JPH02275470A - Colored fine particle and toner for developing electrostatic charge image using this particle - Google Patents

Abstract

PURPOSE:To obtain sharp images by mixing colored spheroidal fine particles which are obtd. by a suspension polymn. and inorg. fine particles, then subjecting the mixture to a heating treatment under specific conditions, and then disintegrating the mixture to obtain the toner. CONSTITUTION:The colored spheroidal fine particles are obtd. by the suspension polymn. of polymerizable monomers compounded with coloring agents and the average particle size thereof is 1 to 100mum. After the colored spheroidal fine particle and the inorg. fine particles smaller in grain size than these particles are mixed, the mixture is subjected to the heating treatment under 30 to 200 deg.C conditions to fuse the colored spheroidal fine particle to each other to form blocked particles; thereafter, the blocked particles are disintegrated to obtain the toner. The particle size of the inorg. fine particle is in a 0.001 to 10mum range and the amt. of the inorg. fine particle to be added is in a 0.01 to 100pts.wt. range per 100pts.wt. colored spheroidal fine particles. The extremely sharp images are formed in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to colored fine particles and a toner for developing electrostatic images using the same. More specifically, the colored fine particles have a coloring agent uniformly dispersed within the particles and the particle surface is modified, and can therefore be used as a coloring agent for toners, paints, inks, resin molded products, etc., and the colored particles. The present invention relates to an electrostatic image developing toner that is made of fine particles and can form clear images when used as a toner for printer devices such as laser printers and liquid crystal printers. [Prior art] Electrophotography involves forming an electrical latent image on a photoreceptor made of a photoconductor material such as selenium, zinc oxide, or cadmium sulfide, and developing this with a powder developer to print on paper, etc. It is transferred to and fixed on. Conventionally, toners used for developing electrostatic images generally contain colorants and other additives (charge control agents,
After melt-mixing and dispersing ingredients (offset inhibitors, lubricants, etc.), the solidified product is finely pulverized and classified to produce colored fine particles of a desired particle size. However, the method of manufacturing toner by pulverization described above has various drawbacks. First, there is a process of manufacturing resin, a process of kneading resin with colorant and other additives, a process of pulverizing solid materials, a process of classifying the pulverized material to obtain colored fine particles of desired particle size, etc. , many steps and various types of equipment are required, and the toner produced by this method is necessarily expensive. In particular, the step of classification is essential in order to obtain toner in the optimum particle size range for forming clear images with less fog, but there are problems in terms of productivity and yield. Second, it is extremely difficult to uniformly disperse colorants and other additives in the resin during the kneading process, and therefore, toners manufactured using this method have problems with poor dispersion of colorants, charge control agents, etc. Therefore, each particle has different triboelectric properties, which leads to a decrease in resolution. Such problems will become more prominent in the future as toner particles become smaller in particle size, which is an essential condition for improving image quality. In other words, there is a limit to the ability to obtain toner with small particle size using current crushers, and even if toner with small particle size can be obtained, variations in the amount of charge will occur due to poor dispersion of the colorant and charge control agent. . In order to improve the various drawbacks of toner produced by these pulverization methods, various methods for producing toner using emulsion polymerization or suspension polymerization have been proposed. (Tokuko Show 36-1
No. 0231, Special Publication No. 10799, Special Publication No. 1979-
518305, Japanese Patent Publication No. 51-14895, etc.) These methods add a colorant substance such as carbon black and other additives to a polymerizable monomer, and emulsify or suspend polymerize the mixture to contain the colorant substance. This is a method of synthesizing toner all at once. With this method it is possible to considerably improve the drawbacks of conventional grinding methods. That is, since it does not involve any pulverization process, there is no need to improve brittleness, and since it is spherical in shape and has excellent fluidity, the triboelectrification property is uniform. However, there are also problems with toner manufacturing methods using polymerization methods. First, since hydrophilic substances such as dispersants and surfactants used during polymerization cannot be completely removed even in a washing process and remain on the surface of the toner, charging properties are easily influenced by the environment. Secondly, the toner obtained by the polymerization method has a spherical shape and a very smooth surface, making it difficult to remove the toner adhering to the photoreceptor, resulting in poor cleaning. To solve these problems, various methods have been proposed in JP-A-61
-255354, JP-A-53-17736, JP-A-63-17460, JP-A-61-167956, etc., but the effects are incomplete and
Alternatively, it may lead to increased costs and is not practical. [Problem to be Solved by the Invention 3 The present inventors have conducted intensive research in view of the above-mentioned current situation, and have found that colored fine particles obtained by processing colored spherical fine particles obtained by suspension polymerization according to a specific procedure are as described above. All problems have been improved, and it is suitable for use in toners for developing electrostatic images, as well as coloring agents for paints, inks, resin moldings, etc., and for developing electrostatic images using the colored fine particles. It has been discovered that by using the toner for printers in printer devices such as laser printers and liquid crystal printers, it is possible to form extremely clear images without any of the problems of the prior art described above, and in completing the present invention. It's arrived. [Means for Solving the Problems] The present invention provides particles whose average particle diameter obtained by suspension polymerization is 1 to 11
After mixing colored spherical fine particles of 00IL and inorganic fine particles having a smaller particle size than the colored spherical fine particles, heat treatment was performed under conditions of 30 to 200°C to fuse the colored spherical fine particles to each other to form a block-like product. The invention relates to colored fine particles which are obtained by crushing the colored fine particles, and toners for developing electrostatic images using the colored fine particles. The colored spherical fine particles in the present invention are obtained by suspension polymerization of a polymerizable monomer containing a colorant using a well-known procedure. Colored spherical fine particles obtained by suspension polymerization are 1
The particle size is ~100 μm, preferably 3-50 μm, more preferably 3.5-20 μm, but this particle size is extremely important in obtaining the colored fine particles of the present invention through the heat treatment and crushing steps. It has important significance. The average particle diameter of spherical polymers obtained by polymerization methods other than suspension polymerization, such as emulsion polymerization, is usually around 0.1 μm, and the fine particles obtained by heating and crushing the polymers are obtained by the production method of the present invention. The particle shape and particle size distribution are significantly different from those of colored fine particles, and even if these are used as a toner, it is not possible to obtain an image of sufficiently satisfactory image quality. Examples of polymerizable monomers used as the polymerizable monomer component in suspension polymerization include the following, and these can be used alone or in combination of two or more types. Styrene, 0-methylstyrene, m-methylstyrene,
Styrenic monomers such as p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, 0-chlorostyrene, m-chlorostyrene, p-chlorostyrene; methyl acrylate , ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate,
Acrylic acid or methacrylic acid monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. ; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile. Workability during crushing can be improved by subjecting the polymerizable monomers to suspension polymerization and heat-treating the resulting colored spherical fine particles under appropriate conditions. If the fusion of the particles during heat treatment progresses too much, the efficiency during subsequent crushing will decrease, and if the fusion is insufficient, a sufficient treatment effect on the particle surface will not be obtained. A crosslinking agent may be used during suspension polymerization in order to avoid fusion of excess polymers. At this time, the amount of crosslinking agent used is preferably in the range of 0.0001 to 5% by weight based on the polymerizable monomer. Examples of such crosslinking agents include divinylbenzene,
Divinylnaphthalene, aromatic divinyl compounds such as derivatives thereof, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetraethylene glycol Diethylenically unsaturated carboxylic acid esters such as dimethacrylate, 3-butanediol dimethacrylate,
All divinyl compounds such as N,N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfonic acid and compounds having three or more vinyl groups are mentioned. Furthermore, polybutadiene, polyisoprene, unsaturated polyester, chlorosulfonated polyolefin, etc. are also effective. Colorants used to obtain colored spherical fine particles are dyes and pigments well known to those skilled in the art, whether organic or inorganic, and specific examples include carbon black, nigrosine dye, aniline blue, calco Oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, oil black, azo oil black, rose bengal, etc. are listed, if necessary. Two or more of these may be used in combination. Moreover, a substance having magnetism and a corresponding magnetic substance can also be used as a coloring agent. Examples of the magnetic material include powders of ferromagnetic metals such as iron, cobalt, and nickel, and powders of metal compounds such as magnetite, hematite, and ferrite. These magnetic substances can be used alone or in combination with the dyes, pigments, etc. as colorants. These colorants may be used as they are, but if a colorant whose surface has been treated with an appropriate method is used, colored fine particles in which the colorant is uniformly dispersed can be obtained. For example, when used in toner, high-quality images can be obtained. For example, when carbon black is used as a coloring agent, it is preferable that
Carbon black graft polymers described in Japanese Patent Application Laid-Open No. 63-265913 are suitable. Also, when using a colorant other than carbon black, a surface-treated colorant obtained by the method described in JP-A-1-118573 is suitable. The amount of the colorant added can vary widely depending on the type of colorant used and the purpose of use of the resulting colored fine particles, but preferably 1 part by weight per 100 parts by weight of the polymerizable monomer.
~200 parts by weight, more preferably 1 to 100 parts by weight. In order to obtain colored spherical fine particles using a colorant, it is usually convenient to carry out suspension polymerization of polymerizable monomers in which the colorant is dissolved or dispersed, but in some cases, spherical particles may be obtained after polymerization. A method may also be used in which the colorant is absorbed into the polymer particles using a suitable solvent. Stabilizers used in suspension polymerization include water-soluble polymers such as boranovinyl alcohol, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, and sodium polymethacrylate; anionic surfactants, and cationic interfaces. There are surfactants such as activators, zwitterionic surfactants, and nonionic surfactants, as well as barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, metal oxide powder, etc. is used. Examples of anionic surfactants include fatty acid salts such as sodium oleate and potassium castor oil, alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfonates. , alkanesulfonic acid salts, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkylphenyl ether sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, and the like. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine; glycerin fatty acid ester, oxyethylene-oxy There are brobylene block polymers, etc. Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride. Examples of the zwitterionic surfactant include lauryl dimethylamine oxide. These stabilizers have a particle diameter of 1
The composition and amount used should be adjusted as appropriate so that the thickness is 100 μm, preferably 3 to 50 μm, and most preferably 3.5 to 20 μm. For example, when using a water-soluble polymer as a stabilizer, 0.01 to 20% by weight, more preferably 0.1 to 10% by weight based on the polymerizable monomer component.
Preferably, it is expressed as % by weight. In the case of the surfactant, it is suitably used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polymerizable monomer component. As the polymerization initiator used in the polymerization, oil-soluble peroxide-based or azo-based initiators that are normally used in suspension polymerization can be used. - For example, benzoyl peroxide,
lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide,
Peroxide initiators such as methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2.2°-azobisisobutyro Nitrile, 2.2°-azobis-(2
, 4-dimethylvaleronitrile), 2,2°-azobis-2,3-dimethylbutyronitrile, 2,2°-azobis-(2-methylbutyronitrile), 2,2°-azobis-2,3 ,3-trimethylbutyronitrile,2,
2'-Azobis-2-isopropylbutyronitrile,
1°-azobis-(cyclohexane-1-carbonitrile), 2.2'-azobis-(4-methoxy-2,
Examples include 4-dimethylvaleronitrile)2-(carbamoylazo)isobutyronitrile, 4,4-azobis-4-cyanovaleric acid, and dimethyl-2,2-azobisisobutyrate. The polymerization initiator has an amount of 0.01 to 2 with respect to the polymerizable monomer.
Preference is given to using 0% by weight, especially 0.1 to 10% by weight. When the polymerizable monomer components are suspension-polymerized in this way to obtain colored spherical fine particles, other polymers such as polyester may be present in the monomer components, and the degree of polymerization is further adjusted. In addition, when the colored fine particles of the present invention are used in a toner for developing an electrostatic image, a magnetic material or a charge control agent may be mixed with a polymerizable monomer. It is also possible to obtain colored fine particles to which the magnetic substance and charge control agent are internally added. The colored spherical fine particles thus obtained have an average particle diameter of 1 to 100 μm, preferably 3 to 50 μm, most preferably 3°5 to 20 μm, and a particle size distribution of 0 to 80%, preferably 1
It exhibits a spherical shape that can be controlled to ~50%. The colored fine particles of the present invention are produced by mixing the colored spherical fine particles obtained by the above procedure and inorganic fine particles having a smaller particle size than the colored spherical fine particles, and then heat-treating the mixture under conditions of 30 to 200°C to form the colored spherical fine particles. It is obtained by bringing them into a fused state and then crushing them to the average particle size of the colored spherical fine particles before being fused. The most ideal form of crushing the colored spherical fine particles to an average particle size before substantial fusion is to fuse the colored spherical fine particles to each other within a range that does not completely eliminate the interface between the colored spherical fine particles. The method is to fuse the block-like materials and crush the individual particles into units of colored spherical fine particles before fusion, thereby returning the colored spherical fine particles to a deformed state before fusion and disintegration. however,
In practice, it is difficult to uniformly control the fusion state at the fusion interface, and the colored fine particles that are usually obtained are colored spherical fine particles that have been deformed and partially missing before being fused and crushed. Obtained as a mixture of attached fine particles. Even with such a mixture, if the average particle size of the colored spherical fine particles obtained is substantially the same as the average particle size of the colored spherical fine particles before fusion and crushing, the properties of the colored fine particles will be the same as in the most ideal form. There is almost no difference in comparison. At this time, if the average particle diameter of the colored fine particles is normally within 20%, preferably within 10%, and more preferably within 5% of the average particle diameter of the colored spherical fine particles, then the colored fine particles and the colored fine particles It can be considered that the average particle diameters of the spherical fine particles are substantially the same. The inorganic fine particles are used to maintain the fusion between the colored spherical fine particles in an optimum state, to significantly improve the subsequent crushability, and to make the colored fine particles obtained by crushing exhibit higher physical properties. Therefore, the particle size of the inorganic fine particles must be smaller than the colored spherical fine particles, and it is preferable to select and use the inorganic fine particles so that the particle size is 172 mm or less of the particle size of the colored spherical fine particles. Examples of inorganic fine particles include alumina, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide,
Silica sand, clay, mica, wollastonite, diatomaceous earth, various inorganic oxide pigments, chromium oxide, cerium oxide, red iron oxide,
Examples include powders and particles such as antimony dioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silica fine powder, silicon carbide, silicon nitride, boron carbide, tungsten carbide, titanium carbide, cerium oxide, and carbon black. , these can be used alone or in combination of two or more. Such inorganic fine particles may be used after being treated with a known hydrophobic treatment method using a titanium coupling agent, a silane coupling agent, a higher fatty acid metal salt, or the like. The method of adding inorganic fine particles is not particularly limited;
This can be done in various ways. For example, when a polymerization monomal component is polymerized, it is added to a water media (method, a method of adding it to a suspension of a colored spherical fine particle obtained after polymerization, a polymerization backward, a moist state immediately after washing. It can be appropriately selected from triblend by adding it to colored spherical fine particles or adding it to powdered colored spherical fine particles after drying, and in some cases, multiple methods can be used in combination. In order to use it for various purposes, the particle size of inorganic fine particles is 0.
．． The thickness is preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm. When the particle size of the inorganic fine particles is smaller than 0.001 μm, the effect of adding the inorganic fine particles, such as the remarkable improvement of the disintegration property, the fluidity when used as a toner for developing an electrostatic image, and the cleaning property, etc. is observed. If the particle size of the inorganic fine particles exceeds 10 um, the effect of adding the inorganic fine particles will be small (and the improvement in image resolution may not be observed when used as a toner for developing electrostatic images). The amount of the inorganic fine particles added can be set within a wide range depending on the type and particle size of the inorganic fine particles used, but if the amount is too small, the effect of adding the inorganic fine particles will be difficult to express (,
If used in an excessively large amount, it may have an adverse effect on chargeability and environmental stability when used as a toner for developing electrostatic images.
．． The amount is preferably from 0.1 to 100 parts by weight, more preferably from 0.1 to 50 parts by weight. In carrying out the present invention, known organic fine particles may be used in combination with inorganic fine particles. Examples of organic fine particles that can be used include crosslinked and non-crosslinked polymer fine particles, organic pigments, and charge control agents. The above heat treatment is an extremely important and essential step for modifying the surface of the colored spherical fine particles. The temperature at that time was 30
If the temperature is less than 0.degree. C., the colored spherical fine particles will not fuse together at all, or even if they do fuse, it will be insufficient, and no significant surface modification effect will be exhibited. On the other hand, if the temperature exceeds 200°C, it will result in an excessively fused state, which will not only make the subsequent crushing process difficult (but also result in the resulting colored fine particles having a very large particle size distribution. 50-150
℃ range. Colored spherical fine particles are fused to each other by such heat treatment, but the fused state can be controlled arbitrarily depending on the desired treatment effect. In order to obtain colored fine particles with excellent physical properties as a toner for charge image development, it is preferable to maintain a fused state in which the interfaces between the particles do not completely disappear, preferably leaving grain boundaries, but inorganic fine particles The addition of has a remarkable effect in achieving such a fused state. That is, when inorganic fine particles are added, grain boundaries are less likely to disappear even if the temperature and time during heat treatment become somewhat excessive. Furthermore, the bulk density of the block-like material obtained by fusion is 0. It is more preferable that the fused state is in the range of 1 to 0.9 kg/cm", particularly 0.2 to 0.7 kg/cm". Such heat treatment may be performed on the colored spherical fine particles after drying, or may be performed simultaneously with the drying process depending on the case, and this heat treatment may be performed under normal pressure, reduced pressure, or increased pressure. I can do it. Furthermore, an appropriate organic solvent may be freely used to further promote fusion during the heat treatment. For crushing, crushers conventionally used industrially to produce powder, particles, etc. can be used without restriction. The particle size and particle size distribution of the colored fine particles obtained in this way can be controlled arbitrarily, but the particle size is 3.
-100 μm, more preferably 3-50 μm, most preferably 3.5-20 μm, and the particle size distribution has a coefficient of variation of particle size of 0-80%, more preferably 0-5
It is preferable to set it to 0%. However, the coefficient of variation of particle diameter referred to here is the percentage of the standard deviation divided by the average particle diameter. The shape of the colored fine particles is not particularly limited, but examples thereof include particles that are macroscopically spherical but have minute irregularities on the surface, non-spherical particles, and the like. The toner for developing an electrostatic image according to the present invention uses the colored fine particles described above, but in order to maintain the appropriate chargeability of the toner, the average particle diameter should be 3 to 50 μm, more preferably The thickness is preferably 3.5 to 20 μm. The colored fine particles can also be used as they are as a toner for developing electrostatic images. Further, additives commonly used in ordinary toners, such as a charge control agent and a fluidizing agent for charge adjustment, may be appropriately blended. The method of incorporating the charge control agent is not particularly limited, and any conventionally known method can be employed. For example, when polymerizing a polymerizable monomer in which a colorant is dispersed, a charge control agent is pre-incorporated into the monomer (method, or the colored fine particles of the present invention are post-treated with a charge control agent). A method such as attaching a charge control agent to the surface of the colored fine particles can be adopted as appropriate.The toner can be suitably used as a toner for developing electrostatic images, as it has excellent flowability and cleaning properties as well as formation properties.
It can also be used as a coloring agent or modifier for paints, inks, and resin compositions. The toner for developing electrostatic images of the present invention uses the above-mentioned colored fine particles, and because it can always form high-quality, fog-free images in any environment without being affected by humidity, it can be used in a wide range of electrophotographic developing devices. Can be used. [Effect of the invention] The colored fine particles of the present invention are obtained by mixing colored spherical fine particles obtained by suspension polymerization and inorganic fine particles, heat-treating the mixture under specific conditions, and then crushing the mixture. As a result, the particle size is uniform and the particle surface is uneven, and the amount of surfactant and dispersant used in suspension polymerization is significantly reduced, and fluctuations in physical properties due to temperature changes are almost eliminated. has been done. Therefore, the colored fine particles of the present invention have a clear image [Example] The present invention will be explained in detail with reference to Examples below, but the present invention is not limited to the following Examples. All parts in the examples are by weight. Synthesis Example 1 2000 parts of deionized water in which 1 part of polyvinyl alcohol was dissolved was charged into a reaction vessel equipped with a stirrer, an inert gas introduction tube, a reflux condenser, and a thermometer. There, 975 parts of styrene and 2 parts of glycidyl methacrylate were prepared in advance.
A mixture of 80 parts of benzoyl peroxide dissolved in 5 parts of a polymerizable monomer was charged and stirred at high speed to form a uniform suspension. Then, while blowing nitrogen gas,
The mixture was heated to .degree. C. and stirred for 5 hours at this temperature to remove the condensate that had undergone the polymerization reaction to obtain a polymer having epoxy groups as reactive groups. 4.0 parts of a polymer having an epoxy group as a reactive group and 1 part of carbon black MA-10OR (manufactured by Mitsubishi Chemical Corporation)
50 parts and a charge control agent (Aizen 5piIon Bl
ack TRH (manufactured by Hodogaya Chemical Industry ■)) were kneaded and reacted using a pressure kneader at 160° C. and 100,100 rpm, and then cooled and pulverized to obtain a carbon black graft polymer as a colorant. Polyvinyl alcohol (PVA2) was added to the same reaction pot as above.
05 Kuraray @ deionized water 8970 dissolved in 30 parts
I prepared a section. Styrene 80 adjusted there in advance
0 parts, 200 parts of n-butyl acrylate, and 0.03 parts of divinylbenzene, and 500 parts of the above carbon black graft polymer as a coloring agent.
parts, 30 parts of azobisisobutyronitrile and 2,2°-
A mixture containing 30 parts of azobis(2,4-dimethylvaleronitrile) was added to T. and stirred at 8000 rpm for 5 minutes using a homomixer (manufactured by Tokushu Kika Kogyo ■) to form a uniform suspension. Next, it was heated to 60°C while blowing nitrogen gas, and stirred at this temperature for S hours to carry out a suspension polymerization reaction, and then cooled to form a suspension of colored spherical particles (1
) was obtained. The obtained suspension (1) of colored spherical fine particles was measured with a Coulter counter (aperture 100 μm), and the average particle diameter was 7.25 μm, and the coefficient of variation per particle diameter was 18.2%. Synthesis Example 2 In a reaction vessel similar to that used in Synthesis Example 1, 8970 parts of deionized water in which 10 parts of the nonionic surfactant Noniball 200 (manufactured by Sanyo Chemical Co., Ltd.) was dissolved was charged. 800 parts of styrene, 20 parts of n-butyl acrylate
0 parts and 1 part of divinylbenzene, 50 parts of Brilliant Carmine 6B (manufactured by Noma Kagaku) as a coloring agent, 30 parts of azobisisobutyronitrile, and 2,2°-azobis(2, A mixture containing 30 parts of 4-dimethylvaleronitrile) was added, and the mixture was heated at 6000 rpm using a T, K, and homomixer (manufactured by Tokushu Kika Kogyo ■).
The mixture was stirred for 5 minutes to form a homogeneous suspension.Next, it was heated to 60°C while blowing nitrogen gas, and stirred at this temperature for 5 hours to perform a suspension polymerization reaction, and then cooled to room temperature to form colored spherical fine particles. A suspension (2) was obtained. The obtained suspension (2) of colored spherical fine particles was measured with a Coulter counter (aperture 10100u), and the average particle diameter was 5.82.
The coefficient of variation in μm and particle diameter was 19.3%. Synthesis Example 3 Carbon black graft polymer 5 used in Synthesis Example 1
Mabico BL-2, which is a powder magnetic material instead of 00 parts
A suspension (3) of colored spherical fine particles was obtained in the same manner as in Synthesis Example 1 except that 450 parts of 00 (manufactured by Titan Kogyo ■) were used. The obtained colored spherical fine particle suspension (3) had an average particle diameter of 9.30 ILm and a particle diameter variation coefficient of 19.0%. Synthesis Example 4 A flask similar to that used in Synthesis Example 1 was charged with 8970 parts of deionized water in which 5 parts of the anionic surfactant sodium dodecylbenzenesulfonate was dissolved. To the pre-prepared polymerizable monomer component consisting of 800 parts of styrene and 200 parts of n-butyl acrylate, 500 parts of the carbon black graft polymer of Synthesis Example 1 and 30 parts of azobisisobutyronitrile were added as a coloring agent. A mixture of 30 parts of 2.2°-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was stirred for S minutes at 8000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo ■) to obtain a homogeneous mixture. 0 as a suspension, then 60 minutes while blowing nitrogen gas.
℃, continued stirring at this temperature for 5 hours to perform a suspension polymerization reaction, and then cooled to room temperature to form a suspension of colored spherical particles (
4) was obtained. The obtained suspension (4) of colored spherical fine particles was measured with a Coulter counter (aperture 100' μm), and the average particle diameter was 5.85 μm, and the coefficient of variation of the particle diameter was 221%. Synthesis Example 5 A carbon black graft polymer was obtained in the same manner as in Synthesis Example 1, and then deionized by dissolving 10 parts of the anionic surfactant Hytenol N-08 (manufactured by Dai-Kogyo Seiyaku Co., Ltd.) in the same flask as above. 8,970 parts of water was charged. 800 parts of styrene, 150 parts of n-butyl acrylate, and polybutadiene N I 5S, which had been prepared in advance, were added thereto.
50 parts of carbon black graft polymer to 50 parts of O-PB-B-3000 (manufactured by Nippon Soda Co., Ltd.)
0 parts, 20 parts of azobisisobutyronitrile and 2.2°
A mixture containing 10 parts of -azobis(2,4-dimethylvaleronitrile) was charged, and the same operations as in Synthesis Example 1 were carried out to obtain a suspension (5) of colored spherical fine particles. As a result of measuring the obtained suspension (5) of colored spherical fine particles with a Coulter counter (aperture 100 am), the average particle diameter was 6°30 μm, and the coefficient of variation of the particle diameter was 19.3
It was %. Synthesis Example 6 In place of 50 parts of polybutadiene in Synthesis Example 5, H
YPALON20 (E,,duontde Nom
Same as Synthesis Example 5 except that 30 parts of benzoyl peroxide was used instead of 20 parts of azobisisobutyronitrile and 10 parts of 2.2° azobis(2,4-dimethylvaleronitrile). The operation was carried out to obtain a suspension a(6) of colored spherical fine particles. The obtained suspension (6) of colored spherical fine particles was measured with a Coulter counter (aperture 100 μm), and the average particle diameter was 5.91 μm, and the coefficient of variation of the particle diameter was 2.5%. Example 1 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 1050
30 parts of precipitated barium sulfate (inorganic pigment C, 177120) with an average particle size of 0.2 μm was added to 0 parts, and after sufficient fractionation, filtration and washing were carried out. Drying and heat treatment were performed to obtain 1530 parts of a block-like product in a fused state with grain boundaries remaining and having a bulk density of 0.45 g/cm and a millet-like shape.This block-like product was coarsely crushed. After that, it was crushed using a supersonic jet crusher ID52 model (manufactured by Nippon Ni-Amatic Kogyo ■) at a feed rate of 13 kg/Hr to obtain colored fine particles (1). As a result of measurement with a Coulter counter (aperture 100 μm), the average particle size was 6.
．． The coefficient of variation in particle size was 17.2% at 95 μm. The colored fine particles (1) were used as they were as toner (1) for developing electrostatic images in an electrostatic copying machine (type 4060 (m
(manufactured by Ricoh) and the results were as shown in Table 1. Example 2 Suspension of colored spherical fine particles obtained in Synthesis Example 2 (2) 1003
One portion was passed through the mouth and washed to obtain a colored spherical fine particle paste. This colored spherical fine particle paste has a colorless charge control agent (
Bontron E-84Orient Chemical Industry ■)
13 parts and 20 parts of ultrafine calcium carbonate (inorganic pigment C, l77220) having an average particle size of 0.1 μm were mixed uniformly. The resulting mixture was dried at 120°C using a hot air dryer.
By drying for hours and heat-treating, 1093 parts of a block-like product having a bulk density of 0.35 g/cm and a millet-like shape were obtained in a fused state with grain boundaries remaining. It was crushed using the same model as in Example 1 at a feed rate of 8 kg/Hr to obtain red colored fine particles (2).The properties of the colored fine particles (2) and the colored fine particles (2)
The results were shown in Table 1 when images were produced using an electrostatic copying machine (type 4060 manufactured by Ricoh) using the toner (2) for developing electrostatic images as it was. Example 3 Suspension of colored spherical fine particles obtained in Synthesis Example 4 (1) 1047
After 5 parts were passed through the mouth and washed, they were dried under reduced pressure at 50°C for 5 hours to obtain 1500 parts of colored spherical fine particles. To the colored spherical fine particles, 30 parts of Aerosil R-972 (hydrophobic Nlica, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed uniformly, followed by heat treatment at 85°C for 1 hour using a hot air dryer to fuse the grain boundaries. A block-like product having a bulk density of 0.38 g/am" was obtained in the shape of millet. This block-like product was crushed using the same machine as in Example 1 at a feed rate of 15 kglor to obtain colored fine particles. (3) was obtained. The properties of the colored fine particles (3) and the colored fine particles (3) were used as they were as a toner (3) for developing an electrostatic image by an electrostatic copying machine (type 4060 manufactured by Ricoh). The results of image generation were as shown in the lt table. Example 4 A suspension of colored spherical fine particles containing a magnetic substance obtained in Synthesis Example 3 (3
) 10,450 parts were passed through the mouth and washed to obtain a paste of colored spherical fine particles containing a magnetic substance. This colored spherical fine particle paste containing a magnetic substance was added with an aqueous paste charge control agent (Bontron S-34 Orient Kagaku Kogyo ■) containing 35% of the active ingredient.
(manufactured by Nippon Shokubai Chemical Co., Ltd.) and Seahoster KE-P30 (spherical silica fine particles with an average particle diameter of 0.3 μm, Nippon Shokubai Chemical Co., Ltd.)
After uniformly mixing 29 parts of (made of cloth), the mixture was heated at 80°C for 3 hours at 40°C.
n+m) Drying under reduced pressure with Ig and heat treatment,
Bulk density is 0.52 g/am in fused state with grain boundaries remaining.
1,493 blocks of block-like material having the shape of a millet stirrer were obtained.This block-like material was heated to 35 k by using the same model as in Example 1.
Colored fine particles (4) were obtained by crushing with a feed amount of glow. The properties of the colored fine particles (4) and the results of image formation using an electrostatic copying machine (NP-5000 manufactured by Canon ■) using the colored fine particles (4) as it is as a toner (4) for developing an electrostatic image. (As shown in Table 1.) Example 5 Suspension of colored spherical fine particles obtained in Synthesis Example 5 (5) 1048
After 0 parts were passed through the mouth and washed, drying was carried out under reduced pressure at 50°C for 5 hours to obtain 1500 parts of colored spherical fine particles. After adding 30 parts of Aerosil R805 (hydrophobic titania, Nippon Aerosil Co., Ltd.) to the colored spherical fine particles and uniformly mixing them, heat treatment was performed at 90°C for 1 hour, resulting in a fused state with grain boundaries remaining and a bulk density of 0. A block-like material having the shape of millet roe with a mass of .20 g/crn was obtained. This block-like material was crushed using the same machine as in Example 1 at a feed rate of 0 kglor to obtain colored fine particles (5). The properties of the colored fine particles (5) and the colored fine particles (5) were used as a toner (5) for developing an electrostatic image to produce an image using an electrostatic copying machine (type 4060 manufactured by Ricoh). The results were as shown in Table 1. Example 6 Suspension of colored spherical fine particles obtained in Synthesis Example 6 (6) 1048
After 0 parts were passed through the mouth and washed, drying was carried out under reduced pressure at 50°C for 5 hours to obtain 1500 parts of colored spherical fine particles. After uniformly mixing 15 parts of cerium oxide (optical lens polishing) with an average particle diameter of 0.4 μm and 10 parts of styrene-acrylic fine particles (glass transition temperature 60°C) with an average particle size of 0.3 μm into the colored spherical fine particles, the mixture was heated to 80°C. Heat treatment 1 was carried out for 1 hour at
A block-like object having the shape of a millet-raised millet of "g/cm" was obtained.
Colored fine particles (6) were obtained by crushing with a feed amount of kglor. The properties of the colored fine particles (6) and the results of image formation using an electrostatic copying machine (type 406o manufactured by Ricoh) using the colored fine particles (6) as they are as the electrostatic image developing toner (6) are as follows. The results were as shown in Table 1. Comparative Example 1 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 1050
After passing 0 parts through the mouth and washing, it was heated to 40 mm at 50°C for 24 hours.
) Colored fine particles for comparison (1) 1150 by drying with Ig under reduced pressure
I got the department. The properties of the comparative colored fine particles (1) and the comparative colored fine particles (1) were used as they were as a comparative electrostatic image developing toner (1) in an electrostatic copying machine (type 4060).
The results of image formation using a Ricoh (manufactured by Ricoh) are shown in Table 1. Comparative Example 2 Styrene-acrylic resin (TB-1000F Sanyo Chemical (
2228 parts, carbon black MA-10OR
(Mitsubishi Kasei ■) 187 parts and a charge control agent (Aizen
5pilon Black TRH) were premixed in a Henschel mixer, melted and kneaded in a pressure kneader at 150° C. for 30 minutes, and then cooled to obtain a toner mass. This toner mass is crushed into 0.1 mm to 2 mm using a coarse crusher.
This coarse toner was finely pulverized using the same model as in Example 1 at a feed rate of 5 kg/Hr, and the pulverized material was passed through an air classifier (DS: Model 2 manufactured by Nippon Pneumatic Kogyo ■).
The mixture was classified to obtain 1500 parts of comparative colored fine particles (2). Particle properties of the comparative colored fine particles (2) and electrostatic copying using the comparative colored fine particles (2) as is as a comparative electrostatic image developing toner (2) ff! (Type 406
The results of image formation using 0.0cm (manufactured by Ricoh) are shown in Table 1. Comparative Example 3 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 1O50
After passing 0 parts through the mouth and washing, dry at 90°C using a hot air dryer for 30 minutes.
After drying and heat treatment for a period of time, 1500 parts of a millet-shaped block with a bulk density of 0.30 g/cm' was obtained in a fused state with grain boundaries remaining. After coarsely crushing this block-like material, 7 kg/lar was crushed using the same model as in Example 1.
Colored fine particles (3) for comparison were obtained by crushing with a feed amount of . The properties of the comparative colored fine particles (3) and the comparative colored fine particles (3) were used as they were as a comparative electrostatic image developing toner (3) in an electrostatic copying machine (type 4060 (
...manufactured by Ricoh), and the results were as shown in Table 1. (Note 1) Crushing (pulverization) processing] The feed amount when using a supersonic jet pulverizer ID52 type (Nippon Pneumatic Kogyo ■!R) was defined as the crushing processing amount. (Note 2) Particle properties Particle diameter: Measured using a Coulter counter (Model TA-II, manufactured by Coulter Electronics INC). Coefficient of variation: Measured using a Coulter counter (Model TA-II, manufactured by Coulter Electronics INC). Frictional charge amount: Iron carrier (made by Dowa iron powder: DSP-1)
28) using a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical ■: Model T) using a mixture with (toner concentration 5% by weight)
B-200). Fluidity: The fluidity of the toner was evaluated visually. o Toner particles exist independently and exhibit smooth flow. ○The toner particles are slightly agglomerated, but exhibit normal flow. Considerable agglomeration of Δ toner particles was observed, and a decrease in fluidity was observed. *Toner particles are significantly aggregated and fluidity is significantly decreased. (Note 3) Image output evaluation Evaluated using an image obtained by copying facsimile test chart N (11) using an electrostatic copying machine Image output type 4060 (manufactured by Ricoh or NP-5000 manufactured by Canon). Fog: Ground is toner The presence or absence of spot-like staining phenomenon was investigated.Fine line reproducibility: Evaluated by the readability of the image obtained by copying the facsimile test chart KL.Cleanability: From the image obtained by copying 1 onto the facsimile test chart evaluated.

Claims (1)

[Claims] 1. The average particle diameter obtained by suspension polymerization is 1 to 100μ
After mixing colored spherical fine particles of m and inorganic fine particles having a smaller particle size than the colored spherical fine particles, heat treatment is performed under conditions of 30 to 200 ° C. to fuse the particles together to form a block-like object, 1. Colored fine particles, characterized in that they are obtained by crushing colored spherical fine particles to an average particle size before substantial fusion. 2. The particle size of the inorganic fine particles added to the colored spherical fine particles is 0.
．． 2. The colored fine particles according to claim 1, having a particle size in the range of 0.001 to 10 μm. 3. Claim 1, wherein the amount of the inorganic fine particles added is in the range of 0.01 to 100 parts by weight per 100 parts by weight of the colored spherical fine particles.
Colored fine particles as described. 4. The colored fine particles according to claim 1, wherein the colored spherical fine particles are obtained by suspension polymerization using a carbon black graft polymer as a colorant. 5. The colored fine particles according to claim 1, wherein the fusion is carried out within a range that does not completely eliminate the interface between the particles. 6. The bulk density of the block-like material is 0.1 to 0.9 g/cm^
3. The colored fine particles according to claim 1, wherein the colored fine particles are in the range of 3. 7. The colored fine particles according to claim 1, having an average particle diameter of 1 to 100 μm. 8. The colored fine particles according to claim 1, which have a coefficient of variation in particle size of 0 to 80%. 9. A toner for developing an electrostatic image using the colored fine particles according to claim 1. 10. The toner for developing electrostatic images according to claim 9, wherein the inorganic fine particles added to the colored spherical fine particles have a particle diameter in the range of 0.001 to 10 μm. 11. The toner for developing electrostatic images according to claim 9, wherein the amount of the inorganic fine particles added is in the range of 0.01 to 100 parts by weight based on 100 parts by weight of the colored spherical fine particles. 12. The toner for developing electrostatic images according to claim 9, wherein the colored spherical fine particles are obtained by suspension polymerization using a carbon black graft polymer as a colorant. 13. The toner for electrostatic thin image development according to claim 9, wherein the fusion is carried out within a range that does not completely eliminate the interface between the particles. 14. The bulk density of the block-like material is 0.1 to 0.9 g/cm
10. The toner for developing an electrostatic image according to claim 9, wherein the toner is in the range of ^3. 15. The toner for developing electrostatic images according to claim 9, wherein the colored fine particles have an average particle diameter in the range of 1 to 100 μm. 16. The toner for developing electrostatic images according to claim 9, wherein the particle size variation coefficient of the colored fine particles is 0 to 80%.