JPH0369107B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a novel tray for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like. BACKGROUND ART Conventionally, as an electrophotographic method, U.S. Patent No. 2297691
No., Special Publication No. 1972-23910, and Special Publication No. 43-
Various methods are described in Japanese Patent No. 24748, etc., but they basically involve applying a uniform electrostatic charge onto a photoconductive insulating layer and irradiating the insulating layer with a light image. An electrostatic latent image is formed, and then the latent image is developed and visualized with fine powder called toner in the art, and if necessary, after transferring the powder image to paper etc., heating, pressure, or solvent treatment is performed. Fixing is carried out using steam or the like. The developing methods applied to these electrophotographic methods can be broadly classified into dry developing methods. The former is further divided into methods using a two-component developer and methods using a one-component developer. Two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner. Also, those belonging to the one-component development method include:
The powder cloud method uses toner particles in a spray state, the contact development method (also called contact development or toner development) uses toner particles in direct contact with the electrostatic latent image surface, and the electrostatic latent image method uses toner particles to form an electrostatic latent image. A jumping development method in which toner particles are charged and flown toward the latent image surface by the electric field of the electrostatic latent image without directly contacting the surface, and development is performed by bringing magnetic conductive toner into contact with the electrostatic latent image surface. There are methods such as the Magne Dry method. As toners applied to these developing methods, paper has conventionally been used as fine powder in which dyes and pigments are dispersed in natural or synthetic resins. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as toner. In addition, as a magnetic toner,
In place of or in addition to the above dyes or pigments, materials containing magnetic particles such as magnetite are used. In the case of a system using a so-called two-component developer, the above-mentioned toner is usually mixed with carrier particles such as glass beads and iron powder. Further, the toner is given a positive or negative charge in advance depending on the polarity of the electrostatic latent image to be developed. In order to charge the toner, it is also possible to use only the triboelectricity of the resin, which is a component of the toner, but with this method, the toner's chargeability is small, so the image obtained by development is prone to fogging. ,
It becomes unclear. Therefore, in order to impart desired triboelectric charging properties to the toner, charge control agents such as dyes and pigments that enhance the charging properties are added. Charge control agents known today in fields such as electrophotography include the following. (1) Things that control the toner to be positively charged Nigrosine, azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627-1983), basic dye (for example, C.I. Basic Yellow 2) (CIBasic Yellow 2 (CI4100)), C.I.Basic.Yellow 3 (CIBasic
Yellow 3), C. Ai. Basic. Red 1 (CIBasic Red 1 (CI45160)), Sea.
Ai. Basic. Red 9 (CIBasic Red
9 (CI42500)), C. Ai. Basic. Violet 1 (CIBasic Violet 1 (C.
I.42535)), C. Ai. Basic. Violet 3 ((CIBasic Violet 3 (CI42555)),
C. Ai. Basic. Violet 10 (C.
I.Basic Violet 10 (CI45170), C. Ai.
Basic. Violet 14 (CIBasic
Violet 14 (CI42510)), C. Ai. Basic. Blue 1 (CIBasic Blue 1 (CI42025)),
C. Ai. Basic. Blue 3 (CIBasic
Blue 3 (CI51005)), C. Ai. Basic. Blue 5 (CIBasic Blue 5 (CI42140)),
C. Ai. Basic. Blue 7 (CIBasic
Blue 7 (CI42595)), C. Ai. Basic. Blue 9 (CIBasic Blue 9 (CI52015)),
C. Ai. Basic. Blue 24 (CIBasic
Blue 24 (CI52030)), C. Ai. Basic. Blue 25 (CIBasic Blue25 (CI52025)),
C. Ai. Basic. Blue 26 (CIBasic
Blue 26 (CI44045)), C. Ai. Basic. Green 1 (CIBasic Green 1 (C.
I.42040)), C. Ai. Basic. Green 4 (CIBasic Green 4 (CI42000)), C.
I.45170, etc.). Lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten-molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), c. Ai. Solvent. Black 3 (C.
I.Solvent Black 3 (CI26150)), Hansa Yellow G (CI11680), Sea. Ai. Mordaunt.
Black 11 (CIMordant Black 11), Sea.
Ai. Pigment. Black 1 (CIPigment
Black1), gilsonite, asphalt, etc. Quaternary ammonium salts, such as benzyldimethyl-hexadecyl ammonium chloride,
decyl-trimethylammonium chloride,
Organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, and zinc oxide, metal complexes such as EDTA and acetylacetone, etc. Polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups. (2) The following substances are used to control the negative chargeability of toner. Special Publication No. 41-20153, No. 43-27596, No. 44-
Metal complex salts of monoazo dyes described in No. 6397 and No. 45-26478. Special Publication No. 55-42752, No. 58-41508, No. 59-
Co of salicylic acid, naphthoic acid, and dicarboxylic acid described in No. 7384, No. 59-7385, etc.;
Metal complexes such as Cr and Fe. Sulfonated copper phthalocyanine pigment. Styrene oligomer with nitro groups and halogens introduced. Chlorinated paraffin, melamine resin, etc. However, as mentioned above, the use of conventional charge control agents still has many problems that need to be improved. That is, many of these charge control agents are derived from the amount of dyeing, and generally have complex structures, inconsistent properties, poor stability, and strong coloring properties. Recently, there are some products that have been proposed that are different from the above-mentioned ones, but none of them exceeds dye- and pigment-based ones in terms of overall performance, and although they have many disadvantages as listed below, In most cases, dye and pigment-based charge control agents are used. In other words, these charge control agents are usually added to the thermoplastic resin that is the binder resin of the toner and are contained in the toner that is prepared through processes such as hot melt dispersion, pulverization, and classification. In the process, the dye and pigment type charge control agents described above often cause problems. For example, as mentioned above, these charge control agents have poor stability as substances and are easily decomposed or deteriorated due to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc. It is easy to cause development that reduces the properties. Furthermore, when a toner containing these dyes and pigments as a charge control agent is developed using a copying machine, the charge control agent decomposes or changes in quality as the number of copies increases, which may cause deterioration of the toner during repeated copying operations. . Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they pose the fatal problem of causing differences in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to achieve more uniform dispersion. For example, basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve their compatibility with thermoplastic resins, but unreacted fatty acids or salt dispersion products often remain on the toner surface. When exposed, it contaminates the carrier or toner carrier, causing a decrease in toner fluidity, fogging, and a decrease in image density. Alternatively, in order to improve the dispersion of these charge control agents in fat, a method has also been adopted in which charge control agent powder and resin powder are mechanically pulverized and mixed in advance and then hot melt-kneaded. However, the inherent poor dispersion cannot be avoided, and the current situation is that sufficient uniformity of charge has not yet been obtained for practical use. Furthermore, there is a problem in that most of the substances generally known as charge control agents are dark in color and cannot be incorporated into bright chromatic color developers. In addition, many charge control agents are hydrophilic,
Due to poor dispersion in these resins, the dye is exposed on the toner surface when the dye is crushed after melt-kneading. Therefore, when the toner is used under high humidity conditions, there is a problem in that good quality images cannot be obtained because these charge control agents are hydrophilic. In this way, when conventional charge control agents are used in toner, charge control agents are generated on the surface of toner particles between toner particles, between toner and carrier, or between toner and toner carriers such as sleeves. This causes variations in the amount of charge generated, and problems such as development fog, toner scattering, and carrier contamination are likely to occur. Further, this failure appears as a noticeable development when copying is repeated many times, resulting in a result that is practically unsuitable for copying machines. Furthermore, under high humidity conditions, the transfer rate of toner images decreases significantly, and many of them become unusable. Even at room temperature and humidity, when the toner is stored for a long period of time, it often undergoes deterioration due to the instability of the charge control agent used and becomes unusable due to poor charging properties. Furthermore, when conventional charge control agents are used in toners, after long-term use, the charge control agents themselves adhere to the surface of the photoreceptor, or their presence promotes toner adhesion (occurrence of filming development). This often causes inconveniences in the cleaning process of the copying machine, such as adversely affecting image formation, causing scratches on the surface of the photoreceptor or cleaning members such as the cleaning blade, or accelerating abrasion of the members. Furthermore, when conventional charge control agents are used in toners, they often have a large effect on the thermal melting properties of the toners and reduce fixing performance. In particular, it worsens high temperature offset performance and increases the tendency for paper etc. to cling to the roller during heat roll fixing.
There are disadvantages such as a reduction in the durability life of the roller. As described above, conventional charge control agents have many problems, and there is a strong demand in the technical field to solve these problems, and although many improvement techniques have been proposed so far, The reality is that nothing that is comprehensively satisfactory in practical terms has yet been found. OBJECTS OF THE INVENTION A general object of the present invention is to provide a new technique for toner charge control that overcomes these problems. A more specific object of the present invention is to stabilize the amount of triboelectric charge between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of one-component development, and to achieve a distribution of the amount of triboelectricity. The purpose of the present invention is to provide a toner that has a sharp and uniform charge and can be controlled to an amount suitable for the developing system used. Still another object is to use a developer for faithfully developing and transferring the latent image, i.e., without toner adhesion in the background area during development, without fogging, and with no toner scattering around the edges of the latent image. To provide a toner with high image density and good halftone reproducibility. Still another object is to provide a toner that maintains its initial characteristics even when used continuously over a long period of time, and that does not agglomerate or change its charging characteristics. Another purpose is to provide a toner that reproduces stable images unaffected by changes in temperature and humidity, and especially toner that has high transfer efficiency and does not cause scattering or transfer omissions during transfer at high or low humidity. be. Still another object is to provide a bright chromatic toner. Still another object is to provide a toner with excellent storage stability that maintains its initial characteristics even during long-term storage. Still another object is to provide a toner that does not stain, abrade, or scratch the electrostatic latent image surface and is easy to clean. Still another object is to provide a toner having good fixing properties, especially a toner that does not have problems with high temperature offset. Summary of the Invention That is, the present invention is directed to a toner for developing an electrostatic image, which is characterized by containing a metal complex having a compound represented by the following general formula [] as a ligand. (However, in the formula, R ₁ to _{R 4} represent H or an alkyl group and may be the same or different. n is 1 to
Indicates an integer of 3. ) The present inventors have discovered that these metal complexes are thermally and temporally stable, have low hygroscopicity, and are high-quality charge control agents that, when included in a developer, provide a developer with excellent electrophotographic properties. I found that. Specific Description of the Invention Typical specific examples of metal complexes (chelate compounds) related to the present invention are shown below. First, when obtaining a symmetrical chelate, a metal salt such as Na or K of the aminocarboxylic acid to be coordinated is
The metallizing agent is dissolved or dispersed in water, or in methanol, ethanol, ethyl cellosolve, etc., and mixed in such a manner that the molar ratio of aminocarboxylic acid to metal is 2:1. Then, it is heated, and a pH adjuster is added and reacted. If the resulting chelate is a slurry, it is collected as is, or if it is a solution, it is diluted with water containing mineral acid and collected for precipitation. In the case of an asymmetric metal complex, one aminocarboxylic acid compound to be coordinated is dissolved or dispersed in water, or dissolved in methanol, ethanol, etc., and a metal-imparting agent is mixed at a molar ratio of 1:1. Then, the mixture is heated, and a PH regulator is added and reacted to obtain a 1:1 type complex. Next, the remaining aminocarboxylic acid compound to be coordinated is added and reacted, and the resulting precipitate is collected. The cake of aminocarboxylic acid chelate thus obtained is recovered after undergoing post-treatments such as purification, drying, and pulverization, if necessary. Methods for incorporating the above compound into the developer include a method of adding it inside the developer and a method of adding it externally. When internally added, the amount of metal complex used depends on the type of binder resin, the presence or absence of additives used as necessary,
It is determined by the toner manufacturing method including the dispersion method, and is not generally limited, but preferably from 0.1 to 100 parts by weight of the binder resin.
It is used in a range of 10 parts by weight (more preferably 0.5 to 5 parts by weight). In addition, when adding externally, for 100 parts by weight of resin,
0.01 to 10 parts by weight is desirable. Further, conventionally known charge control agents can also be used in combination with the charge control agent of the present invention. Colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, Rhodamine 6G Hake, chrome yellow, quinacridone, benzidine yellow, Any conventionally known dyes and pigments such as rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes and pigments, and anthraquinone dyes can be used alone or in combination. Binder resins used in the present invention include monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, and styrene-propylene copolymers. Coalescence, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylotrile copolymer, styrene-vinyl methyl ether copolymer,
Styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-
Styrenic polymers such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl Methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon Examples include resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., which can be used alone or in combination. Further, in order to provide a toner particularly suitable for pressure fixing, the following binder resins can be used alone or in combination. Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, poly 4
fluorinated ethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio: 5-30:95-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer) polymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin),
Polyvinylpyrrolidone, methyl vinyl ether
Maleic anhydride copolymer, maleic acid-modified phenolic resin, phenol-modified terpene resin. Further, when the toner of the present invention is used as a two-component developer, it is mixed with carrier powder. All known carriers can be used in the present invention, including magnetic powders such as iron powder, ferrite powder, and nickel powder;
Examples include glass beads and the like, and those whose surfaces are treated with resin or the like. Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite;
Metals such as cobalt, nickel, or these metals together with aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium,
Bismuth, cadmium, calcium, manganese,
Examples include alloys with metals such as selenium, titanium, tungsten, and vanadium, and mixtures thereof. It is desirable that these ferromagnetic materials have an average particle size of about 0.1 to 2 μm, and the amount to be included in the toner is approximately 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably 100 parts by weight of the resin component. 40 to 150 parts by weight. Furthermore, additives other than those mentioned above may be mixed into the toner of the present invention, if necessary. As an additive,
For example, lubricants such as Teflon and zinc stearate,
Or abrasives such as cerium oxide, carbon silicon, etc.
Other examples include fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, conductivity imparting agents such as carbon black and tin oxide, and fixing aids such as low molecular weight polyethylene. In order to prepare the toner for developing an electrostatic image according to the present invention, the chelate charge control agent according to the present invention is added to
The above-mentioned binder resin, pigment or dye as a coloring agent, magnetic material, additives, etc. as required are thoroughly mixed in a ball mill or other mixer, and then heated in a heat kneader such as a heated roll, kneader, or extruder. A pigment or dye is dispersed or dissolved in the resin by melting, kneading and kneading to make the resins compatible with each other, and after being cooled and solidified, it is crushed and classified to obtain a toner with an average particle size of 5 to 20μ. I can do it. Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization method and a toner production method for obtaining a toner can be applied. Effects of the Invention As described above, the toner of the present invention containing the above metal complex as a charge control agent has a uniform amount of frictional charge between toner particles, and the amount of charge can be easily controlled. In addition, the toner is extremely stable as it does not change in quality during use and the amount of triboelectric charge does not vary or decrease. This eliminates problems such as development fog, toner scattering, and contamination of electrophotographic materials and copying machines, as described above, and also reduces toner aggregation, clumping, and low-temperature fluidity during storage, which were major problems in the past. This is a toner that does not undergo development and can withstand long-term storage, and the toner image has excellent abrasion resistance, fixing properties, and adhesive properties. The excellent effects of these toners include charging, exposure,
When used in a repetitive transfer copying system in which development and transfer operations are continuously repeated, the effect is even more magnified. Further, since there is little color tone disturbance caused by the charge control agent, it is possible to form color images with excellent colors when used as a color electrophotographic toner. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Styrene/butyl acrylate copolymer (80/
20) (Weight average molecular weight Mw: approx. 300,000) 100 parts Carbon black (Mitsubishi #44) 10 parts Low molecular weight polyethylene wax 2 parts Compound example (1) 2 parts After mixing the above materials well in a blender, 150 parts
The mixture was kneaded using two rolls heated to ℃. After allowing the kneaded product to air, it was roughly pulverized using a cutter mill, pulverized using a jet air stream, and further classified using an air classifier to obtain fine toner powder having a particle size of 5 to 20 μm. For 100 parts of iron powder carrier with an average particle size of 50 to 80μ,
A developer was prepared by kneading 5 parts of the above toner. Further, the amount of triboelectric charge of the toner in the developer was measured by a conventional blow-off method. Next, a negative electrostatic image is formed on the OPC photoreceptor by a conventionally known electrophotographic method, and this is powder-developed using the above-mentioned developer using a magnetic brush method to create a toner image, which is then transferred to plain paper. It was fixed by heating. The resulting transferred image had a sufficiently high density of 1.29, had no fogging, and had no toner scattering around the image, resulting in a good image with high resolution. Transfer images were continuously created using the above developer to examine durability, but the transferred images after 30,000 sheets were also completely dull compared to the initial images. Further, during the durability test, the above-mentioned filming development related to toner on the photoreceptor was not observed at all, and no problems were found in the cleaning process. Also, there were no troubles in the fixing process at this time, and at the end of the 30,000-sheet durability test, the fuser was observed and there were no scratches or damage to the rollers, and there was almost no dirt from offset toner, so there were no practical problems at all. . In addition, when the environmental conditions were set to 35℃ and 85%, the image density was 1.26, a value that was almost unchanged from normal temperature and humidity, and clear images were obtained without fogging or scattering, and the durability was almost unchanged up to 30,000 sheets. Nakatsuta.
Next, a transferred image was obtained at a low temperature of 15° C. and low humidity of 10%, and the image density was as high as 1.31, solid black was developed and transferred extremely smoothly, and the image was excellent with no scattering or hollow spots. Durability tests were conducted under these environmental conditions. Although copies were made continuously and intermittently, the density variation was ±0.2 up to 30,000 copies, which was sufficient for practical use. Comparative Example 1 Instead of 2 parts of Compound Example (1), 2 parts of Nigrosine dye (Nigrosine Base EX manufactured by Orient Chemical Industry Co., Ltd.)
A developer was obtained in the same manner as in Example 1, except that a portion was used, and images were obtained in the same manner as in Example 1 by performing development, transfer, and fixing. There is little fog at room temperature and humidity, but the image density is
It was low at 1.06, and line drawings were scattered, and solid blacks were noticeably rough. We investigated the durability and found that the density decreased to 0.83 after 30,000 sheets. Also, during the durability test, after about 10,000 sheets, the toner material formed a thin, streak-like film on the surface of the photoreceptor, which began to appear as lines on the image. This is so-called filming, and it is thought that the charge control agent changes the lubricity of the toner powder. Furthermore, during durability testing, the fixed image tended to get caught up in the fixing roller during the fixing process, making it difficult to peel it off from the roller. When an image was obtained under conditions of 35°C and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. Transfer efficiency was also low at 69%. When an image was obtained under conditions of 15°C and 10%, the image density was as low as 0.91, and there was severe scattering, fogging, roughness, and noticeable transfer omissions. Continuous image production was performed, but the density became 0.53 after about 30,000 sheets, making it impractical. Example 2 A developer was obtained in the same manner as in Example 1, except that 3 parts of Compound Example (2) was used instead of 2 parts of Compound Example (1), and an image was obtained in the same manner by carrying out development transfer fixing. The detailed results are shown in Tables 1 and 2, and satisfactory results almost the same as in Example 1 were obtained. Example 3 A developer was obtained in the same manner as in Example 1, except that 2 parts of Compound Example (3) was used instead of 2 parts of Compound Example (1), and images were obtained in the same manner by performing development, transfer, and fixing. The detailed results are shown in Tables 1 and 2, and satisfactory results almost the same as in Example 1 were obtained. Example 4 A developer was obtained in the same manner as in Example 1, except that 2 parts of Compound Example (4) was used instead of 2 parts of Compound Example (1), and images were obtained in the same manner by performing development, transfer, and fixing. The detailed results are shown in Tables 1 and 2, and satisfactory results substantially similar to those of Example 1 were obtained. Example 5 Styrene/butyl acrylate (80/20) copolymer (weight average molecular weight Mw: approx. 300,000) 100 parts Triiron tetroxide EPT-500 (manufactured by Toda Kogyo) 60 parts Low molecular weight polypropylene wax 2 parts Compound example (1) 2 parts After mixing the above ingredients well in a blender, 150
The mixture was kneaded using two rolls heated to ℃. After the kneaded material was left to cool naturally, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using jet air flow, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20μ. . Next, 0.4 parts of hydrophobic colloidal silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed with 100 parts of the fine powder using a sample mill to prepare a one-component magnetic toner. Further, the amount of triboelectric charge of this toner was measured by a conventional blow-off method. Apply this toner to a commercially available copying machine (product name NP-
15OZ (manufactured by Canon Inc.) was used to produce an image, and almost the same good results as in Example 1 were obtained. Example 6 In Example 5, 3 parts of Compound Example (2) was used in place of 2 parts of Compound Example (1). Other than that, a developer was obtained in the same manner as in Example 5, and development,
Transfer and fixing were performed to obtain an image in the same manner. Detailed results are shown in Tables 1 and 2, and almost the same results as in Example 5 were obtained. Example 7 A developer was obtained in the same manner as in Example 5, except that 2 parts of Compound Example (3) was used instead of 2 parts of Compound Example (1), and development, transfer, and fixing were carried out in the same manner. Got the image. Detailed results are shown in Tables 1 and 2, but Example 5
Almost the same satisfactory results were obtained. Comparative Example 2 Instead of 2 parts of Compound Example (1) in Example 5,
A developer was obtained in the same manner as in Example 5, except that 2 parts of benzyl-dimethyl-hexadecyl ammonium chloride was used, and an image was obtained in the same manner. At room temperature and humidity, there was little fog, but the image density was low at 0.81, line drawings were scattered, and solid blacks were noticeably rough. We investigated the durability and found that the temperature dropped to 0.48 after 30,000 sheets. Further, the problems in the film development and fixing steps during durability were almost the same as in Comparative Example 1 and were undesirable. When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.72, and fogging, scattering, and roughness increased, making it unusable. Transfer efficiency was also low at 63%. When an image was obtained under conditions of 15°C and 10%, the image density was as low as 0.73, and there was severe scattering, fogging, roughness, and noticeable transfer omissions. Continuous image production was performed, but the density became 0.59 after 30,000 sheets, making it impractical. Example 8 Styrene/butyl acrylate (80/20) copolymer (average molecular weight Mw: approximately 300,000) 100 parts Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound example (1) 2 parts The above materials were blended After mixing well at 150℃
The mixture was kneaded using two heated rolls. After the kneaded material is allowed to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet air flow, and further classified using an air classifier to obtain fine toner powder with a particle size of 5 to 20 μm. Ta. Further, the amount of triboelectric charge of the toner was measured by a conventional blow-off method. Next, 50 parts of carrier iron powder having a particle size of 50 to 80 μm was mixed with 100 parts of the toner to prepare a developer. This developer was put into a developer container 1 of a developing device shown in the accompanying drawings, and a developing operation was performed. That is, in this device, at the lower opening of the container 1,
A cylindrical toner carrier 2 made of stainless steel with a roughened surface was housed so as to substantially close this, and was rotated in the direction of arrow a at a circumferential speed of 66 mm/sec. On the other hand, an iron blade 3 whose tip is placed 200 μm from the sleeve surface is placed at the outlet on the downstream side in the rotational direction of the sleeve 2 of the container 1, and a fixed magnet 4 is placed inside the sleeve 2. The N pole, which is the main magnetic pole, was arranged so that the angle θ between the line connecting the N pole and the center of the sleeve, the center of the sleeve, and the tip of the blade 3 was 30°. Under these conditions, as the sleeve 2 rotates,
Inside the container 1, a magnetic brush 5 is formed by carrier iron powder contained in the developer. circulates along the periphery of the sleeve 2 below the
A thin layer 16 of toner is formed on the surface of the sleeve 2 that has passed through the blade 3. In this example, the toner thin layer of about 80 μm thick thus formed is used in the developing section (nearest section) to face each other at an interval of about 300 μm.
A negative electrostatic image of -600V and -1500V in the dark area was developed on a conventional drum 7 rotating in the direction of arrow b at a circumferential speed of 60 mm/sec. At this time, a bias voltage having a frequency of 800 Hz, a peak-to-peak value of 1.4 KV, and a center value of -300 V was applied between the sleeve 2 and the photosensitive drum 7 by the power source 8. When the image was printed in this way, a good image with a bright blue color was obtained. No change in concentration was observed,
Thereafter, good images were obtained even after printing up to 30,000 sheets while replenishing toner. Normal temperature-normal humidity (25℃,
Tables 1 and 2 summarize the evaluation results under various environmental conditions: 60% RH), high temperature and high humidity (35°C, 85% RH), and low temperature and low humidity (15°C, 10% RH).

【table】

【table】 [Brief explanation of drawings]

The drawing is a schematic cross-sectional view of an example of a developing device suitable for applying the toner according to the present invention. 1... Developer container, 2... Toner carrier, 3...
... Doctor blade, 4 ... Fixed magnet, 5 ... Magnetic brush, 6 ... Toner, 7 ... Electrostatic latent image carrier, 16 ... Thin layer toner.

Claims (1)

[Scope of Claims] 1. A toner for electrostatic charge development, comprising a metal complex having a compound represented by the following general formula [] as a ligand. (However, in the formula, R ₁ to _{R 4} are the same or different groups and represent H or an alkyl group, and n represents an integer of 1 to 3.) 2 Metal complex of a ligand represented by the general formula [] The toner for electrostatic charge development according to claim 1, wherein is a complex of Ni, Zn, Cr, and Co.