereof include diols such as dipropylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and mixtures thereof. Of these, bisphenol A, derivatives thereof, alkylene oxide adducts, and neopentyl glycol are particularly preferable.
[0058]
The molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.
[0059]
The apparatus is HPLC 8120 series manufactured by Tosoh Corporation, the column is TSKgel superHM-H H4000 / H3000 / H2000 (7.8 mm diameter, 150 mm × 3), eluent THF (tetrahydrofuran), flow rate 0.6 ml / min, sample concentration 0.1 %, Injection amount 20 μL, detector RI, measurement temperature 40 ° C., pre-measurement treatment is performed by dissolving a sample in THF and filtering with a 0.45 μm filter to measure a resin component from which an additive such as silica has been removed. The measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.
[0060]
The softening point of the binder resin is 1 cm by a flow tester (CFT500) manufactured by Shimadzu Corporation. ^Three The sample was heated at a rate of temperature increase of 6 ° C./min. ^Five N / m ² The temperature at which the piston stroke starts to rise is the outflow start temperature (Tfb) from the relationship between the temperature rise characteristic in the relationship between the piston stroke and the temperature of the plunger. ), 1/2 of the difference between the lowest value of the curve and the end point of the outflow is obtained, and the temperature at the point of adding the lowest value of the curve is the melting temperature (softening point Tm) in the 1/2 method.
[0061]
The glass transition point of the resin was raised to 100 ° C. using a differential scanning calorimeter, left at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 K / min. The temperature at the point of intersection between the extension line of the baseline below the glass transition point and the tangent line indicating the maximum slope from the peak rising portion to the peak apex when the thermal history is measured.
[0062]
For the melting point of the endothermic peak by DSC, a differential calorimeter DSC-50 manufactured by Shimadzu Corporation was used. The temperature was raised to 200 ° C. at 5 K / min, rapidly cooled to 10 ° C. for 5 minutes, allowed to stand for 15 minutes, then raised to 5 K / min, and determined from the endothermic (melting) peak. The amount of sample put into the cell was 10 mg ± 2 mg.
[0063]
As the colorant, a colorant usually used for black toners and full color toners can be used, and any of inorganic pigments, organic pigments and organic dyes, or a combination thereof may be used. Specific examples of these include carbon black, nigrosine dye, aniline blue, chrome yellow, phthalocyanine blue, oil red, phthalocyanine green, hansa yellow, rhodamine dye, quinacridone, benzidine yellow, triallylmethane dye, monoazo, Examples thereof include disazo dyes and condensed azo dyes, and these known dyes and pigments can be used alone or in combination.
[0064]
In the case of a full color toner, C.I. I. Acetoacetic acid arylamide monoazo yellow pigments such as CI Pigment Yellow 1,3,74,97,98; I. Acetoacetic acid arylamide-based disazo yellow pigments such as CI Pigment Yellow 12, 13, 14, and 17; I. Solvent Yellow 19, 77, 79, C.I. I. Disperse Yellow 164 is blended, and C.I. I. Pigment Yellow 93, 180, and 185 benzimidazolone systems are good for photoconductor filming, and the durability can be improved by using the toner containing a low melting point wax.
[0065]
C. I. Magenta pigments such as CI Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5; I. Magenta dyes such as Solvent Red 49, 52, 58, 8; I. One or two or more kinds of cyan dye pigments of phthalocyanine and derivatives thereof such as Pigment Blue 15: 3 are blended. The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin.
[0066]
The wax may be one or a mixture of paraffinic, olefinic, natural and synthetic fatty acid ester, fatty acid amide, long chain alkyl ketone resin and modified silicone resin. Is an olefin wax such as low molecular weight polyethylene, low molecular weight polypropylene, copolymer polyethylene, ester wax having natural and synthetic long chain aliphatic groups, ketone having a long chain alkyl group, silicone having an alkyl group or phenyl group, Higher fatty acids or higher fatty acid amides may be mentioned. The amount used is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the polymer.
[0067]
As a particularly preferable material, the toner multilayer is obtained by adding 1 to 20 parts by weight of a wax having an iodine value of 25 or less and a saponification value of 30 to 300 to 100 parts by weight of the binder resin. The repulsion due to the charge effect of the toner at the time of transfer can be alleviated, and it is possible to suppress the transfer efficiency from being lowered, the loss of characters during transfer, and the reverse transfer. More preferably, the binder resin has an acid value of 1 to 40 mgKOH / g.
[0068]
The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. If it is 0.1 parts by weight or less, the effect of improving the fixing property cannot be obtained, and if it is 20 parts by weight or more, there is a problem in storage stability.
[0069]
When the iodine value is larger than 25, the repulsion due to the charge effect of the toner is difficult to be mitigated during the toner multi-layer transfer in the primary transfer. The environmental dependency is large, and the change in the charging property of the material becomes large during long-term continuous use, which hinders the stability of the image. When the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and photoconductor filming and chargeability are deteriorated. In addition, the dispersibility with the charge control agent becomes poor, leading to filming, fusion, and a decrease in chargeability during continuous use. If it exceeds 300, the dispersibility of the wax in the resin deteriorates, and the repulsion due to the charge action of the toner is difficult to be alleviated. In addition, fog and toner scattering increase. When the resin acid value is less than 1 mgKOH / g, the repulsion due to the charge effect of the toner is difficult to be mitigated during the toner multilayer transfer. When the resin acid value is larger than 40 mgKOH / g, the environmental resistance is deteriorated and the fog is increased. In particular, transferability is likely to deteriorate under low humidity, and at this time, transferability can be maintained by using it together with an external additive.
[0070]
The thing whose melting | fusing point by DSC method is 50-100 degreeC is preferable. More preferably, the iodine value is 15 or less, the saponification value is 50 to 250, the melting point by DSC method is 55 to 90 ° C., more preferably, the iodine value is 5 or less, the saponification value is 70 to 200, and the melting point by DSC method is 60 to 85 ° C.
[0071]
Furthermore, the material whose volume increase rate at the time of 10 degreeC change at the temperature more than melting | fusing point is 2 to 30% is preferable. When it changes from solid to liquid when it melts with heat during fixing, the adhesion between the toners is further strengthened, the fixing property is further improved, and the releasability from the fixing roller is also improved. Offset property is also improved. When it is smaller than 2, the effect is small, and when it is larger than 30, the dispersibility is lowered.
[0072]
Further, the heat loss at 220 ° C. of the wax is preferably 8% by weight or less. When the weight loss by heating is greater than 8% by weight, it remains in the binder resin during the heat-kneading, greatly reducing the glass transition point of the binder resin and impairing the storage stability of the toner. It adversely affects the development characteristics and causes fogging and filming of the photoreceptor intermediate transfer member.
[0073]
The wax having an iodine value of 25 or less and a saponification value of 30 to 300 has a molecular weight characteristic in gel permeation chromatography (GPC), a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a weight average molecular weight. The ratio of number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01 to 8, the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, molecular weight 5 × 10 ² ~ 1x10 ^Four It is preferable to have at least one molecular weight maximum peak in this region. More preferably, the number average molecular weight is 500-4500, the weight average molecular weight is 600-9000, the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / number average molecular weight) is 1.01-7, Z average molecular weight and number average. The molecular weight ratio (Z average molecular weight / number average molecular weight) is 1.02 to 9, more preferably the number average molecular weight is 700 to 4000, the weight average molecular weight is 800 to 8000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average). (Molecular weight / number average molecular weight) is 1.01 to 6, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 8.
[0074]
When the number average molecular weight is less than 100 and the weight average molecular weight is less than 200, the storage stability is deteriorated. Molecular weight maximum peak is 5 × 10 ² If it is located in a smaller range, the dispersibility of the charge control agent is deteriorated together with the wax. The storage stability of the toner is deteriorated, filming of the photosensitive member and the transfer member, vertical stripes on the developing roller, and scraping failure on the cleaning roller may occur.
[0075]
The number average molecular weight is greater than 5000, the weight average molecular weight is greater than 10,000, the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is greater than 8, and the ratio of the Z average molecular weight to the number average molecular weight (Z (Average molecular weight / number average molecular weight) is greater than 10, and the molecular weight maximum peak is 1 × 10 ^Four If it is located in a range larger than this area, the mold release action is weakened, and fixing functions such as fixing performance and offset resistance are deteriorated.
[0076]
As the wax, Meadowfoam oil derivatives, carnauba wax, jojoba oil derivatives, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, montan wax, ceresin wax, rice wax and other natural waxes, Fischer Tropus wax, etc. These materials such as synthetic wax are preferable, and can be used alone or in combination of two or more. In particular, carnauba wax having a melting point of 76-90 ° C., candelilla wax having 66-80 ° C., hydrogenated jojoba oil having 64-78 ° C., hydrogenated meadowfoam oil having 74-78 ° C. or 74 At least one or two or more waxes selected from the group consisting of rice waxes having a temperature of ˜90 ° C. are more preferable.
[0077]
Saponification value refers to the number of milligrams of potassium hydroxide KOH required to saponify 1 g of a sample. This is the sum of acid value and ester value. To determine the saponification value, a sample is saponified in an alcohol solution of about 0.5 N potassium hydroxide, and then excess potassium hydroxide is titrated with 0.5 N hydrochloric acid.
[0078]
The iodine value refers to the amount of halogen absorbed when halogen is allowed to act on a sample, and expressed in terms of g relative to 100 g of the sample. This is the number of grams of iodine absorbed by 100 g of fat, and the higher this value, the higher the degree of unsaturation of the fatty acid in the sample. Add iodine and mercury (II) chloride alcohol solution or iodine chloride glacial acetic acid solution to chloroform or carbon tetrachloride solution of sample and titrate the remaining iodine without reaction with sodium thiosulfate standard solution to absorb iodine Calculate the amount.
[0079]
For the measurement of the loss on heating, the weight of the sample cell is precisely weighed to 0.1 mg (W1 mg), and 10 to 15 mg of the sample is put in this, and then weighed to 0.1 mg (W2 mg). The sample cell is set on a differential thermobalance, and the measurement is started with a weighing sensitivity of 5 mg. Temperature control is performed by the following program. After the measurement, the weight loss when the sample temperature reaches 220 ° C. is read to 0.1 mg by the chart (W3 mg). The apparatus is TGD-3000 manufactured by Vacuum Riko, the heating rate is 10 ° C./min, the maximum temperature is 220 ° C., the holding time is 1 min, and the heating loss (%) = W 3 / (W 2 −W 1) × 100. .
[0080]
Further, in this embodiment, as external additives, fine metal oxide powders such as silica, alumina, titanium oxide, zirconia, magnesia, ferrite, magnetite, titanates such as barium titanate, calcium titanate, strontium titanate, zirconic acid Zirconates such as barium, calcium zirconate, strontium zirconate, or mixtures thereof are used. The external additive is hydrophobized as necessary.
[0081]
Silicone oil-based materials treated with silica include dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, cyclic dimethyl silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, methacrylic acid. Treated with at least one of modified silicone oil, mercapto modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, amino modified silicone oil, chlorophenyl modified silicone oil Silica is preferably used. For example, SH200, SH510, SF230, SH203, BY16-823, BY16-855B, etc. manufactured by Toray Dow Corning Silicone may be mentioned. For the treatment, a method of mixing inorganic fine powder and a material such as silicone oil with a mixer such as a Henschel mixer, a method of spraying a silicone oil-based material onto silica, or a solution in which a silicone oil-based material is dissolved or dispersed in a solvent Then, after mixing with silica fine powder, there is a method of removing the solvent to prepare. The silicone oil-based material is preferably blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the inorganic fine powder.
[0082]
As silane coupling agents, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzylmethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, There are vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane, and the like. The silane coupling agent treatment is a dry treatment in which the vaporized silane coupling agent is reacted with a fine powder made into a cloud by stirring or the like, or a wet treatment in which a silane coupling agent in which the fine powder is dispersed in a solvent is dropped. Processed by law.
[0083]
It is also preferable to treat the silicone oil-based material after the silane coupling treatment.
[0084]
The inorganic fine powder having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil, or epoxy-modified silicone oil. In order to further improve the hydrophobic treatment, a combination treatment with hexamethyldisilazane, dimethyldichlorosilane, or other silicone oil is also preferable. For example, it is preferable to treat with at least one of dimethyl silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil.
[0085]
For drying loss (%), about 1 g of a sample is placed in a container that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Dry in a hot air dryer (105 ° C ± 1 ° C) for 2 hours. After cooling in a desiccator for 30 minutes, the weight is precisely weighed and calculated from the following formula.
[0086]
Loss on drying (%) = Loss on drying (g) / Sample amount (g) × 100
For ignition loss, about 1 g of a sample is placed in a magnetic crucible that has been dried, allowed to cool, and precisely weighed in advance, and weighed accurately. Ignite for 2 hours in an electric furnace set to 500 ° C. After standing to cool in a desiccator for 1 hour, its weight is precisely weighed and calculated from the following formula.
[0087]
Ignition loss (%) = Loss due to ignition (g) / Sample quantity (g) x 100
For the determination of the degree of hydrophobicity, 0.2 g of the product to be tested is weighed into 50 ml of distilled water charged in a 250 ml beaker. At the tip, methanol is dropped from a burette invaded in the liquid until the total amount of the inorganic fine powder is wet. At that time, slowly stir slowly with an electromagnetic stirrer. The degree of hydrophobicity is calculated by the following equation from the amount of methanol a (ml) essential for complete wetting.
[0088]
Hydrophobic degree = (a / (50 + a)) × 100 (%)
Moreover, it is preferable that the moisture adsorption amount of the processed inorganic fine powder is 1 wt% or less. Preferably it is 0.5 wt% or less, More preferably, it is 0.1 wt% or less, More preferably, it is 0.05 wt% or less. When the content is more than 1 wt%, chargeability is deteriorated and filming on the photoconductor during durability is caused. The water adsorption amount was measured with a continuous vapor adsorption device (BELSORP18: Nippon Bell Co., Ltd.) for the water adsorption device.
[0089]
The ignition loss is 1.5 to 20 wt%, more preferably 5 to 19 wt%. The ignition loss of the inorganic fine powder of 30 nm to 120 nm is preferably 1.5 to 18 wt%, more preferably 5 to 16 wt%.
[0090]
At this time, the inorganic fine powder is preferably 6 to 120 nm. It is also suitable for use in combination of large and small within this particle size. For example, a configuration in which a combination of 6 to 20 nm and 30 to 120 nm is used. It can be set as the structure which has the function of fluidity | liquidity and durability. When it is larger than 120 nm, the fluidity of the toner is not improved and the storage stability is lowered. When it is smaller than 6 nm, aggregation is deteriorated and uniform external addition treatment becomes difficult. In addition, filming on the photosensitive member is easily induced. The amount is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight per 100 parts by weight of the toner base particles. If the amount is less than 0.1 parts by weight, the fluidity of the toner is not improved. If the amount is more than 5 parts by weight, the floating silica increases and the inside of the apparatus is contaminated.
[0091]
Also, any known charge control agent can be used alone or in combination. For example, as a negative charge, metal chelates, metal salts of organic acids, metal-containing dyes, amide group-containing compounds, phenol compounds And their metal salts, urethane bond-containing compounds, and the like.
[0092]
Moreover, as a polymerization initiator used in this invention, a well-known thing is used in a normal temperature range. For example, azo or diazo polymerization initiators such as 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), peroxides such as benzoyl peroxide and lauroyl peroxide And a polymerization initiator. These polymerization initiators are generally used in an addition amount of 1 to 10% by weight of the polymerizable monomer.
[0093]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. In the examples, “parts” means parts by weight.
[0094]
Example 1
After adding 432 parts of 0.1 molar sodium phosphate aqueous solution to 480 parts of distilled water and heating to 65 ° C., 13500 min using Ultra Disperser (LK22 manufactured by Yamato Scientific Co., Ltd.) ^-1 Was stirred. To this, 64 parts of a 1.3 molar calcium chloride aqueous solution was gradually added dropwise, and then stirred at the same temperature for 15 minutes to prepare an aqueous medium containing calcium phosphate.
[0095]
Separately, a mixed liquid of 68 parts of styrene, 12 parts of 2-ethylhexyl acrylate, and 24 parts of hydrogenated jojoba wax (WA1) was heated to dissolve the wax, and a 2,2′-azobisisobutyro was added to the transparent liquid. 4 parts of nitrile was added and dissolved, and this monomer solution was added to the above dispersion, and 13500 min at 65 ° C. under a nitrogen atmosphere. ^-1 Was stirred for 10 minutes to granulate the polymerizable monomer system. Thereafter, the liquid temperature was raised to 80 ° C. while stirring with a stirring rod equipped with a Teflon blade, and a polymerization reaction was carried out for 1 hour.
[0096]
Next, the liquid temperature was lowered to 65 to 70 ° C., and separately, 8 parts of magenta pigment (Fuji Fast Carmine 520 manufactured by Fuji Dye Co., Ltd.) and a charge control agent (Bontron E manufactured by Orient Chemical Co., Ltd.) using a disperser (paint conditioner manufactured by Red Devil). -81) 3.2 parts of ethyl alcohol, 112 parts of ethyl alcohol, 100 parts of zirconia beads having a diameter of 1 mm, and a pigment alcohol dispersion previously dispersed, 68 parts of styrene, 12 parts of 2-ethylhexyl acrylate, polyester resin (acid value 15 .8) A polymerizable monomer composition consisting of 8 parts and 4 parts of 2,2′-azobisisobutyronitrile was sequentially added, and 13500 min using an ultradisperser (LK22 manufactured by Yamato Scientific Co., Ltd.). ^-1 For 10 minutes at the same temperature. Subsequently, the liquid temperature was raised to 80 ° C. while stirring with a stirring bar equipped with a Teflon blade, and a polymerization reaction was performed for 5 hours.
[0097]
Thereafter, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and the mixture was filtered, washed with water, and dried to obtain a polymerized toner. The obtained toner had a volume average particle size of 6.5 μm and a sharp particle size distribution. This toner base is referred to as toner M1.
[0098]
The particles were dispersed in an epoxy resin, sliced to a thickness of 2 μm with a microtome after curing, and the dispersibility of the colorant was examined using an optical microscope. It was found to be well dispersed.
[0099]
(Example 2)
After adding 432 parts of 0.1 molar sodium phosphate aqueous solution to 360 parts of distilled water and heating to 65 ° C., 13500 min using Ultra Disperser (LK22 manufactured by Yamato Scientific Co., Ltd.) ^-1 Was stirred. To this, 64 parts of a 1.3 molar calcium chloride aqueous solution was gradually added dropwise, and then stirred at the same temperature for 15 minutes to prepare an aqueous medium containing calcium phosphate.
[0100]
Separately, a mixed liquid of 68 parts of styrene, 12 parts of butyl acrylate, and 24 parts of paraffin wax (WA2) (mp 70 ° C.) was heated to dissolve the wax, and the 2,2′-azobisisobutyro was added to the transparent liquid. 4 parts of nitrile was added and dissolved, and this monomer solution was added to the above dispersion, and 13500 min at 65 ° C. under a nitrogen atmosphere. ^-1 Was stirred for 10 minutes to granulate the polymerizable monomer system. Thereafter, the liquid temperature was raised to 80 ° C. while stirring with a stirring rod equipped with a Teflon blade, and a polymerization reaction was carried out for 1 hour.
[0101]
Next, the temperature of the liquid was lowered to 65 to 70 ° C., and separately, 8 parts of magenta pigment (Fuji Fast Carmine 520 manufactured by Fuji Dye Co., Ltd.) and a charge control agent (Bontron E manufactured by Orient Chemical Co., Ltd.) using a disperser (paint conditioner manufactured by Red Devil) -81) 3.2 parts of dimethylformamide, 112 parts of dimethylformamide, 100 parts of zirconia beads having a diameter of 1 mm, and a dimethylformamide dispersion of pigment, 68 parts of styrene, 12 parts of butyl acrylate, acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd.) Dainar BR-77 Acid value 18.5) 8 parts of a polymerizable monomer composition consisting of 4 parts of 2,2′-azobisisobutyronitrile was added in order, and Ultradisperser (LK22 manufactured by Yamato Scientific Co., Ltd.) 13500min using ^-1 For 10 minutes at the same temperature. Subsequently, the liquid temperature was raised to 80 ° C. while stirring with a stirring bar equipped with a Teflon blade, and a polymerization reaction was performed for 5 hours.
[0102]
Thereafter, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and the mixture was filtered, washed with water, and dried to obtain a polymerized toner. The obtained toner had a volume average particle diameter of 7.1 μm and a sharp particle size distribution. This toner base is referred to as toner M2.
[0103]
The particles were dispersed in an epoxy resin, sliced to a thickness of 2 μm with a microtome after curing, and the dispersibility of the colorant was examined using an optical microscope. It was found to be well dispersed.
[0104]
(Example 3)
After adding 432 parts of 0.1 molar sodium phosphate aqueous solution to 480 parts of distilled water and heating to 65 ° C., 13500 min using Ultra Disperser (LK22 manufactured by Yamato Scientific Co., Ltd.) ^-1 Was stirred. To this, 64 parts of a 1.3 molar calcium chloride aqueous solution was gradually added dropwise, and then stirred at the same temperature for 15 minutes to prepare an aqueous medium containing calcium phosphate.
[0105]
Separately, a mixed liquid of 68 parts of styrene, 12 parts of 2-ethylhexyl acrylate, and 24 parts of hydrogenated meadow foam oil (WA3) was heated to dissolve the wax, and the resulting 2,2′-azobisisobutyrate was dissolved in the transparent liquid. 4 parts of nitrile was added and dissolved, and this monomer solution was added to the above dispersion, and 13500 min at 65 ° C. under a nitrogen atmosphere. ^-1 Was stirred for 10 minutes to granulate the polymerizable monomer system. Thereafter, the liquid temperature was raised to 80 ° C. while stirring with a stirring rod equipped with a Teflon blade, and a polymerization reaction was carried out for 1 hour.
[0106]
Next, the temperature of the liquid is lowered to 65 to 70 ° C., and separately, 8 parts of a cyan pigment (phthalocyanine blue) and a charge control agent (Bontron E-81 manufactured by Orient Chemical Co., Ltd.) are used in a disperser (paint conditioner manufactured by Red Devil). 2 parts of tetrahydrofuran, 112 parts of tetrahydrofuran, a tetrahydrofuran dispersion of a pigment previously dispersed using 100 parts of zirconia beads having a diameter of 1 mm, 68 parts of styrene, 12 parts of 2-ethylhexyl acrylate, 8 parts of a polyester resin (acid value 15.8), A polymerizable monomer composition composed of 4 parts of 2,2′-azobisisobutyronitrile was sequentially added, and 13500 min using an ultradisperser (LK22 manufactured by Yamato Scientific Co., Ltd.). ^-1 For 10 minutes at the same temperature. Subsequently, the liquid temperature was raised to 80 ° C. while stirring with a stirring bar equipped with a Teflon blade, and a polymerization reaction was performed for 5 hours.
[0107]
Thereafter, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and the mixture was filtered, washed with water, and dried to obtain a polymerized toner. The obtained toner had a volume average particle size of 6.2 μm and a sharp particle size distribution. This toner base is referred to as toner C3.
[0108]
Toner bases M3, M4, and M5 were prepared in the same manner as in Example 1 except that WA3, WA4, and WA5 were used as waxes, respectively.
[0109]
Toner bases C1, C2, C4 and C5 were prepared in the same manner as in Example 3 except that WA1, WA2, WA4 and WA5 were used as waxes, respectively.
[0110]
The toner bases Y1, Y2, Y3, Y4, and Y5 are the same as in Example 1 except that WA1, WA2, WA3, WA4, and WA5 are used as waxes, and Pigment Yellow 180 (manufactured by Clariant) is used as a yellow pigment. Created in the same way.
[0111]
Toner bases B1, B2, B3, B4, and B5 are the same as in Example 1 except that WA1, WA2, WA3, WA4, and WA5 are used as waxes, and carbon black MA100S (manufactured by Mitsubishi Chemical Corporation) is used as a black pigment. Created in the same way.
[0112]
These particles were dispersed in an epoxy resin, sliced to a thickness of 2 μm with a microtome after curing, and the dispersibility of the colorant was examined using an optical microscope. Was found to be well dispersed.
[0113]
(Comparative Example 1)
In Example 2, polymerized particles were obtained using the same dispersion medium system as in Example 2 except that the whole amount was added at once from the beginning. The obtained particles had a volume average diameter of 7.4 μm and a sharp particle size distribution. This toner base is m6. Further, toner bases that were produced in the same manner as in Comparative Example 1 using cyan, yellow, and black pigments are denoted by c6, y6, and b6. When these particles were evaluated for dispersibility of the colorant using an optical microscope, some colorant aggregates were observed.
[0114]
The electrophotographic apparatus used in this example is shown in FIG.
[0115]
FIG. 1 is a cross-sectional view showing a configuration of an image forming apparatus for forming a full-color image used in this embodiment. In FIG. 1, the outer casing of the color electrophotographic printer is omitted. Printer internal inspection and maintenance such as when the transfer belt unit 2 in the printer is attached / detached or when a paper jam occurs, etc. is performed by tilting and opening the front plate to largely release the inside of the printer. The attaching / detaching operation of the transfer belt unit 17 is designed to be parallel to the rotation axis generating line direction of the photosensitive member.
[0116]
The transfer belt unit 17 includes a transfer belt 12, a first color (yellow) transfer roller 10Y made of an elastic body, a second color (magenta) transfer roller 10M, a third color (cyan) transfer roller 10C, and a fourth color (black). Transfer roller 10K, drive roller 11 made of aluminum roller, second transfer roller 14 made of elastic body, second transfer driven roller 13, belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, and opposed to the cleaner blade A roller 15 is provided at a position to be used.
[0117]
At this time, the distance from the first color (Y) transfer position to the second color (M) transfer position is 35 mm (second color (M) transfer position to third color (C) transfer position, third color (C) The fourth color (K) transfer position is the same distance from the transfer position), and the peripheral speed of the photoconductor is 100 mm / s.
[0118]
The transfer belt 12 is used by kneading a conductive filler in an insulating polycarbonate resin and forming a film with an extruder. In the present example, a film obtained by adding 5 parts by weight of conductive carbon (for example, ketjen black) to 95 parts by weight of polycarbonate resin (for example, Iupilon Z300, manufactured by Mitsubishi Gas Chemical) as the insulating resin was used. Further, the surface is coated with a fluororesin, the thickness is about 100 μm, and the volume resistance is 10 ⁷ -10 ¹² Ω · cm, surface resistance is 10 ⁷ -10 ¹² Ω / □. This is to improve dot reproducibility. Another reason for this is to effectively prevent loosening and charge accumulation due to long-term use of the transfer belt 12. The reason why the surface is coated with a fluororesin is to effectively prevent toner filming on the transfer belt surface due to long-term use. Volume resistance is 10 ⁷ If it is smaller than Ω · cm, retransfer is likely to occur. ¹² If it is larger than Ω · cm, the transfer efficiency deteriorates.
[0119]
The first transfer roller is a carbon conductive foamed urethane roller having an outer diameter of 10 mm, and the resistance value is 10 ² -10 ⁶ Ω. During the first transfer operation, the first transfer roller 10 is pressed against the photoreceptor 1 with a pressing force of 1.0 to 9.8 (N) via the transfer belt 12, and the toner on the photoreceptor is transferred onto the belt. Is done. Resistance value is 10 ² If it is smaller than Ω, retransfer is likely to occur. 10 ⁶ Larger transfer defects are more likely to occur than Ω. If it is less than 1.0 (N), transfer defects occur, and if it is greater than 9.8 (N), transfer character omission occurs.
[0120]
The second transfer roller 14 is a carbon conductive foamed urethane roller having an outer diameter of 15 mm, and the resistance value is 10 ² -10 ⁶ Ω. The second transfer roller 14 is pressed against the transfer roller 13 via the transfer belt 12 and a transfer medium 19 such as paper or OHP. The transfer roller 13 is configured to be driven to rotate by the transfer belt 12. In the second transfer, the second transfer roller 14 and the counter transfer roller 13 are pressed against each other with a pressing force of 5.0 to 21.8 (N), and the toner is transferred from the transfer belt onto the recording material 19 such as paper. The Resistance value is 10 ² If it is smaller than Ω, retransfer is likely to occur. 10 ⁶ Larger transfer defects are more likely to occur than Ω. If it is smaller than 5.0 (N), transfer failure occurs. If it is larger than 21.8 (N), the load increases and jitter tends to occur.
[0121]
In FIG. 1, four sets of image forming units 18Y, 18M, 18C, and 18K for each color of yellow (Y), magenta (M), cyan (C), and black (B) are arranged in series as shown in the figure. Has been.
[0122]
Each of the image forming units 18Y, 18M, 18C, and 18K is composed of the same constituent members except for the developer contained therein, so that the Y image forming unit 18Y will be described to simplify the description, and the units for other colors The description of is omitted.
[0123]
The image forming unit is configured as follows. 1 is a photoconductor, 3 is a pixel laser signal light, 4 is a developing roller made of silicone rubber having a JIS-A hardness of 60 ° and having an outer diameter of 12 mm, and is pressed against the photoconductor with a force of 21 N and rotated in the direction of the arrow. To do. Reference numeral 6 denotes a supply roller made of a conductive urethane sponge having an outer diameter of 10 mm, which supplies the toner in the toner hopper to the developing roller. A metal blade 5 forms a toner layer on the developing roller. Although the power supply is omitted, a direct current of −230 V and an alternating voltage of 500 V (pp) and a frequency of 1 kHz are applied to the developing roller 4. A DC bias of −330 V is applied to the supply roller 6.
[0124]
A charging roller 2 having an outer diameter of 12 mm made of epichlorohydrin rubber is applied with a DC bias of −1 kV. The surface of the photoreceptor 1 is charged to -450V. 8 is a cleaner, 9 is a waste toner box, and 7 is toner.
[0125]
The paper is transported from below the transfer unit 17 so that the paper 19 is fed by a paper feed roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are pressed. A conveyance path is formed.
[0126]
The toner on the transfer belt 12 is transferred to the paper 19 by +1300 V applied to the second transfer roller 14, and includes a fixing roller 201, a pressure roller 202, a fixing belt 203, a heating medium roller 204, and an induction heater unit 205. It is conveyed to the fixing unit and fixed there.
[0127]
FIG. 2 shows the fixing process. A belt 203 is placed between the fixing roller 201 and the heat roller 204. A predetermined load is applied between the fixing roller 201 and the pressure roller 202, and a nip is formed between the belt 203 and the pressure roller 202. An induction heater unit 205 including a ferrite core 206 and a coil 207 is provided on the outer peripheral surface of the heat roller 204, and a temperature sensor 208 is provided on the outer surface.
[0128]
The belt has a structure in which 30 μm of Ni is used as a base, silicone rubber is 150 μm thereon, and further, PFA tube is 30 μm.
[0129]
The pressure roller 202 is pressed against the fixing roller 201 by a pressure spring 209. The recording material 211 having the toner 210 moves along the guide plate 212.
[0130]
A fixing roller 201 as a fixing member is a silicone rubber having a rubber hardness (JIS-A) of 20 degrees according to JIS standard on the surface of an aluminum hollow roller metal core 213 having a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm. An elastic layer 214 having a thickness of 3 mm is provided. A silicone rubber layer 215 is formed thereon with a thickness of 3 mm and has an outer diameter of about 20 mm. It receives a driving force from a driving motor (not shown) and rotates at 100 mm / s.
[0131]
The heat roller 204 is a hollow pipe having a thickness of 1 mm and an outer diameter of 20 mm. The surface temperature of the fixing roller was controlled to 170 ° using a thermistor.
[0132]
The pressure roller 202 as a pressure member has a length of 250 mm and an outer diameter of 20 mm. This is provided with a 2 mm thick elastic layer 217 made of silicone rubber having a rubber hardness (JIS-A) of 55 degrees according to JIS standards on the surface of a hollow roller metal core 216 made of aluminum having an outer diameter of 16 mm and a thickness of 1 mm. . The pressure roller 202 is rotatably installed, and a nip width of 5.0 mm is formed between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.
[0133]
The operation will be described below. In the full color mode, all of the first transfer rollers 10 of Y, M, C, and K are pushed up and press the photoreceptor 1 of the image forming unit via the transfer belt 12. At this time, a DC bias of +800 V is applied to the first transfer roller. An image signal is sent from the laser beam 3 and is incident on the photoreceptor 1 whose surface is charged by the charging roller 2 to form an electrostatic latent image. The toner 7 on the developing roller 4 in contact with the photoreceptor 1 and rotating in the opposite direction visualizes the electrostatic latent image formed on the photoreceptor 1.
[0134]
At this time, the image forming speed of the image forming unit 18Y (100 mm / s equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are 0.5 to 1.5% slower than the transfer belt speed. Is set to
[0135]
In the image forming process, the Y signal light 3Y is input to the image forming unit 18Y, and image formation with Y toner is performed. Simultaneously with the image formation, the first transfer roller 10Y causes the Y toner image to be transferred from the photoreceptor 1Y to the transfer belt 12. At this time, a DC voltage of +800 V was applied to the first transfer roller 10Y.
[0136]
With a time lag between the first color (Y) first transfer and the second color (M) first transfer, M signal light 3M is input to the image forming unit 18M, and image formation with M toner is performed. Simultaneously with the image formation, the M toner image is transferred from the photosensitive member 1M to the transfer belt 12 by the action of the first transfer roller 10M. At this time, the first color (Y) toner is formed and the M toner is transferred. Similarly, image formation with C (cyan) and K (black) toners is performed, and a YMCK toner image is formed on the transfer belt 12 by the action of the first transfer rollers 10C and 10B simultaneously with the image formation. This is a so-called tandem method.
[0137]
On the transfer belt 12, toner images of four colors are positioned and overlapped to form a color image. After the transfer of the final B toner image, the four color toner images are collectively transferred to the paper 19 fed from a paper feed cassette (not shown) at the same time by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a DC voltage of +1.3 kV was applied to the second transfer roller 14. The toner image transferred to the paper was fixed by a pair of fixing rollers 201 and 202. The paper was then discharged out of the apparatus through a pair of discharge rollers (not shown). The residual transfer toner remaining on the intermediate transfer belt 12 was cleaned by the action of the cleaning blade 16 to prepare for the next image formation.
[0138]
Toners B4 and B5 are the same as those in Example 3 using waxes W4 and W5, respectively. Examples other than magenta pigments, cyan pigments Pigment Blue 15: 3 (Daiichi Seika), yellow pigments Pigment Yellow 180 (Clariant) and black carbon black MA100S (Mitsubishi Chemical) It was created by the same method as 1.
[0139]
Tables 1 and 2 show the waxes used, Table 3 shows the external additive, and Table 4 shows the toner formulation.
[0140]
[Table 1]

[0141]
[Table 2]

[0142]
[Table 3]

[0143]
[Table 4]

[0144]
Table 5 shows the results of image output using the electrophotographic apparatus shown in FIG. In Table 6, the state of transfer failure at the character portion in a full-color image in which three colors of toner are superimposed, and the paper wrapping property around the fixing belt during fixing were evaluated.
[0145]
[Table 5]

[0146]
[Table 6]

[0147]
The image forming apparatus shown in FIG. 1 was used to produce an image using the toner produced as described above. As a result, there were no horizontal line disturbances, toner scattering, character voids, etc. An image with an extremely high resolution and high image quality that reproduced an image line of / mm was obtained, and an image with a high density of 1.3 or more was obtained. In addition, the ground cover of the non-image area did not occur. Furthermore, even in the long-term durability test of 10,000 sheets of A4 paper, both the fluidity and the image density showed little change and stable characteristics. In addition, the uniformity when the entire solid image was taken at the time of development was also good. There is no development memory. Even during continuous use, no abnormal image of the vertical muscles occurred. Also, in the transfer, the void is at a level that causes no practical problem, and the transfer efficiency is about 98%. Further, the filming of the toner on the photosensitive member and the transfer belt was at a level where there was no practical problem. There was no defective cleaning of the transfer belt. Also, there is almost no toner disturbance or toner skipping during fixing. Further, even in the cleaner process in which the remaining toner at the time of transfer is recovered by development without using the cleaning blade 8, the recovery can be performed smoothly, and the history of the previous image does not remain. In addition, in the full-color image in which the three colors overlap, no transfer failure occurred, and no paper wrapping around the fixing belt occurred during fixing.
[0148]
However, the toners of tm6, ty6, tc6, and tb6 cause a slight filming of the photosensitive member, and transfer defects and scattering of characters during transfer are larger than those of other toners. A lot of fog occurred. When the entire solid image was taken at the time of development, the second half was blurred. An abnormal image of vertical streaks due to the fusion of foreign matter occurred on the developing blade during continuous use. When the three-color image was output, the paper was wound around the fixing belt.
[0149]
Next, 1.2 g / cm of adhesion amount on OHP paper ² The above solid image was formed, and an offset resistance test was performed with a fixing device using a belt not coated with oil at a process speed of 100 mm / s. As a result, no OHP jam occurred in the fixing nip portion. Further, in the full-solid image of plain paper, no offset occurred until the 122,000th sheet. Further, even when a silicone or fluorine-based fixing belt was used and no oil was applied, no deterioration of the belt surface was observed.
[0150]
In addition, the transmittance and the resistance to offset at high temperatures were evaluated. The process speed was 100 mm / s, the fixing temperature was 180 ° C., and the transmittance was measured with a spectrophotometer U-3200 (Hitachi) to measure the transmittance of 700 nm light. The results of OHP transmittance and offset resistance are shown in (Table 7).
[0151]
[Table 7]

[0152]
The OHP transmittance was 80% or higher, the high temperature offset generation temperature was 200 ° C. or higher, and a good fixing property was exhibited even with a fixing roller not using oil. Also, almost no aggregation was observed in the storage stability at 60 ° C. for 5 hours.
[0153]
However, the toner of tm6 was hardened in the storage stability test, and the high temperature offset generation temperature was low.
[0154]
【The invention's effect】
As described above, at least a wax and a colorant are added to the polymerizable monomer in an aqueous medium. Suspension A method for producing a toner to be polymerized, comprising dissolving a wax in a part of a polymerizable monomer in an aqueous medium. Suspension A toner comprising: a first step of polymerizing; and a second step of adding a water-soluble organic solvent dispersion of a colorant and the remainder of the polymerizable monomer to the solution obtained by the first step to perform suspension polymerization. The manufacturing method simplifies the manufacturing method, and Suspension During the polymerization of the particles, re-aggregation of the colorant in the particles can be prevented, and a toner having a high coloring power can be obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of an image forming apparatus used in an embodiment of the present invention.
FIG. 2 is a cross-sectional view showing a configuration of a fixing unit used in an embodiment of the present invention.
[Explanation of symbols]
1 Photoconductor
4 Development roller
5 blade
7 Toner
10 First transfer roller
12 Transfer belt
14 Second transfer roller
18 Image forming unit
201 Fixing roller
202 Pressure roller

Claims (10)

The polymerizable monomer with the addition of at least a wax and a colorant, a method of manufacturing toner to be suspended polymerized in an aqueous medium,
A first step of suspending polymer in the aqueous medium by dissolving the wax in a part of the polymerizable monomer,
A toner comprising: a second step of adding a water-soluble organic solvent dispersion of the colorant and the remainder of the polymerizable monomer to the solution obtained by the first step and subjecting the solution to suspension polymerization. Manufacturing method. Wherein in the first step, method for producing a toner according to claim 1, characterized in that by adding an acid value of from 5 or more organic materials having a carboxyl group is suspended polymerized in the aqueous medium.   2. The toner production method according to claim 1, wherein the amount of the polymerizable monomer to be subjected to suspension polymerization in the first step is 30 to 60% of the total amount of the polymerizable monomer.   The toner production method according to claim 1, wherein in the second step, an organic material having a carboxyl group and having an acid value of 5 or more is added and suspension polymerization is performed.   The toner manufacturing method according to claim 1, wherein the water-soluble organic solvent in which the colorant is dispersed is selected from ethyl alcohol, tetrahydrofuran, and dimethylformamide. The wax has a number average molecular weight of 100 to 5000, a weight average molecular weight of 200 to 10,000, and a ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) in the molecular weight distribution in gel permeation chromatography (GPC). Is 1.01 to 8, the ratio of the Z average molecular weight to the number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, and the molecular weight is 5 × 10 ² to 1 × 10 ^4. The toner production method according to claim 1, wherein the toner has a peak.   The toner production method according to claim 1, wherein the wax is an ester wax having an iodine value of 25 or less and a saponification value of 30 to 300.   A toner produced by the toner production method according to claim 1. An image carrier;
A plurality of toner image forming stations having developing means for developing the electrostatic latent image formed on the image carrier with toner according to claim 8;
An image forming apparatus comprising: a transfer unit that sequentially and continuously transfers the toner images developed by the developing unit onto a transfer medium. An image carrier;
A plurality of toner image forming stations having developing means for developing the electrostatic latent image formed on the image carrier with toner according to claim 8;
Primary transfer means for successively transferring the toner images visualized by the developing means on the transfer body by bringing an endless belt-shaped transfer body into contact with the image carrier;
An image forming apparatus comprising: a secondary transfer unit that collectively transfers the toner images transferred onto the transfer body onto a transfer medium.

Images