JPH05267042A - Organic magnetic material, manufacture thereof and magnetic toner containing said material and magnetic ink - Google Patents

Abstract

PURPOSE:To obtain a stable organic magnet material, which is synthesized easily has excellent reproducibility and displays ferromagnetism, by composing an organic magnetic material of a condensation polymer having specific ferrocene polymer structure. CONSTITUTION:A condensation polymer having ferrocene polymer structure shown in formula (R<1> and R<2> represent a hydrogen atom or an alkyl group respectively and (n) the degree of polymerization and an integer of one or more) is dissolved into N,N-dimethylformamide. Potassium-t-butoxyd is charged to the solution, agitated at room temperature and reacted. A reaction mixture is poured into water, agitated, filtered, purified and decompression-dried, thus acquiring a red-orange-colored solid. A magnetic hysteresis curve is obtained regarding the solid acquired. Accordingly, magnetism can be displayed at room temperature, thus obtaining excellent magnetizing characteristics. The magnetic material can be formed and film-formed easily.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic magnetic material, a method for producing the same, a magnetic toner and a magnetic ink using the magnetic material, and more specifically, a ferrocene polymer having ferromagnetism, a method for producing the same, and a method for producing the same. Useful for magnetic toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. using the polymer and for printing, inkjet printer, thermal transfer ribbon, hot melt printer, writing instrument, etc. Regarding magnetic ink.

[0002]

2. Description of the Related Art Magnetic materials include permanent magnets, high magnetic permeability materials, constant magnetic permeability materials, magnetostrictive materials, etc. in the acoustic field, electric / electronic field, automobile field, medical field, communication field, magnetic recording field, etc. Widely used in the field of. In particular, organic magnetic materials have advantages such as low density, good dispersibility in a binder resin, and many white or light-colored ones, as compared with inorganic magnetic materials, and their development has attracted attention in recent years. .. As the organic magnetic material, for example, a black powdery polymer [Nature, produced by heating or irradiating with ultraviolet rays 1,4-bis (2,2 ′, 6,6′-tetramethyl-1-oxyl) butaine] 326 , 370 (1987)], 1,
Black insoluble polymer obtained by polymerizing 3,5-triaminobenzene with iodine [Synth. Metal, 19 , 7
09 (1987)] and the like.

Magnetic materials are used in a wide range of fields as described above, and one of the uses thereof is magnetic toner. The magnetic toner is an electrostatic latent image carrier such as an electrophotographic photoreceptor (a conductive support provided with a photoconductive layer) or an electrostatic recording body (a conductive support provided with a dielectric layer). It is used as a developer in the one-component magnetic toner developing method which is one of the methods for developing the electrostatic latent image formed on the above.

In this developing method, the conductive magnetic toner is held on the sleeve by the magnetic force of the magnet provided in the conductive and non-magnetic carrier sleeve, and the magnetic toner is statically moved by the relative movement of the sleeve and the magnet. 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, and the magnetic toner is charged with an electric charge having a polarity opposite to that of the latent image. It is a method of inducing and developing. 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.Therefore, the toner has a high resistance and is applied to the toner carrier by the layer thickness regulating member. The so-called high-resistance triboelectrification type magnetic toner developing method in which a uniform thin layer is formed and triboelectrified and the toner is supplied to a latent image carrier to develop the latent image is so-called.

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

One of the uses of magnetic materials is magnetic ink. Magnetic ink is generally a magnetic substance, a pigment,
It is composed of a vehicle in which a resin and a dispersion solvent 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 (JP-A-59-14).
7217), ink in which a magnetic material is dispersed in wax (Japanese Patent Laid-Open No. 62-267379), and the like are known.

[0007]

However, any of the above-mentioned organic magnetic materials is difficult to synthesize, has a problem of reproducibility, has an extremely low temperature for exhibiting magnetism, or has a problem in that it does not exist in air. There is a problem such as stability.

Further, in the one-component magnetic toner, an inorganic magnetic material such as ferrite or magnetite is generally used as a magnetic material, but the toner in which the 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 magnetic ink, the magnetic substance is usually made of a metal oxide such as ferrite, chromium oxide, Mn-Bi alloy, Mn-Al alloy, Fe-Ni alloy, Sn-Fe alloy, etc. The compatibility between the body and the vehicle, etc. is poor, and the magnetic material easily aggregates, resulting in poor dispersibility. In addition, after the image formation, the magnetic ink is dried, and thus cracks are likely to occur. Furthermore, since the color of the magnetic ink of the magnetic ink is dark (for example, black, dark brown, brown, etc.), coloring is difficult,
There is a problem that the colors of pigments and dyes are not reflected as they are.

Accordingly, an object of the present invention is to provide a stable organic magnetic material exhibiting ferromagnetism, which is easy to synthesize, has good reproducibility, and a method for producing the same. Further, an object of the present invention is to obtain a good image which is uniform and has a low density, has good handleability as a toner, has good agitation property in a developing device, and does not cause a toner scattering phenomenon. Another object of the present invention is to provide a magnetic toner capable of achieving the above, and to provide a magnetic ink in which a magnetic material has excellent compatibility with a vehicle and the like and has good dispersibility and which does not impair the color of a dye.

[0011]

The present inventor has completed the present invention as a result of extensive studies to achieve the above object. That is, according to the present invention, the following general formula [I]

[Chemical 1] (In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group, and n represents an integer of 1 or more in terms of the degree of polymerization.)
An organic magnetic material comprising a condensation polymer having a ferrocene polymer structure represented by (Claim 1).
Will be provided.

According to the present invention, the following general formula [II]

[Chemical 2] (Wherein R ¹ represents a hydrogen atom or an alkyl group) and the following general formula [III]

[Chemical 3] (In the formula, R ² represents a hydrogen atom or an alkyl group, and R ³ represents an alkyl group) and is reacted with a benzenephosphonic acid ester represented by the above general formula [I]. A method for producing a condensation polymer (claim 2) is provided.

Further, according to the present invention, in a magnetic toner containing at least a binder resin and a magnetic substance, the magnetic substance is composed of a condensation polymer represented by the general formula [I]. (Claim 3) is provided, and in a magnetic ink containing at least a magnetic substance, a dye and a vehicle, the magnetic substance comprises a condensation polymer represented by the general formula [I]. Claim 4) is provided.

A condensation polymer having a ferrocene polymer structure represented by the above general formula [I] according to the present invention (hereinafter, referred to as
It may be simply referred to as a ferrocene polymer), depending on the purpose of use, it can be used in the form of powder, as a molded product of an appropriate shape, or in the form of being applied to a support (molding and film formation are It is very useful because it has a wide range of applications such as magnetic tapes, magneto-optical memories, and magnetic shielding materials.

First, the organic magnetic material of the present invention and the method for producing the same will be described in detail below. The ferrocene polymer according to the present invention has a structural unit represented by the general formula [I], and the polymer comprises a dicarbonyl compound represented by the general formula [II] and a benzenephosphonic acid represented by the general formula [III]. Obtained by reaction with an ester.

In the above general formulas [I] and [II], R
¹ represents either a hydrogen atom or an alkyl group, and specific examples of the alkyl group include, for example, a methyl group, an ethyl group and n.
-Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like can be mentioned. Among them, hydrogen atom and methyl group are preferable because of easy production. Further, in the general formulas [I] and [III], R ² represents either a hydrogen atom or an alkyl group, and among them, a hydrogen atom or a methyl group is preferable because of easy production. Further, in the above-mentioned general formula [III], R ³ represents an alkyl group, but an ethyl group is particularly preferable because it is easy to produce.

The reaction of the dicarbonyl compound represented by the general formula [II] with the benzenephosphonic acid ester represented by the general formula [III] is carried out in the presence of a base in a polar solvent from room temperature to the boiling point of the solvent used. It can be performed in a temperature range. In this case, examples of the base used include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium-t-butoxide, sodium amide, sodium hydride, potassium hydride, lithium diisopropylamide, n-butyl. Examples thereof include lithium, and it is particularly preferable to use potassium-t-butoxide.

Examples of the reaction solvent include alcohol solvents such as methanol and ethanol, ether solvents such as diethyl ether, ethylene glycol dimethyl ether, dioxane and tetrahydrofuran, aromatic solvents such as benzene, toluene and xylene, N, N-dimethylformamide, dimethylsulfoxide and the like can be used, and the use of N, N-dimethylformamide is particularly preferable.

In the reaction, the dicarbonyl compound represented by the general formula [II], the equivalent carbonyl compound represented by the general formula [III], the equivalent or excess equivalent of the base and the solvent are mixed at the same temperature at a predetermined temperature. The reaction is carried out, or first, the benzenephosphonate ester represented by the general formula [III] is dissolved in a solvent, and then the base and the dicarbonyl compound represented by the general formula [II] are sequentially added, followed by reaction at a predetermined temperature. .. After completion of the reaction, it is poured into a large amount of water and the obtained solid is collected, or the obtained solid is dissolved in any organic solvent and fractionated, and the organic solvent is distilled off to give a compound of the general formula [I] An organic magnetic material having a ferrocene polymer structure represented by can be obtained in high yield.

Specific examples of the organic magnetic material having a ferrocene polymer structure represented by the general formula [I] in the present invention obtained as described above include those having the structural units shown in Table 1. The invention is not limited to these.

[0021]

[Table 1]

Next, the magnetic toner of the present invention will be described in detail. 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, as the magnetic substance, the above-mentioned general formula [I] is used.
By using the ferrocene polymer represented by
The toner material can be composed of an organic material, and the toner can have a uniform structure. Moreover,
The density of the ferrocene polymer is usually 1.1 to 1.8.
Since it is g / cm ^3, it is lighter than the inorganic magnetic material, and as a result, the weight of the toner can be reduced.

In the toner of the present invention, the content of the magnetic substance composed of the ferrocene polymer in the toner is 15
It is preferable that the content be ˜80% by weight.

The toner containing the ferrocene polymer has a lower magnetic force than the toner containing the inorganic magnetic material. Therefore, 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 ensures a sufficient magnetic force as a magnetic toner, and the ferrocene polymer magnetic material does not impair the magnetic force and is lightweight. This is very preferable because it is possible to obtain a toner which is excellent in uniform dispersibility and has high magnetic properties while being lightweight.

In this case, the inorganic magnetic material used together is a ferromagnetic material exhibiting ferromagnetism or ferrimagnetism. Examples of the ferromagnetic material include Fe, Ni, Co and alloys thereof,
An oxide such as CrO ₂ is a spinel type ferrite (MnFe ₂ O ₄ , Fe ₃ O ₄ , γ-Fe ₂ ) as a ferrimagnetic material.
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 may of course contain a colorant, and all the pigments and dyes conventionally used as colorants for toner are 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.

Since the ferrocene polymer magnetic material is used in the present invention, a clear color image can be obtained even when the toner of the present invention is used as a color one-component magnetic toner. As the colorant for forming the toner of the present invention for color development, all known colorants can be used. Examples of yellow colorants include chrome yellow, benzidine yellow,
Hansa yellow, naphthol yellow, quinoline yellow, etc. can be used. As the magenta colorant, for example, Rhodamine 6G lake, Watching Red, Rose Bengal, Rhodamine B or the like can be used. Examples of cyan colorants that can be used include phthalocyanine blue, methylene blue, victorian blue, aniline blue, and ultramarine blue.

Also in the case of color development, in the toner of the present invention, when the ferrocene polymer magnetic material and the inorganic magnetic material are used in combination, the toner is lightweight and excellent in uniform dispersibility 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, in the magnetic ink of the present invention, as described above, since the ferrocene polymer represented by the general formula [I] is used as the magnetic material, the entire ink composition is composed of an organic material. As a result, the compatibility between the magnetic substance and the vehicle is good, the dispersibility of the magnetic substance is also excellent, the coloring is easy, and a vivid color is exhibited. Obtainable.

The magnetic ink of the present invention using the above magnetic material is produced 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 and an additive in which a magnetic material, a pigment, an oil, a resin, a dispersion solvent and the like are combined is 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.

The dispersion solvent is 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, cross-linking 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.

In the case of an aqueous magnetic ink, a composition comprising a vehicle and an additive in which a magnetic material, a dye, a resin, a water-solubilizing agent, a cosolvent, water and the like are combined is obtained. 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 additives, 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 by a magnetic head, a certificate,
It can also be used for printing magnetic cards such as tickets, printing banknotes, adding information such as secret documents, or maintaining information. The printing at that time can be colorized. 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.

[0045]

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.

Example 1 (Synthesis of a Condensation Polymer Having a Ferrocene Polymer Structure of Specific Example) 0.24 g (1 mmol) of 1,1′-ferrocene dicarboxaldehyde (R ¹ = H) and P-benzenephosphonate ester (R ² = H, R ³ = C ₂ H ₅ ) 0.3
8 g (1 mmol) was dissolved in N, N-dimethylformamide, and 0.36 g of potassium-t-butoxide was dissolved therein.
(3 mmol) was added, and the mixture was stirred at room temperature and reacted for 6 hours. Then, the reaction mixture was poured into 300 ml of water, stirred, filtered, purified and dried under reduced pressure to give a red-orange solid.
31 g was obtained.

The elemental analysis values of the obtained compound were as follows. The calculated value is C ₂₀ H ₁₆ Fe. The infrared absorption spectrum of this compound is shown in FIG. When the obtained solid was measured for magnetization, a hysteresis curve as shown in FIG. 2 was obtained.

Example 2 (Synthesis of a Condensation Polymer Having a Ferrocene Polymer Structure of Specific Example) m-Benzenephosphonate (R ² =
H, R ³ = C ₂ H ₅ ) 0.38 g (1 mmol) was added to N, N
-Dissolved in dimethylformamide, there potassium-t
-Butoxide 0.36 g (3 mmol) was added at room temperature. After stirring for a while, a solution of 0.24 g (1 mmol) of 1,1′-ferrocene dicarboxaldehyde (R ¹ = H) in N, N-dimethylformamide was added dropwise. After completion of dropping, the mixture was stirred for 7 hours to cause a reaction. Then, the reaction mixture was poured into 300 ml of water, stirred, and then filtered and purified,
It was dried under reduced pressure to obtain 0.29 g of a reddish orange solid.

The elemental analysis values of the obtained compound were as follows. The calculated value is C ₂₀ H ₁₆ Fe. The infrared absorption spectrum of this compound is shown in FIG. Further, when the magnetization of the obtained solid was measured, a hysteresis curve as shown in FIG. 4 was obtained.

Example 3 (Magnetic toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound obtained in Example 1 (organic magnetic material) 50 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 by a roll mill at 130 to 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 1.2 g / cm ^3.
Toner was obtained.

When this toner was put into Mylicopy M-10 (manufactured by Ricoh Company) 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 4 (Magnetic toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound obtained in Example 2 (organic magnetic material) 100 parts Magnetite (inorganic) (Magnetic substance) 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 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 3, a clear image was obtained.
Further, when this toner was put into a machine with improved speed as in Example 3, the toner was not scattered.

Example 5 (Magnetic color toner) Styrene / n-butyl methacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound obtained in Example 1 (organic magnetic material) 100 parts Rhodamine 6G Lake 2 parts After thoroughly 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 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 1.2 g / cm ^3.
Toner was obtained.

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

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 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 5. As a result, the toner was a mixture of a nearly colorless inorganic magnetic material, so a clear brown image was obtained, but the toner 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 6 (Magnetic ink) Lake red C 20 parts Phenolic resin 25 parts Spindle oil 30 parts Toluene 13 parts Carnauba wax 5 parts Soybean oil fatty acid 2 parts Compound obtained in Example 1 (organic magnetic material) 5 parts The above components were mixed and dispersed to obtain an oily 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.

Example 7 (Magnetic Ink) Naphthol Red HFG 15.0 parts Shellac aqueous varnish 60.0 parts Polyethylene wax 4.0 parts Water 15.5 parts Silicone 0.5 parts The compound obtained in Example 2 (organic) Magnetic Material) 5.0 parts 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 performed using the obtained ink,
The obtained printed matter was clear and had a very good red image, which could be read by the magnetic head.

Example 8 (magnetic ink) Lake Red C 3.5 parts n-heptyl p-hydroxybenzoate 92.5 parts Compound (organic magnetic material) obtained in Example 1 4.0 parts After sufficiently stirring, mixing and dissolving, a membrane filter was used for filtration to obtain a hot melt magnetic ink.

When printing was performed using the obtained ink,
The resulting print was clear and had a very good red image. In addition, reading with a magnetic head was also possible.

[0064]

The organic magnetic material according to claim 1 has the ferrocene polymer structure represented by the general formula [I], exhibits magnetism at room temperature, and has good magnetization characteristics. Moreover, since the magnetic material of the present invention is easily molded and formed into a film, it can be used in the form of powder or as a suitable molded product, or in a form coated on a support, depending on the purpose of use.
It can be used very effectively in a wide range of applications such as magnetic tapes, magneto-optical memories, and magnetic shielding materials.

Further, since the production method of claim 2 is a reaction of a dicarbonyl compound having a ferrocene group and a benzenephosphonate, according to this method, the compound of the general formula [I ] It is possible to obtain a condensation polymer represented by the above formula, and this method can be said to be an industrially extremely advantageous method.

Further, the magnetic toner according to claim 3 has the following outstanding features because it has a constitution in which an organic magnetic material comprising a condensation polymer having a ferrocene polymer structure represented by the general formula [I] is blended. Produce an effect. (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 rotating developing sleeve rotary copying machine. (C) When used for color development, a color image can be obtained in which the color of the coloring material can be clearly produced. Further, since the magnetic ink according to claim 4 has a constitution in which an organic magnetic material made of a condensation polymer having a ferrocene polymer structure represented by the general formula [I] is blended, the following excellent effects are exhibited. .. (D) For printing, ink jet printer, thermal transfer,
It can be used for hot-ment printers, writing instruments, etc. (E) Colorization is possible. (F) Since the compatibility of the magnetic material with the resin is good, the dispersibility of the magnetic material is good. (G) A crack and the like do not occur after printing, and a clear and very good image can be obtained. (H) Prints obtained using this magnetic ink can be read by a magnetic head, and can be used for printing certificates, tickets, etc., printing banknotes, adding information such as secret documents, and for maintenance. ..

[Brief description of drawings]

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

2 shows a magnetic hysteresis curve of a condensation polymer having a ferrocene polymer structure obtained in Example 1. FIG.

FIG. 3 is an infrared absorption spectrum diagram of a condensation polymer having a ferrocene polymer structure obtained in Example 2.

FIG. 4 shows a magnetic hysteresis curve of a condensation polymer having a ferrocene polymer structure obtained in Example 2.

Claims (4)

[Claims] 1. The following general formula [I]: (In the formula, R ¹ and R ² each represent a hydrogen atom or an alkyl group, and n represents an integer of 1 or more in terms of the degree of polymerization.)
An organic magnetic material comprising a condensation polymer having a ferrocene polymer structure represented by: 2. The following general formula [II]: (In the formula, R ¹ represents a hydrogen atom or an alkyl group) and a dicarbonyl compound represented by the following general formula [III]: (In the formula, R ² represents a hydrogen atom or an alkyl group, and R ³ represents an alkyl group.) A benzenephosphonic acid ester represented by the above formula is reacted. I] A method for producing a condensation polymerization product. 3. A magnetic toner containing at least a binder resin and a magnetic substance, wherein the magnetic substance comprises the condensation polymer represented by the general formula [I] according to claim 1. 4. A magnetic ink containing at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance comprises the condensation polymer represented by the general formula [I] according to claim 1.