JPH08241809A - Organic magnetic material,its manufacturing process,magnetictoner containing it and magnetic ink - Google Patents

Abstract

PURPOSE: To provide an organic magnetic material having good reproducibility and exhibiting ferromagnetism at room temperatures by a simple synthesis method, by coupling an alkaline metal with a specified tetraazaporphyrin derivative or porphyrin derivative. CONSTITUTION: An alkaline metal is coupled with a tetraazaporphyrin derivative expressed by a formula I or a porphyrin derivative expressed by a formula II. In the formula I, M is selected from the group consisting of two hydrogens, a diamagnetic metal, or a compound of diamagnetic metal. Although the diamagnetic metal or compound of diamagnetic metal may be only one type, a mixture of two or more types may also be used. A is an aromatic nucleus forming base that may have a substituent and can contain nitrogen at 1, 4 level. Reaction to be carried out is so-called doping, and annealing is subsequently carried out, if necessary. The ratio of the alkaline metal to the tetraazaporphyrin derivative to be used for the reaction is not more than 6, preferably 1 to 4, in terms of mol ratio.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymeric metal complex and a method for producing the same. Magnetic materials are widely used as permanent magnets, high magnetic permeability materials, and magnetostrictive materials in many fields such as acoustic materials, electric machines, electronic fields, automobile fields, medical fields, communication fields, and magnetic recording fields. In particular, organic magnetic materials have advantages such as a lower density, better dispersibility in binder resin, and many white or light-colored materials, as compared with inorganic magnetic materials. Attention has been paid. The organic magnetic material of the present invention is particularly useful as a magnetic toner.

The present invention further relates to a magnetic toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like using the polymer metal complex and for printing, inkjet printer, thermal transfer ribbon, The present invention relates to a magnetic ink useful for hot melt printers, writing instruments and the like.

In addition to the above-mentioned application examples, this material is
It can be applied to ultra-high frequency devices, absorbers, shields and filters, and magnetic control devices.

For example, 1,4 bis (2,2 ', 6,6'-tetramethyl-1oxyl) butadiyne obtained by the study of Korshak et al. Was heated or irradiated with ultraviolet rays to obtain a black powder polymer [Nature 3
26 370 (1987)], a black insoluble polymer obtained by polymerizing 1,3,5-triaminobenzene with iodine according to the research of Torrance [Synth. Meta
1, 19 709 (1987)], polycarbene by the study of Iwamura et al. (Chemical Society of Japan, 1987, No. 459).
5) and the like have been reported as organic ferromagnets. However, all of them are difficult to synthesize, there is a problem in reproducibility, only a few percent of ferromagnetism is expressed, the temperature of magnetism is extremely low, it is unstable in air. The important issues required for practical magnetic materials, such as occurrences, remain unsolved.

Also, Otani et al. Have disclosed an organic magnetic material composed of a condensed polycyclic aromatic resin (COPNA) prepared from a condensed polycyclic aromatic compound using p-xylylene glycol as a linking agent, as disclosed in JP-A-62-521. In addition, the organic magnetic material made of a thermosetting resin having a higher heat resistance is proposed in the above-mentioned technology by substituting benzaldehyde or benzenedialdehyde for p-xylylene glycol. Kaisho 62-28208
Proposed as No. 0. It is said that ferromagnetism appears at room temperature, but the reproducibility was very poor because the polymer structure was not clearly understood.

Also in the metal complex system, Japanese Patent Laid-Open No. 4-7.
4193, J. Am. Chem. Soc. , 11
0, 782 (1988) and J. Chem. So
c. Chem. Commun. , 642 (1988)
As described above, a polynuclear metal complex of different metal alternating sequence type having a chain structure of one or more dimensions is synthesized.

On the other hand, Grigorian of the present inventor has reported that metal phthalocyanine doped with an alkali metal exhibits magnetism [Materials Scie].
nce vol. XIV, No. 14, P121,
1988].

Further, JP-A-1-118515, JP-A-1-96215, JP-A-1-96216, JP-A-1-99217, JP-A-2-55765, and JP-A-6-15615.
3-205666, JP-A-1-277251, JP-A-1-277252, JP-A-1-277253, JP-A-4-191091 and Solid State Physical Vol.
18, No. 5 (1983) and the like, poly (2,6-
Magnetic material pyridinediyl methylidene nitrilo hexamethylene nitrilase Lome Chile Den) (PPH substantially) the PPH-H ₂ SO ₄ as the polymer complex salt reacted with ferrous sulfate in a polymer called also been synthesized.

Further, by utilizing a tetraazaporphyrin derivative used as a part of the structure of the compound of the present invention, a magnetic substance or a charge transfer type of a polytetraazaporphyrin iron complex is disclosed in JP-A-62-192383. Attempts have also been made to construct magnetic materials [Adv. Mater. , 498 (199
2)]. However, none of them has a Curie temperature lower than that of the magnetic material of the present invention, and those having ferromagnetism at room temperature have very poor reproducibility and are not practical.

The magnetic material is used in a wide range of fields as described above, and one of its uses is a 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. The toner is carried on the electrostatic latent image, and 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, so that the magnetic toner is charged with a 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 development 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 triboelectric charging 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 a mainstream method.

By the way, recently, a developing system using this 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 a 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 has been 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, 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 (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.

[0014]

As described above, in a system in which ferromagnetism is exhibited with good reproducibility, the temperature is limited to a low temperature, the synthesis method is complicated, and ferromagnetism is exhibited at room temperature. In the system, it is a fact that an organic magnetic material for practical use has not yet been obtained due to extremely poor reproducibility.

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 obtained by dispersing the inorganic magnetic material 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, is poor in handleability as a toner, is poor in agitating property in the developing device, and is also high in 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 is formed, the magnetic ink is dried and then cracks are likely to occur. Furthermore, since the magnetic ink has a dark color of the inorganic magnetic material (for example, black, black brown, brown, etc.), coloring is difficult,
There is a problem that the colors of pigments and dyes are not reflected as they are.

In order to solve the above problems, the present inventors have proposed Japanese Patent Application No. 6-54530 as follows.

Embedded image E _x Q _y (wherein E is one or more alkali metals, and Q is the following general formula:

[Chemical 10] (In the formula, M is selected from the group consisting of magnetic metals and compounds of magnetic metals, and these magnetic metals or compounds of magnetic metals may be only one kind, but may be used as a mixture of two or more kinds. A may have a substituent

[Chemical 11] Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II]

[Chemical 12] (In the formula, M and A have the same definitions as above.) A porphyrin derivative, wherein x is 6 or less and y is 1. ] A magnetic composition containing an organic magnetic material is proposed.

Previous application of the present inventors (Japanese Patent Application No. 6-545)
No. 30) In the invention, the central metal M of the polymer metal complex is a magnetic metal, mainly Fe, Co, Ni, Mn, C in the one-component system.
Transition metals such as r or rare earth metals, Fe in binary systems
/ Co, Fe / Ni, Ni / Co, Fe / Pt, Fe /
In contrast to Fe / Co / Ni in the ternary system such as Cd and Fe / Pb, in the present invention, two hydrogen or Cu, Zn, Ga, Ge, Si, Ag, Cd, and I are used as M.
It has been discovered that when a metal such as n, Sn, Sb, Au, Hg, Tl, Pb, or Bi, which exhibits diamagnetism as a metal unit, is used, the product exhibits ferromagnetism. It is something that is emitted. It is quite surprising that the use of these diamagnetic metals makes the magnetic properties of the resulting product very uniform and easy to handle as a magnetic material.

Therefore, the object of the present invention is to achieve extremely reproducible
It is an object of the present invention to provide a novel organic magnetic material having good uniformity, exhibiting ferromagnetism at room temperature, and being easy to control color, 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 a good handleability as a toner, has a good stirring property in a developing device, and does not cause a toner scattering phenomenon. To provide a magnetic toner capable of achieving a magnetic substance having excellent compatibility with a vehicle and the like,
It is an object of the present invention to provide a magnetic ink having good dispersibility and not impairing the color of the dye.

[0020]

The first aspect of the present invention is to provide the following general formula [I]:

[Chemical 13] (In the formula, M is selected from the group consisting of two hydrogen or a diamagnetic metal or a compound of a diamagnetic metal, and these diamagnetic metal or a compound of a diamagnetic metal may be only one kind. It may be used as a mixture of two or more species, and A may have a substituent.

Embedded image Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II]

[Chemical 15] The present invention relates to an organic magnetic material having an alkali metal bound to a porphyrin derivative. In short, the basis of the present invention is to generate a spin by causing an alkali metal to attack a tetraazaporphyrin derivative or a porphyrin derivative of the general formula [I] having a diamagnetic metal M at the center of the structure, thereby generating spin. It is in the point of exhibiting magnetism. In the present invention, the degenerate excited state of the tetraazaporphyrin or porphyrin derivative (e
It is considered that magnetism appears by selective reduction with respect to the (g orbital). Therefore, the selected tetraazaporphyrin derivative or porphyrin derivative has a skeleton symmetry of D
It is preferable to retain ₄ h symmetry. Therefore, this must be taken into consideration when introducing a substituent. Further, generally, increasing the molecular weight also leads to reducing the magnetization per unit weight.

The substituent is a halogen, an alkyl group, an alkoxy group, an amino group, a nitro group, an aryl group, a carboxylic acid group, a carboxylic acid ester group, an aralkyl group, an alkenyl group, an aryloxy group, an alkylthio group or an arylthio group. be able to.

M is two hydrogen or Cu, Zn,
Ga, Ge, Si, Ag, Cd, In, Sn, Sb, A
u, Hg, Tl, Pb, Bi, etc., which do not exhibit ferromagnetism in a simple metal, that is, by using a diamagnetic metal or a metal compound thereof, a product having extremely uniform magnetic properties can be obtained. be able to.

The organic magnetic material has a composition represented by the following general formula [III]

Embedded image _{E x Q y ......... [III]} ( wherein, E is one or two or more alkali metals, tetraazaporphyrin derivatives or porphyrin derivatives Q is represented by the general formula [I] And x is 6
Hereinafter, y is 1. ) Is preferable.

The organic magnetic material of the present invention has the following general formula [I
V]

Embedded image (K) _4-X (Na) _x (Q ₁ ) _y ... [IV] (In the formula, Q ₁ represents a tetraazaporphyrin derivative, and X is a number of 4 or less. The value differs depending on the type of M. y is usually 1.) It is preferable that the composition is represented by the formula. The reason is that this organic magnetic material can also change the magnetic characteristics by changing the variation factor in the composition.

The second aspect of the present invention is the following general formula [I]

Embedded image (In the formula, M is selected from the group consisting of two hydrogen or a diamagnetic metal or a compound of a diamagnetic metal, and these diamagnetic metal or a compound of a diamagnetic metal may be only one kind. It may be used as a mixture of two or more species, and A may have a substituent.

[Chemical 19] Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II]

Embedded image (In the formula, M and A have the same definitions as described above.) A method for producing an organic magnetic material, which comprises reacting a porphyrin derivative with an alkali metal.

The above reaction is so-called doping,
Annealing is continuously carried out if necessary, but when this reaction is carried out in a gas phase in a closed system, that is, in a state where the alkali metal is vaporized, the yield and the magnetic properties are improved. That is, it is preferable that the metal tetraazaporphyrin derivative and the alkali metal are each kept in a non-contact state in the reaction system, the system is kept in a vacuum state to some extent to control the temperature, and both are reacted in a gas phase. The reaction temperature is not particularly limited, but 450
℃ or more, preferably 480 ℃ or more, particularly preferably 5
It is preferable to carry out the reaction at around 00 ° C. This allows the saturation magnetization to exceed 20 emu / g. Even at a reaction temperature of about 480 ° C., the saturation magnetization can exceed 20 emu / g by lengthening the reaction time.

The molar ratio of the alkali metal to the metal tetraazaporphyrin derivative used in the above reaction is 6 or less, preferably 1 to 4. For example, when copper phthalocyanine is selected as the metal tetraazaporphyrin derivative and potassium is selected as the alkali metal, copper phthalocyanine and potassium can be used in a molar ratio of 1: 4.

By selecting the type of diamagnetic metal of the metal tetraazaporphyrin derivative used in the above reaction, the magnetic properties (type of magnetism, Curie temperature, etc.) of the resulting compound can be controlled. For example, in order to exhibit ferromagnetism stably, reproducibly and uniformly at room temperature, two hydrogen or Cu, Zn, Ga, Ge and S are added to the M of the metal tetraazaporphyrin derivative.
i, Ag, Cd, In, Sn, Sb, Au, Hg, T
By using a diamagnetic metal, such as 1, Pb, Bi, etc., which does not exhibit ferromagnetism in a simple substance of metal, a very uniform and reproducible organic magnetic material can be obtained. Further, as the diamagnetic metal compound, for example, Si—O bond or Pb— in which diamagnetic metal and oxygen are bonded is used.
The compound which has an O bond can be mentioned. The alkali metal used in the reaction is not particularly limited, but K, Na, Rb, Cs or a mixture thereof is particularly preferable, and K and Na are particularly preferable.

In the organic magnetic material of the present invention, the form of ferromagnetic interaction can be controlled by combining the center M of the tetraazaporphyrin derivative or the porphyrin derivative and the type of alkali metal to be doped. .

Regarding the reaction method for obtaining the present organic magnetic material, for the sake of simplicity, a reaction apparatus as shown in FIG. 1 is assembled and doping is performed in that system. The tetraazaporphyrin derivative and the alkali metal are kept in non-contact with each other, and a certain degree of vacuum (for example, 0.01 torr)
By keeping both of these and vaporizing them and reacting them in the gas phase, the present organic magnetic material in which the alkali metal is sufficiently bound to the tetraazaporphyrin derivative or the porphyrin derivative can be effectively obtained. When an alkali metal having a large ionic radius is used, the reaction temperature is slightly different.

Next, a third aspect of the present invention is a magnetic toner containing at least a magnetic substance and a binder resin, wherein the magnetic substance is the organic magnetic material according to claim 1, 2, 3 or 4. And a magnetic toner.

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. Variations in magnetic properties and electrical properties easily occur between particles. In addition, 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 polymeric metal complex of the present invention as the magnetic material, the toner material can be made of an organic material, and the toner can have a uniform structure. Moreover, the density of the polymeric metal complex is lighter than that of 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 material composed of the polymer metal complex in the toner is 15 to 8
It is preferably set to 0% by weight. Further, if necessary, it is possible to mix with an inorganic magnetic material.

As the binder resin constituting the toner of the present invention, those which have been used as the binder resin for toner so far can be basically applied. Specifically, polystyrene,
Homopolymers of styrene such as polychloroethylene and polyvinyltoluene, and their substitution products; styrene-Pchlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers. , 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, polyurethane, polyamide, epoxy resin,
Polyvinyl butyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like,
You may use these individually or in mixture of 2 or more types.
Here, the range of the molecular weight, the molecular weight distribution, the degree of crosslinking, etc. of each resin is determined so that the melt viscosity of the toner becomes a predetermined value.

Further, in the toner of the present invention, in addition to imaging the color of the polymer metal complex itself, a colorant can of course be contained, and pigments and pigments conventionally used as toner colorants can be added. All of the dyes are applied. 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, 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. .

In the present invention, since the above-mentioned polymer metal complex type magnetic material is used, a clear color image can be obtained even when the toner of the present invention is used as a color one-component magnetic toner. it can. As the colorant for forming the toner of the present invention for color development, all known colorants can be used. As the yellow colorant, for example, chrome yellow, benzidine yellow, Hansa yellow, naphthol yellow, quinoline yellow and the like 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, it is possible to use the polymer metal complex magnetic material and the inorganic magnetic material together.

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 and a lubricant such as fatty acid metal salt may be contained.

Next, a fourth aspect of the present invention is a magnetic ink containing at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance is the organic magnetic material according to any one of claims 1, 2, 3 and 4. Magnetic ink.

Also in the magnetic ink, when the conventional inorganic substance is used as the magnetic substance, the compatibility with the vehicle or the like is poor as described above, so that 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 is dried after image formation.

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

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, an oil-based magnetic ink can be obtained with a composition comprising a vehicle in which a magnetic material, a dye, an oil, a resin, a dispersion solvent and the like are combined, and an additive.

Specific examples of the above-mentioned dyes 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 HFR, carbon black, aniline black, titanium oxide, tartrazine lake, rhodamine 6
G rake, methyl violet rake, basic 6G
Examples include lakes, brilliant green lakes, and nigrosine. Of course, a vivid image can be obtained only by the color of the polymer metal complex itself without adding a dye.

The above-mentioned vehicle is composed of oil, resin, dispersion solvent and the like, and specific examples of the oil include linseed oil, sesame oil, soybean oil, castor oil, dehydrated castor oil, lysovarnish, maleated oil, Vinylated oil, urethane oil, machine oil, spindle oil and the like can be mentioned. As the resin, rosin, shellac, copal, dammar, gilsonite, zein, lime rosin, ester gum, phenol resin, xylene resin, urea resin, melamine resin, ketone resin, coumarone / 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, polyvinyl butyral, chlorinated polypropylene,
Examples thereof include styrene resin, epoxy resin, polyurethane and cellulose derivative.

As the dispersion solvent, n-hexane,
Examples thereof include n-heptane, toluene, xylene, methyl alcohol, isopropyl alcohol, ethylene glycol, triethylene glycol, diethylene glycol, glycerin, methyl cellosolve, carbitol, ethyl acetate, acetone, methyl ethyl ketone.

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, triphenyl phosphate, Examples thereof include n-heptyl p-hydroxybenzoate and dicyclohexyl phthalate. Specific examples of the above-mentioned dyes and additives are the same as those in the case of oil-based magnetic ink.

In the case of aqueous magnetic ink, a composition comprising a vehicle and an additive in which a magnetic substance, 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, 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, diethylethanolamine, dimethylethanolamine,
Morpholine and the like, and as a cosolvent, ethyl alcohol, isopropyl alcohol, ethyl acetate,
Examples include methyl ethyl ketone.

Further, as the above-mentioned additives, there are abrasion resistance improvers such as petroleum wax and polyethylene wax, nonionic activators, and defoaming agents 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, it 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. 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.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Using the reaction system shown in FIG. 1, the reaction system was sufficiently evacuated to vaporize 1 part of purified copper (II) phthalocyanine and 4 parts of metal potassium, respectively, and both were vapor-phased. And reacted (doping) for 1 hour. As a result, potassium-doped copper phthalocyanine (abbreviated as K-CuPc) was obtained.
Fig. 2 shows the magnetic field dependence of the magnetization at 10 (K) of this product.
Shown in This material exhibited ferromagnetic behavior at room temperature.

Example 2 In the same manner as in the reaction system shown in Example 1, 1 part of purified metal-free phthalocyanine (M is 2 hydrogens) and 4 parts of metal potassium were reacted (doped) for 1 hour. As a result, potassium-free metal-free phthalocyanine (K
-H abbreviated as ₂ Pc) was obtained. FIG. 3 shows the magnetic field dependence of the magnetization of this material at 30 (K).

Example 3 In the same manner as in the reaction system shown in Example 1, 1 part of purified zinc (II) phthalocyanine and 4 parts of metallic potassium were reacted (doping) for 1 hour. Thus, potassium-doped zinc phthalocyanine (abbreviated as K-ZnPc) was obtained. The magnetic field dependence of the magnetization of this product at 300 (K) is shown in FIG. 4, and that at 10 (K) is shown in FIG.

Example 4 In the same manner as in the reaction system shown in Example 1, 1 part of purified lead phthalocyanine and 4 parts of metallic potassium were reacted (doping) for 1 hour. As a result, potassium-doped lead phthalocyanine (abbreviated as K-PbPc) was obtained. The magnetic field dependence of the magnetization of this product at 300 (K) is shown in FIG. 6, and that at 10 (K) is shown in FIG.

Example 5 (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 Part After thoroughly stirring and mixing the mixture having the above composition with a Henschel mixer, it was heated and melted with 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. This toner is My Recopy M-10
(Ricoh Co., Ltd.) and put out an image, a clear image was obtained. Further, even when 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 6 (Magnetic toner) Styrene / n-butylmethacrylate copolymer 100 parts Quaternary ammonium salt (charge control agent) 2 parts Compound obtained in Example 1 (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 5, a clear image was obtained. When this toner was put into a machine with improved speed as in Example 5, no toner scattering occurred.

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 thoroughly stirred and mixed with a Henschel mixer, and then heated and melted at 130 to 140 ° C. for 30 minutes with 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 had a clear brown image because it was a toner containing a nearly colorless inorganic magnetic material, but the toner density was 1 As high as 0.6 g / cm ³ , the toner was pulverized during development, and toner scattering and image stains occurred.

Example 7 (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 The above composition After thoroughly stirring and mixing the mixture of (1) with a Henschel mixer, it was heated and melted at 130 to 140 ° C. for 30 minutes with 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 1.2 g / cm ^3.
Toner was obtained. This toner is My Recopy M-10
(Ricoh Co., Ltd.), and when an image was formed, a clear blue image was obtained.

Example 8 (Magnetic ink) Phenolic resin 25 parts Spindle oil 30 parts Toluene 13 parts Carnauba wax 5 parts Soybean oil fatty acid 2 parts Compound (organic magnetic material) obtained in Example 1 5 parts The above components are mixed. By dispersing, an oily magnetic ink was obtained.
When printing was performed on art paper using the obtained ink, the obtained printed matter was a clear and very good blue image, which could be read by a magnetic head.

The embodiment sections are listed below. 1. The following general formula [I]

[Chemical 21] (In the formula, M is selected from the group consisting of two hydrogen or diamagnetic metals or compounds of diamagnetic metals, and these diamagnetic metals or diamagnetic metal compounds may be only one kind, You may use it as a mixture of 2 or more types. Moreover, A may have a substituent as follows.

[Chemical formula 22] Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II]

[Chemical formula 23] (In the formula, M and A have the same definitions as above.) An organic magnetic material having an alkali metal bound to a porphyrin derivative. 2. M is Cu, Zn, Ga, Ge, Si, Ag,
The organic magnetic material according to item 1 above, which is selected from the group consisting of Cd, In, Sn, Sb, Hg, Tl, Pb, and Bi. 3. The composition of the organic magnetic material is represented by the following general formula [III]

Embedded image _{E x Q y ......... [III]} ( wherein, E is one or two or more alkali metals, tetraazaporphyrin derivatives or porphyrin derivatives Q is represented by the general formula [I] And x is 6
Hereinafter, y is 1. ) An organic magnetic material as described in 1 or 2 above. 4. The composition of the organic magnetic material is represented by the following general formula [IV]

Embedded image (K) _4-X (Na) _x (Q ₁ ) _y (IV) (wherein, Q ₁ represents a tetraazaporphyrin derivative, x is a number of 4 or less, and y is 1) The organic magnetic material according to item 3 above is represented by the formula (1). 5. The preceding paragraph 1, wherein the saturation magnetization is 1 to 30 emu / g,
The organic magnetic material according to 2, 3, or 4. 6. The following general formula [I]

[Chemical formula 26] (In the formula, M is selected from the group consisting of two hydrogen or a diamagnetic metal and a compound of a diamagnetic metal. These diamagnetic metals or compounds of a diamagnetic metal may be one kind, but 2 You may use it as a mixture of 2 or more types.
In addition, A may have a substituent below

[Chemical 27] Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II]

[Chemical 28] (In the formula, M and A have the same definitions as described above.) A method for producing an organic magnetic material, which comprises reacting a porphyrin derivative with an alkali metal. 7. 7. The method for producing an organic magnetic material as described in 6 above, wherein the reaction is carried out in a closed system in a state where the alkali metal is vaporized. 8. A magnetic composition containing the organic magnetic material according to the above 1, 2, 3, 4 or 5. 9. In a magnetic toner containing at least a magnetic substance and a binder resin, the magnetic substance is the above-mentioned 1, 2, 3, 4 or 5
A magnetic toner comprising the above-mentioned organic magnetic material. 10. The content of the organic magnetic material in the magnetic toner is 15
The magnetic toner according to item 9 above, which is ˜80 wt%. 11. In a magnetic ink containing at least a magnetic substance, a dye and a vehicle, the magnetic substance is
Alternatively, a magnetic ink comprising the organic magnetic material described in 5 above. 12. An oil-based magnetic ink comprising the organic magnetic material according to the above 1, 2, 3, 4 or 5, a pigment, an oil, a vehicle containing a resin and a dispersion solvent. 13. A water-based magnetic ink containing the organic magnetic material according to the above 1, 2, 3, 4 or 5, a pigment, a resin, a water-solubilizing agent and a vehicle containing water. 14. A hot melt magnetic ink containing the organic magnetic material according to the above 1, 2, 3, 4 or 5, a dye, and a hot melt vehicle.

[0065]

【effect】

Effects of Claims 1 to 6 (1) It was possible to provide an organic magnetic material having extremely good reproducibility and uniformity, exhibiting ferromagnetism at room temperature, and retaining magnetic characteristics that can be put to practical use. (2) The color of the obtained organic magnetic material can be adjusted depending on the central metal and the kind of the skeleton of the tetraazaporphyrin derivative or the porphyrin derivative. (3) The intensity of magnetization can be controlled by the combination of the types of central metal and alkali metal. (4) A material suitable for thinning can be selected depending on the combination of the central metal and the alkali metal. (5) The present invention can provide an organic magnetic material having a saturation magnetization of 1 to 30 emu / g, and particularly 20 emu.
It is amazing that we were able to provide more than / g.

Effect of claim 7 Furthermore, the magnetic toner of claim 7 has the following excellent effect because it is composed of the organic magnetic material composed of the polymer metal complex. (1) Each component is uniformly mixed in the toner particles, the density is low, and it is difficult to be brittle. (2) Therefore, it can be suitably used for a high speed rotating developing sleeve rotary copying machine. (3) When used for color development, it is possible to obtain a color image that can clearly show the color of the coloring material or the polymer metal complex itself.

Effect of Claim 8 Further, since the magnetic ink of Claim 8 has a constitution in which the organic magnetic material composed of the polymer metal complex is mixed, the following excellent effects are exhibited. (1) It can be used for printing, inkjet printers, thermal transfer, hot melt printers, writing instruments, etc. (2) Colorization is possible. (3) Since the compatibility of the magnetic material with the resin is good, the dispersibility of the magnetic material is good. (4) A clear and very good image can be obtained without causing cracks or the like after printing. (5) The printed matter 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 shows a reactor used in Examples of the present invention.

FIG. 2 is a graph showing the magnetic field dependence at 10 (K) of the organic-metal composite magnetic material obtained in Example 1. The vertical axis represents the unit of magnetization EMU, and the horizontal axis represents the magnetic intensity (Gauss).

FIG. 3 is a graph showing the magnetic field dependence of the magnetization at 30 (K) of the organic-metal composite magnetic material obtained in Example 2. The vertical axis represents the unit of magnetization EMU, and the horizontal axis represents the magnetic intensity (Gauss).

FIG. 4 is a graph showing the magnetic field dependence of the magnetization at 300 (K) of the organic-metal composite magnetic material obtained in Example 3. The vertical axis represents the unit of magnetization EMU, and the horizontal axis represents the magnetic intensity (Gauss).

5 is a graph showing the magnetic field dependence of the magnetization of the organic-metal composite magnetic material obtained in Example 3 at 10 (k). FIG. The vertical axis represents the unit of magnetization EMU, and the horizontal axis represents the temperature (K).
Is.

FIG. 6 is a graph showing the magnetic field dependence of the magnetization at 300 (k) of the organic-metal composite magnetic material obtained in Example 4. The ordinate represents the unit of magnetization EMU, and the abscissa represents the temperature (K).

FIG. 7 is a graph showing the magnetic field dependence of the magnetization at 10 (k) of the organic-metal composite magnetic material obtained in Example 4. The vertical axis represents the unit of magnetization EMU, and the horizontal axis represents the temperature (K).
Is.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shinichiro Nakajima 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd.

Claims (8)

[Claims] 1. The following general formula [I]: (In the formula, M is selected from the group consisting of two hydrogen or a diamagnetic metal or a compound of a diamagnetic metal, and these diamagnetic metal or a compound of a diamagnetic metal may be only one kind, but 2 They may be used as a mixture of two or more species, and A may have a substituent: Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II] (In the formula, M and A have the same definitions as above.) An organic magnetic material having an alkali metal bound to a porphyrin derivative. 2. The M is Cu, Zn, Ga, Ge, S
i, Ag, Cd, In, Sn, Sb, Hg, Tl, P
2. The compound selected from the group consisting of b and Bi.
The described organic magnetic material. 3. A composition represented by the following general formula of said organic magnetic material [III] ## STR4 ## _{E x Q y ......... [III]} ( wherein, E is one or two or more alkali metals, Q is a tetraazaporphyrin derivative or porphyrin derivative represented by the above general formula [I], and x is 6
Hereinafter, y is 1. ) Represented by 1)
The described organic magnetic material. 4. The composition of the organic magnetic material has the following general formula [IV]: (K) _4-X (Na) _x (Q ₁ ) _y ... [IV] (wherein, Q ₁ is 4. The organic magnetic material according to claim 3, wherein the organic magnetic material represents a tetraazaporphyrin derivative, x is a number of 4 or less, and y is 1.). 5. The following general formula [I]: (In the formula, M is selected from the group consisting of two hydrogen or a diamagnetic metal and a compound of a diamagnetic metal. These diamagnetic metals or compounds of a diamagnetic metal may be one kind, but 2 You may use it as a mixture of 2 or more types.
In addition, A may have a substituent below. Represents an organic residue, two hydrogen atoms or a bond selected from the group consisting of ) Or a tetraazaporphyrin derivative represented by the general formula [II] (In the formula, M and A have the same definitions as above.) A method for producing an organic magnetic material, which comprises reacting a porphyrin derivative with an alkali metal. 6. The method for producing an organic magnetic material according to claim 5, wherein the reaction is carried out in a closed system in a state where the alkali metal is vaporized. 7. A magnetic toner containing at least a magnetic material and a binder resin, wherein the magnetic material is the organic magnetic material according to claim 1, 2, 3 or 4. 8. A magnetic ink containing at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance is the magnetic ink according to claim 1.
A magnetic ink comprising the organic magnetic material described in 2, 3, or 4.