JPH1083903A - Organometallic composite magnetic material, and magnetic toner and magnetic ink using magnetic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reproducibility and dispersibility by separating at least a part of metals in organometallic complex from the complex, and dispersing the metal as uniform fine particles having a specific diameter in the organometallic complex and its residue. SOLUTION: In the complex magnetic material, at least a part of metals in the organometallic complex is separated from the complex and dispersed, as uniform fine particles having a diameter of 100nm or less, in the organometallic complex and its residue. As the metals of the organometallic complex, transition metals such as Fe, Co, Ni, Mn and Cr, or rare earth metals are employed. Further, as the organic metal, a tetraazaporphyrin derivative represented by formula I or a porphyrin derivative represented by formula II (in this formula, M denotes a mixture of one or more materials selected from metals and metallic compounds, and A denotes an organic residue selected from formula II which may include a substituent, two hydrogen atoms, or a bond) is employed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic-metal composite magnetic material useful as a magnetic material, and a magnetic toner and a magnetic ink using the same. More specifically, the present invention relates to an organic-metal composite magnetic material in which metal fine particles are dispersed in an organic material, and a magnetic toner and a magnetic ink using the same.

[0002]

2. Description of the Related Art As a technique related to the composite of a metal material and an organic material, for example, there is a surface treatment of carbon fiber with a metal. This is, as typified by the description in JP-A-60-16805, by using a solution or dispersion of metal ions, metal fine particles or ceramic fine particles, dipping the carbon fiber into the solution, and then drying and heat-treating. It is obtained.

Further, as represented by Japanese Patent Application Laid-Open No. 60-155715, a method is known in which a metal salt is formed on a functional group on the surface of carbon fiber, followed by heat treatment. Also, a method of dipping in an electroplating solution or an electroless plating solution, a method of applying a plating solution to fibers by spraying (Japanese Patent Application Laid-Open No. 60-119269), and a method of further coating a metal material, (Cryogenics 1) by vapor deposition or sputtering using as an evaporation source
984 24.636) are also known.

[0004] All of the above methods aim at improving the wettability at the interface between the matrix and the fiber when the carbon fiber and the plastic are combined.

It is also known to carry out the same treatment as described above for the purpose of activating the surface of carbon fiber, activated carbon, activated carbon fiber or the like, thereby depositing metal fine particles on the surface.

[0006] In each of these, a metal is deposited near the surface of carbon, and it is difficult to say that the composite material is a uniform composite of an organic material and a metal. When the organic-metal composite material is applied to a conductive material, a magnetic material, or the like having a bulk function, a material in which carbon and metal are uniformly dispersed is required.

For the production and application of metal fine particles, see JP-A-2-300205, JP-A-2-284966,
JP-A-1-252514, JP-A-3-296918
And Japanese Patent Application Laid-Open No. 63-133601 are typical, but none of them have achieved excellent dispersibility because of their large particle size.

Attempts have been made to combine such materials, especially those using iron as the metal. For example, a method in which a monomer mixture of vinylferrocene and divinylbenzene or a mixed polymer of vinylferrocene and polydivinylbenzene is heat-treated at high pressure (J. Meter. Sc)
i. , 18.2811), but in this case, there are drawbacks such as formation of spheres, problems in homogeneity, and poor yield.

Also, a method of condensing acetylferrocene and furfural [Chem. Lett. . 277 (1
974), ibid. 843 (1972)] or a method of condensing and curing vinylferrocene and furfuryl alcohol, followed by heat treatment [Amorphous Magnetism]
In Plenua (1973)], it ignites in the air thermally and over time, and there remains a major problem in terms of stability. At the same time, since the crystal structure of carbon, which is a matrix component, hardly develops, no sufficient graphite layer is formed, which is not suitable for applications such as conductive materials.

[0010] On the other hand, as for the metal component to be dispersed, research has been advanced only on particularly stable ferrocene type.

Although magnetic materials are used in a wide range of fields, one of the uses is magnetic toner. The magnetic toner is an electrostatic latent image carrier such as an electrophotographic photosensitive member (a photoconductive layer provided on a conductive support) or an electrostatic recording member (a dielectric layer provided on a conductive support). This is used as a developer in a one-component magnetic toner developing method, which is one of the methods for developing the electrostatic latent image formed thereon.

In this developing method, the conductive magnetic toner is held on the sleeve by a magnetic force of a magnet provided in a conductive and non-magnetic carrier sleeve, and the magnetic toner is statically moved by a relative motion between the sleeve and the magnet. It is carried on an electrostatic latent image, and in this state, a conductive path is formed between the conductive support of the electrostatic latent image carrier, the sleeve and the magnetic toner, and the magnetic toner is charged with a charge having a polarity opposite to that of the latent image. This is a method of induction and development. In recent years, the conductive toner used in the induction development method has poor transferability at high humidity and makes it difficult to use plain paper. A so-called high-resistance friction-charging type magnetic toner developing method of forming a uniform thin layer, frictionally charging the toner, supplying the toner to a latent image carrier, and developing the latent image, is mainly used.

[0013] Recently, the development method using this one-component magnetic toner has attracted attention because of the advantages of miniaturization and low cost of the apparatus. A color development system using a one-component magnetic toner has also attracted attention. In addition, due to an increase in the amount of information in recent years, there is a strong demand for faster processing in copiers and printers.

One of uses of the magnetic material is a magnetic ink. Magnetic inks are generally magnetic, pigmented,
It is composed of a vehicle, an additive, and the like in which a resin and a dispersion solvent are combined, and is used for an oil-based ink, a water-based ink, a hot melt ink, and the like. For example, an ink in which a magnetic substance is colloidally dispersed in an organic solvent such as kerosene or glycerin or water (JP-A-59-14)
No. 7217), an ink in which a magnetic substance is dispersed in wax (Japanese Patent Application Laid-Open No. 62-267379) and the like are known.

However, in the one-component magnetic toner, an inorganic magnetic material such as ferrite or magnetite is generally used as the magnetic material. However, a toner in which the inorganic magnetic material is dispersed in a binder resin is used. There is a problem that it is difficult to achieve uniform dispersion in the particles, and it becomes brittle at the time of stirring the toner in the developing device and in the process of producing the toner. In addition, ferrite, inorganic magnetic material such as magnetite, the density of a generally 3 g / cm ³ or more, particularly those used in the magnetic toner to a 5-6 g / cm ^3, the inorganic magnetic material The toner contained in the toner in an amount of 20 to 80% by weight has a high density, poor handling properties as a toner, poor stirring properties in a developing device, and high driving energy. In addition, when the density is high, the centrifugal force of the toner increases when the machine is operated at high speed, and a phenomenon called toner scattering occurs.

Usually, the magnetic ink is made of a metal oxide such as ferrite, chromium oxide, Mn-Bi alloy, Mn-Al alloy, Fe-Ni alloy, Sn-Fe alloy, etc. Poor compatibility between body and vehicle, etc., magnetic material is likely to aggregate, and dispersibility is poor. In addition, cracks are likely to occur after the magnetic ink dries after image formation. Further, the magnetic ink is difficult to color because the color of the inorganic magnetic material is dark (for example, black, black brown, brown, etc.),
There is a problem that the colors of pigments and dyes are not directly reflected.

[0017]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a stable organic-metal composite magnetic material exhibiting extremely good reproducibility and dispersibility and exhibiting ferromagnetism. Furthermore,
An object of the present invention is to provide a uniform, low density, good handleability as a toner, and good stirring properties in a developing device,
Moreover, it is an object of the present invention to provide a magnetic toner capable of obtaining a good image without occurrence of a toner scattering phenomenon, and to provide a magnetic ink in which a magnetic substance is excellent in compatibility with a vehicle or the like and has good dispersibility. .

[0018]

According to the present invention, first, at least a part of the metal in the organometallic complex is released from the complex, and the organometallic complex and its residue are formed as uniform fine particles having a particle size of about 10 nm. An organic-metal composite magnetic material characterized by being dispersed therein is provided. Secondly, there is provided the organic-metal composite magnetic material according to the first aspect, which is obtained by heat-treating a tetraazaporphyrin derivative represented by the following general formula [I] or a porphyrin derivative represented by the following general formula [II]: Is done.

Embedded image (Wherein, M is selected from the group consisting of metals and metal compounds, and these metals or metal compounds may be only one type or a mixture of two or more types.
May have a substituent

Embedded image An organic residue selected from the group consisting of two hydrogen atoms or a bond. )

Embedded image (In the formula, M and A are the same as described above.) Third, the metal in the metal complex or the M is Fe, C
The organic-metal composite magnetic material according to the first or second aspect is a metal selected from the group consisting of o, Ni, Mn, Cr, and a rare earth metal. Fourth, the substituent is a halogen atom, an alkyl group, an alkoxy group, an amino group, a nitro group, an aryl group, a carboxylic acid group, a carboxylic ester group, an aralkyl group, an alkenyl group, an aryloxy group, an alkylthio group or an arylthio group. The organic-metal composite magnetic material according to the second aspect is provided. Fifthly, there is provided the organic-metal composite magnetic material according to the second aspect, wherein the heat treatment is performed in a vacuum at a temperature of 500 ° C. or more. Sixth, in a magnetic toner containing at least a binder resin and a magnetic material, the magnetic material is made of the organic-metal composite magnetic material described in the first, second, third, fourth or fifth. A featured magnetic toner is provided. Seventh, in a magnetic ink containing at least a magnetic substance, a dye and a vehicle, the magnetic substance is the first,
A magnetic ink comprising the organic-metal composite magnetic material described in the second, third, fourth or fifth aspect is provided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. In the organic-metal composite magnetic material of the present invention, at least a part of the metal in the organometallic complex is released from the complex, and the particle size is 10
It is characterized in that it is dispersed in the organometallic complex and its residue as uniform fine particles of about nm. That is, since at least a portion of the metal in the complex is released from the complex and dispersed in the complex and its residues as uniform fine particles, the organic compound exhibits extremely good reproducibility, good dispersibility, and ferromagnetic stability.
It becomes a metal composite magnetic material.

The metal in the organometallic complex may be any metal capable of forming a complex, such as Fe, Co, Ni, M
Transition metals such as n and Cr or rare earth metals are preferred.

Further, typical examples of the organic metal include a tetraazaporphyrin derivative represented by the following general formula [I] and a porphyrin derivative represented by the following general formula [II].

Embedded image

Embedded image (Wherein, M is selected from the group consisting of metals and metal compounds, and these metals or metal compounds may be only one type or a mixture of two or more types.
May have a substituent

Embedded image An organic residue selected from the group consisting of two hydrogen atoms or a bond. )

It should be noted that A in the general formulas [I] and [II]
Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an amino group, a nitro group, an aryl group, a carboxylic acid group, a carboxylic ester group, an aralkyl group, an alkenyl group, an aryloxy group, an alkylthio group and an arylthio group. Can be

The organic-metal composite magnetic material of the present invention is obtained by subjecting the above-mentioned organometallic complex, for example, a tetraazaporphyrin derivative represented by the general formula [I] or a porphyrin derivative represented by the general formula [II] to heat treatment. Is obtained by That is, the organometallic complex is placed in a vacuum (for example, 0.
(1 torr or less), heat treatment is performed to release at least a part of the metal in the organometallic complex from the complex, and disperse the organometallic complex and its residue as fine metal particles having a particle size of about 10 nm.

Next, the heat treatment for obtaining the organic-metal composite magnetic material will be described. The heat treatment reaction referred to here is a so-called decomposition reaction, and by performing the heat treatment in a gas phase in a closed system, the yield of the target magnetic material is improved and the magnetic properties are improved. Further, by maintaining the reaction system in a vacuum, the heat treatment reaction can be performed at around 500 ° C. The heat treatment reaction time is at least 1 hour, preferably at least 3 hours, particularly preferably at least 5 hours.

In the following, a specific example will be described. For example, metal tetraazoporphyrin is added to a reaction vessel (see FIG. 1) in an amount of 0.1.
The organic-metal composite magnetic material can be obtained by enclosing while maintaining a vacuum of about 01 torr, controlling the temperature (600 ° C.), and performing a heat treatment reaction for 5 hours.
In FIG. 1, 1 indicates an organometallic complex, 2 indicates a reaction vessel (made of Pyrex glass), and 3 indicates a furnace. The heat treatment temperature is 500 ° C. or more, preferably 600 ° C. or more, and particularly preferably 700 ° C. or more. The value of the saturation magnetization of the obtained material can be freely controlled by the heat treatment reaction temperature. Heat treatment temperature can be selected. FIG. 2 shows the relationship between the heat treatment temperature of iron phthalocyanine and the value of the saturation magnetization.

Next, the magnetic toner of the present invention will be described in detail. The magnetic toner of the present invention is a magnetic toner containing at least a binder resin and a magnetic material, wherein the magnetic material is the organic-metal composite magnetic material of the present invention.

When a conventional inorganic substance is used alone as a magnetic substance, the dispersibility of the magnetic substance is poor because the toner material other than the magnetic material (and external additives) is an organic material. Variations in magnetic properties and electrical properties tend to occur between particles. In addition, the toner is easily broken during the production process and agitation in the developing device, and the density of the magnetic material is high, so that the toner becomes high in density, and there is a problem in handleability and the like.

However, by using the organic-metal composite magnetic material of the present invention as the magnetic material, the toner material can be composed of an organic material, and the toner can have a uniform composition. Moreover, the density of the organic-metal composite magnetic material is lighter than that of the inorganic magnetic material, so that the weight of the toner can be reduced.

In the toner of the present invention, the content of the magnetic substance comprising the organic-metal composite magnetic material in the toner is as follows:
It is preferable that the content be 15 to 80% by weight. Moreover, it is also possible to mix with an inorganic magnetic material as needed.

As the binder resin constituting the toner of the present invention, those which have been used as a binder resin for a toner can be basically applied. Specifically, polystyrene,
Styrene such as polychloroethylene, polyvinyltoluene and the like and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, 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-chloromethacrylic acid Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Styrene-based copolymers such as polymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride,
Polyvinyl acetate, polyethylene, polypropylene, polyester, polyvinyl butyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, Examples thereof include paraffin waxes, which may be used alone or in combination of two or more. Here, the range of the molecular weight, the molecular weight distribution, the degree of crosslinking and the like of each resin is determined so that the melt viscosity of the toner becomes a predetermined value.

In the toner of the present invention, a colorant can be incorporated in addition to imaging the color of the organic-metal composite magnetic material itself, and it has been conventionally used as a colorant for toner. All pigments and dyes apply. Specifically, carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, calco oil blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, phthalocyanine green, hand yellow G, rhodamine 6C lake, Chrome yellow, quinacridone, benzidine yellow, malanaide green, Hansa yellow G, malachide green hexalate, oil black, azo oil black, rose bengal, monoazo dye, pigment disazo, pigment trisazo 4,
Quaternary ammonium salts, metal salts of salicylic acid and salicylic acid derivatives, and mixtures thereof.

Further, in the case of color development, the organic-metal composite magnetic material and the inorganic magnetic material can be used in combination in the toner of the present invention.

Further, the toner of the present invention may contain a charge controlling agent for controlling the charge of the toner, a fluidizing agent such as colloidal silica, a metal oxide such as titanium oxide and aluminum oxide, a carbonized An abrasive such as silicon and a lubricant such as a fatty acid metal salt can be contained.

Next, the magnetic ink of the present invention will be described in detail. The magnetic ink of the present invention is a magnetic ink containing a magnetic substance, a dye, and a vehicle, wherein the magnetic substance is made of the organic-metal composite magnetic material.

When a conventional inorganic substance is used as the magnetic substance in the magnetic ink, the compatibility with the vehicle or the like is poor as described above, and therefore, the magnetic substance is easily aggregated and the dispersibility is poor. As a result, there is a problem that cracks are likely to occur after the magnetic ink dries after the image is formed.

However, in the magnetic ink of the present invention, as described above, since the organic-metal composite magnetic material is used as a magnetic material, the entire ink composition can be composed of an organic material. As a result, the compatibility between the magnetic material and the vehicle is good, the dispersibility of the magnetic material is excellent, the coloring is easy, the color is vivid, and an excellent image can be obtained with the present magnetic ink. .

The magnetic ink of the present invention using the above magnetic material is produced as an oily, aqueous or hot melt ink.

For example, in the case of an oil-based magnetic ink, it is obtained with a composition comprising a vehicle in which a magnetic substance, a dye, an oil, a resin, a dispersion solvent and the like are combined, and additives. In this case, specific examples of the dye include Fast Yellow G, Hansa Brilliant Yellow 5GX, Disazo Yellow AAA,
Naphthol red HFG, lake red C, benzimidazolone carmine HF3C, dioxazine violet, phthalocyanine blue, indakotron blue, phthalocyanine green, benzimidazolone brown H
FR, carbon black, aniline black, titanium oxide, tartrazine lake, rhodamine 6G lake, methyl violet lake, basic 6G lake, brilliant green lake, nigrosine and the like.

The vehicle is composed of oil, resin, dispersing solvent, etc. Specific examples of oil include linseed oil, soybean oil, soybean oil, castor oil, dehydrated castor oil, lysovarnish, maleated oil, and vinylated oil. Oil, urethane oil, machine oil, spindle oil and the like. In addition, as the resin, rosin, shellac, copal, dammar, gilsonite,
Zein, lime rosin, ester gum, phenolic resin,
Xylene resin, urea resin, melamine resin, ketone resin,
Coumarone / indene resin, petroleum resin, terpene resin, cyclized rubber, chloride rubber, alkyd resin, polyamide resin, acrylic resin, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol,
Examples include polyvinyl butyral, chlorinated polypropylene, styrene resin, epoxy resin, polyurethane, and cellulose derivatives.

As the dispersing solvent, n-hexane,
n-heptane, toluene, xylene, methyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, diethylene glycol, glycerin, methyl cellosolve, carbitol, ethyl acetate,
Acetone, methyl ethyl ketone and the like can be mentioned.

The additives include a wax, a dryer, a dispersant, a wetting agent, a crosslinking agent, a stabilizer, a thickener, a gelling agent, a defoaming agent, and a photopolymerization initiator.

In the case of hot melt magnetic ink,
It is obtained with a composition comprising a magnetic substance, a dye, a hot melt vehicle and additives. In this case, specific examples of the hot melt vehicle include carnauba wax, beeswax,
Anhydrous lanolin, paraffin wax, montan wax, ozokerite, ceresin, vaseline, polyethylene wax,
Paraffin chloride, fatty acid amide, phenyl salicylate,
Examples include triphenyl phosphate, n-heptyl p-hydroxybenzoate, dicyclohexyl phthalate, and the like. Specific examples of the dye and the additive include those similar to those of the oil-based magnetic ink.

In the case of an aqueous magnetic ink, it is obtained with a composition comprising a vehicle and a combination of a magnetic substance, a dye, a resin, a water-solubilizing agent, a co-solvent, water and the like. In this case, specific examples of the dye include those similar to those of the oil-based magnetic ink.

Specific examples of the resin include starch, dextrin, alginate, cellulose ester, polyvinyl alcohol, polyacrylamide, polyethylene oxide, shellac, styrenated shellac, rosin maleic resin, casein, acrylic copolymer, and vinyl acetate-based resin. Resin, vinyl chloride resin, synthetic rubber latex, polyurethane, polyester, alkyd resin, rosin ester,
Epoxy esters and the like can be mentioned. In addition, as a water-solubilizing agent, ammonia water, monoethanolamine, monoisopropanolamine, ethyl monoethanolamine,
Diethylethanolamine, dimethylethanolamine, morpholine and the like, and as a cosolvent,
Ethyl alcohol, isopropyl alcohol, ethyl acetate, methyl ethyl ketone and the like can be mentioned.

The additives include petroleum wax,
Examples of the agent include a friction resistance improver such as polyethylene wax, a nonionic activator, and a defoamer such as silicone and alcohol.

The magnetic ink thus obtained can be used for ink jet printers, thermal transfer, hot melt printers, writing instruments, and the like. Moreover,
A magnetic signal can be added by the contained magnetic material, and can be read by a magnetic head, and a certificate,
It can also be used for printing a magnetic card such as a ticket, printing a bill, adding information such as a secret document, or maintaining information. The printing at that time can be colorized. Further, since the magnetic material has good compatibility with a resin or the like, the magnetic material has good dispersibility and does not cause cracks or the like after printing.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 Using the reaction system shown in FIG. 1, 10 parts of purified iron (II) phthalocyanine was sealed, and the system was evacuated to 0.01 torr. This was heat-treated at 600 ° C. for 5 hours, and after completion of the reaction, was gradually cooled to room temperature to obtain a sample. This sample was a ferromagnetic material. FIG. 3 shows the magnetic field dependence of the magnetization at room temperature, and FIG. 4 shows the ESR spectrum. FIG. 5 shows a view of the sample observed with an electron microscope. As can be seen from FIG. 5, the size of the iron fine particles is uniformly dispersed at around 10 nm.

Examples 2 to 15 Samples were obtained using the organometallic complexes shown in Table 1 at the temperature shown in Table 1 under the same conditions as in Example 1 except for the above conditions. Table 1 shows the saturation magnetization of the obtained sample.

[0050]

[Table 1] Note) Pc: phthalocyanine Por: porphyrin Nc: naphthalocyanine

Example 16 (Magnetic Toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound (organic-metal composite magnetic material) obtained in Example 1 50 parts 5 parts of carbon black After sufficiently stirring and mixing the mixture having the above composition with a Henschel mixer, the mixture was heated and melted at 130 to 140 ° C. for 30 minutes with a roll mill, and then cooled to room temperature. The kneaded product was pulverized and classified to obtain a toner having a particle size of 4 to 5 μm and a density of 1.2 g / cm ³ .

When this toner was put into Myricopy M-10 (manufactured by Ricoh Company) and an image was formed, a clear image was obtained. Even when toner was put into a machine in which this copying machine was improved at a speed of 50 sheets / minute, toner scattering did not occur.

Example 17 (Magnetic Toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts 100 parts of the compound (organic-metal composite magnetic material) obtained in Example 1 Magnetite (inorganic magnetic material) 10 parts Carbon black 5 parts After the mixture having the above composition was sufficiently stirred and mixed by a Henschel mixer, the mixture was heated and melted at 130 to 140 ° C. for 30 minutes by a roll mill, and cooled to room temperature. The kneaded product was pulverized and classified to obtain a toner having a particle size of 4 to 5 μm and a density of 1.4 g / cm ³ .

When an image was formed using this toner in the same manner as in Example 16, a clear image was obtained. Further, even when this toner was put in a machine whose speed was improved in the same manner as in Example 16, no toner was scattered.

Comparative Example Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Yttrium iron garnet (inorganic magnetic material) 100 parts I. Pigment Brown 2 parts After the mixture having the above composition was sufficiently stirred and mixed with a Henschel mixer, the mixture was heated and melted at 130 to 140 ° C. for 30 minutes with a roll mill, and then cooled to room temperature. This kneaded material is pulverized and classified, and has a particle size of 5 to 10 μm and a density of 1.6 g / cm ^3.
Was obtained.

Using this toner, an image was formed in the same manner as in Example 17. As a result, the toner contained a nearly colorless inorganic magnetic material, so that a clear brown image was obtained. The density was as high as 1.6 g / cm ^3, and the toner was pulverized during development, causing toner scattering and image stains.

Example 18 (Magnetic color toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound (organic-metal composite magnetic material) obtained in Example 1 100 Part The mixture having the above composition was sufficiently stirred and mixed with a Henschel mixer, and then heated and melted at 130 to 140 ° C. for 30 minutes using a roll mill, and then cooled to room temperature. The kneaded product was pulverized and classified to obtain a toner having a particle size of 4 to 5 μm and a density of 1.2 g / cm ³ .

When this toner was placed in Myricopy M-10 (manufactured by Ricoh Company) and an image was formed, an extremely clear blue image was obtained.

Example 19 (Magnetic ink) Phenol resin 25 parts Spindle oil 30 parts Toluene 13 parts Carnauba wax 5 parts Soybean oil fatty acid 2 parts Compound (organic-metal composite magnetic material) obtained in Example 1 5 parts Above The components were mixed and dispersed to obtain an oil-based magnetic ink.

When printing was performed on art paper using the obtained ink, the obtained printed matter was a clear and very good red image, and could be read by a magnetic head.

[0061]

According to the organometallic composite magnetic material of the present invention, at least a part of the metal in the organometallic complex is released from the complex, and the organometallic complex and its residue are formed as uniform fine particles having a particle size of about 10 nm. Because it was dispersed in the concrete, specifically, those obtained by heat treatment of the tetraazaporphyrin derivative represented by the general formula (I) or the porphyrin derivative represented by the general formula (II) As a result, the following outstanding effects are achieved. (B) It is possible to provide a magnetic material with good reproducibility, in which the metal released from the organometallic complex is well dispersed in the form of fine particles in the system, exhibits ferromagnetism at room temperature, and retains magnetic properties that can withstand practical use. it can. (B) In the heat treatment of the organometallic complex, the magnetic properties (saturation magnetization) can be arbitrarily controlled by changing the heat treatment reaction temperature.

The magnetic toner according to the sixth aspect has the following excellent effects because it is configured to contain the organic-metal composite magnetic material according to the first to fifth aspects. (A) Since each component is uniformly blended in the toner particles, the density is low, the brittleness does not easily occur, and there is no scattering property, so that the handleability as a toner is good. (B) Therefore, it can be suitably used for a high-speed rotating developing sleeve rotary copying machine. (C) When used for color development, it is possible to obtain a color image in which the color of the coloring material or the organometallic complex itself can be clearly produced.

The magnetic ink according to the seventh aspect has the following excellent effects because it is configured to contain the organic-metal composite magnetic material according to the first to fifth aspects. (D) For printing, for ink jet printer, for thermal transfer,
It can be used for hotment printers, writing instruments, and the like. (E) Colorization is possible. (F) Since the compatibility between the magnetic material and the resin or the like is good, the dispersibility of the magnetic material is good. (G) A clear and very good image is obtained without cracks or the like after printing. (H) The printed matter obtained by using the magnetic ink can be read by a magnetic head, and can be used for printing of certificates, tickets, etc., printing of banknotes, addition of information such as secret documents, and maintenance. .

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a heat treatment reaction system.

FIG. 2 is a graph showing a relationship between a heat treatment temperature of iron phthalocyanine and a saturation magnetization.

FIG. 3 is a graph showing the magnetic field dependence of the magnetization of a heat-treated body of iron phthalocyanine at 600 ° C.

FIG. 4 ESR of heat-treated iron phthalocyanine at 600 ° C.
It is a spectrum diagram.

FIG. 5 is a diagram obtained by observing a heat-treated body of iron phthalocyanine at 600 ° C. with an electron microscope.

Claims (7)

[Claims] 1. An organic-metal, wherein at least a part of the metal in the organometallic complex is released from the complex and dispersed in the organometallic complex and its residue as uniform fine particles having a particle size of 100 nm or less. Composite magnetic material. 2. The organic-metal composite magnetic material according to claim 1, which is obtained by heat-treating a tetraazaporphyrin derivative represented by the following general formula [I] or a porphyrin derivative represented by the following general formula [II]. Embedded image (Wherein, M is selected from the group consisting of metals and metal compounds, and these metals or metal compounds may be only one type or a mixture of two or more types.
May have a substituent: An organic residue selected from the group consisting of two hydrogen atoms or a bond. ) (In the formula, M and A are the same as described above.) 3. The method according to claim 1, wherein the metal or M in the metal complex is F
3. The organic-metal composite magnetic material according to claim 1, which is a metal selected from the group consisting of e, Co, Ni, Mn, Cr and rare earth metals. 4. The method according to claim 1, wherein the substituent is a halogen atom, an alkyl group, an alkoxy group, an amino group, a nitro group, an aryl group,
Carboxylic acid group, carboxylic acid ester group, aralkyl group,
The organic-metal composite magnetic material according to claim 2, which is an alkenyl group, an aryloxy group, an alkylthio group, or an arylthio group. 5. The organic-metal composite magnetic material according to claim 2, wherein the heat treatment is performed in a vacuum at a temperature of 500 ° C. or more. 6. A magnetic toner containing at least a binder resin and a magnetic material, wherein the magnetic material comprises the organic-metal composite magnetic material according to claim 1, 2, 3, or 5. . 7. A magnetic ink containing at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance is
A magnetic ink comprising the organic-metal composite magnetic material according to 2, 3, 4, or 5.