METHOD OF PRODUCTION OF MAGNETIC PARTICLES

Abstract: Magnetic particles, particularly magnetic iron oxide particles, magnetic cobalt-containing iron oxide particles and magnetic metallic iron particles, which have a long axis diameter of 300 nm or less, an axial ratio of 5 or less, and a specific surface area of 40 m²/g (measured by BET method), and are useful as a recording element for a magnetic recording medium, and a method for the production thereof, which comprises reacting an aqueous solution containing trivalent iron ion with an equivalent or more amount of an aqueous alkali solution at a temperature of 30°C or lower, aging the produced ferric hydroxide, subjecting the ferric hydroxide to hydrothermal reaction in an autoclave to produce α-ferric oxyhydroxide particles, filtering and drying the particles, and then reducing the particles with heating and optionally further oxidizing them, and also a magnetic recording medium prepared from the magnetic particles.

Description: MAGNETIC PARTICLES AND METHOD OF PRODUCTION THEREOF The present invention relates to magnetic particles, more particularly, magnetic iron oxide particles, magnetic cobalt-containing iron oxide particles and magnetic metallic iron particles which are useful as a recording element for a magnetic recording medium, and a method for the production thereof. Various magnetic particles such as Foe 304 particles, r-Fe203 particles, or intermediates thereof, magnetic cobalt-containing iron oxide particles and magnetic metallic iron particles have widely been used as a recording element for a magnetic recording medium and these magnetic particles are usually produced by reducing -ferric oxyhydroxide (a-FeOOH) particles or reducing a-FeOOH and then oxidizing it, said ferric oxyhydroxide particles used therein being usually producing by adding an aqueous alkali solution to an aqueous ferrous salt solution at 30 to 600C and airoxidizing the resulting ferrous hydroxide. However, according to the known method, particles of the ferrous hydroxide grow well to give Or-ferric oxyhydroxide particles having a large axial ratio, and when this product is reduced with heating or reduced and thereafter oxidized, there are hardly obtainable magnetic iron oxide particles having uniform particle size distribution and having fine particle size while the axial ratio thereof is large. When the fine ferric oxyhydroxide particles are prepared by the conventional method, the resulted particles are very thin because of the high axial ratio. Accordingly, when the particles are reduced with heating, it tends to occur sintering, which results in deformation thereof, and hence, there are hardly obtainable the desired magnetic particles having improved magnetic characteristics. In view of the facts that the particles shape of the a-ferric oxyhydroxide particles affects largely on the magnetic characteristics of the magnetic particles, the present inventors have intensively studied on improvement of the preparation method of ferric oxyhydroxide particles. As a result, it has been found that when an aqueous solution containing a trivalent iron ion is added to an equivalent or more amount of an aqueous alkali solution at a temperature of 300C or lower, followed by aging the produced ferric hydroxide and subjecting the ferric hydroxide to hydrothermal reaction in an autoclave, there can be obtained ferric oxyhydroxide particles having a long axis diameter of 300 nm or less, an axial ratio of 5 or less 2 and a specific surface area of 40 m /g or less (measured by BET method) which can give magnetic particles having excellent magnetic characteristics by reduction thereof. An object of the present invention is to provide magnetic particles which are useful as a recording element for a magnetic recording medium. Another object of the invention is to provide magnetic iron oxide particles. A further object of the invention is to provide magnetic cobalt-containing iron oxide particles. A still further object of the invention is to provide magnetic metallic iron particles. A still further object of the invention is to provide a magnetic recording medium prepared by using the magnetic particles as set forth above. A still further object of the invention is to provide a-ferric oxyhydroxide particles having a small axial ratio and uniform particle size distribution which can give the desired magnetic particles. Another object of the invention is to provide a method for the production of the magnetic particles as set forth above. These and other objects and advantages of the invention will be apparent to persons skilled in the art from the following description. According to the method of the present invention, an aqueous solution containing a trivalent iron ion is added to an equivalent or more amount of an aqueous alkali solution to produce ferric hydroxide, wherein the reaction is carried out at a temperature of 300C or lower, and then the ferric hydroxide is aged. Accordingly, the ferric hydroxide particles are appropriately grown, and such ferric hydroxide particles can give ferric oxyhydroxide particles having a small axial ratio and uniform particle size distribution by subjecting them to hydrothermal reaction in an autoclave. The a-ferric oxyhydroxide particles thus obtained are fine and have a long axis diameter of 300 nm of less, and hence, the magnetic particles obtained therefrom by reduction thereof show excellent magnetic characteristics such as excellent coercive force and also excellent dispersibility to a binder when it is used for the production of magnetic paint compositions, and hence, the magnetic tape prepared therefrom has excellent surface smoothness, lower noise level, and excellent electro-transfer properties. Moreover, owing to the uniform particle distribution, the magnetic particles have excellent distribution of coercive force, and hence, magnetic tape prepared therefrom has excellent orientation property and erasability. The cobalt-containing iron oxide particles produced by the present invention have excellent stability of magnetic properties with temperature and time. Besides, owing to the small 2 specific surface area such as 40 m /g or less of the a-ferric oxyhydroxide particles, the metallic iron particles obtained therefrom by reduction thereof show excellent corrosion resistance, too. In the method of the present invention, when the reaction of the aqueous solution containing a trivalent iron ion with the aqueous alkali solution is carried out at a temperature of higher than 300C, it is difficult to control the growth of ferric hydroxide particles, which results in difficulty of production of the desired ferric oxyhydroxide fine particles having uniform particle distribution, and hence, the reaction is preferably at a temperature of 300C or lower, i.e. in the range of from the freezing point of the solution to 300C. When the reaction temperature is lower, the control of the growth of ferric oxyhydroxide particles is more easy, and hence, preferred reaction temperature is 200C or lower, particularly in the range of -20C to 200C. The aging of ferric hydroxide is carried out at a temperature of 1000C or lower for 10 minutes or more, usually at room temperature for 30 minutes or more, preferably for 3 to 70 hours. When the aging period of time is too short, the growth of ferric hydroxide particles becomes insufficient, and on the other hand, when the aging period of time is too long, the growth of ferric hydroxide particles becomes too excess, which tends to result in difficulty of production of the desired ferric oxyhydroxide particles having uniform particle size distribution. The aqueous solution containing a trivalent iron ion is prepared by dissolving one or more of various water-soluble ferric salts such as ferric chloride, ferric sulfate, ferric nitrate, etc. in water, or dissolving one or more of various water-soluble ferrous salts such as ferrous chloride, ferrous sulfate, ferrous nitrate, etc. in water and then oxidizing it with an oxidizing agent (e.g. hydrogen peroxide, sodium chlorate), wherein the iron salts are contained in the aqueous solution in the form of trivalent iron ion. The iron salts are contained in the aqueous solution in a concentration of 0.5 mole/liter or less, preferably 0.01 to 0.2 mole/liter. The aqueous alkali solution, to which the aqueous solution containing a trivalent iron ion is added, is an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc., and the alkali metal hydroxide is used in an amount equivalent or more to the amount of trivalent iron ion in order to produce advantageously the desired ferric hydroxide particles having a suitable particle size. Preferred amount of the alkali metal hydroxide is in the range of 3 to 10 moles to I mole of the trivalent iron ion. When the concentration of the aqueous alkali solution is too high, the product becomes ununiform and shows widely spreaded particle size distribution. Accordingly, the concentration of the free alkali is preferably in 1 mole/lite or less, more preferably in the range of 0.1 to0.8 mole/liter. The aqueous solution containing a trivalent iron ion is reacted with an aqueous alkali solution containing an alkali metal hydroxide in an equivalent or more to the trivalent iron ion at a temperature of 300C or lower to produce ferric hydroxide, followed by aging the ferric hydroxide particles at room temperature, by which there is obtained an aqueous suspension of ferric hydroxide particles having an appropriate degree of growth of particles. The suspension is subjected to hydrothermal reaction in an autoclave to give ferric oxyhydroxide fine particles having uniform particle size distribution and a small axial ratio. The hydrothermal reaction in an autoclave for producing ferric oxyhydroxide is preferably carried out at a temperature of 120 to 2500C, more preferably 150 to 2200C, since when it is carried out at lower than l200C, the crystallization required much longer time, and on the other hand, when it is carried out at higher than 2500C, the product is unfavorably contaminated with CY-Fe203 particles. The desired magnetic iron oxide particles are produced from the -ferric oxyhydroxide particles in the following manner. The ferric oxyhydroxide particles obtained above are washed with water, filtered and then dried. The dried particles are reduced with heating at a temperature of 250 to 4000C, or alternatively are oxidizing in air at a temperature of about 2000C or higher after reduction, by which there are produced magnetic fine acicular particles of r-Fe203, Fe3O4 or intermediates thereof which have a small axial ratio, uniform particle size distribution, improved magnetic characteristics such as large coercive force and large squareness ratio, and further, improved dispersibility and orientation property. When the reduction is carried out at a temperature of 2500C or higher, the magnetic characteristics of the particles are improved, and with raising the temperature, the reduction is more promoted. However, when the temperature is over 400 C, undesirable sintering occurs to result in lowering of coercive force of the particles. Accordingly, the reduction is preferably carried out at a temperature of 250 to 4000C. In order to improve more the coercive force of the magnetic iron oxide particles, cobalt is added to the iron oxide particles. Such magnetic cobaltcontaining iron oxide particles are produced in the following manner. The iron oxide particles obtained above are dispersed in an aqueous solution containing a cobalt salt and optionally further a ferrous salt and thereto is added an aqueous alkali solution, and the mixture is reacted, by which the iron oxide containing cobalt are formed on the seeds of iron oxide particles. Alternatively, the iron oxide particles are dispersed in an aqueous solution containing a cobalt salt and a complexing agent and then subjected to hydrothermal reaction at 150 to 2000C, by which the cobalt atoms are uniformly penetrated within the iron oxide particles. Both methods can give the desired magnetic cobalt-containing iron oxide particles having uniform particle size distribution and having a long axis diameter of 300 nm or less, an axial ratio of 5 or less, a specific surface area of 40 m2/g or less (measured by BET method), and a coercive force of 23.9 KA/m or more. The magnetic particles produced by the latter method contain uniformly the cobalt atoms within the particles, and hence, they can give a magnetic recording medium having isotropic magnetic components. The magnetic particles produced by the former method contain predominantly the cobalt atoms at the surface region of the particles, and hence, when these particles are heated at a temperature of 300 to 6000C, the cobalt atoms are uniformly diffused within the particles to give the magnetic particles having characteristics similar to the product of the latter method. The cobalt salt used in the above methods includes cobalt primary sulfate, cobalt primary chloride, cobalt primary nitrate, or the like. The ferrous salt which is optionally added to the solution includes ferrous sulfate, ferrous chloride, ferrous nitrate, or the like. The aqueous alkali solution is preferably an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The aqueous alkali solution should have a concentration of the alkali metal hydroxide sufficient to precipitate the cobalt hydroxide and ferrous hydroxide. Thus, the aqueous alkali solution has a concentration of an alkali metal hydroxide of 2 to 10 mole to 1 mole of the cobalt and ferrous ions. The reaction temperature is preferably 50 0C or lower in order to proceed the reaction uniformly. The complexing agent used in the latter method includes sodium citrate, sodium tartrate, or the like. The magnetic cobalt-containing iron oxide particles thus produced have a uniform particle size distribution and hence have a narrow coercive force distribution, excellent stability of magnetic properties with temperature and time, excellent electro-transfer property. According to the present invention, magnetic metallic iron particles are also produced in the following manner. The ferric oxyhydroxide particles obtained above are washed with water, filtered and then dried, and the dried particles are reduced with a reducing gas (e.g. under hydrogen gas stream) at a temperature of 300 to 6000C, by which there are obtained the desired magnetic metallic iron fine particles having uniform particle size distribution and further having a long axis diameter of 300 nm or less, an azial ratio of 5 or less, a specific surface area of 40 m2/g or less (measured by BET method), and also improved corrosion resistance. Before subjecting the a-ferric oxyhydroxide particles to reduction with heating, the particles may optionally be treated with a silicone compound (e.g. sodium silicate) or an aluminum compound (e.g. aluminum sulfate) in order to prevent unfavorable sintering or deformation of the a-ferric oxyhydroxide. A magnetic recording medium is prepared from the magnetic iron oxide particles, magnetic cobaltcontaining iron oxide particles or magnetic metallic iron particles obtained above in a usual manner, for example in the following manner. The magnetic particles are mixed with a binding resin, an organic solvent and any conventional additives to prepare a magnetic paint composition. The magnetic paint composition is applied to a base (e.g. a polyester film) by a conventional means, for example, with a roll coater, and then, the product is dried. The binding resin includes all conventional binding resins such as vinyl chloride-vinyl acetate copolymer, polyvinylbutyral, polyurethane resins, or nitrocellulose. The organic solvent includes all conventional organic solvents, such as toluene, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, or ethyl acetate, which may be used alone or in combination of two or more thereof. The magnetic paint composition may optionally contain other additives such as dispersing agents, lubricating agents, polishing agents, antistatic agents, or the like. The present invention is illustrated by the following Examples, but should not be construed to be limited thereto. Example 1 A solution of ferric chloride (FeC13.6H2O) (10 moles) in water (30 liters) (i e. an aqueous ferric chloride solution) and a solution of sodium hydroxide (60 moles) in water (60 liters) (i.e. an aqueous sodium hydroxide solution) are prepared. The aqueous ferric chloride solution is added to the aqueous sodium hydroxide solution at OOC to produce brown precipitates. The mixture is aged at room temperature for 18 hours, and the supernatant liquid is partly removed. The remaining solution is put in an autoclave and subjected to hydrothermal reaction at l800C for one hour. After the reaction, the produced yellow precipitates are separated and washed with water, filtered and then dried to give ferric oxyhydroxide particles, which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an axial ratio of 4,0, and a specific surface area of 34 m2/g (measured by BET method). The a-ferric oxyhydroxide particles (800 g) are spreaded on a quartz board and put within a tubular electric furnace, and then are reduced by passing therethrough hydrogen gas at rate of 5 liters/minute at 3000C to give Fe3O4 particles, which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an axial ratio of 4.0, a specific surface area of 32.1 m2/g (measured by BET method), a coercive force of 21.9 KA/m, and a squareness ratio of 0.4. A part of the magnetic particles obtained above is oxidized by heating at 2500C in air to give r -Fe2O3 particles, which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an axial ratio of 4,0, a specific surface area of 32,1 m2/g (measured by BET method), a coercive force (Hc) of 19.9 KA/m, and a squareness ratio 10 r/(Ys) of 0.4. By using the r-Fe2O3 particles thus obtain, a magnetic paint composition is prepared in the follows ing formulation. Ingredients Parts by weight r-Fe2O3 particles 80 VAGH (vinyl chloride-vinyl acetate-vinyl alcohol copolymer, 11 manufacture by U.C.C. in U.S.A.) Vandex T-5250 (urethane elastomer, 7 manufacture by Dainippon Ink Co.) Colonate L (a trifunctional low molecular weight isocyanate com- 2 pound, manufactured by Nippon Polyurethane Kogyo K.K.) Cyclohexanone 60 Toluene 60 The above ingredients are mixed well in a ball mill for 72 hours to give a magnetic paint composition. The magnetic paint composition is applied to a polyester base film in a thickness of 4 mm (in dry state) and dried. After surface treatment, the film is cut in a fixed width to give a magnetic tape. Example 2 In the same manner as described in Example 1 except that the temperature at the step of adding the aqueous ferric chloride solution to the aqueous sodium hydroxide solution is 10 C, there are obtained #-Fe2O3 particles which have a long axis diameter of 200 nm, a short axis diameter of 50 nm, a specific surface 2 area of 25.0 m /g (measured by BET method), a coercive force (Hc) of 23.9 KA/m, and a squareness ratio (5r/s) of ).45. By using the,-Fe203 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 3 In the same manner as described in Example 1 except that the temperature at the step of adding the aqueous ferric chloride solution to the aqueous sodium hydroxide solution is 20 C, there are obtained t -Fe2O3 particles which have a long axis diameter of 240 nm, a short axis diameter of 60 nm, an axial ratio of 4,0, a specific surface area of 25 m2/g (measured by BET method), a coercive force (Hc) of 25.5 KA/m, and a squareness ratio (r/ms) of 0.45. By using the T-Fe2O3 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 4 In the same manner as described in Example 1 except that the aqueous ferric chloride solution is a solution of ferric chloride (15 moles) in water (30 liters), and the aqueous sodium hydroxide solution is a solution of sodium hydroxide (60 moles) in water (60 liters), and the aqueous ferric chloride solution is added to the aqueous sodium hydroxide solution at -20C, there are obtained r-Fe203 particles which have a long axis diameter of 100 nm, a short axis diameter of 30 nm, an axial ratio of 3.3, a 2 specific surface area of 33.4 m /g (measured by BET method), a coercive force (Hc) of 18.3 KA/m, and a squareness ratio (6r/s) of 0.4. By using the t-Fe203 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 5 In the same manner as described in Example 1 except that the aqueous ferric chloride solution is replaced by an aqueous solution containing a trivalent iron ion which is prepared by dissolving ferrous sulfate CFeSO4.7H2O) (10 moles) in water (30 liters), adding thereto sulfuric acid (250 ml) and further sodium chlorate (200 g) and heating the mixture at 600C, there are obtained ferric oxyhydroxide particles which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an azial ratio of 4.0, and a specific surface area of 35 m2/g (measured by BET method). Likewise, the magnetic magnetite particles (Fe304 particles) and the magnetic maghemite particles e203 particles) are obtained. Reference Example 1 A solution of ferrous sulfate (FeSO4.7H2O) (10 moles) in water (40 liters) (aqueous ferrous sulfate solution) and a solution of sodium hydroxide (70 moles) in water (40 liters) (aqueous sodium hydroxide solution) are prepared. The aqueous sodium hydroxide solution is added to the aqueous ferrous sulfate solution at 250C to produce pale green precipitates. While heating the suspension at 400C in a constant temperature water bath, air is blown in the suspension at a rate of 10 liters/minute and the oxidation reaction is continued for 6 hours. The resulting yellow precipitates are separated, washed with water, filtered and then dried to give a-ferric oxyhydroxide particles. The ferric oxyhydroxide particles are reduced and then oxidized in the same manner as described in Example 1 to give t-Fe203 particles which have a long axis diameter of 200 nm, a short axis diameter of 30 nm, an axial ratio of 6.7, a 2 specific surface area of 50 m /g (measured by BET method), a coercive force (Hc) of 14.3 KA/m, and a squareness ratio (5r/s) of 0.3. By using the t-Fe203 particles, a magnetic tape is prepared in the same manner as described in Example 1. Reference Example 2 In the same manner as described in Reference Example 1 except that the aqueous sodium hydroxide solution is added to the aqueous ferrous sulfate solution at 250C to produce pale green precipitates and the suspension is air-oxidized while heating at 500C in a constant temperature water bath, there are obtained t-Fe203 particles which have a long axis diameter of 280 nm, a short axis diameter of 40 nm, an axial ratio of 7, a specific surface area of 40 m2 /9 (measured by BET method), a coercive force (Hc) of 18.3 KA/m, and a squareness ratio #R/#S) of 0.35. By using the T-Fe2O3 particles, a magnetic tape is prepared likewise. As to the magnetic tapes prepared in the above Examples and Reference Examples, the coercive force (Hc), residual magnetic flux density (Br), squareness ratio (Br/Bs), DC S/N (direct current, a ratio of signal to noise) and ACs/N (alternating current, a ratio of signal to noise) were measured. The results are shown in Table 1. Table 1 EMI18.1 <tb> Ex. <SEP> Coercive <SEP> Residual <SEP> Squareness <SEP> 0 <SEP> DCS/N <SEP> <SEP> ACS/N <SEP> <tb> <SEP> No. <SEP> force <SEP> magnetic <SEP> ratio <tb> <SEP> Hc <SEP> CKA/m) <SEP> flux <SEP> Br/Bs <SEP> QaB) <SEP> (dB) <tb> <SEP> density <tb> <SEP> Br <SEP> (T) <tb> <SEP> Ex. <SEP> 1 <SEP> 21.5 <SEP> J <SEP> <SEP> 0.148 <SEP> 0.78 <SEP> +0.6 <SEP> +1.0 <tb> t <SEP> 2 <SEP> 24.7 <SEP> 1 <SEP> 0.155 <SEP> 0.80 <SEP> 0 <SEP> 0 <tb> <SEP> " <SEP> 3 <SEP> 26.3 <SEP> 1 <SEP> <SEP> 0.158 <SEP> 0.81 <SEP> -0.3 <SEP> -0.8 <tb> <SEP> " <SEP> 4 <SEP> 19.9 <SEP> 0.146 <SEP> 0.76 <SEP> +0.8 <SEP> +1.2 <tb> <SEP> Ref. <tb> <SEP> Ex. <SEP> 1 <SEP> 15.9 <SEP> 0.12 <SEP> 0.70 <SEP> -0.8 <SEP> -1.2 <tb> # <SEP> " <SEP> 2 <SEP> # <SEP> 19.9 <SEP> # <SEP> 0.128 <SEP> # <SEP> <SEP> 0.72 <SEP> -1.0 <SEP> -1.6 <tb> As is clear from the above results, the magnetic tapes (in Examples 1 to 4) of the present invention showed superior coercive force, residual magnetic flux density and squareness ratio and lower DCs;/N and ACs/N in comparison with those of the convenional magnetic tapes (Reference Examples 1 and 2), which means that the magnetic recording medium obtained by the present invention is superior to the conventional magnetic recording medium in terms of dispersibility, orientation property and also surface smoothness with sufficiently low noise. Example 6 The r-Fe2O3 particles (800 g) obtained in Example 2 are dispersed in a solution of cobalt sulfate (0.4 mole) and ferrous sulfate (1.2 mole) in water (3 liters), and thereto is added a solution of sodium hydroxide (16 moles) in water (3 liters). The dispersion is heated to 450C and stirred for 6 hours with keeping this temperature. The resulting magnetic particles are separated, washed well with water to remove the reaction solution, and then dried to give magnetic cobalt-containing iron oxide particles, which have a long axis diameter of 200 nm, a short axis diameter of 50 nm, an axial ratio of 4, a specific surface area of 22.1 m2/g (measured by BET method), a coercive force of 51.7 KA/m, and a cobalt atom content of 2.57 % by weight. By using the magnetic cobalt-containing Tape203 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 7 The Foe 0 particles (800 g) obtained in Example 1 are dispersed in a solution of cobalt sulfate (0.4 mole) in water (3 liters) and thereto is added a solution of sodium hydroxide (4 moles) in water (3 liters). The dispersion is heated to 400C and stirred for 8 hours with keeping this temperature. The resulting magnetic particles are separated, washed well with water to remove the reaction solution, and then dried to give magnetic cobalt-containing iron oxide particles, which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an axial ratio of 4, a specific surface area of 29,8 m2/g (measured by BET method), a coercive force of 45.7 KA/m, and a cobalt atom content of 2.84 % by weight. By using the cobalt-containing Fe3O4 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 8 In the same manner as described in Example 6 except that the T-Fe2O3 particles obtained in Example 2 are replaced by the #-Fe2O3 particles obtained in Example 1, there are obtained magnetic cobalt-containing iron oxide particles which have a long axis diameter of 140 nm, a short axis diameter of 35 nm, an axial ratio of 4, a specific surface area of 28.2 2 m /g (measured by BET method), a coercive force of 50.2 KA/m, and a cobalt atom content of 2.52 % by weight. By using the magnetic cobalt-containing iron oxide particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 9 The ,-Fe2O3 particles (800 g) obtained in Example 2 are dispersed in a solution of cobalt chloride (CoCl2.6H2O) (.0.8 mole) in water (2 liters) and thereto is added an aqueous solution (2 liters) containing sodium citrate (0.3 mole) and sodium tartrate (0.15 mole) as a complexing agent, and the mixture is subjected to hydrothermal reaction at 2000C for 3 hours. After the reaction, the produced cobalt-containing r-Fe203 particles are separated by filtration, washed with water, dried, and then oxidized by heating at 2000C for 3 hours in air to give magnetic cobalt-containing iron oxide particles which have a long axis diameter of 200 nm, a short axis diameter of 50 nm, an axial ratio of 4, a specific surface area of 24,5 m2/g (measured by BET method), a coercive force of 65.3 KA/m, a saturated magnetization (ms) of 9.06 x 10 3 Wb.m/kg, a squareness ratio (mr/s) of 0.78, and a cobalt atom content of 5.90 % by weight. By using the magnetic cobalt-containing 1-Fe2o3 particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 10 In the same manner as described in Example 9 except that the ,-Fe2O3 particles obtained in Example 2 are replaced by the r-Fe2O3 particles obtained in Example 1, there are obtained magnetic cobalt-containing iron oxide particles which have a long axis diameter of 120 nm, a short axis diameter of 30 nm, an axial ratio of 4, a specific surface area of 2 29.8 m /g (measured by BET method), a coercive force of 63.5 KA/m, a saturated magnetization (pus) of 8.08 x 10 3 Wb.m/kg, a squareness ratio (Cr/s) of 0.77, and cobalt atom content of 5.78 % by weight. Reference Example 3 A solution of ferrous sulfate (FeSO4.7E2O) (10 moles) in water C40 liters) (aqueous ferrous sulfate solution) and a solution of sodium hydroxide (70 moles) in water (40 liters) (aqueous sodium hydroxide solution) are prepared. The aqueous sodium hydroxide solution is added to the aqueous ferrous sulfate solution at 250C to produce pale green precipitates. While heating the suspension at 400C in a constant temperature water bath, air is blown into the suspension at a rate of 19 liters/minute, and the oxidation reaction is continued for 6 hours. The resulting yellow precipitates are separated, washed with water, filtered, and then dried to give ferric oxyhydroxide particles. The ferric oxyhydroxide particles are reduced with heating and then oxidized to obtain r-Fe2O3 particles in the same manner as described in Example 1. The t-Fe203 particles are subjected to hydrothermal reaction in the same manner as described in Example 9, by which cobalt atoms are uniformly substituted within the iron oxide particles to give magnetic cobalt-containing t-Fe203 particles which have a long axis diameter of 200 nm, a short axis diameter of 30 nm, an axial ratio of 6.7, a specific surface area of 47,9 m2/g (measured by BET method), a coercive force of 51.7 KA/m, and cobalt atom content of 5.89 % by weight. By using the magnetic cobalt-containing -Fe2O3 particles, a magnetic tape is prepared in the same manner as described in Example 1. In order to study the coercive force distribution of the magnetic cobalt-containing iron oxide particles obtained in Example 6 and Reference Example 3, the distribution of the anisotropic magnetic field was measured by using a vibrating magnetometer. The results are shown in the accompanying Figure 1, wherein the graph A shows the distribution of the anisotropic magnetic field of the magnetic particles obtained in Example 6, and the graph B shows the distribution of the anisotropic magnetic field of the magnetic particles obtained in Reference Example 3. As is clear from the graphs, the magnetic cobalt-containing iron oxide particles of the present invention have narrower distribution of the anisotropic magnetic field than that of the product in Reference Example, which means that the magnetic cobalt-containing iron oxide particles of the present invention has excellent coercive force distribution. Besides, in order to study the stability of magnetic properties of the cobalt-containing iron oxide particles obtained in Examples 6 to 10 and Reference Example 3, the demagnetization by heating was measured and then the print-through was tested. The demagnetization by heating was measured as follows. The magnetic particles to be tested were packed in a vessel (diameter: 6 mm, height: 3 mm) and were saturatedly magnetized in a magnetic field of 796 KA/m at room temperature, and then, the saturated remanent magnetization (Irs) was measured. Thereafter, the saturatedly magnetized particles were kept at 600C for 2 hours and taken out at room temperature, and then the remanent magnetization (Ir) was measured. Based on the data thus obtained, the demagnetization by heating was calculated by the following formula: Demagnetization by heating (%) EMI24.1 The print-through was tested as follows: The magnetic particles to be tested were packed in a vessel (diameter: 6 mm, height: 3 mm) and kept in a magnetic field of 3.2 KA/m at 600C for one hour, and then, the remanent magnetization (Ir3 2) was measured at room temperature, and thereafter, the particles were saturatedly magnetized in a magnetic field of 796 KA/m, and then, the saturated remanent magnetization (Irs) was measured. Based on the data thus obtained, the print-through was calculated in decibel by the following formula: Print-through (dB) EMI25.1 The results are shown in the following Table 2. Table 2 EMI25.2 --------------------------------------------------------------------------- <tb> <SEP> Ex. <SEP> 6 <SEP> Ex. <SEP> 7 <SEP> Ex. <SEP> 8 <SEP> Ex. <SEP> 9 <SEP> Ex.10 <SEP> Ref. <SEP> Ex. <SEP> 3 <tb> <SEP> Demagneti <tb> zation <SEP> by <SEP> 0.2 <SEP> 0.4 <SEP> 0.2 <SEP> 2.2 <SEP> 2.4 <SEP> 5.2 <tb> <SEP> heating <tb> <SEP> --------------------------------------------------------------------------- <tb> Print-through <SEP> 57.1 <SEP> 55.2 <SEP> 56,8 <SEP> 51.0 <SEP> 50.3 <SEP> 44.6 <tb> <SEP> (dB) <tb> As is clear from the above table, the magnetic cobalt-containing iron oxide particles of the present invention (in Examples 6 to 10) have all less demagnetizatiom by heating and less print-through in comparison with those of the conventional magnetic cobalt-containing iron oxide particles (Reference Example 3), which means that the magnetic cobalt-containing iron oxide particles of the present invention have excellent heat stability. Moreover, as to the magnetic tapes obtained in Examples 6 to 10 and Reference Example 3, the coercive force (Hc), residual magnetic flux density (Br), sguareness ratio (Br/Bs), DCs/N, and ACs/N were measured, and further erasability was tested. The erasability was tested as follows: A signal of 1 KHz was recorded on the magnetic tape to be tested at an input of +5dB, and it was erased with an erasing current of 20 % larger than the erasing current which could make the erasability of a standard magnetic tape (BASS C401R) to be 0.5 dB, and then the difference between the regenerated output signal before and after the erasing was calculated, which was shown by "dB". The results are shown in Table 3. Table 3 EMI27.1 Ex. <SEP> coercive <SEP> # <SEP> Residual <SEP> # <SEP> Sguareness <SEP> # <SEP> DCS/N <SEP> ACS/N# <SEP> eras- <SEP> # <tb> No. <SEP> force <SEP> magnetic <SEP> ratio <SEP> ability <tb> <SEP> Hc <SEP> (KA/m) <SEP> flux <SEP> Br/Bs <SEP> (dB) <SEP> (dB) <SEP> (dB) <tb> <SEP> density <tb> <SEP> Br <SEP> (T) <tb> Ex. <SEP> 6 <SEP> 54.9 <SEP> 0.175 <SEP> 0.80 <SEP> 0 <SEP> 0 <SEP> 75.1 <tb> 7 <SEP> 47.1 <SEP> 0.180 <SEP> 0.80 <SEP> +0.2 <SEP> +0.2 <SEP> 72.0 <tb> 8 <SEP> 8 <SEP> 53.3 <SEP> 0.173 <SEP> 0.80 <SEP> +0.3 <SEP> +0.3 <SEP> 71.2 <tb> l <SEP> 9 <SEP> 68.5 <SEP> 0.165 <SEP> 0.82 <SEP> 0 <SEP> 0 <SEP> 63.0 <tb> <SEP> 10 <SEP> 67.2 <SEP> 0.160 <SEP> 0.81 <SEP> +0.1 <SEP> +0.1 <SEP> 61.8 <tb> Ref. <tb> Ex. <SEP> 3 <SEP> 58.1 <SEP> 0.120 <SEP> 0.70 <SEP> -1.1 <SEP> -1.8 <SEP> 54.0 <tb> As is clear from the above table, the magnetic tapes prepared from the magnetic cobalt-containing iron oxide particles of the present invention (Examples 6 to 10) show higher coercive force, residual magnetic flux density and squareness ratio, and lower DCS/N and ACS/N and superior erasability in comparison with the conventional magnetic tape (Reference Example 3), which means that the magnetic recording medium prepared from the magnetic cobaltcontaining iron oxide particles of the present inventtion have excellent magnetic characteristics and improved erasability with less noise. Example 11 The ferric oxyhydroxide particles (800 g) obtained in Example 6 are dispersed in water (40 liters), and thereto are added an aqueous solution (10 liters) of sodium hydroxide (concentration: 1 mole/liter) and an aqueous solution (1.3 liter) of sodium orthosilicate (concentration: 1 mole/liter), and the mixture is neutralized until pH 8 or less by blowing carbon dioxide with stirring, by which silicic acid sol is deposited on the surface of particles. The particles are separated, washed with water and dried to give ferric oxyhydroxide particles which are coated with the silicate compound. The ferric oxyhydroxidewparticles coated with a silicate compound on the surface thereof (800 g) are spreaded on a quartz board and put in a tubular electric furnace, and then are reduced by passing therethrough hydrogen gas at a rate of 20 liters/ minute at 4500C to give magnetic metallic iron particles, which have a long axis diameter of 180 nm, a short axis diameter of 50 nm, an axial ratio of 2 3.6, and a specific surface area of 28 m /g (measured by BET method). By using the magnetic metallic iron particles, a magnetic tape is prepared in the same manner as described in Example 1. Example 12 In the same manner as described in Example 11 except that the coating treatment of a silicate compound onto the -ferric oxyhydroxide particles is omitted, there are obtained magnetic metallic iron particles which have a long axis diameter of 150 nm, a short axis diameter of 50 nm, an axial ratio of 3, and a specific 2 surface area of 25 m /g (measured by BET method). By using the magnetic metallic iron particles, a magnetic tape is prepared in the same manner as described in Example 1. Reference Example 4 A solution of ferrous sulfate (FeSO4.7H2O) (10 moles) in water (:40 liters) (an aqueous ferrous sulfate solution) and a solution of sodium hydroxide (70 moles) in water (40 liters) (an aqueous sodium hydroxide solution) are prepared, and the aqueous sodium hydroxide solution is added to the aqueous ferrous sulfate solution at 250C to obtain pale green precipitates. While heating the suspension at 500C in a constant temperature water bath, air is blown in the suspension at a rate of 10 liters/minute and the oxidation reaction is continued for 6 hours. The resulting yellow precipitates are separated, washed with water, filtered and then dried to give ferric oxyhydroxide particles which have a long axis diameter of 270 nm, a short axis diameter of 30 nm, an axial ratio of 9, and a specific surface area of 48 m2/g (measured by BET method). The ferric oxyhydroxide particles thus obtained are subjected to the coating treatment with a silicate compound in the same manner as described in Example 11, and further reduced with heating likewise to give magnetic metallic iron particles which have a long axis diameter of 270 nm, a short axis diameter of 30 nm, an axial ratio of 9, and specific 2 surface area of 45 m /g (measured by BET method). By using the magnetic metallic iron particles, a magnetic tape is prepared in the same manner as described in Example 1. As to the magnetic metallic iron particles obtained in Examples 11 and 12 and Reference Example 4, the corrosion resistance was tested in the following manner. The magnetic metallic iron particles to be tested were allowed to stand at 600C and 90 % RH (relative humidity), and the saturated magnetization was measured at a fixed time interval. The obtained values are shown by the ratio (lowering ratio) to the saturated magnetization of the magnetic metallic iron particles before test (as 100 %). The results are shown in Table 4. Table 4 EMI31.1 <tb> Ex. <SEP> No. <SEP> Corrosion <SEP> resistance <tb> <SEP> (saturated <SEP> magnetization, <SEP> %) <tb> <SEP> After <tb> 3 <SEP> days <SEP> 10 <SEP> days <SEP> # <SEP> 20 <SEP> days <SEP> # <SEP> 60 <SEP> days <tb> Ex. <SEP> 11 <SEP> 3.0 <SEP> 6.0 <SEP> 7.8 <SEP> 10.2 <tb> <SEP> " <SEP> 12 <SEP> 2.5 <SEP> 4.9 <SEP> 6.4 <SEP> 8.4 <tb> Ref. <SEP> <tb> Ex. <SEP> 4 <SEP> 7.1 <SEP> 14.0 <SEP> 18.5 <SEP> 24.2 <tb> As is clear from the above table, the magnetic metallic iron particles of the present invention (Examples 11 and 12) show less lowering of saturated magnetization in comparison with the conventional magnetic metallic iron particles (Reference Example 4), which means that the magnetic metallic iron particles of the present invention have excellent corrosion resistance. Besides, as to the magnetic tapes prepared in Examples 11 and 12 and Reference Example 4, the coercive force (Hc), residual magnetic flux density (Br), squareness ratio (Br/Bs), DC5/N and AC /N were measured, and further the corrosion resistance was tested. The corrosion resistance was tested in the following manner: The magnetic tapes to be tested were allowed to stand at 600C and 90 t mi, and the maximum magnetic flux density was measured at a fixed time interval. The obtained values are shown by the ratio (lowering ratio) to the maximum magnetic flux density of the magnetic tapes before test (as 100 %). The results are shown in Table 5. EMI33.1 Ex. <SEP> No. <SEP> Coercive <SEP> Residual <SEP> Squareness <SEP> DCS/N <SEP> ACS/N <SEP> Corrosion <SEP> resistance <tb> <SEP> force <SEP> magnetic <SEP> ratio <SEP> (dB) <SEP> (dB) <SEP> (maximum <SEP> magnetic <SEP> flux <SEP> density, <SEP> %) <tb> <SEP> Hc <SEP> (KA/m) <SEP> flux <SEP> (Br/Bs) <SEP> (dB) <SEP> (dB) <SEP> ----------------------------------- <SEP> densit <SEP> After <tb> <SEP> Br <SEP> (T) <SEP> 3 <SEP> days <SEP> 10 <SEP> days <SEP> 20 <SEP> days <SEP> 60 <SEP> days <tb> ----------------------------------------------------------------------------------------------------- Ex. <SEP> 11 <SEP> 96.3 <SEP> 0.292 <SEP> 0.76 <SEP> +0.8 <SEP> +1.2 <SEP> 1.2 <SEP> 2.4 <SEP> 3.1 <SEP> 4.0 <tb> " <SEP> 12 <SEP> 86.8 <SEP> 0.269 <SEP> 0.71 <SEP> 0 <SEP> 0 <SEP> 1.0 <SEP> 1.9 <SEP> 2.5 <SEP> 3.3 <tb> Ref. <tb> Ex. <SEP> 4 <SEP> 109.8 <SEP> 0.244 <SEP> 0.64 <SEP> -1.2 <SEP> -1.8 <SEP> 2.8 <SEP> 5.6 <SEP> 7.5 <SEP> 9.8 <tb> ----------------------------------------------------------------------------------------------------- Table As is clear from the above table, the magnetic tapes prepared from the magnetic metallic iron particles of the present invention (Examples 11 and 12) show higher residual magnetic flux density and squareness ratio, lower DCS/N and ACS/N' and smaller lowering ratio of maximum magnetic flux density in corrosion resistance test in comparison with the conventional magnetic tape (Reference Example 4), which means that the magnetic recording medium prepared from the magnetic metallic iron particles of the present invention have excellent magnetic characteristic and further excellent corrosion resistance.

Claims: What is claimed is: 1. A method for the production of magnetic iron oxide particles, which comprises reacting an aqueous solution containing a trivalent iron ion with an equivalent or more amount of an aqueous alkali solution at a temperature of 300C or lower, aging the produced ferric hydroxide, subjecting the ferric hydroxide to hydrothermal reaction in an autoclave to produce a-ferric oxyhydroxide particles, filtering and drying the particles, and then reducing the particles with heating and optionally further oxidizing them. 2. A method according to claim 1, wherein the resulting iron oxide particles are dispersed in an aqueous solution containing a cobalt salt and thereto is added an aqueous alkali solution and thereby a layer containing predominantly cobalt is formed on the surface region of the particles. 3. A method according to claim 2, wherein the aqueous solution containing a cobalt salt contains further a ferrous ion. 4. A method according to claim 1, wherein the resulting iron oxide particles are dispersed in an aqueous solution containing a cobalt salt and the dispersion is subjected to hydrothermal reaction and thereby the cobalt is substituted within the particles. 5. A method for the production of magnetic metallic iron particles, which comprises reacting an aqueous solution containing a trivalent iron ion with an equivalent or more amount of an aqueous alkali solution at a temperature of 300C or lower, aging the produced ferric hydroxide, subjecting the ferric hydroxide to hydrothermal reaction in an autoclave to produce ferric oxyhydroxide particles, filtering and drying the particles, and then reducing the particles with a reducing gas with heating. 6. A method according to claim 5, wherein the a-ferric oxyhydroxide particles are coated with a silicate compound or an aluminum compound before the reduction thereof. 7. Magnetic iron oxide particles which have a long axis diameter of 300 nm or less, an axial ratio 2 of 5 or less and a specific surface area of 40 m or less (measured by BET method). 8. The magnetic iron oxide particles according to claim 7, which have a layer containing predominantly cobalt on the surface region of the seeds of the particles and have a long axis diameter of 300 nm or less, an axial ratio of 5 or less, a specific surface area 2 of 40 m /g or less (measured by BET method) and a co- ercive force of 23.9 KA/m or more. 9. Magnetic cobalt-containing iron oxide particles which are substituted with cobalt atoms and have a long axis diameter of 300 nm, an axial ratio of 5 or less and a coercive force of 39.8 RA/m or more. 10. Magnetic metallic iron particles which have a long axis diameter of 300 nm, an axial ratio 2 of 5 or less, a specific surface area of 40 m /g or less (measured by BET method). 11. A magnetic recording medium which is prepared by using the magnetic particles as set forth in any one of claim 7, 8, 9 or 10.

Inventors: ADO, KAZUAKI, ASAI, TAKASHI, KISHIMOTO, MIKIO, KITAOKA, SUSUMU, NOBUOKA, SOICHIRO
Applicants: AGENCY OF INDUSTRIAL SCIENCE AND TECHNOLOGY, HITACHI MAXELL LTD.
Application year: 1982
Main classification: H01F1
IPC codes: G11B5