JPH06271796A - Magnetic ink - Google Patents

Abstract

PURPOSE:To obtain a magnetic ink which comprises a dispersible magnetic material excellent in compatibility with vehicles, etc., and useful for printing, ink jet printer, etc., by mixing a magnetic material obtained by heat-treating a phthalocyanine compound, a coloring matter and a vehicle. CONSTITUTION:This magnetic ink comprises at least a magnetic material, a coloring matter and a vehicle, in which an organic material obtained by heat-treating a phthalocyanine compound is used as the magnetic material. Use of such a thermally modified phthalocyanine as the magnetic material makes the material well compatible with vehicles and highly dispersible so that a clear image can be obtained. The organic magnetic material is obtained by heat-treating a phthalocyanine compound, preferably by heat-treating the same at 200-900 deg.C in an inert gas.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic ink used for printing, ink jet printer, thermal transfer, hot melt printer, writing instrument and the like.

[0002]

2. Description of the Related Art Generally, a magnetic ink is composed of a vehicle in which a magnetic substance, a pigment, a resin, a dispersion solvent and the like are combined, an additive and the like, and is used for an oil-based ink, a water-based ink, a hot melt ink or the like. ,
For example, JP-A-59-147217 discloses an ink in which a magnetic substance is colloidally dispersed in an organic solvent such as kerosene or glycerin, or water, and JP-A-62-26.
Japanese Patent No. 7379 describes an ink in which a magnetic material is dispersed in wax.

[0003]

However, in these magnetic inks, the magnetic substance is ferrite, chromium oxide, or M.
n-Bi alloy, Mn-Al alloy, Fe-Ni alloy, Sn
-Because it is composed of a metal oxide such as an Fe alloy, the compatibility between the magnetic substance and the vehicle is poor, and the magnetic substance easily aggregates and the dispersibility is poor. After the image formation, the magnetic ink is dried and cracked. There were drawbacks such as easy occurrence. An object of the present invention is to overcome the above-mentioned drawbacks and to have excellent compatibility with a vehicle or the like, which is composed of a magnetic material having good dispersibility, for printing,
It is to provide a magnetic ink used for an inkjet printer or the like.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that the use of an organic magnetic material obtained by heat-treating a phthalocyanine compound as a magnetic material can achieve the above-mentioned object. The inventors have found that the above is achieved and completed the present invention. That is, according to the present invention, in a magnetic ink containing a magnetic substance, a dye and a vehicle as a main component, the magnetic ink is an organic magnetic substance obtained by heat-treating a phthalocyanine compound. Provided. As described above, the magnetic ink of the present invention uses the heat-treated modified phthalocyanine as the magnetic material, and therefore has good compatibility between the magnetic material and the vehicle and the like, and has excellent dispersibility of the magnetic material to obtain a clear image. You can

The magnetic ink of the present invention will be described in detail below. The organic magnetic material used in the present invention is a modified phthalocyanine compound obtained by heat-treating a phthalocyanine compound, and a preferred one is a modified phthalocyanine compound obtained by heat-treating the phthalocyanine compound at 200 ° C. or higher and 900 ° C. or lower in an inert gas. . As the inert gas, for example, nitrogen, argon, helium or the like is used. In the present invention, it is 30 in an argon atmosphere.
It is preferable to perform heat treatment in the range of 0 to 800 ° C. The reaction pressure may be from normal pressure to 300 Pa under reduced pressure. Specific examples of the phthalocyanine compound before the heat treatment include, for example, 2,3,9,10,16,17,23,24.
-Octacyanophthalocyanine, 2,3,9,10,1
Examples include 6,17,23,24-octacarboxyphthalocyanine, tetrakis (1,4-diaminophthalazino) porphyrazine, octacyanonaphthalocyanine, and the like, with or without a central metal.

The modified phthalocyanine compound obtained by the present invention usually has a spin concentration of at least 1 × 10 ¹⁷ / g or more, that is, 1 ×, as measured by electron spin resonance (ESR).
Since it has a content of 10 ¹⁸ / g or more, it exhibits magnetism and becomes a preferable organic magnetic material.

The magnetic ink of the present invention using the above magnetic material is used as an oil-based, water-based or hot-melt ink. For example, in the case of an oil-based magnetic ink, a composition including a vehicle in which a magnetic material, a dye, 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, Indanthrone Blue, Phthalocyanine Green, Benzimidazolone Brown H
Examples thereof 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, and specific examples of the oil include linseed oil, shinai oil, soybean oil, castor oil, dehydrated castor oil, lysovarnish, maleated oil, vinylated oil. Oil, urethane oil, machine oil,
Spindle oil etc. are mentioned. Resins include 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, cyclization 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, styrene resin, epoxy resin, polyurethane, Examples include cellulose derivatives. 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 wax, dryer, dispersant, wetting agent, cross-linking agent, stabilizer, thickener, gelling agent, defoaming agent and photopolymerization initiator. Further, in the case of hot melt magnetic ink, a composition comprising a magnetic material, a dye, a hot melt vehicle and an additive is obtained. 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, p.
Examples include n-heptyl hydroxybenzoate and dicyclohexyl phthalate. Specific examples of the dye and the additive include those similar to the case of the oil-based magnetic ink.

Further, in the case of aqueous magnetic ink, a magnetic material,
It is obtained with a composition consisting of a vehicle in which a dye, a resin, a water-solubilizing agent, a cosolvent and water 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, chloride. Examples include vinyl resins, synthetic rubber latex, polyurethane, polyester, alkyd resins, rosin esters, and epoxy esters.

Examples of the water-solubilizing agent include aqueous ammonia, monoethanolamine, monoisopropanolamine, ethylmonoethanolamine, diethylethanolamine, dimethylethanolamine and morpholine. Examples of the auxiliary solvent include ethyl alcohol, isopropyl alcohol, ethyl acetate and methyl ethyl ketone. Examples of the additives include friction resistance improvers such as petroleum wax and polyethylene wax, nonionic activators, 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 substance, magnetically readable, and it can be used for printing certificates, tickets, etc., printing banknotes, secret documents, etc., or for maintenance of information. it can. Furthermore, since the magnetic material has good compatibility with resins and the like, it has good dispersibility and does not cause cracks or the like after printing.

[0013]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these.
In addition, the part shown below means a weight part.

Synthesis Example 1 [Synthesis of 2,3,9,10,16,17,23,24-octacyanophthalocyanine heat-treated material-based magnetic material] 1,
2,4,5-Tetracyanobenzene (3.56 g) was dissolved in 1-propanol (200 ml), heated and reduced, and a solution of metallic lithium (35 mg) dissolved in 1-propanol (40 ml) was slowly added dropwise to the solution. Heat reduction. Then, it is cooled, 1-propanol is distilled off, and toluene is added to obtain a green powder. Furthermore, it is washed with toluene and purified to obtain 2,3,9,10,16,17,23,2.
4-octacyanophthalocyanine 1.67 g (yield = 4
6.8%) was obtained. 500 at atmospheric pressure under argon flow
Where heat treatment is performed, 2, 3, 9, 10, 16, 1
A 7,23,24-octacyanophthalocyanine heat-treated material-based magnetic material was obtained. The spin concentration determined by ESR was 2.3 × 10 ¹⁸ / g. Further, when the magnetization characteristic was measured by a vibration sample type magnetization measuring device (VSM), a ferromagnetic hysteresis was drawn. The magnetization curve of this product is shown in Fig. 1.
The infrared absorption curve is shown in FIG.

Example 1 Aniline black 25 parts Xylene resin 20 parts Machine oil 30 parts Toluene 13 parts Candelilla wax 5 parts Soybean oil fatty acid 2 parts Magnetic material obtained in Synthesis Example 1 5 parts The above components were mixed and dispersed. An oily magnetic ink having good dispersibility was obtained. When printing was performed using this ink, the obtained printed matter was a clear and very good image, and magnetically readable.

Example 2 Phthalocyanine blue 3.5 parts n-heptyl p-hydroxybenzoate 92.5 parts Magnetic substance obtained in Synthesis Example 1 4.0 parts Membrane filter after sufficiently mixing and dispersing the above components. The hot melt magnetic ink having good dispersibility was obtained. When an ink-jet printer was used to print with this ink, the resulting print was clear and had a very good image. In addition, magnetic reading was also good.

Example 3 Laked C 15.0 parts Shellac aqueous varnish 60.0 parts Polyethylene wax 4.0 parts Water 15.5 parts Silicone 0.5 parts Magnetic substance obtained in Synthesis Example 1 5.0 parts The above components Was mixed and dispersed to obtain a water-soluble magnetic ink having good dispersibility. The composition of the above shellac aqueous varnish was 33 parts shellac, 2 parts diethylethanolamine, and 1 part ethanol.
3 parts and 52 parts of water. When printing was performed using this ink, the obtained printed matter was a clear and very good image, and magnetically readable.

[0018]

As described above, according to the present invention, since the magnetic ink is formed by using the organic magnetic material obtained by heat-treating the phthalocyanine compound, it has excellent compatibility with the resin and good dispersibility. It is possible to obtain a magnetic ink in which a formed image is clear and cracks do not occur.
Furthermore, printed matter obtained from this magnetic ink can be read magnetically, printing certificates, tickets, etc., printing bills,
It can also be used for adding and maintaining information such as confidential documents.

[Brief description of drawings]

1 is a thermal modification 2, 3, 9, 1 obtained in Synthesis Example 1.
The magnetization curve of 0,16,17,23,24-octacyanophthalocyanine is shown.

2 is a thermal metamorphism obtained in Synthesis Example 1, 2, 3, 9, 1.
The infrared absorption spectrum of 0,16,17,23,24-octacyano phthalocyanine is shown.

Claims (3)

[Claims] 1. A magnetic ink comprising at least a magnetic substance, a dye and a vehicle, wherein the magnetic substance is an organic magnetic substance obtained by heat-treating a phthalocyanine compound. 2. The magnetic ink according to claim 1, wherein the organic magnetic substance is a modified phthalocyanine compound obtained by heat-treating a phthalocyanine compound at 200 to 900 ° C. in an inert atmosphere. 3. The organic magnetic substance has a spin concentration of 1 × 10 ¹⁷ / g.
The magnetic ink according to claim 1 or 2, which is the above.