JPH05134451A - Magnetic toner and magnetic ink - Google Patents

Abstract

PURPOSE:To make a magnetic toner suitable for use in a copying machine with a developing sleeve rotating at a high speed by adding a dehydrogenated compound of a specified ferrocene polymer as a magnetic substance. CONSTITUTION:This magnetic toner contains at least a binding resin and a magnetic substance and this magnetic substance is an org. magnetic substance obtd. by dehydrogenating the principal chain of a ferrocene polymer represented by the formula with an oxidizing agent. In the formula, R is alkyl, aryl, alkenyl, aralkyl or aralkenyl and (n) is the degree of polymn. The ferrocene polymer is a ferrocene/benzaldehyde condensation polymer, a ferrocene/cinnamic aldehyde condensation polymer, a ferrocene/crotonaldehyde condensation polymer, a ferrocene/n-nonylaldehyde condensation polymer, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic toner and a magnetic ink using a magnetic material made of a specific polymer, and more specifically, a magnetic toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like. The present invention relates to a magnetic ink useful for toners, printing, inkjet printers, thermal transfer ribbons, hot melt printers, writing instruments, and the like.

[0002]

2. Description of the Related Art Conventionally, an electrostatic latent image of an electrophotographic photoreceptor (having a photoconductive layer provided on a conductive support) or an electrostatic recording body (having a dielectric layer provided on a conductive support) has been used. As a method of developing an electrostatic latent image formed on an image bearing member, a so-called one-component magnetic toner developing method is known in which development is performed with a developer containing only magnetic toner. In this method, the magnetic force of a magnet provided in a conductive and non-magnetic carrier sleeve holds the conductive magnetic toner on the sleeve, and the relative movement of the sleeve and the magnet causes the magnetic toner on the electrostatic latent image. Carry to
In this state, a conductive path is formed between the conductive support of the electrostatic latent image carrier and the sleeve and the magnetic toner,
This is a method in which the magnetic toner is induced by inducing an electric charge having a polarity opposite to that of the latent image and developing.

Further, in recent years, the conductive toner used in the induction developing method has poor transferability at high humidity, making it difficult to use plain paper. The so-called high resistance triboelectric charging type magnetic toner developing method in which a uniform thin layer is formed on a carrier, and the toner is triboelectrified and the toner is supplied to the latent image carrier to develop the latent image, is the mainstream.

By the way, recently, the developing system using the one-component magnetic toner has been attracting attention because it has advantages of downsizing of the apparatus and low cost. Further, with the development of a multicolor color copy image forming method in recent years, a color developing method using a one-component magnetic toner has also attracted attention. Further, due to the increase in the amount of information in recent years, there has been a strong demand for speeding up of processing in copying machines and printers.

However, in a one-component magnetic toner, an inorganic magnetic material such as ferrite or magnetite is generally used as a magnetic material. However, a toner in which an inorganic magnetic material is dispersed in a binder resin is a toner. There is a problem that it is difficult to achieve uniform dispersion in the particles, and the toner becomes brittle when the toner is stirred in the developing device and in the toner production process. 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 containing 20 to 80% by weight has a high density, poor handleability as a toner, poor agitability in the developing device, and high driving energy. In addition, if the density is high, the centrifugal force of the toner increases when the machine speed is increased, and the phenomenon of toner scattering occurs.

Further, in the case of color development, since the inorganic magnetic material such as ferrite and magnetite is black or dark brown, the conventional one-component system for color composed of the inorganic magnetic material, the binder resin and the colorant is used. The magnetic toner has a problem that the color tone becomes blackish and a clear color image cannot be obtained. That is, even if the coloring agent is added to the binder resin, the color peculiar to the magnetic material cannot be completely hidden. Therefore, it has been proposed to whiten or color the magnetic material (JP-A-51-42539, JP-A-5-4539).
No. 1-46131 and Japanese Patent Laid-Open No. 58-25643) are all insufficient for concealing the color tone of the magnetic material and obtaining an image of the desired color tone.

In order to solve such a drawback, the present inventor has previously used, as a magnetic material, a condensed polycyclic polynuclear aromatic type ferromagnetic resin or poly-bis-2,6-pyridinediylmethylidene methyltridenetrilohexamethylene nitrilomethylic acid. A magnetic toner using an organic magnetic material composed of an organic metal complex such as lidene / iron sulfate or a magnetic toner using a combination of the organic magnetic material and an inorganic magnetic material has been proposed (JP-A-3-33865, JP-A-3-33).
866, JP-A-3-140966, JP-A-3-14
0967). A toner using such an organic magnetic material is lighter in weight and excellent in dispersibility than a toner using an inorganic magnetic material, and thus has the advantage that a clear color image can be obtained without toner scattering. However, it has some drawbacks such as weak magnetic force and poor moldability, and further improvement is desired.

On the other hand, magnetic ink is generally a magnetic material,
It is composed of a vehicle in which a dye, a resin, a dispersion solvent and the like are combined, additives and the like, and is used in oil-based ink, water-based ink, 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 (Japanese Patent Laid-Open No. Sho 5).
9-147217), ink in which a magnetic substance is dispersed in wax (Japanese Patent Laid-Open No. 62-267379), and the like are known.

However, in these magnetic inks, the magnetic substance is ferrite, chromium oxide, Mn-Bi alloy, Mn-A.
Since it is made of a metal oxide such as 1-alloy, Fe-Ni alloy, Sn-Fe alloy, etc., the compatibility between the magnetic substance and the vehicle etc. is poor, and the magnetic substance easily aggregates, resulting in poor dispersibility. In addition, after the image formation, the magnetic ink is dried, and thus cracks are likely to occur.

[0010]

As described above, in the magnetic toner, a magnetic toner having a small density and an excellent dispersibility as well as an excellent magnetic property and a good moldability has not yet been found. In the present situation, no magnetic ink having excellent dispersibility and excellent compatibility between the magnetic substance and the vehicle has been found.

Therefore, an object of the present invention is to provide a magnetic toner and a magnetic material which are uniform and have a low density, improved magnetic properties, and of course a clear color image, and excellent compatibility with vehicles. It is to provide a magnetic ink having good dispersibility.

[0012]

As a result of intensive studies, the present inventor has found that the above object can be achieved by using an organic magnetic material composed of a specific ferrocene polymer as a magnetic material, and completed the present invention. Came to do.

That is, according to the present invention, in a magnetic toner containing at least a binder resin and a magnetic substance, the magnetic substance has the following general formula:

[Chemical 1] (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. And a main component of the ferrocene polymer represented by the formula (1) is dehydrogenated with an oxidizing agent.

Further, according to the present invention, in a magnetic ink containing at least a magnetic substance, a dye and a vehicle,
The magnetic substance has the following general formula

[Chemical 1] (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. And a main component of a ferrocene polymer represented by the formula (1) is dehydrogenated with an oxidizing agent.

First, the magnetic toner of the present invention will be described in detail below. When the conventional inorganic substance is used alone as the magnetic substance, the dispersibility of the magnetic substance is poor because the toner material other than the magnetic substance (and the external additive) is an organic material, and as a result, the toner particles are dispersed among the toner particles. Variations in magnetic properties and electrical properties are likely to occur. Moreover, the toner tends to be crushed during the production process and stirring in the developing device, and the density of the magnetic material is high, so that the toner has a high density and there is a problem in handleability.

However, by using the ferrocene polymer as the magnetic material, the toner material can be made of an organic material, and the toner can have a uniform structure. Furthermore, since the density of the ferrocene polymer is usually 1.1 to 1.8 g / cm ^3, it is lighter than the inorganic magnetic material, and as a result, the weight of the toner can be reduced.

The ferrocene polymer is, for example, COPN, which is a high-molecular magnetic material proposed by the present inventors.
Stronger magnetism than A (condensed polycyclic polynuclear aromatic) type ferromagnetic resin, and superior in moldability compared to poly-bis-2,6-pyridinediylmethylidene nitrilohexamethylene nitrilomethylidene / iron sulfate. ing.

The ferrocene polymer used as a magnetic material in the present invention has the following general formula:

[Chemical 1] (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. ) Is obtained by dehydrogenating the main chain of the ferrocene polymer represented by the formula (1) with an oxidizing agent. Although it is known that the ferrocene polymer is useful as an organic magnetic substance, the ferrocene polymer used in the present invention is
The polymer main chain has been subjected to dehydrogenation treatment with an oxidant, and particularly has ferromagnetism.

Specific examples of the ferrocene polymer include ferrocene / benzaldehyde condensation polymer dehydrogenation compound, ferrocene / cinnamic aldehyde condensation polymer dehydrogenation compound, ferrocene / crotonaldehyde condensation polymer dehydrogenation compound, ferrocene / n-nonylaldehyde condensation polymer. Examples thereof include dehydrogenated compounds. The content of the magnetic material made of the ferrocene polymer in the toner is preferably 15 to 80% by weight.

The toner containing the ferrocene polymer has a higher magnetic force than the toner containing the COPNA resin, but has a lower magnetic force than the toner containing the inorganic magnetic material. Therefore, also in the present invention, when the ferrocene polymer magnetic material and the inorganic magnetic material are used together as the magnetic material, the inorganic magnetic material secures a sufficient magnetic force as the magnetic toner, and the ferrocene polymer magnetic material impairs the magnetic force. Therefore, it is possible to reduce the weight of the toner, and as a result, it is possible to obtain a toner that is light in weight, excellent in uniform dispersibility, and has high magnetic properties.

In this case, the inorganic magnetic material used in combination means
A ferromagnet or a ferromagnet that exhibits ferrimagnetism.
Ferromagnetic materials include oxides of Fe, Ni, Co and their alloys, CrO _{2 and the} like, and ferrimagnetic materials include spinel type ferrites (MnFe ₂ O ₄ , Fe ₃ O ₄ , γ-F).
e ₂ O ₃ , NiZnFe ₄ O ₈ , ZnFe ₂ O _{4 and the} like), garnet (Y ₃ Fe ₆ O _{12 and the} like) and the like, respectively.

The weight ratio of the organic magnetic material to the inorganic magnetic material is 95: 5 to 60:40, preferably 90:10.
~ 70: 30. If the usage ratio is less than 95: 5, the background stain is likely to occur, and if it exceeds 60:40, the density of the toner is high and the handleability as a toner is the same as when the inorganic magnetic material is used alone. Not only is it worse, the agitation property in the developing machine is also poor, the driving energy is also increased, and further, toner scattering tends to occur when the machine speed is increased, which is not preferable. The content of these magnetic substance mixtures in the toner is 5 to 80% by weight, preferably 20 to 60% by weight.

As the binder resin for forming the toner of the present invention, all known binder resins can be used. For example, polystyrene, styrene-styrene copolymers such as styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / maleic acid copolymer, styrene / maleic acid ester copolymer, polymethylmethacrylate, polybutylmethacrylate, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in admixture of two or more.

Further, the toner of the present invention can of course contain a colorant, and all the pigments and dyes conventionally used as colorants for toner can be applied. Specifically, carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, chalco oil blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, phthalocyanine green, hand yellow G, rhodamine 6C lake, Examples include chrome yellow, quinacridone, benzidine yellow, malachite green, malachite green hexalate, oil black, azo oil black, rose bengal, monoazo dyes and pigments, disazo dyes and pigments, trisazo dyes and pigments, and mixtures thereof.

Also in the case of color development, in the toner of the present invention, if the ferrocene polymer magnetic material and the inorganic magnetic material are used in combination, the toner is lightweight and excellent in uniform dispersion and has high magnetic properties. It is preferable because a toner can be obtained.

In the toner of the present invention, if necessary, a charge control agent for controlling the charge of the toner, a fluidizing agent such as colloidal silica, a metal oxide such as titanium oxide or aluminum oxide, or carbonization. An abrasive such as silicon, a lubricant such as a fatty acid metal salt and the like can be contained.

Next, the magnetic ink of the present invention will be described in detail. Also in the magnetic ink, when a conventional inorganic material is used as the magnetic material, the compatibility with the vehicle or the like is poor as described above, and therefore the magnetic material easily aggregates and the dispersibility is poor. As a result, there is a problem that cracks are likely to occur after the magnetic ink is dried after image formation.

However, as described above, the magnetic ink of the present invention has the following general formula as a magnetic substance.

[Chemical 1] (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. Since an organic magnetic material obtained by dehydrogenating the main chain of the ferrocene polymer represented by the formula (1) is used with an oxidizing agent, the above problems can be solved.

That is, in the magnetic ink of the present invention, by using the ferrocene polymer magnetic material, the entire ink composition can be composed of an organic material, and as a result,
Good compatibility and dispersibility of magnetic material with vehicle,
With this magnetic ink, a clear image can be obtained.
Further, in the present invention, since the magnetic substance is a resin,
In the case of oil-based ink or the like, the magnetic material can also serve as the resin component in the vehicle, and it is possible to provide an oil-based magnetic ink that does not necessarily require the resin component in the vehicle. In this case, the compatibility and dispersibility of the magnetic substance with respect to the vehicle and the like are further improved, the ink composition is simplified, and the ink preparation process is simplified.

Specific examples of the ferrocene polymer used as a magnetic substance in the magnetic ink of the present invention include ferrocene / benzaldehyde condensation polymer dehydrogenation compounds and ferrocene / cinnamic aldehyde condensation polymer dehydrogenation compounds as in the case of magnetic toners. , Ferrocene / crotonaldehyde condensation polymer dehydrogenation compound, ferrocene / n
-Nonyl aldehyde condensation polymer dehydrogenation compounds and the like.

The magnetic ink of the present invention using the above magnetic material is manufactured as an oil-based, water-based or hot-melt ink.

For example, in the case of an oil-based magnetic ink, a composition comprising a vehicle in which a magnetic material, a pigment, an oil, a resin, a dispersion solvent and the like are combined, and an additive are obtained. 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
Examples include FR, carbon black, aniline black, titanium oxide, tartrazine lake, rhodamine 6G lake, methyl violet lake, basic 6G lake, brilliant green lake, and nigrosine.

The vehicle is composed of oil, resin, dispersion solvent and the like. Specific examples of the oil include linseed oil, shinai oil, soybean oil, castor oil, dehydrated castor oil, lysovarnish, maleated oil, vinylated oil. Examples include oils, urethane oils, machine oils, spindle oils, and the like. As the resin, rosin, shellac, copal, dammar, gilsonite,
Zein, lime rosin, ester gum, phenolic resin,
Xylene resin, urea resin, melamine resin, ketone resin,
Coumaron / indene resin, petroleum resin, terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, acrylic resin, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol,
Examples thereof include polyvinyl butyral, chlorinated polypropylene, styrene resin, epoxy resin, polyurethane, and cellulose derivative. Further, as described above, the ferrocene polymer-based magnetic material can also be used as the resin component.

As the dispersion 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, etc. are mentioned.

Examples of the additives include waxes, dryers, dispersants, wetting agents, crosslinking agents, stabilizers, thickeners, gelling agents, defoamers and photopolymerization initiators.

In the case of hot melt magnetic ink,
It is obtained with a composition consisting of a magnetic material, a pigment, 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, petrolatum, polyethylene wax,
Chlorinated paraffin, fatty acid amide, phenyl salicylate,
Examples thereof include triphenyl phosphate, n-heptyl p-hydroxybenzoate, and dicyclohexyl phthalate. Specific examples of the dye and the additive include the same as in the case of the oil-based magnetic ink.

Further, the aqueous magnetic ink can be obtained by a composition comprising a vehicle in which a magnetic material, a dye, a resin, a water-solubilizing agent, a cosolvent, water and the like are combined, and an additive. In this case, as a specific example of the dye, the same one as in the case of the oil-based magnetic ink can be mentioned.

Specific examples of the resin include starch, dextrin, alginate, cellulose ester, polyvinyl alcohol, polyacrylamide, polyethylene oxide, shellac, styrenated shellac, rosin maleic acid resin, casein, acrylic copolymer, vinyl acetate resin. Resin, vinyl chloride resin, synthetic rubber latex, polyurethane, polyester, alkyd resin, rosin ester,
An epoxy ester etc. are mentioned. As the water-solubilizing agent, ammonia water, monoethanolamine, monoisopropanolamine, ethylmonoethanolamine,
Diethyl ethanol amine, dimethyl ethanol amine, morpholine and the like can be mentioned, and as the cosolvent,
Examples thereof include ethyl alcohol, isopropyl alcohol, ethyl acetate, methyl ethyl ketone and the like.

As the additive, petroleum wax,
Examples include abrasion resistance improvers such as polyethylene wax, nonionic activators, and defoamers such as silicones and alcohols.

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 magnetically, and it can be used for printing certificates, tickets, etc., printing banknotes, secret documents, etc., or for maintaining information. You can also Further, since the magnetic material has good compatibility with resin and the like, it has good dispersibility and does not cause cracks or the like after printing. Moreover, in the case of oil-based magnetic ink, the resin component in the vehicle is not necessarily required, so the compatibility and dispersibility are further improved, the ink composition is simplified, and the preparation process can be simplified.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The parts and% shown below are based on weight.

Reference Example 1 (Synthesis of ferrocene / cinnamic aldehyde condensation polymer)
200 g of ferrocene, 80 g of cinnamic aldehyde, 25.8 g of anhydrous ferric chloride and N, N-dimethylformamide 1
50 ml was mixed and heated to 140 ° C. with stirring under a nitrogen stream. Next, 100 g of cinnamic aldehyde dissolved in 375 ml of xylene was added dropwise over 1 hour. Water generated by the reaction with xylene was distilled out of the system by azeotropic distillation. The temperature was further raised to 150 ° C. and the reaction was carried out for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, and the resulting resin was separated by filtration and purified.
281 g of a brown resin (yield 86.5%) was obtained. The infrared absorption spectrum of this resin is shown in FIG.

Reference Example 2 (Dehydrogenation Synthesis of Ferrocene / Cinnamic Aldehyde Condensation Polymer Magnetic Material ... 1) 10 g of the ferrocene polymer obtained in Reference Example 1 and 6 g of benzoquinone were sufficiently dissolved in 100 ml of N, N-dimethylformamide. Then, using a high-pressure mercury lamp (UM-102 manufactured by Ushio Inc.), light irradiation was carried out for 12 hours under stirring in an argon stream. After the light irradiation, the sample solution was purified by reprecipitation with methanol to obtain 9.0 g of a magnetic substance resin (yield 90.0%). The infrared absorption spectrum of this resin is shown in FIG.

Reference Example 3 (Dehydrogenation Synthesis of Ferrocene / Cinnamic Aldehyde Condensation Polymer Magnetic Material ... 2) 10 g of the ferrocene polymer obtained in Reference Example 1 and 2,3 dichloro-5,6-dicyano-p
-12.6 g of benzoquinone was sufficiently dissolved in 1500 ml of N, N-dimethylformamide, and under an argon stream, 1
The mixture was heated under reflux for 2 hours. Then, the sample solution was reprecipitated and purified with methanol to obtain 7.3 g of the magnetic resin (yield 73
%) Was obtained.

Example 1 Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Ferrocene polymer magnetic material obtained in Reference Example 2 50 parts Carbon black 5 parts Mixture of the above composition After thoroughly stirring and mixing with a Henschel mixer, the mixture was heated and melted at 130 to 140 ° C. for 30 minutes with a roll mill, and this was cooled to room temperature. This kneaded product is crushed and classified to have a particle size of 5 to 10 μm and a density of 1.1 g / cm ^3.
Toner was obtained.

When this toner was put in Mylicopy M-10 (manufactured by Ricoh Co., Ltd.) and an image was formed, a clear image was obtained. Further, even if the toner was put into a machine in which this copying machine was improved to a speed of 50 sheets / minute, the toner was not scattered.

Example 2 Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Ferrocene polymer magnetic material obtained in Reference Example 2 100 parts Magnetite (inorganic magnetic material) 10 parts Carbon Black 5 parts The mixture having the above composition was sufficiently stirred and mixed by a Henschel mixer, and then heated and melted at 130 to 140 ° C. for 30 minutes by a roll mill, and this was cooled to room temperature. This kneaded product is crushed and classified to have a particle size of 5 to 10 μm and a density of 1.4 g / cm ^3.
Toner was obtained.

When an image was formed using this toner in the same manner as in Example 1, a clear image was obtained.
Further, when this toner was put in a machine with improved speed as in Example 1, no toner scattering occurred.

Example 3 Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Ferrocene polymer magnetic material obtained in Reference Example 2 100 parts C.I. I. Pigment Brown 3 2 parts The mixture having the above composition was sufficiently stirred and mixed by a Henschel mixer, and then heated and melted at 130 to 140 ° C. for 30 minutes by a roll mill and cooled to room temperature. This kneaded product is crushed and classified to have a particle size of 5 to 10 μm and a density of 1.1 g / cm ^3.
Toner was obtained.

When this toner was put in Mylicopy M-10 (manufactured by Ricoh Company) and an image was formed, a clear brown image was obtained.

Comparative Example 1 Styrene / n-butylmethacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Magnetite 150 parts After thoroughly stirring and mixing the mixture having the above composition with a Henschel mixer, 130-roll mill. It was heated and melted at 140 ° C. for 30 minutes and cooled to room temperature. This kneaded product is crushed and classified to have a particle size of 5 to 10 μm and a density of 2.2 g / cm ^3.
Toner was obtained.

When an image was formed using this toner in the same manner as in Example 1, a clear image was obtained.
However, when this toner was put into a machine in which the speed was improved to 50 sheets / minute as in Example 1, the toner was scattered and contamination inside the machine was observed.

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

An image was formed using this toner in the same manner as in Example 3. As a result, a clear brown image was obtained because the toner contained a nearly colorless inorganic magnetic material. 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 4 Aniline black 25% Xylene resin 20% Machine oil 30% Toluene 13% Candelilla wax 5% Soybean oil fatty acid 2% Ferrocene polymer magnetic material obtained in Reference Example 2 5% The above components are mixed and dispersed. Thus, an oily magnetic ink was obtained.

When printing was performed using the obtained ink,
The obtained printed matter was a clear and very good image, and magnetically readable.

Example 5 Phthalocyanine blue 3.5% n-Heptyl p-hydroxybenzoate 92.5% Ferrocene polymer magnetic substance 4.0% obtained in Reference Example 2 After sufficiently mixing and dissolving the above components A hot melt magnetic ink was obtained by filtration with a membrane filter.

When an ink-jet printer was used to print with the obtained ink, the obtained printed matter was clear and
It was a very good image. Also, magnetic reading was possible.

Example 6 Laked C 15.0% Shellac aqueous varnish 60.0% Polyethylene wax 4.0% Water 15.5% Silicone 0.5% Ferrocene polymer magnetic substance obtained in Reference Example 2 5.0% The above components were mixed to obtain an aqueous magnetic ink. (Note that
The composition of the above shellac aqueous varnish is 33% shellac, 2% diethylethanolamine, 13% ethanol, 5% water.
2%. )

When printing was carried out using the obtained ink,
The resulting print was clear, had a very good image and was magnetically readable.

Example 7 Carbon black 30% Ferrocene polymer magnetic substance obtained in Reference Example 2 15% Lysovarnish 30% Xylene 15% Candelilla wax 7% Soybean oil fatty acid 3% The above components were mixed and dispersed to prepare an oily magnetic ink. Obtained.

When printing was carried out using the obtained ink,
The obtained printed matter was a clear and very good image, and magnetically readable.

[0063]

The magnetic toner according to the first aspect of the present invention has the following excellent effects because it has a constitution in which a specific ferrocene polymer magnetic material is mixed in the binder resin. (A) Each component is uniformly mixed in the toner particles, the density is low, and it is hard to be brittle. (B) Therefore, it can be suitably used for a high speed developing sleeve rotary type copying machine.

Further, since the magnetic toner of claim 2 has a composition in which the mixture of the ferrocene polymer magnetic material and the inorganic magnetic material is blended, the following outstanding effects are added. (C) Sufficient magnetic force as a magnetic toner is secured.

Furthermore, the magnetic toner according to claim 3 is the color developing toner in which the ferrocene polymer-based magnetic material or a mixture of the magnetic material and the inorganic magnetic material is blended. The added effect is added. (D) It is possible to obtain a color image that can clearly show the color of the coloring material.

Further, the magnetic ink of claim 4 has the following outstanding effects because it has a composition in which the ferrocene polymer magnetic material is mixed. (E) Since the compatibility of the magnetic material with the resin is good, the dispersibility of the magnetic material is good. (F) A clear and good image can be obtained without causing cracks or the like after printing. (G) The printed matter obtained by using the magnetic ink can be read magnetically and can be used for printing certificates, tickets, etc., printing banknotes, adding information such as secret documents, and for maintenance.

Furthermore, in the oil-based magnetic ink of claim 5, the ferrocene polymer magnetic material also serves as the resin in the vehicle, so the compatibility and dispersibility are further improved, the ink composition is simplified, and the preparation process is also simplified. The effect of being added is added.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of a ferrocene polymer obtained in Reference Example 1.

FIG. 2 is an infrared absorption spectrum diagram of a ferrocene polymer-based magnetic material obtained in Reference Example 2.

Claims (5)

[Claims] 1. In a magnetic toner containing at least a binder resin and a magnetic material, the magnetic material has the following general formula: (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. ) A magnetic toner comprising an organic magnetic material obtained by dehydrogenating the main chain of a ferrocene polymer represented by the formula (1). 2. The magnetic toner according to claim 1, wherein the magnetic material is a mixture of the organic magnetic material and the inorganic magnetic material. 3. A magnetic toner containing at least a binder resin, a magnetic substance and a colorant, wherein the magnetic substance is the one according to claim 1. 4. A magnetic ink containing at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance has the following general formula: (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. ) A magnetic ink comprising an organic magnetic material obtained by dehydrogenating the main chain of a ferrocene polymer represented by the formula (1). 5. In an oil-based magnetic ink containing a vehicle in which at least a magnetic substance, a dye and an oil, a resin, a dispersion solvent and the like are combined, the magnetic substance and resin are represented by the following general formula: (In the formula, R is an alkyl group, an aryl group, an alkenyl group,
Represents an aralkyl group or an alkenyl group, and n
Represents the degree of polymerization. ) An oil-based magnetic ink comprising an organic magnetic material obtained by dehydrogenating the main chain of a ferrocene polymer represented by the formula (1).