Toners for use in electrophotography and production thereof

Abstract: There is disclosed a method of producing toner particles for use in electrophotography which comprises: suspending a radical polymerizable monomer which contains carbon black as a colorant and a charge controlling agent therein in an aqueous phase; suspension polymerizing the monomer to provide spherical polymer particles of 1-30 µm in diameter; treating the suspension containing the polymer particles with a continuous, wet type agitation mill, to deform the polymer particles. A further method of producing toner particles is disclosed which comprises: producing sphreical polymer particles by suspension polymerization of a monomer; making finely divided triboelectric or electroconductive particles or both onto the surface of the polymer particles; and then mechanically pressing the polymer particles to deform the polymer particles as well as to fix the particles on the surface of the polymer particles. A still further method of producing toner particles is disclosed which comprises: producing spherical polymer particles of 20-300 µm in diameter by suspension polymerization of a monomer; and then crushing and classifying the polymer particles into toners of 1-30 µm in size preferably after deforming the polymer particles.

Description: FIELD OF THE INVENTION This invention relates to toners for use in electrophotography and production thereof. BACKGROUND OF THE INVENTION Toners or developing agents in the form of finely divided particles for developing electrostatic latent images in electrophotography have been heretofore produced by a so-called crushing method. According to this method, a colorant such as carbon black, an electric charge controlling agent such as a certain dyestuff, and an anti-offset agent such as a wax are mixed and kneaded together with a melted thermoplastic resin, thereby to disperse them in the resin, cooling, crushing and pulverizing the resultant solid mixture with, for example, a jet mill, to powders of a desired particle size. In this method, it is necessary that the resin used be brittle so that a mixture of the resin and the additives as mentioned above be readily crushed. However, when a resin used is too brittle, the resultant toner is excessively finely divided during the use in an electrophotographic apparatus, and contaminates the inside of the apparatus or forms fog on developed positive images. On the other hand, when a resin used is readily melted, the resultant toner is apt to aggregate together and is undesirably reduced in fluidity, but also there takes place filming on an photoconductive body to deteriorate quality of positive images. It is also necessary that individual toner particles have colorants and charge controlling agents equally and finely dispersed therein, and be capable of being equally electrified so as to produce high quality positive images. However, according to the conventional crushing method, colorants and charge controlling agents are unequally divided among individual toner particles with varied particle sizes. Thus, it is inevitable that positive images have background contamination as well as fog thereon. The apparatus is also contaminated. In particular, a charge controlling agents has an important effect upon copying performance of toners, but since the known charge controlling agents are in many cases 1-20 µm in particle size, much time is needed to disperse the agent in a resin and thus producitivity is low. Moreover, as a matter of fact, the agent can not be uniformly dispersed in a resin even after kneading over a long period of time. As above set forth, the conventional crushing method has many disadvantages, and therefore there have been proposed in recent years many methods to produce toners directly by suspension or emulsion polymerization of a radical polymerizable monomer which contains colorants therein such as carbon black. In these methods, an oily monomer phase is polymerized in an aqueous phase containing a suspending agent dissolved therein such as polyvinyl alcohol. Accordingly, at least some portions of the suspending agent remain inevitably on the surface of the resultant polymer particles even after repeated washing, so that the polymer particles are very sensitive to humidity. Thus, such toners are low in triboelectricity under high humidity, and are apt to produce noncharged or reversely charged toners during the use, to provide a toner image with undesired fog or a toner image with an insufficient darkness. It is an advantage of the toners produced by a conventional suspension or emulsion polymerization method that the toner is substantially spherical and has a high fluidity so that there is no need of adding a fluidizing agent such as silica to the toner. But, because of that sphericity, the toner is inferior in "blade cleanability". In an electrostatic photography using plain paper as a substrate on which toner images are fixed, an latent image is formed on the surface of an photoconductive body to which electrostatic charges have been given, the latent image is developed by the toner to a toner image, and the toner image is transferred onto a substrate, and then the toner image is fixed thereon, to provide a copy. Therefore, it is necessary that the toner remaining on the photoconductive body is removed therefrom after the toner image has been transferred onto the substrate to copy in succession. As one of the methods for removing the toner remaining on the photoconductive body, a blade cleaning method is known according to which the toner is scraped off with a cleaning blade after the toner image has been transferred onto the substrate. The blade is formed of various elastomers, among which a polyurethane elastomer is most preferred from the standpoit of mechanical properties such as resistance to abrasion. In such a blade cleaning method, sperical toner particles enter beneath the blade when the blade scrapes the photoconductive body and roll between the blade and the surface of photoconductive body, so that the toner remains on the photoconductive body after the cleaning of the body with the blade. Thus, in the production of toner particles by suspension polymerization, there has been proposed a method in which spherical polymer particles are agitated in a suspension medium at a high rate before the completion of the polymerization so that the spherical polymer particles are deformed, as described in Japanese Patent Application Laid-open No. 62-266560. However, according to the method, the polymer particles are apt to aggregate to each other on account of unreacted monomers remaining in the reaction system or the deformed polymer particles are restored to their original spherical particles at relatively high temp eratures where the polymer particles are readily deformed, on account of surface tension they possess. Namely, effective deformation of spherical polymer particles is not attained. Agitiation of the polymer particles at small rates or at low temperatures also fails to effectively deform the sperical polymer particles, although the aggregation of the particles is restrained. Furthermore, the polymer particles produced by the suspension polymerization have rather a wide particle size distribution. Thus, large spherical particles might be readily deformed, but small particles are not, and accordingly there arises a wide distribution in degree of deformation. Accordingly, as a further defect of the above method, small spherical particles remain undeformed and such small spherical particles elude cleaning by a blade on the photoconductive body. A further method of producing toners has been recently proposed in which finely divided particles are adhered and fixed onto the toner particles by a so-called impact method, as described in Japanese Patent Application Laid-open No. 62-129866. However, since toner particles have a significant size distribution, it is necessary that the finely divided particles are of not more than about 1 µm so that they are successfully fixed on the individual toner particles accordingto this method. Little improvement in blade cleanability is attained with such toner particles having such fine particles foced thereon. Meanwhile, there is disclosed a method of improving triboelectricity of toner particles in Japanese Patent Application Laid-open No. 62-140636 or No. 62-246075. In this methods, finely divided triboelectric or electroconductive particles are forcibly made to collide with the surface of toner particles at high velocity, or toner particles are softened in a hot air stream and such particles are adhered onto the surface of toner particles. This method is not applicable, however, to deformed toner particles since the deformed toner particles have a tendency to become spherical under the conditions employed. In conclusion, no method has hitherto been known which improves both triboelectricity and blade cleanability of toner particles. STATEMENTS OF OBJECTS The present invention has been accomplished to solve the problems involved in the conventional toner particles and their production. Therefore, the general object of the invention is to provide toners for use in electrophotography which are improved in blade cleanability and a method for the production of such toners. More specifically, it is an important object of the invention to provide toners which contain carbon black and a charge controlling agent divided equally and finely among individual particles, and are free from undesirable effects deriving from a suspension agent used in suspension polymerization, and in addition, which are deformed and has excellent blade cleanability, and hence produce high quality toner images irrespectively of ambient conditions. It is also an object of the invention to provide a method for producing such toners. BRIEF DESCRIPTION OF DRAWINGS Other features and advantages of the invention will be apparent from the following description taken in connection with the accompanying drawings, in which: Figure 1 is a sectional view of a continuous, wet type agitation mill preferably used for the production of deformed polymer particles according to the present invention; DETAILED DESCRIPTION OF THE INVENTION Production of Deformed Toners Using Wet Type Agitation Mill According to the invention, there is provided a flat disklike toner particle having a diameter of 3-30 µm, a thickness of 1-15 µm and a flatness of not more than 0.5 as the flatness of disklike toner particle is herein defined as a ratio of average thickness to average diameter of the particle A further toner particle of the invention is flat and oval and has a major axis 3-30 µm in length, a minor axis 1-25 µm in length and a flatness of not more than 0.5 as the flatness of oval toner particle is herein defined as a ratio of twice the average thickness to the sum of average major axis and the average minor axis. The toner particles of the invention mav be a mixture of the disklike and oval toner particles. Either flat shape is referred to as deformed particles. Such toner particles of the invention can be produced by suspending a radical polymerizable liquid monomer containing carbon black and a charge controlling agent in water, suspension polymerizing the monomer to provide spherical polymer particles composed of a matrix of the polymer and the carbon black and charge controlling agent dispersed the-rein and. having a diameter of 1-30 µm, and treating the suspension containing the polymer particles at temperatures in the range of ± 10 degrees C of the glass transition temperature of the matrix forming the polymer particles with a continuous, wet type agitation mill, thereby to deform the polymer particles so that they have a flat dislike or flat oval shape. More specifically, the above mentioned flat dislike or flat, oval toner particle is advantageously produced by a method comprising the folowing steps carried out in sequence: (a) the step of dispersing carbon black and a charge controlling agent minutely and uniformly both as finely divided particles of not more than 1 µm in particle size in a radical polymerizable liquid monomer; (b) the step of adding an azobisnitrile polymerization initiator to the resultant monomer composition, suspending the composition in water- containing polyvinyl alcohol as a suspending agent, suspension polymerizing the monomer to provide spherical polymer particles composed of a matrix of the polymer and the carbon black and charge controlling agent dispersed therein and having a diameter of 1-30 µm, and treating the suspension containing the polymer particles at temperatures in the range of ± 10 degrees C of the glass transition temperature of the matrix forming the polymer particles with a continuous wet type agitation mill, thereby to deform the spherical particles into flat dislike or flat oval particles; (c) the step of saponifying the polyvinyl alcohol; (d) the step of recovering, drying and washing the polymer particles, and when necessary classifying to a desired particle size. Any radical polymerizable monomer which is known as usable for the production of toner by suspension polymerization is usable in the invention. Therefore, such monomers include,for example, styrene, substituted styrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene or p-chlorostyrene; vinyl esters such as vinyl acetate or vinyl propionate; acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate or α-chloromethyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl, methacrylate, n-octyl methacrylate, dodecyl methacrylate, 1-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, α-chloromethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or glycidyl methacrylate; unsaturated nitriles such as acrylonitrile or methacrylonitrile; α, β-unsaturated carboxylic acids such as acrylic acid or methacrylic acid; and vinylpyridines such as 2-vinylpyridine or 4-vinylpyridine. These monomers are used singly or as a mixture of two or more. Among these, however, styrene or a mixture of styrene and acrylic or methacrylic acid esters are preferred. A polyfunctional monomer may be used together with the above mentioned monomers to improve fixation and anti-offset properties of toners. There may be mentioned as such a polyfunctional monomer, for example, divinylbenzene or ethylene glycol dimethyacrylate. However, a variety of polyfunctional monomers are already known in the art, and any one of these may be used, if desired. The polyfunctional monomer may be used normally in amounts of not more than about 1 % by weight based on the radical polymerizable monomer. When the polyfunctional monomer is used in excess, the resultant polymer particles are too high in melting points to fix sufficiently on a substrate. According to the invention, carbon black as a colorant and a charge controlling agent are dispersed minutely and finely both as finely divided particles of not more than 1 µm in particle size in the radical polymerizable monomer. For this purpose, the monomer and carbon black are stirred in the presence of a peroxide polymerization initiator with, for example, a ball mill. The peroxide polymerization initiator used includes, for instance, benzoyl peroxide, lauroyl peroxide, o-chlorobenzoyl peroxide and o-methoxy benzoyl peroxide, and especially lauroyl peroxide is preferred. Usually the mixture of the monomer and carbon black is stirred in the presence of the peroxide polymerization initiator over a period of several hours, thereby to dispese the carbon black evenly in the monomer as finely divided particles of not more than 1 µm in particle size, preferably of not more than 0.5 µm in particle size. The dispersion of carbon black in the monomer may be carried out at room temperatures, but if desired, at elevated tempertures, for example, at about 50-80°C to accelerate the dispersion. Carbon black is used in amounts of about 2-10 parts by weight in relation to 100 parts by weight of the radical polymerizable monomer. In turn, the peroxide polymerization initiator is used usually in amounts of about 10-50 parts, preferably of about 10-40 parts by weight, in relation to 100 parts by weight of carbon black used. The use of the peroxide polymerization initiator in amounts of less than about 10 parts by weight in relation to 100 parts by weight of carbon black used fails to disperse carbon black minutely and uniformly in the monomer, whereas the use of the peroxide polymerization initiator in amounts of more than about 50 parts by weight in relation to 100 parts by weight of carbon black used, the decomposition fragments of the initiator remain in the resultant polymer particles. Such polymer particles undesirably smell bad when being heated and melted to fix on a substrate during electrophotographic process. The use of an azobisnitrile polymerization initiator, such as azobisisobutyronitrile or azobisdimethylvaleronitrile, in place of a peroxide polymerization initiator in the step of the carbon black dispersion, fails to uniformly and minutely disperse carbon black in the monomer, but carbon black aggregates together, and most of the carbon black used are dispersed as large particles in the monomer. Furthermore, the monomer in part polymerizes in the presence of the azobisnitrile polymerization initiator, to increase the viscosity of the mixture of the monomer and the carbon black. This adversely affects the preparation of suspension of fine droplets of the monomer composition in an aqueous medium. In the dispersion of carbon black in the monomer in the presence of a peroxide polymerization initiator, the carbon black and the peroxide may be added together to the monomer and then the carbon black may be dispersed in the monomer by use of, for instance, a ball mill, or the carbon black may be in advance dispersed preliminarily in the monomer and then a peroxide may be dissolved thereinto, followed by stirring, for example, in an autoclave. Any colorant may be used together with carbon black, if needed. Such colorants may or may not be soluble in the monomer. There are mentioned such colorants in, for example, Japanese Patent Application Laid-open No. 62-246073. When a colorant insoluble in the monomer is used, such a colorant may be dispersed minutely and uniformly in the monomer with aid of a peroxide polymerization initiator or other suitable dispersing agent in the same manner as carbon black is dispersed in the monomer. After the dispersion of carbon black in the monomer as set forth above, a charge controlling agent is then dispersed evenly as finely divided particles in the monomer mixture with carbon black. Usually a charge controlling agent is added to the monomer mixture together with a dispersing agent soluble in the monomer, and the resultant mixture is stirred for, for example, about 50-200 hours, with a ball mill, thereby to pulverize and disperse the agent evently as finely divided particles of not more than about 0.5 µm, preferably of not more than about 0.3µm in the monomer. This dispersion may also be carried out at elevated temperatures such as at about 50-80°C to accelerate the dispersion. The charge controlling agent is used usually in an amount of about 0.01-10 parts, preferably of about 0.05-5 parts, most preferably of about 0.1-1 parts by weight, in relation to 100 parts by weight of the monomer used. The charge controlling agent used is at least one selected from the group consisting of a powder of an inorganic compound, a powder of an organic compound including metallized dyes and pigments, and organic carboxylic acid metal salts, and a powder of an organic polymer. The powder of inorganic compound as a charge controlling agent includes, for example, nitrides, carbides, oxides, sulfates, carbonates, titanic acid salts, phosphoric acid salts, silicates and hexafluorosilicates. More specifically, there may be mentioned as such inorganic compounds, for example, nitrides such as boron nitride; carbides such as titanium carbide, tungsten carbide, zirconium carbide, boron carbide or silicon carbide; oxides such as silica, chromium oxide, cerium oxide, zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, copper oxide, nickel oxide or zinc oxide; strontium sulfate, barium sulfate, calcium sulfate, aluminum sulfate, magnesium sulfate or copper sulfate; carbonates such as calcium carbonate or magensium carbonate; phosphoric acid salts such as calcium phosphate; silicates of such as zirconium, copper, cobalt, nickel, magnesium calcium, strontium, barium, aluminum or zinc; hexafluorosilicates of such as sodium, calcium, strontium, barium, zinc or aluminum. Further examples include emery, alundum, garnet, corundum, lime, tripolyphosphate, halloycite, bentonite, molybdenum acid chelate pigments and acidic terra. These inorganic charge controlling agent may be coated with silane or titanium coupling agents. The coupling agent used is selected depending upon the triboelectricity of toners required. When a negatively charged toner is to be produced, a coupling agent which is readily negatively charged is used, for example, dichlorosilanes, and when a positively charged toner is to be produced, a coupling agent which is readily positively charged is used, for example, aminosilanes. Some examples of these coupling agents are described hereinbefore. As the powder of organic compond as a charge controlling agent at usable a variety of compounds including metallized dyes and pigments but also carboxylic acid metal salts. There may be mentioned as a positive charge controlling agent, for example, an electron donating dye, such as a nigrosine dye represented by: wherein X⁻ is an anion species, an alkoxylated amine, an alkyl amide or a quaternary ammonium salt. On the other hand, there may be mentioned as a negative charge controlling agent, for example, an electron accepting dye, such as a chromium containing dye represented by: wherein X⁺ is a cation species, and "Spiron Black TRH" (from Hodogaya Kagaku Kogyo K.K., Japan) represented by: wherein X⁺ is a cation species. There may be further mentioned as a negative charge controlling agents, for example, sulfonyl amines of copper phthalocyanines, oil black, naphthenic acid metal salts and zinc stearate, resinous acid soaps. A variety of organic polymers are also known as usable as a charge controlling agent, and a polymer is suitably selected depending upon the triboelectricity of toners required. When a negatively charged toner is to be produced, a polymer which is readily negatively charged is used, for example, a polymer or a copolymer of a monomer having an aromatic nucleus as an electron attracting group, such as styrene or derivatives thereof. Therefore, such polymers include, for example, polystyrene, styrene-butyl acrylate copolymer, styrene-2-ethylhexyl acrylate copolyner or styrene-butyl methacrylate copolymer. Polymers containing therein halogen atoms such as chlorine or fluorine are also usable as negative charge controlling agents, and they may be exemplified by polyvinyl chloride. When a positively charged toner is to be produced, a polymer which is readily positively charged is used, for example, polymethyl methacrylate, polybutyl methacrylate or polyamides. These polymeric charge controlling agents preferably have glass transition temperatures of not less than about 70°C. The organic polymer used as a charge controlling agent is preferably produced by emulsion polymerization in the absence of an emulsifier so that the resultant polymer contains no emulsifier. However, an organic polymer produced in the presence of an emulsifier may be used if the emlusifier is removed. Those charge controlling agent as described above may be used singly or as a mixture of two or more. The dispersing agent used to disperse the charge controlling agent in the monomer may be either a low molecular weight substance or a high molecular weight substance. The low molecular weight substance includes, for example, surfactants, silane coupling agents, titanium coupling agents and oligomeric organic materials which contain therein isocyanate or epoxy groups. More specifically, there may be mentioned as surfactants, for example, anionic surfactants such as fatty acid salts, alkylsulfuric acid esters, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, dialkylsulfosuccinic acid esters, alkylphosphoric acid esters, naphthalenesulfonic acid-formalin condensates or polyoxyethylene alkylsulfuric acid salts; nonionic sufactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, glycerine fatty acid esters or oxyethylene-oxypropylene block polymers; and cationic surfactants such as alkyl amines or quaternary ammonium salts. The silane coupling agent may be exemplified by γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycydoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, 3,3,4,4,5,5,6,6,6-nonafluorohexlytrichlorosilane and 3,3,4,4,5,5,6,6,6-nonafluorohexylmethyldichlorosilane. Further, there may be mentioned as reactive silanes, for example, methyltrimethoxsilane, phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane. The titanium coupling agent may be exemplified by isopropyltriisostearoyl titanate, isopropyltris(dioctylpyroohosphate) titanate, isopropyltris(N-aminoethylaminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra2,2-diallyloxymethyl-1-butyl bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropylisostearoyldiacryl titanate, isopropyltri(dioctylphosphate) titanate, isopropyltricumylphenyl titanate and tetraisopropylbis(dioctylphosphite)titanate. On the other hand, the high molecular weight dispersing agent preferably includes homopolymers or copolymers which have functional groups therein, such as carboxyls, sulfones, hydroxyls, halogens, epoxys, cyanos, nitriles, butyrals, esters, carbonyls or aminos. More specifically, the high molecular weight polymeric dispersing agent includes, for instance, vinyl (co)polymers, rubber polymers, cellulosic polymers and cross-linkable polymers. The vinyl (co)polymers includes, for example, styrene-acrylic acid copolymers, styrene-dimethylaminoethyl methacrylate copolymers, styrene-methacrylic acid copolymers, styrene-2-hydroxyethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-glycidyl methacrylate copolymers, methyl methacrylate-acrylic acid copolymers, methyl methacrylate-dimethylaminoethyl methacrylate copolymers, methyl methacrylate-methacrylic acid copolymers, methyl methacrylate-2-hydroxyethyl methacrylate copolymers, methyl methacrylate-acrylonitrile copolymers, methyl methacrylate-glycidyl methacrylate copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-vinyl alcohol copolymers, polyvinyl butyral resins, vinylidene chloride-acrylonitrile copolymers, acrylonitrile-butyl acrylate-2-hydroxyethyl methacrylate copolymers, ethylene-vinyl acetate copolymers, polyvinyl acetate resins and partially sulfonated polystyrene resins. The rubber polymer includes, for example, acrylonitril-butadiene copolymers, and the cellulosic polymer includes, for example, nitrocellulose and acetyl cellulose. The cross-linkable polymer includes, for instance, epoxy resins, phenoxy resins and urethane resins. These polymers may be used singly or as a mixture of two or more. Most preferably, there is used, as a dispersing agent, a polymer having functional groups therein which have a strong interaction with a charge controlling agent used. By way of example, when an electron accepting dyes such as metallized azo dyes or an electron accepting organic complex is used as a negatively triboelectrified charge controlling agent, ethylene-vinyl acetate copolymers are preferably used as a dispersing agent. In the dispersion of the charge controlling agent in the monomer, the amount of the dispersing agent used varies depending on the particle size of the charge controlling agent used, however, it is usually in amounts of about 1-100 parts, preferably of about 10-50 parts by weight, in relation to 100 parts by weight of the charge controlling agent used. When excessive amounts of the dispersing agent are used, the resultant mixture which contains the monomer, carbon black and charge controlling agent is too high, and the finely pulverizing of the charge controlling agent is not attained. When the dispersing agent is used only in small amounts, the charge controlling agent is not uniformly dispersed in the monomer. Similarly to the dispersion of carbon black in the monomer, the charge controlling agent may be in advance preliminarily dispersed in the monomer using, for example, a ball mill, and then the dispersing agent may be dissolved in the monoer, followed by stirring, or the dispersing agent may be aaded to the monomer together with the charge controlling agent and stired using, for example, a ball mill. Some of the charge controlling agents have been found to inhibit undesired polymerization of monomers in an aqueous medium in suspension polymerization, which will be described in more detail hereinafter. Such a charge controlling agent is exemplified by "Spiron Black TRH" (by Hodogaya Kagaku Kogyo K.K., Japan), a chromium containing azo dye. Therefore, this dye is preferably used in the invention both as a charge controlling agent and as a polymerization inhibitor in an aqueous medium in suspension polymerization. However, if desired, the dye may be dispersed in monomers only as a polymerization inhibitor in an aqueous medium in suspension polymerization, apart from its original function as a charge controlling agent. In this case, other charge controlling agents may be dispersed together with the dye in monomers. In the method of the invention, carbon black and a charge controlling agent are dispersed evenly as finely divided particles in the monomer as hereinbefore described, and if necessary an additional amount of the monomer are further added to the dispersion, and then an azobisnitrile polymerization initiatoris added to the dispersion, to form a monomer composition. The azobisnitrile polymerization initiator usable includes, for example, azobisdimethylvaleronitrile and azobisdimethylisobutyronitrile, however, azobisdimethylvaleronitrile is especially preferred since it is highly soluble in the monomer. The monomer composition in the form of a dispersion thus containing an azobisnitrile polymerization initiator is then dispersed in an aqueous medium as small droplets by use of, for example, a homozinizer, and is heated so that suspension polymerization proceeds to produce spherical polymer particles. When no azobisnitrile polymerization initiator is added anew to the monomer composition, substantially no suspension polymerization occurs even under heating, since substantially all the peroxide polymerization initiator which has been added to the monomer in the stage of the dispersion of carbon black in the monomer are decomposed during the dispersion, and therefore it is necessary that a polymerization initiator be anew added to the monomer in the stage of suspension polymerization. The polymerization initiator added in the stage of polymerization should be an azobisnitrile polymerization initiator, not a peroxide. The addition of a peroxide polymerization initiator is substantially useless since the initiator fails to polymerize the monomer, or if polymerization takes place, the resultant polymer has a very low molecular weight, and has no sufficient anti-offset properties. The azobisnitrile polymerization initiator is used usually in amounts of about 1-10 parts, preferbly of about 2-5 parts by weight, in relation to 100 parts by weight of the monomer used. When the amount is less than about 1 part by weight in relation to 100 parts by weight of the monomer used, the polymerization proceeds only very slowly, and it is substantially impossible to polymerize the monomer in a high polymerization rate, while when the amount is more than about 100 parts by weight in relation to 100 parts by weight of the monomer used, the resultant polymer is low in molecular weight, and is insufficient in anti-offset properties. As previously described, the mixture of the monomer, carbon black, as azobisnitrile polymerization initiator, and optionally a charge controlling agent are mixed with water, and severely stirred by use of, for example, a homogenizer, to provide an aqueous dispersion of droplets of the monomer composition of 1-30 µm in diameter in the aqueous medium. It is preferred that the water as a dispersion medium in suspension polymerization contains polyvinyl alcohol as a suspending agent which has usually an average polymerization degree of 500-3000 and a saponification degree of about 80-99 mole %. The polyvinyl alcohol is contained in water usually in an amount of 0.1-5 % by weight. The water may further contain a water soluble inorganic salts such as sodium chloride, sodium sulfate or aluminum sulfate to inhibit the polymerization of the monomer in an aqueous phase. The suspension is then stirred at temperatures usually of about 40-95°C, preferably of about 50-90°C, to carry out suspension polymerization of the monomer to provide substantially true spherical polymer particles of 1-30 µm in diameter which has a flatness of not less than 0.98, the flatness being defined hereinafter. In accordance with the invention, the suspension which contains the resultant substantially true spherical polymer particels is treated with a continuous wet type agitation mill in the presence of polyvinyl alcohol as a suspending agent at temperatures in the range of ± 10 degrees C of the glass transition temperature of the matrix forming the polymer, thereby to deform the spherical particles into flat dislike or flat oval particles. The continuous wet type agitation mill is known. As illustrated in Fig. 1, the mill contains an annular stator 11 having a triangular section and a rotor 12 therein similar to the stator in shape. A milling zone l3 is formed as an annular gap of a small breadth between the stator and the rotor. The milling zone contains a milling medium 14 therein to impart mechanical impact to suspended particles to deform them so that they get flat. The suspension is introduced into the milling zone through an inlet 15 at the lower part of the mill and travels along the gap, and is then separated from the medium at a separator 16. The suspension which contains deformed polymer particles are obtained from an outlet 17. While the polymer particles in the suspension are deformed in the milling zone, warm water is supplied to passages 18 within the stator and the rotor to control the temperature of the suspension. The milling medium also travels centrifugally along the milling zone having a W-shaped section and returns to the inlet. Zirconia, glass or steel spherules of, for example, about 0,3-1.5 mm in diameter are used as the milling medium, although not limited thereto. It is necessary that treatment of the suspension containing the polymer particles with the annular, continuous, wet type agitation mill is carried out at temperatures in the range of ± 10 degrees C of the glass transition temperature of the matrix which forms the polymer. When the suspension is treated at temperatures lower than the glass transition temperature of the polymer by 10°C, the polymer particles crushed, rather than deformed. On the other hand, when the suspension is treated at temperatures higher than the glass transition temperature of the polymer by 10°C, the polymer particles are apt to aggregate to each other to form mass, but also the polymer particles become spherical again on account of surface tension even after the particles have been deformed, so that deformation efficiency is low. The treatment is carried out usually over a period of 0.5-10 hours, preferably 2-5 hours. The use of an annular, continuous, wet type agitation mill has an advantage that the rotor produces a larger shearing force in the direction of rotation than a ball mill or a sand mill, and can exert anisotropic stress on the particles, so that they are effectively deformed even when they have a significant particle size distribution. Namely, the particles are deformed irrespectively of their diameters, so that the resultant toner particles have a greatly improved blade cleanability. In addition, such particles make contact with a substrate with a large surface area when transferred from a photoconductive body, and thus fixed thereon at relatively low temperatures. Similarly, the individual particles have a large contact area on a substrate, so that a small amount of such particles produces dark images, and consumption of toner is reduced. As above set forth, there is obtained a flat dislike polymer particle having a diameter of 3-30 µm, a thickness of 1-15 µm and a flatness of not more, than 0.5, or a flat oval polymer particle having a major axis 3-30 µm in length, a minor axis 1-25 µm in length and a flatness of not more than 0.5 according to the invention. According to the invention, after the deformation of the particles as described hereinbefore, the polyvinyl alcohol used as a suspending agent in the stage of the suspension polymerization and deformation of the polymer particles may be saponified. In one method, the saponification of the polyvinyl alcohol may be carried out by adding a saponification agent to the suspension containing the polymer particles. In another method, the particles are separated from the suspension, and the particles may be treated with a saponification agent. The saponification is carried out using an alkali or an acid. When an alkali is used, the amount thereof may be between about an equivalent to and about 1000 times as much as the equivalent of the vinyl acetate component contained in the polyvinyl alcohol used, and preferably in an amount of about 5-50 times the equivalent of the vinyl acetate component. However, the amount is not critical, and an amount less than the equivalent may satisfactoriry saponify the polyvinyl alcohol used. If necessary, a minimum amount of the saponification agent required may be determined by a simple experiment well known in the chemistry of polyvinyl alcohol. The alkali used as a saponification agent includes, for example, sodium hydroxide and potassium hydroxide. In a preferred embodiment, the saponification may be carried out as follows. An aqueous solution of a lower aliphatic alcohol, such as methanol, ethanol, propanol, among which methanol is most preferred, in amounts of about 1-50 % by volume, preferably of about 5-30 % by volume, containing an alkali, is added to a suspension containing the polymer particles, and the mixture is stirred at temperatures of about 30-70°C for about 1-10 hours, although these reaction conditions are not critical. The use of a lower aliphatic alcohol, such as methanol, in the alkali saponification of the polyvinyl alcohol is advantageous in that the alcohol raises wettability of the polymer particles to water, thereby to carry out the saponification in a short period of time. Further, methanol in particular is used, the vinyl acetate unit in the polyvinyl alcohol reacts with methanol to produce methyl acetate by an ester exchange reaction, so that the saponification reaction proceeds rapidly. After the saponification in this manner, in particular the polyvinyl alcohol remaining on the surface of the polymer particles, the polymer particles are separated, washed with water or preferably with an aqueous alcohol solution as previously mentioned, and then washed with an aqueous solution or an aqueous alcohol solution which contains an acid such as hydrochloric acid to neutralize the alkali used, and finally the particles are washed with water or an aqueous alcohol solution. As the washing for the particles after the saponification is preferred an aqueous alcohol solution, and especially an aqueous methanol solution which contains methanol in amounts of about 1-50 %, preferably of about 5-30 % by volume. The washing for neutralizing the alkali contains an acid usually in amounts of equivalent at most to the amount of the alkali used in the saponification. The washing for the particles after the neutralization of alkalis is also preferably an aqueous alcohol solution, and especially an aqueous methanol solution which contains methanol in amounts of about 1-50 %, preferably of about 5-30 % by volume. The saponification of the polyvinyl alcohol may be alternatively carried out using an acid. By way of example, an aqueous solution or preferably an aqueous alcohol solution as before described of an acid such as sulfuric acid or hydrochloric acid is added to a suspension of the polymer particles, stirred under heating, neutralized with an alkali, washed with water, and dried. After the saponification of the polyvinyl alcohol, the polymer particles may be dried, and if necessary classified, to provide a toner for use in electrophotography. As above set out, carbon black and a charge controlling agent are minutely and evenly dispersed in a radical polymerizable monomer, the monomer is suspension polymerized to spherical polymer particles of 1-30 µm in diameter, the particles are deformed into flat dislike or flat oval particles, and then the polyvinyl alcohol remaining on the particles may be removed therefrom by saponification and washing. Thus, the resultant toner is insensitive to humidity and has a high stability to change of ambient conditions. Further, the toner is deformed in shape so that it has an excellent blade cleanability and is readily fixed on a substrate at a relatively low temperature. Dispersion at carbon black and a charge controlling agent into a radical polymerizable monomer, polymerization of such a monomer composition containing the carbon black and charge controlling agent in the presence of polyvinyl alcohol as a suspensing agent, and saponification of the polyvinyl alcohol is substantially the same throughout herein the specification. Therefore, such description may be omitted occasionally hereinafter if invention is not rendered unclear. The toner particles according to the invention may be used either as a two-component toner, a nonmagnetic one-component toner, or a magnetic one-component toner. In the production of a magnetic toner, a magnetic powder is preferably mixed with and dispersed in the monomer with a suitable means such as a ball mill, and then the monomer is mixed with carbon black and optionally with a charge controlling agent, followed by suspension polymerization of the monomer in the manner as hereinbefore described. In the production of a magnetic toner, a ferrite or a magnetite is used in an amount of about 30-300 parts, preferably of about 30-100 parts by weight, in relation to 100 parts by weight of the monomer. When the polymer particles are used as a toner in a two-component developing manner, the particles are mixed with a carrier material well known in the art to form a two-component toner. The carrier material usable includes, for example, an iron powder, a ferrite powder, a powder mixture of resins and magnetic substances, and a magnetite powder. In a two-component toner, the polymer particles are used usually in an amount of about 2-20% by weight, preferably of about 5-10 % by weight of the toner. EXAMPLES The invention will now be described with reference to examples which relates to non-magnetic two-component toners, however, the invention is not limited thereto. EXAMPLE Production of Deformed Toners Using Wet Agitation Mill Example 1 An amount of 5 parts by weight of carbon black "Diablack" (tradename) #52 (volatile matters 0.8 %, pH 8.0, particle size 27 mµ, from Mitsubishi Kasei Kogyo K.K. , Japan) and 1 part by weight of lauroyl peroxide were added to and mixed with 50 parts by weight of styrene in a ball mill for 30 minutes to preliminarily disperse the carbon black in the monomer. The mixture was then further agitated in an autoclave at 70°C for 1 hour. In this monomer- mixture with carbon black, the carbon black was found about 0.1 µm in particle size and there took no sedimentation in the dispersion. An amount of 0.4 parts by weight of an ethylene-vinyl acetate copolymer "Soablene CH" (tradename, from Nippon Gosei Kagaku Kogyo K.K., Japan) as a dispersing agent and 1.0 part by weight of a negative charge controlling agent, a dyestuff named "Spiron Black TRH" (tradename, from Hodogaya Kagaku Kogyo K.K., Japan) were added to the dispersion, and stirred with a ball mill for 100 hours, to provide a monomer composition. After this dispersion procedure, the dyestuff powder was found of about 0.3 µm in particle size, and was found not to sediment in the dispersion. To the resultant dispersion were then added 37 parts by weight of styrene, 13 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of divinylbenzene, 3 parts by weight of azobisdimethylvaleronitrile and 3 parts by weight of polypropylene wax as an anti-offset agent, to form a monomer composition of which components are shown in Table 1. The monomer composition was then added to 300 parts by weight of water containing 3 parts by weight of polyvinyl alcohol (having an average polymerization degree of 1700 and a saponification degree of 80 mole %) as a suspending agent, and the mixture was agitated using a homogenizer (Model 610 from K.K. Nippon Seiki Seisakusho, Japan) at 6000 rpm to disperse the monomer composition in the water. Monomer Composition Phase (parts by weight) Styrene 87 2-Ethylhexyl acrylate 13 Divinylbenzene 0.2 Carbon black 5.0 Spiron Black TRH 1.0 Polypropylene wax 3 Azobisdimethylvaleronitrile 3 Aqueous Phase (parts by weight) Polyvinyl alcohol 3 Deionized water 300 The resultant aqueous dispersion was stirred at 70°C for 5 hours, and then at 90°C for another 1 hour. The resultant spherical polymer particles were found to have a glass transition temperature of 63°C. The particle size distribution of the polymer particles is shown in the Table 2. The suspension was then continuously fed into an continuous, annular, wet type agitation mill (Kobol Mill from Shinko Foudler K.K.), as an example of such a mill is shown in Fig, 1, and the polymer particles were deformed under the conditions of temperature, suspension travelling speed and rotor peripheral speed shown in the Table 2. Zirconia spherules of 0.75-1.0 mm in diameter were used as a milling medium. The charge rate of the medium in the milling zone was 70 %. A mixture of 77 % by volume of water and 23 % by volume of methanol containing sodium hydroxide in an amount of equivalents ten times the vinyl acetate component of the polyvinyl alcohol used was added to the suspension and stirred at 50°C for 3 hours to saponify the polyvinyl alcohol. The resultant deformed flat polymer particles were recovered and washed with water, and then with aqueous solution containing hydrochloric acid in an amount equivalent to the amount of sodium hydroxide used to neutralize the sodium hydroxide. The polymer particles were dried under reduced pressures to provide toner particles. The flatness, triboelectric charge (blow-off method) and amount of reversely charged toner particles were determined. Further, blade cleanability, nip gap and toner consumption were measured by applying the toner to an electrostatic copying machine. The results are shown in the Table 2. The shape, average size and flatness of toner particles were measured with randomly selected 50 particles on through electromicrophotographs. The triboelectric charge of the toner particles was measured by a blow-off method with a mixture of the particles and iron carrier powder with the latter in an amount of 5 % by weight based on the mixture. The amount of reversely charged toner particles was determined by means of an electric charge distribution analyzer (from Hosokawa Micron K.K., Japan). The blade cleanability was measured as follows. After 10000 times copying using an electrostatic copying machine Rheodry 4515 from Toshiba K.K., Japan, at normal temperature and normal humidity, the surface of the electroconductive body after the blade cleaning and toner images formed on paper were observed. In the. table 2, the results are shown in three grades: A, electroconductive body was completely cleaned and toner images were of high quality; B, electroconductive body was partly uncleaned and toner images were partly contaminated; C, electroconductive body remained substantially uncleaned. The nip gap is a measure of fixability of toners on a substrate, and the smaller the nip gap, the better the fixability. The nip gap was measured as follows. Using a fixability testing roll machine composed of a heat roll of polytetrafluoroethylene and a back-up roll of a silicone rubber and with varied nip gaps, toners were fixed on paper. In the Table 2 were given the values of nip gap where toners were fixed at a fixing rate of not less than 90 %. The fixability of- toners was measured by change in darkness when toner images were rubbed after a predetermined time passed since the toners had been fixed. The toner consumption was measured as follows. Using an LED printer K-II from Japan Kenteck K.K. with a surface electric potential adjusted so as to provide toner images having a darkness of 1.2, 1000 sheets of compies were made, and the power consumption by that time was measured. Example 2 The supension prepared in the Example 1 was treated with the same agitation mill as in the Example 1 under the conditions shown in the Table 2, and otherwise in the same manner, toner particles were produced. The results are shown in the Table 2. Comparative Example 1-6 With or without saponification and deformation treatment of polymer particles as designated in the Table 2, toner particles were produced. The results are shown in the table 2.

Claims: A flat disklike toner particle for use in electrophotography, the toner particle having a diameter of 3-30 µm, a thickness of 1-15 µm and a flatness of not more than 0.5, the flatness of flat dislike toner particles being defined as the ratio of average thickness to average diameter of the particles. A flat oval toner particle for use electrophotography, the toner particle having a major axis of 3-30 µm in length, a minor axis of 1-25 µm in length and a flatness or not more than 0.5, the flatness of the flat oval toner particles being defined as the ratio of twice the average thickness to the sum of the lengths of the average major axis and the average minor axis. A method of producing a deformed toner particle for use in electrophotography as claimed in claim 1 or 2, which comprises: suspending a radical polymerizable liquid monomer containing carbon black and a charge controlling agent in water; suspension polymerizing the monomer to provide spherical polymer particles composed of a matrix of the polymer and the carbon black and charge controlling agent dispersed therein, having a diameter of 1-30 µm; and treating the suspension containing the polymer particles at temperatures in the range of +/-10 degrees C of the glass transition temperature of the matrix forming the polymer particles with a continuous wet type agitation mill. A method according to claim 3, of producing a deformed toner particle for use in electrophotography which comprises the following steps carried out in sequence: (a) dispersing both carbon black and a charge controlling agent minutely and uniformly as finely divided particles of not more than 1 µm in particle size in a radical polymerizable liquid monomer; (b) adding an azobisnitrile polymerization initiator to the resultant monomer composition, suspending the composition in water containing polyvinyl alcohol as a suspending agent, suspension polymerizing the monomer to provide spherical polymer particles composed of a matrix of the polymer and the carbon black and charge controlling agent dispersed therein, having a diameter of 1-30 µm, and treating the suspension containing the polymer particles at temperatures in the range of +/-10 degrees C of the glass transition temperature of the matrix forming the polymer particles with a continuous wet type agitation mill thereby to deform the spherical particles into flat disklike or flat oval particles; (c) saponifying the polyvinyl alcohol; and (d) recovering, drying and washing the polymer particles, and when necessary classifying to a desired particle size.

Inventors: MIKI TAKASHI C O BANDO CHEMICA, NAGAMI HARUSHI C O BANDO CHEMI, UCHINO MITSUHIRO C O BANDO CHE, YAMASHIRO JIRO C O BANDO CHEMI, MIKI, TAKASHI, C/O BANDO CHEMICAL INDUSTRIES L, NAGAMI, HARUSHI, C/O BANDO CHEMICAL INDUSTRIES LTD, UCHINO, MITSUHIRO, C/O BANDO CHEMICAL INDUSTRIES L, YAMASHIRO, JIRO, C/O BANDO CHEMICAL INDUSTRIES LTD
Applicants: BANDO CHEMICAL IND, BANDO CHEMICAL INDUSTRIES, LIMITED
Application year: 1990
Main classification: G03G9
IPC codes: G03G9