JPH02273757A - Colored fine particle and toner for developing electrostatic charge image using this particle - Google Patents

Abstract

PURPOSE:To obtain the toner which can form sharp images and has excellent cleanability by mixing colored spheroidal fine particles 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. CONSTITUTION:The colored spheroidal fine particles obtd. by subjecting a polymerizable monomer compounded with coloring agents to suspension polymerization are so formed as to have 0.5 to 200mum average particle size. The colored spheroidal fine particles obtd. in such a manner and the inorg. fine particles smaller in grain size than the colored spheroidal fine particles are mixed and thereafter, the mixture is subjected to the heating treatment under conditions of 30 to 200 deg.C to fuse the colored spheroidal fine particles to each other; thereafter, the mixture is disintegrated. The inorg. fine particles maintain the fusion of the colored spheroidal fine particle to each other in the optimum state to improve the subsequent disintegratability; in addition, the higher physical properties are developed by the colored spheroidal fine particle obtd. by the disintegration. The toner which can form the sharp images without generating cleaning defects is obtd. in this way.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to colored fine particles and a toner for developing an electrostatic image 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 bulking agents in the resin during the crosstalk process, so toners manufactured using this method have poor dispersion of colorants, charge control agents, etc. Because of this, the triboelectric properties of each particle are different, 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, hydrophilic substances such as dispersants and surfactants used during polymerization cannot be completely removed even during the cleaning process and remain on the toner surface, making charging properties more susceptible to 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. The effect may be incomplete, or it may lead to increased costs, making it impractical.

[Problems to be solved by the invention]

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 improved in all the above-mentioned problems. In addition to toners for developing electrostatic images, they are suitably used as coloring agents for paints, inks, resin moldings, etc., and toners for developing electrostatic images using the colored fine particles can be used in laser printers, liquid crystal printers, etc. The present inventors have discovered that by using the present invention in a printer device such as the above, it is possible to form extremely clear images without any of the problems of the prior art described above, and have completed the present invention.

[Means to solve the problem]

In the present invention, the average particle diameter obtained by suspension polymerization is from 0.5 to
After mixing colored spherical fine particles of 200 um with 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 object. 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 0
．． 5 to 200 μm, preferably 1 to 100 μm, more than 2
The particle size is preferably 1 to 50 μm, and this particle size has extremely important significance in obtaining the colored fine particles of the present invention through the steps of heat treatment and crushing. Polymerization method other than suspension polymerization 1 For example, the average particle diameter of a spherical polymer obtained by emulsion polymerization is usually around 0.1 μm, and the fine particles obtained by heating and crushing this 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-butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. ; ethylene, propylene, butylene, vinyl chloride,
Vinyl acetate, acrylonitrile. When carrying out suspension polymerization of the polymerizable monomer components, if an appropriate crosslinking agent is added to impart an appropriate crosslinked structure to the resulting colored spherical fine particles, it will be easier to use during the process from heat treatment to crushing. This is preferable because it improves workability. In other words, if the fusion of particles during heat treatment progresses too much, the efficiency during subsequent crushing will decrease, and if fusion is insufficient, sufficient treatment effect on the particle surface is required. Therefore, in order to achieve a suitable state of fusion between particles, the crosslinking agent should be present in the polymerizable monomer component in an amount of 0.005 to
It is preferably used in an amount in the range of 30% by weight and 0.
．． More preferably, it is used in an amount ranging from 0.05 to 5% by weight. Examples of such crosslinking agents include the following. (A) A compound having at least two polymerizable unsaturated groups in the molecule; (B) A group consisting of at least one polymerizable unsaturated group in the molecule, and a carboxyl group, a hydroxyl group, a sulfonyl group, and a phenol group. (C) A compound having at least one functional group of at least one kind selected from (C) a compound having a small number of functional groups (both having two functional groups) that can be crosslinked by addition or condensation reaction by heating, active energy rays, or other appropriate means; In the process of polymerizing the compound, (D) a compound capable of ion crosslinking such as a polyvalent metal compound, and (E) a polymerizable monomer component, heat,
Compounds with few radicals (two radicals can be generated in the molecule) by active energy rays, a polymerization initiator, or other appropriate means. Compounds (A) include aromatic divinyl benzene, divinylnaphthalene, and derivatives thereof. Compound,
Diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc. Unsaturated carboxylic acid ester, N. There are divinyl compounds such as N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfonic acid, and those having three or more vinyl groups. Furthermore, polybutadiene, polyisoprene, unsaturated polyester and Japanese Patent Publication No. 57-56507, Japanese Patent Application Publication No. 59-2
21304, JP-A-59-221305, JP-A-59-
Reactive polymers described in JP-A No. 221306, JP-A No. 59-221307, etc. can also be used as the compound (A). When a carbon black graft polymer is used as a coloring agent in the process of polymerizing monomer components, the compound (B) is a reactive group remaining in a portion of the carbon black graft polymer, such as an aziridine group, an oxazoline group, or an epoxy group. It imparts a crosslinked structure to colored spherical fine particles by reacting with groups and the like. However, at this time, in order to make the crosslinking reaction proceed more efficiently, a monomer (B-i) having a functional group such as an aziridine group, an oxazoline group, an epoxy group, an N-hydroxyalkylamide group, or a thioepoxy group is polymerized. Examples of the monomer (B-i) that may be included in the monomer component include the following. Hs ■ CH. CM, = C-C-NH-C1, CH, OH and C
H. The compound (C) is, for example, a low molecular weight compound or a high molecular compound having a small number (both two) of epoxy groups, oxazoline groups, etc. in the molecule, such as polyepoxy (Bunacol EX-211゜Buna:]-) L, EX-3
13, Dena: l-LE EX-314, and Bunacol E
X-321 (manufactured by Nagase Kasei Kogyo ■), 2-p-phenylene-bis-(2-oxazoline), 2-2°-(1,3-
phenylene)bis(2-oxazoline), 2-(1-
aziridinyl)-2-oxazoline, RPS (Dow
chea+1ca1 (reactive polystyrene), etc. In addition, in this RPS, the monomer (C-i) must be included in the polymerizable monomer component.
) is, for example, compound (B). Examples of the compound (D) include ZnO, Zn(OH)z,
^1-Os, AI(OH)s, MgO, Mg(
OH)*, sodium methoxide, sodium ethoxide, and the like. However, when crosslinking is performed using compound (D), compound (B) is added to the polymerizable monomer component.
) must be included. Compound (E) is, for example, the following formula (where X is 99 and n is an integer of 4 to 5). However, in order to crosslink using these compounds (C), the functional (wherein, R is H or CHs, x is an integer from 3 to 400,
n represents an integer of 2 or more. ) is a chlorosulfonated polyolefin. 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, as required. For example, two or more of these may be used in combination. Substances that have magnetism, that is, magnetic substances that have coloring properties can also be used as colorants. Examples of magnetic substances that have coloring properties include powders of ferromagnetic metals such as iron, cobalt, and nickel, and magnetite. , powder of metal compounds such as 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
-270767t: The carbon black graft polymer described in No. 270767t is suitable. In addition, when using a colorant other than carbon black, a surface-treated colorant obtained by the method described in Japanese Patent Application No. 62-275849 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. To obtain colored spherical fine particles using a colorant, it is usually convenient to carry out suspension polymerization of a polymerizable monomer component in which the colorant is dissolved or dispersed, but in some cases, after polymerization, A method may also be used in which the coloring agent is absorbed into the spherical polymer particles using a suitable solvent. Stabilizers used in suspension polymerization include water-soluble polymers such as polyvinyl alcohol, starch, methylcellulose, carboxymethylcellulose, hydroxyethylsellose, sodium polyacrylate, and sodium polymethacrylate; anionic surfactants, and cationic surfactants. 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. , dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts, and the like. Nonionic + raw 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 fatty acid ester, Examples include oxybrobylene block polymers. 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 make it possible for the resulting colored spherical fine particles to have a particle size of 0.
．． The composition and amount used should be adjusted appropriately so that the thickness is 5 to 200 μm. For example, when a water-soluble polymer is used as a stabilizer, it is preferably used in an amount of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the polymerizable monomer component. In the case of surfactant, 0.01 to the polymerizable monomer component
The content is preferably 10% by weight, more preferably 0.1% to 5% by weight. 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, kiemene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2°-azobisisobutyl Lonitrile, 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,
1.1'-azobis-(cyclohexane-1-carbonitrile), 2.2'-azobis-(4-methoxy-
2,4-dimethylvaleronitrile)2-(carbamoylazo)inbutyronitrile, 4,4°-azobis-4-
Examples include 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. Known additives such as chain transfer agents may be appropriately blended. In addition, when the colored fine particles of the present invention are used in a toner for developing electrostatic images, a magnetic substance or a charge control agent is blended with a polymerizable monomer, and the colored particles containing the magnetic substance or charge control agent are added internally. Fine particles can also be obtained. The colored spherical fine particles thus obtained have a spherical shape whose particle size and particle size distribution can be controlled arbitrarily. 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 fusing them together and then crushing them. 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 1/2 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 (
Various methods can be used, such as adding the polymerizable monomer component to an aqueous medium during polymerization, adding it to a suspension of colored spherical particles obtained after polymerization, filtration after polymerization, It can be added to wet colored spherical fine particles immediately after washing, or added to powdered colored spherical fine particles after drying to select an appropriate triblend. In some cases, multiple methods may be used in combination. You can also. In order to use it for this purpose, 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. If the particle size of the inorganic fine particles is smaller than o or ooi μm, the effect of adding the inorganic fine particles, such as significant improvement in the disintegration property, fluidity when used as a toner for developing electrostatic images, cleaning property, etc., may not be observed. There is. When the particle size of the inorganic fine particles exceeds Loum, the effect of adding the inorganic fine particles becomes small, and an 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 vary widely 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, charge control agents, etc. can be mentioned. Heat treatment is an extremely important and essential step for modifying the surface of colored spherical fine particles. If the temperature at that time is less than 30℃, 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 occur.On the contrary, if the temperature exceeds 200℃ In case,
The temperature is preferably in the range of 50 to 150°C, which not only makes the subsequent pulverization process difficult due to excessive fusion, but also causes the resulting colored fine particles to have an extremely large particle size distribution. The whitened 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 developing electrostatic images, it is preferable to maintain a fused state in which the interfaces between the particles do not completely disappear, preferably leaving grain boundaries. Addition of fine particles has a remarkable effect on achieving such a fused state. In other words, if inorganic fine particles are added, the grain boundaries will be difficult to disappear even if the temperature and time during heat treatment are somewhat excessive. It is more preferable to obtain a fused state with a bulk density of 0.1 to 0.9 g/cm. Such heat treatment may be performed on the colored spherical fine particles after drying. Depending on the case, it may be carried out simultaneously with the drying step. Also, this heat treatment can be carried out under normal pressure, reduced pressure or increased pressure.Furthermore, an appropriate organic solvent is used to further promote fusion during the heat treatment. For crushing, any crusher that has traditionally been used industrially to produce powder, particles, etc. can be used without any restrictions. The colored fine particles obtained in this way are The particle size distribution could be controlled arbitrarily, but the particle size was 3.
~200 μm, more preferably 3 to 100 μm, most preferably 3 to 50 μm, and the particle size distribution has a coefficient of variation of particle size of 0 to 80%, more preferably 0 to 50 μm.
% is preferable. 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 electrostatic image developing toner according to the present invention uses the colored fine particles described above. 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 for incorporating the charge control agent is not particularly limited (any conventionally known method can be adopted. A method in which the colored fine particles of the present invention are included in a monomer, a method in which the colored fine particles of the present invention are post-treated with a charge control agent and the charge control agent is attached to the surface of the colored fine particles, etc. can be appropriately adopted. The toner is made using the above-mentioned colored fine particles and can always form high-quality, fog-free images in any environment without being affected by humidity, so it can be used in a wide range of electrophotographic developing devices. [Effects of the Invention] The colored fine particles of the present invention are obtained by mixing colored spherical fine particles obtained by suspension polymerization with inorganic fine particles, heat-treating the mixture under specific conditions, and then crushing the mixture. 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 changes in humidity are almost eliminated. The colored fine particles of the present invention can be suitably used as a toner for developing electrostatic images that can form clear images and have excellent fluidity and cleaning properties, and can also be used as a coloring agent for other paints, inks, and resin compositions. Alternatively, it can also be used as a modifier. [Examples] The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to the following Examples. All values are based on 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. 975 parts of styrene and 2 parts of glycidyl methacrylate
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.Next, the mixture was stirred at high speed for 80 parts 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. 400 parts of a polymer having an epoxy group as a reactive group and 1 carbon black MA-10OR (manufactured by Mitsubishi Chemical Corporation)
50 parts and a charge control agent (Aizen 5pilonBla
ck TRH (manufactured by Hodogaya Chemical Industry ■)) were kneaded and reacted at 220° C. and 100 rpm using a pressurized Neegu, followed by cooling and pulverization to obtain a carbon black graft polymer as a coloring agent. Polyvinyl alcohol (PVA2) was added to the same reaction pot as above.
05 Kuraray ■) 30 parts of deionized water 8970 dissolved in
I prepared a section. Styrene 80 adjusted there in advance
0 parts, 200 parts of n-butyl acrylate, and 3 parts of divinylbenzene, 150 parts of the above-mentioned carbon black graft polymer as a coloring agent, 30 parts of azobisisobutyronitrile, and 2.2° - A mixture containing 30 parts of azobis(2,4-dimethylvaleronitrile) was charged and stirred for 5 minutes at 8000 rpm using a T, K, and Homo mixer (manufactured by Tokushu Kika Kogyo ■) to form a uniform suspension. 6 while blowing nitrogen gas.
The mixture was heated to 0° C. and stirred for 5 hours at this temperature to carry out a suspension polymerization reaction, and then cooled to obtain a suspension (1) of colored spherical fine particles. The obtained suspension (1) of colored spherical fine particles was measured with a Coulter counter (aperture 100 μm), and the average particle diameter was found to be 7.25 μm. 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 Nonipol 200 (manufactured by Sanyo Kasei ■) was dissolved was charged. 800 parts of styrene, 2 parts of n-butyl acrylate
A polymerizable monomer component consisting of 00 parts and 3 parts of divinylbenzene, 50 parts of Brilliant Carmine 6B (manufactured by Noma Chemical Co., Ltd.) as a coloring agent, and 30 parts of azobisisobutyronitrile.
T, K,
6000 r with a homo mixer (manufactured by Tokushu Kika Kogyo ■)
pm for 5 minutes to form a homogeneous suspension. Next, the mixture was heated to 60° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and then cooled to room temperature to obtain a suspension of colored spherical particles (2). The obtained suspension (2) of colored spherical fine particles was measured with a Coulter counter (aperture 100 μm), and the average particle diameter was 5.5 μm.
It was 82 μm. Synthesis Example 3 Carbon black graft polymer 1 used in Synthesis Example 1
Mabico BL-2, which is a powdered magnetic material instead of 50 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 suspension (3) of colored spherical fine particles had an average particle diameter of 9.30 parts m. Example 1 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 1015
Precipitated sulfuric acid with an average particle size of 0.2 μm in 0 parts...! After adding 30 parts of barium (inorganic pigment C: 177120) and thoroughly dispersing it, it was filtered and washed, dried at 90°C for 5 hours using a hot air dryer, and heat treated to form a molten material with grain boundaries remaining. 1,180 parts of a block-like material having a bulk density of 0.45 g/co (manufactured by Kogyo) 13
Colored fine particles (1) are crushed with a feed rate of kg/Hr.
I got it. The obtained colored fine particles (1) were placed in a counter in a coulter (
As a result of measurement with an aperture of 100 μm), the average particle diameter was 6.95 μm, and the coefficient of variation of particle diameter was 17.2%. The colored fine particles (1) were used as they were as toner (1) for developing an electrostatic image, and an image was produced using an electrostatic copying machine (type 4060 manufactured by Ricoh Co., Ltd.).The results are shown in Table 1. Example 2 Suspension of colored spherical fine particles obtained in Synthesis Example 2 (2) 1005
0 part 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 135°C for 2 hours using a hot air dryer.
By drying for hours and heat-treating, 1093 parts of a block-like material having a bulk density of 0.35 g/am'' in a fused state with grain boundaries remaining was obtained. 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)
Using this product as it was as toner (2) for developing electrostatic images, images were produced using an electrostatic copying machine (type 4060 manufactured by Ricoh Co., Ltd.), and the results were as shown in Table 1. Example 3 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 1015
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 1150 parts of colored spherical fine particles. After adding 30 parts of Aerosil R-972 (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd.) to the colored spherical fine particles and mixing them uniformly, heat treatment was performed at 110°C for 1 hour using a hot air dryer to fuse the particles leaving grain boundaries. A block-like material having a bulk density of 0.38 g/cm" was obtained. This block-like material was crushed using the same machine as in Example 1 at a feed rate of 15 kg/Hr. Colored fine particles (3) were obtained. The properties of the colored fine particles (3) and the colored fine particles (3) were used as a toner (3) for developing an electrostatic image using an electrostatic copying machine (type 4060 manufactured by Ricoh). ), the results are shown in Table 1. 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.
) 41 parts and Seahoster KE-P30 (spherical silica fine particles with an average particle size of 0.3 μm, Nippon Shokubai Chemical Co., Ltd.)
After uniformly mixing 29 parts of 40 +
Drying under reduced pressure with u+Hg and heat treatment were performed to obtain a bulk density of 0.52 g/c+o in a fused state with grain boundaries remaining.
1493 parts of a block-like product having the shape of millet roe were obtained. This block-like object was 35 kg using the same model as in Example 1.
The colored fine particles (4) were obtained by crushing at a feed rate of /Hr. 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. were as shown in Table 1. Comparative Example 1 Suspension of colored spherical fine particles obtained in Synthesis Example 1 (1) 10
After passing 150 parts through the mouth and washing, drying at 50° C. for 24 hours under reduced pressure at 40° Hg gave colored fine particles for comparison (1) 1150
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 ■
(manufactured by Mitsubishi Kasei), 187 parts of carbon black MA-10OR (manufactured by Mitsubishi Kasei), and a charge control agent (Aizen 5).
25 parts of Pilon Black TRH) were pre-mixed in a Henry Chill mixer, and mixed in a 0-pressure kneader.
After melting and kneading at 50° C. for 30 minutes, the mixture was cooled to obtain a toner mass. This toner mass is crushed by a coarse crusher to a size of 0.1 mm to 21110 mm.
1, and this coarse toner is passed through a supersonic jet pulverizer I.
5 using type D52 (manufactured by Nihon Newyachik Kogyo)
Fine pulverization was carried out at a feed rate of kg/Hr, and the pulverized product was classified using an air classifier (manufactured by MDS Nippon Pneumatic Kogyo ■) to obtain 1500 parts of comparative colored fine particles (2). The particle properties of the comparative colored fine particles (2) and the comparative colored fine particles (2) were used as they were as the comparative electrostatic image developing toner (2) for electrostatic copying f! ! (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) 1015
After passing 0 parts through the mouth and washing, dry at 90℃ using a hot air dryer for 5 minutes.
After drying and heat treatment for a period of time, 1150 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, it was crushed using a supersonic jet crusher ID5Z type (manufactured by Nippon Pneumatic Kogyo ■) to obtain colored fine particles (3) for comparison. 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).
The results of image formation using a Ricoh (manufactured by Ricoh) are shown in Table 1. (Note 1) Crushing (pulverization) processing amount The feed amount when using a supersonic jet pulverizer model ID52 (manufactured by Nippon 22-Matic Kogyo ■) was defined as the crushing (pulverizing) 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 measuring device (manufactured by Toshiba Chemical ■: Model T) using a mixture (toner concentration 5% by weight) of
B-200). Fluidity: The fluidity of the toner was evaluated visually. One particle of 0 toner exists independently and shows smooth flow. Q Toner particles are slightly agglomerated but exhibit normal flow. Considerable aggregation of the Δ toner particles was observed, and a decrease in fluidity was observed. ×Agglomeration of toner particles is significant, and a significant decrease in fluidity is observed. (Note 3) Image output evaluation Evaluation was made using an image obtained by copying facsimile test chart F&L1 using an electrostatic copying machine Image output type 4060 (manufactured by Ricoh or NP-5000 manufactured by Canon ■). Fogging: The presence or absence of a phenomenon in which the gland becomes speckled with toner was investigated. Fine line reproducibility: Evaluation was made based on the readability of an image obtained by copying a facsimile test chart kl. Cleanability: Facsimile test chart F&L1
Evaluation was made from images obtained by copying.

Claims (1)

[Claims] 1. The average particle diameter obtained by suspension polymerization is 0.5 to 20
After mixing colored spherical fine particles of 0 μm 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 object. Colored fine particles characterized in that they are obtained by crushing the particles. 2. The colored fine particles according to claim 1, wherein the colored spherical fine particles are obtained by suspension polymerization of a polymerizable monomer component containing a crosslinking agent in a range of 0.005 to 30% by weight. 3. 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. 4. 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. 5. 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. 6. 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. 7. 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. 8. The colored fine particles according to claim 1, having an average particle diameter of 3 to 200 μm. 9. The colored fine particles according to claim 1, which have a coefficient of variation of particle diameter of 0 to 80%. 10. A toner for developing an electrostatic image using the colored fine particles according to claim 1. 11. The toner for developing electrostatic images according to claim 10, wherein the colored spherical fine particles are obtained by suspension polymerization of a polymerizable monomer component containing a crosslinking agent in a range of 0.005 to 30% by weight. 12. The toner for developing electrostatic images according to claim 10, 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. 13. The toner for developing electrostatic images according to claim 10, 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. 14. The toner for developing electrostatic images according to claim 10, wherein the colored spherical fine particles are obtained by suspension polymerization using a carbon black graft polymer as a colorant. 15. The toner for developing electrostatic images according to claim 10, wherein the fusion is carried out within a range that does not completely eliminate the interface between the particles. 16. The bulk density of the block-like material is 0.1 to 0.9 g/cm
11. The toner for developing an electrostatic image according to claim 10, wherein the toner is in the range of ^3. 17. The toner for developing an electrostatic image according to claim 10, wherein the colored fine particles have an average particle diameter in the range of 3 to 200 μm. 18. The toner for developing an electrostatic image according to claim 10, wherein the particle size variation coefficient of the colored fine particles is 0 to 80%.