JPH0560098B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a new toner 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 Publication 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 roughly divided into dry developing methods and wet 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. Examples of one-component development methods include the powder cloud method, in which toner particles are sprayed, and the contact development method, in which toner particles are brought into direct contact with the electrostatic latent image surface (contact development, or toner development method). (also referred to as development), a jumping development method in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown towards the latent image surface by the electrolysis of the electrostatic latent image; magnetic conductivity; There is the MagneDry method, which develops by bringing toner into contact with the electrostatic latent image surface. As toners applied to these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. 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. Furthermore, magnetic toners containing magnetic particles such as magnetite instead of or in addition to the dyes or pigments described above are used. In the case of a system using a so-called two-component developer, the above 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 impart a charge to the toner, it is possible to utilize 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 chargeability to the toner, charge control agents such as dyes and pigments that enhance the chargeability 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 dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627-1983), basic dyes (for example, CIBasic Yellow 2 (CI41000), CI
Basic Yellow 3, CIBasic Red 1 (C.
I.45160), CIBasic Red 9 (CI42500), CI
Basic Violet 1 (CI42535), CIBasic
Violet 3 (CI42555), CIBasic Violet 10 (C.
I.45170), CIBasic Violet 14 (CI42510), C.
I.BasicBlue 1 (CI42025), CIBasic Blue
3 (CI51005), CIBasic Blue 5 (CI42140)
,
CIBasic Blue 7 (CI42595), CIBasic
Blue 9 (CI52015), CIBasic Blue 24 (C.
I.52030), CIBasic Blue 25 (CI52025), CI
Basic Blue 26 (CI44045), CIBasic Green
1 (CI42040), CIBasic Green 4 (C.
I.42000), CI45170, 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.), CISolvent Black 3 (C.
I.26150), Hansa Yellow G (GI11680), CI
Mordant Black 11, CIPigment Black 1,
Gilsonite, asphalt, etc. Quaternary ammonium salts, such as benzylmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica, inorganic fine powders such as acid value zinc, EDTA , metal complexes of acetylacetone, etc. Polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups. (2) Devices that control the toner to be negatively charged: Japanese Patent Publications 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 allogens 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 dyes and pigments, 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 altered by decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc., resulting in development that reduces charge controllability. easy. Furthermore, if a toner containing these dyes and pigments as a charge control agent is developed using a copying machine, the charge control agent may decompose or change in quality as the number of copies increases, causing deterioration of the toner during repeated copying operations. be. 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 at present, 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. Further, many charge control agents are hydrophilic, and due to poor dispersion in these resins, dyes are exposed on the toner surface when the toner 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 may cause variations in the amount of charge to be applied, resulting in development fog, toner scattering,
Problems such as 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 efficiency 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 a conventional charge control agent is used in a toner, the charge control agent itself adheres to the surface of the photoreceptor due to long-term use, or its presence promotes toner adhesion (occurrence of filming development).
This often causes inconveniences in the cleaning process of the copying machine, such as adversely affecting the formation of latent images, causing scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, 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, there are disadvantages such as deterioration of high-temperature offset performance, increased tendency for paper or the like to stick to the roller during heat roll fixing, and reduced durability 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 The general purpose 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 of charge suitable for the developing system used. Another purpose is to develop a developer that faithfully develops and transfers the latent image, that is, toner adhesion in the background area during development, and prevention of fog and toner withdrawal around the edges of the latent image. Without,
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 objective is to provide a toner that reproduces stable images unaffected by changes in temperature and humidity, and in particular, a toner with high transfer efficiency that does not cause scattering or transfer omissions during transfer at high humidity or constant humidity. It is in. Yet 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 is easy to clean and that does not stain, abrade, or scratch the charged latent image surface. 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 The toner for developing electrostatic images of the present invention has been developed to achieve the above-mentioned object. [In the formula, R ₁ , R ₂ , R ₄ , and R ₅ are hydrogen, halogen, nitro group, amino group that may have a substituent, alkyl group (C ₁ to C ₁₈ ), and a substituent. R ₁ and R ₂ and R ₄ and R ₅ represent a sulfamoyl group which may optionally have substituents, or a group forming a ring which may have substituents, R ₃ ,
R ₆ is hydrogen, alkyl group (C ₁ to _{C 9} ), benzyl group,
or represents a phenyl group which may have a substituent, and Me represents a divalent metal. ] It is characterized by containing the chelate compound represented by these. That is, the present inventors have discovered that the chelate compound represented by the general formula [] in the present invention not only exhibits excellent charge control properties when contained in a toner, but also is stable under heating and use over time. The present invention was completed based on the finding that it has properties that are extremely effective for achieving the above-mentioned objects, such as having low hygroscopicity and being essentially colorless or light-colored. The present invention will be explained in more detail below. In the following descriptions, "parts" and "%" represent quantitative ratios.
are based on weight unless otherwise specified. Specific Description of the Invention In the present invention, the following general formula [] [In the formula, R ₁ and R ₂ are hydrogen, halogen, nitro group,
An amino group that may have a substituent, an alkyl group (C ₁ to C ₁₀ ), a sulfamoyl group that may have a substituent, or a ring that may have a substituent at R ₁ and R ₂ may be formed. R ₃ represents hydrogen, an alkyl group (C ₁ to _{C 9} ), a benzyl group, or a phenyl group that may have a substituent.] If an aminocarboxylic acid represented by A chelate compound is obtained that provides a charge control agent that best meets the objectives of the invention. In addition, the central metal atoms that form chelate compounds include Ni, Co, Zn, Cd, Cu, Fe, Mn, Hg,
Examples include divalent metal atoms such as Pb, among which
Zn, Co, Ni and Cu are preferred, especially Ni, Co,
Zn is most preferably used. The chelate compound represented by the general formula [ ] is
It is synthesized by chelating an aminocarboxylic acid represented by the general formula [ ] by a known method. 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. Next, 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. Examples of aminocarboxylic acids represented by the general formula [] include anthranilic acid, 3-methylanthranilic acid, 3-ethylanthranilic acid, 3-n-butylanthranilic acid, 3-stearylanthranilic acid, 5-methylanthranilic acid, 5-ethylanthranilic acid, 5-isopropylanthranilic acid, 5-tert-butylanthranilic acid, 5-lauryl anthranilic acid, 3,5-dimethylanthranilic acid, 3,5-diethylanthranilic acid, 3,
5-di-butylanthranilic acid, 3-methyl-5
-isopropylanthranilic acid, 3-methyl-5
-tert-butylanthranilic acid, 4-chloroanthranilic acid, 5-chloroanthranilic acid, 5-nitroanthranilic acid, 5-acetomaminoanthranilic acid, 5-sulfamoylanthranilic acid, 3
-amino-2-naphthoic acid, 1-amino-2-naphthoic acid, 7-ethyl-3-amino-2-naphthoic acid, 7-heptyl-3-amino-naphthoic acid,
6-N-methylsulfemoyl-3-amino-2
-naphthoic acid, 8-oxy-3-amino-2-naphthoic acid, 1-aminotetralin-2-carboxylic acid, 2-aminotetralin-3-carboxylic acid, 6
-tert-butyl-1-aminotetralin-2-carboxylic acid, N-methylanthranilic acid, 4-chloro-N-methylanthranilic acid, N-phenylanthranilic acid, N-2,3-xylylanthranilic acid, N -Bezylanthranilic acid, 3-N-methylamino-2-naphthoic acid, 3-N-benzyl-
Examples include amino-2-naphthoic acid and 1-aminoanthraquinone-2-carboxylic acid. Production Example 1 Synthesis of nickel anthranilic acid chelate 54.8 g (0.4 mol) of anthranilic acid was added to a solution of 16 g (0.4 mol) of caustic soda dissolved in 1 part water and completely dissolved. This solution was heated to 80°C. 25.9 g (0.2 mol) of nickel chloride was dissolved in 150 ml of water, and this aqueous solution was gradually added dropwise to the above solution. After the dropwise addition was completed, stirring was continued at 80°C for 1 hour, and then the mixture was cooled to room temperature while stirring. After cooling, it was filtered and washed with water until the pH of the liquid became neutral. After washing with water, it was dried at 90°C. This produces about 65g of pale light blue powder.
I got it. Production Example 2 Synthesis of 5-methylanthranilate zinc chelate 27.3 g (0.2 mol) of zinc chloride was added to 500 ml of ethylene glycol. 5-methylanthranilic acid
60.4 g (0.4 mol) was slowly added to the above solution.
After the addition, stirring was continued for 2 hours at 130°C, and then the mixture was dispersed in water 3. After dispersion, the solution was filtered and washed with water until the pH of the solution became neutral.
After washing with water, it was dried at 90°C. This gave about 40 g of white powder. Production Example 3 Synthesis of N-methylanthranilic acid nickel chelate 23.8 g (0.1 mol) of nickel acetate was added to 500 ml of ethyl cellosolve and stirred. Heat to 50℃,
30.2 g (0.2 mol) of N-methylanthranilic acid was slowly added. After reacting for 2 hours while refluxing at about 130°C, the mixture was dispersed in water 2. After 1 hour, it was filtered and washed with water until the pH of the liquid became neutral. Drying was performed at 90°C. As a result, about 29 g of pale light blue powder was obtained. Production Example 4 Synthesis of N-phenylanthranilic acid cobalt chelate 24.9 g (0.1 mol) of cobalt acetate was added to 500 ml of dimethylformamide and completely dissolved. Heat to 50℃ and add 42.6g of N-phenylanthranilic acid.
(0.2 mol) was added gradually. After reacting for 3 hours while refluxing at about 145°C, heating was stopped.
When cooled to 100℃, disperse in 2 parts of water and 1
After an hour, it was filtered and washed with water. When washing with water, the pH of the liquid is
This was done until it became neutral. Drying was performed at 90°C. This gave about 40 g of a pale reddish-gray powder. Specific examples of the chelate compound represented by the general formula [ ] include the following. Compound example Generally, the aminocarboxylic acid chelate is preferably used in toner preparation as having an average particle size in the range of 10 to 0.01 microns, particularly 2 to 0.1 microns. Aminocarboxylic acid chelate as mentioned above,
The toner of the present invention can be obtained by blending a binder resin and a colorant into a toner (colored fine powder) containing a binder resin and a colorant as essential components. As for the blending form, there is a so-called internal addition form in which the compound is encapsulated in the toner uniformly or in a capsule form, and a so-called internal addition form in which the compound is mixed and attached to the toner.
Any of the so-called externally added forms can be adopted. When internally added, the amount of aminocarboxylic acid chelate used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method, including the dispersion method. Although not limited to, it is preferably 0.1 to 20 parts by weight (more preferably 0.5 to 20 parts by weight) per 100 parts by weight of the binder resin.
10 parts by weight). In addition, when adding externally, to 100 parts by weight of resin,
0.01 to 10 parts by weight is desirable. Note that, if necessary, a conventionally known electrification control agent can also be used in combination with the charge control agent of the present invention. As the binder resin of the toner, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene- Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl 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-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer,
Styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-
Styrenic copolymers such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic ester copolymer; polymethyl methacrylate, Butyl 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
ethylene fluoride, etc.), epoxy resins, polyester resins, styrene-butadiene copolymers (monomer ratio: 5-30:95-70), olefin copolymers (ethylene-acrylic acid copolymers, ethylene-acrylic ester copolymers) polymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenolic resin, Phenol-modified terbene resin. Coloring agents include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, and rose bengal. Conventionally known dyes and pigments such as , triallylmethane dyes, monoazo dyes, disazo dyes and pigments can be used alone or in combination. 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 and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper,
Lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys with metals such as manganese, 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, for example, colloidal silica, titanium oxide,
Examples include fluidity imparting agents such as 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 produce the toner for developing an electrostatic image according to the present invention, the aminocarboxylic acid chelate charge control agent according to the present invention is combined with the binder resin as described above, a pigment or dye as a coloring agent, and optionally a magnetic material. Materials, additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins compatible with each other. Disperse or dissolve, cool and solidify,
By pulverizing and classifying, toner having an average particle size of 5 to 20 μm can be obtained. 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. Furthermore, as described above, the toner of the present invention can also be obtained by externally adding a charge control agent to a toner that has been formed by removing all or part of the charge control agent. Toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means. Effects of the Invention As described above, the toner of the present invention containing an aminocarboxylic acid chelate 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 photosensitive materials and copying machines as described above, as well as problems such as toner aggregation, clumping, and low-temperature fluidity during storage, which were conventionally major problems. It is a toner that can withstand long-term storage without causing any problems, and also has excellent abrasion resistance, fixing properties, and adhesive properties of toner images. 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. Furthermore, since there is little color tone disturbance caused by the charge control agent, it is possible to form color images with excellent colors by using it 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 nickel anthranilate chelate After mixing the above materials well in a blender, 150 parts
The mixture was kneaded using two rolls heated to ℃. After the kneaded material is left to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet air stream, and further classified using an air classifier to obtain fine toner powder with a particle size of 5 to 20μ. Obtained. 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 photoconductor using a conventionally known electrophotographic method, and this is powder developed using the above developer using a magnetic brush method to create a toner image, which is transferred to plain paper. The film was then heat-fixed. The resulting transferred image had a sufficiently high density of 1.24, 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 1.20, 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, when a transferred image was obtained at 15°C and 10% low temperature and humidity, the image density was as high as 1.29, 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 A developer was obtained in the same manner as in Example 1, except that 2 parts of nigrosine dye (Nigrosine Base EX manufactured by Orient Chemical Industry Co., Ltd.) was used instead of 2 parts of nickel anthranilate chelate, and development, transfer, and fixing were carried out. Images were obtained similarly. There was little fogging at room temperature and humidity, but the image density was low at 1.06, line drawings were scattered, and solid blacks were noticeably rough. We investigated the durability and found that the density decreased to 0.8 after printing 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 is thought to be due to the charge control agent changing 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 zinc 5-methylanthranilate chelate was used instead of 2 parts of nickel anthranilate chelate, and an image was obtained in the same manner by carrying out development, transfer and fixing. The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results 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 nickel anthranilate chelate was replaced with 2 parts of nickel anthranilate chelate, and development, transfer, and fixing were carried out. Images were obtained similarly. The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results 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 cobalt 3-lauryl-5-methylanthranilate chelate was used instead of 2 parts of nickel athranilate chelate, and development, transfer, and fixing were carried out in the same manner. Got the image. The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in 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 Anthranilic acid 2 parts of nickel chelate After mixing the above ingredients well in a blender,
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 copier (product name NP-
150Z (manufactured by Canon Inc.) to produce an image, good results almost the same as in Example 1 were obtained. Example 6 In Example 5, 3 parts of N-methylanthranilic acid nickel chelate was used instead of 2 parts of nickel anthranilic acid chelate. 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 Example 5 except that 2 parts of cobalt 3-n-butylanthranilate chelate was used instead of 2 parts of nickel anthranilate chelate.
A developer was obtained in the same manner as above, and an image was obtained in the same manner by performing development, transfer, and fixing. Detailed results are shown in Tables 1 and 2, but Example 5
Almost the same satisfactory results were obtained. Comparative Example 2 A developer was obtained in the same manner as in Example 5, except that 2 parts of benzyl-dimethyl-hexadecyl ammonium chloride was used instead of 2 parts of nickel anthranilate chelate, 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 0.8, line drawings were scattered, and solid black scratches were noticeable. 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 Nickel anthranilate chelate 2 parts The above materials were blended in a blender. 150℃ after mixing well
The mixture was kneaded using two heated rolls. After cooling the kneaded material by natural method, 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 20μ. 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 absorbed so as to almost occlude this, and this 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 station, which is the main magnetic pole, was arranged so that the angle θ between the line connecting it 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 approximately 80 μm thick thus formed is used in the developing section (nearest portion) to face each other at an interval of approximately 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 density was observed, and good images were obtained even after printing up to 30,000 images 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] Examples 9 to 16 The aminocarboxylic acid chelates used in Examples 1 to 8 were, in order, zinc anthranilate chelate (Example 9) and zinc 3,5-di-tertbutylanthranilate chelate (Example 10). ), 3-
Zinc methylanthranilate chelate (Example 11),
3,4-dimethylanthranilic acid nickel chelate (Example 12), zinc anthranilic acid chelate (Example 13), 3,5-di-tert-butylanthranilic acid zinc chelate (Example 14), 3-methylanthranilic acid Examples 1 to 8 were carried out in the same manner as in Examples 1 to 8, except that zinc chelate (Example 15) and zinc anthranilate chelate (Example 16) were used to obtain the results shown in Tables 3 and 4 below, respectively. Examples 17 to 24 The aminocarboxylic acid chelates used in Examples 1 to 8 were respectively converted into Chelate Compound Example 19 (Example 17), Compound Example 20 (Example 18), and Compound Example 21 (Example 19). , Compound example 22 (Example 20), Compound example 19 (Example 21), Compound example 20 (Example 22), Compound example 21 (Example 23), Compound example 19 (Example 24) were carried out. The same procedure as in Examples 1 to 8 was carried out to obtain the results shown in Tables 5 and 6 below.

【table】

【table】

【table】

【table】 [Brief explanation of the drawing]

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)

[Claims] 1. General formula [In the formula, R ₁ , R ₂ , R ₄ , and R ₅ are hydrogen, halogen, nitro group, amino group that may have a substituent, alkyl group (C ₁ to C ₁₈ ), and a substituent. R ₁ and R ₂ and R ₄ and R ₅ represent a sulfamoyl group which may optionally have substituents, or a group forming a ring which may have substituents, R ₃ ,
R ₆ is hydrogen, alkyl group (C ₁ to _{C 9} ), benzyl group,
or represents a phenyl group which may have a substituent, and Me represents a divalent metal. ] A toner for developing an electrostatic image, characterized by containing a chelate compound represented by the following. 2 Chelate-forming metal Me is Zn, Ni, Co and
The toner for developing an electrostatic image according to claim 1, which is any one of Cu.