JP2009084115A - Method for producing iron nitride powder, iron nitride powder and magnetic recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for producing an iron nitride powder composed of fine particles, and to provide a magnetic recording medium containing the iron nitride powder and suitable for high density recording. <P>SOLUTION: The method for producing the iron nitride powder comprises subjecting iron oxide particles to a sintering preventing treatment, a reduction treatment, and a nitriding treatment in this order. Particles are produced by subjecting an aqueous iron salt solution containing an iron (II) salt and/or an iron (III) salt to a neutralization treatment, and the produced particles are subjected to an oxidation treatment and/or a reduction treatment thereby magnetite particles are obtained. The obtained magnetite particles are used as the above iron oxide particles. The neutralization treatment is carried out by adding at least one kind of aqueous solution selected from the group comprising aqueous ammonia, an aqueous ammonium salt solution, and an aqueous urea solution to the above aqueous iron salt solution. The sintering preventing treatment comprises adding a sintering preventing agent to the solution containing the above iron oxide particles and then adding a neutralizing agent to the solution to which the sintering preventing agent has been added to neutralize it. As the above neutralizing agent, at least one kind selected from the group comprising ammonia, carbon dioxide gas and acetic acid is used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an iron nitride powder suitable as a ferromagnetic powder for use in a magnetic recording medium for high density recording. The present invention further relates to an iron nitride powder suitable for high-density recording and a magnetic recording medium containing the iron nitride powder.

  In recent years, means for transmitting terabyte-class information at a high speed have been remarkably developed, and it has become possible to transfer images and data having enormous information. Along with the improvement of this data transfer technique, recording / reproducing apparatuses and recording media for recording, reproducing and storing information are required to have a higher recording capacity.

  Regarding magnetic tape, there are various uses such as audio tape, video tape, computer tape, etc. Especially in the field of data backup tape, with the increase in the capacity of the hard disk to be backed up, several 10 to 800 GB per volume. Those with recording capacity have been commercialized. Also, a large capacity backup tape exceeding 1 TB has been proposed, and it is essential to increase the recording capacity.

As an approach from the viewpoint of manufacturing a magnetic recording medium for increasing the recording capacity, improvement of magnetic powder has been studied. As the magnetic powder, ferromagnetic metal powder and hexagonal ferrite powder are widely used. In recent years, magnetic recording media containing iron nitride powder have been proposed. For example, Patent Documents 1 to 3 disclose magnetic recording media using iron nitride powder containing an Fe ₁₆ N ₂ phase. The iron nitride powder containing the Fe ₁₆ N ₂ phase is known to be advantageous for high-density recording because it has a huge magnetic moment and a large saturation magnetization. Patent Documents 1 and 2 describe that rare earth elements are deposited on starting materials such as magnetite during the production of iron nitride powder. Such a deposition process is performed to prevent sintering between particles.
WO03 / 79332 JP 2004-335019 A JP 2006-196115 A

  In order to achieve high density recording, it is important to use magnetic powder having excellent magnetic properties (saturation magnetization, coercive force, etc.) as magnetic powder and to make the magnetic powder fine particles. However, as a result of the inventor's investigation, when iron nitride powder is produced by the method described in Patent Documents 1 to 3, a large amount of inter-particle sintering occurs despite the anti-sintering treatment, and fine-grain iron nitride It has proven difficult to obtain a powder. Since iron nitride powder with a large amount of inter-particle sintering is inferior in magnetic properties and dispersibility when preparing a magnetic layer coating solution, magnetic recording media prepared using such iron nitride powders have surface smoothness and electromagnetic properties. Conversion characteristics are low and not suitable for high density recording.

  Accordingly, an object of the present invention is to provide means for producing fine iron nitride powder and to provide a magnetic recording medium suitable for high-density recording including fine iron nitride powder.

As a result of intensive studies to achieve the above object, the present inventor has obtained the following knowledge.
In the Examples of Patent Documents 1 to 3, sodium hydroxide is used as a neutralizing agent during the rare earth element deposition treatment. Sodium contained in the neutralizing agent remains in the particles even after the deposition treatment, and it is extremely difficult to completely remove them by a washing treatment such as washing with water, and is considered to remain in the particles before nitriding. The present inventor has obtained new knowledge that sodium in the neutralizing agent promotes sintering during reduction. Furthermore, in the Examples of Patent Documents 1 and 2, sodium hydroxide is also used in wet synthesis of magnetite particles. However, wet-synthesized magnetite particles tend to be dense aggregates, and when sodium is present in the particles, it tends to be a ferromagnetic metal powder sintered between particles. If such a ferromagnetic metal powder is subjected to nitriding treatment, it is nitrided in a sintered state, and it becomes difficult to obtain fine iron nitride powder.
The inventor has further studied based on the above knowledge, prevents alkali metal from mixing at the time of magnetite particle production, and at least selected from the group consisting of ammonia, carbon dioxide and acetic acid as a neutralizing agent at the time of sintering prevention treatment. By using one kind, it was found that fine particles of iron nitride were obtained by preventing alkali metal such as sodium from being mixed into the particles before the reduction treatment, and the present invention was completed.

That is, the above object has been achieved by the following means.
[1] A method for producing an iron nitride powder, comprising subjecting iron oxide particles to sintering prevention treatment, reduction treatment and nitriding treatment in this order,
Particles are formed by subjecting an iron salt aqueous solution containing iron (II) salt and / or iron (III) salt to neutralization treatment, and optionally, magnetite by subjecting the formed particles to oxidation treatment and / or reduction treatment. Particles are obtained, the obtained magnetite particles are used as the iron oxide particles, and the neutralization treatment is performed using at least one aqueous solution selected from the group consisting of aqueous ammonia, aqueous ammonium salt solution, and aqueous urea solution as the iron salt. By adding to the aqueous solution,
The sintering prevention treatment includes adding a sintering inhibitor to the solution containing the particles, neutralizing the solution after adding the sintering inhibitor by adding a neutralizing agent, and the neutralization. A method for producing iron nitride powder, which uses at least one selected from the group consisting of ammonia, carbon dioxide and acetic acid as an agent.
[2] The average particle size is in the range of 10 to 25 nm, and an alkali metal content iron nitride powder based on Fe ₁₆ N ₂ or less 0.02 mass%.
[3] The iron nitride powder according to [2], which has a coercive force in the range of 143 to 279 kA / m.
[4] The iron nitride powder according to [2] or [3], which has a saturation magnetization in the range of 55 to 110 A · m ² / kg.
[5] A magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on a nonmagnetic support,
The ferromagnetic powder is a magnetic recording medium that is an iron nitride powder manufactured by the manufacturing method according to [1] or an iron nitride powder according to any one of [2] to [4].

  According to the present invention, fine iron nitride powder having an average particle size of 10 to 25 nm can be provided. An iron nitride powder that does not contain an alkali metal or has a very low content of alkali metal has high purity, has little demagnetization after wet heat storage when applied to a medium, and has little increase in the coefficient of friction before and after storage. Thus, according to the present invention, it is possible to provide a magnetic recording medium having excellent electromagnetic conversion characteristics, storage stability, and running durability over time.

[Method of producing iron nitride powder]
The method for producing iron nitride powder of the present invention includes subjecting iron oxide particles to a sintering prevention treatment, a reduction treatment, and a nitriding treatment in this order. In the method for producing iron nitride powder of the present invention, particles are formed by subjecting an iron salt aqueous solution containing iron (II) salt and / or iron (III) salt to neutralization, and optionally, the formed particles are oxidized. Magnetite particles are obtained by performing treatment and / or reduction treatment, and the obtained magnetite particles are used as the iron oxide particles. The neutralization treatment at the time of producing the magnetite particles is performed by adding at least one aqueous solution selected from the group consisting of aqueous ammonia, aqueous ammonium salt solution, and aqueous urea solution to the aqueous iron salt solution. Further, the sintering prevention treatment includes adding a sintering inhibitor to the solution containing the particles, neutralizing the solution after the addition of the sintering inhibitor by adding a neutralizing agent, and As the neutralizing agent, at least one selected from the group consisting of ammonia, carbon dioxide and acetic acid is used. As described above, fine particles of iron nitride powder can be obtained by preventing mixing of alkali metals such as sodium during production.
Below, the manufacturing method of the iron nitride powder of this invention is demonstrated in detail.

The shape of the iron oxide particles used as a raw material particles material particles is preferably an isotropic shape such as a cubic or spherical. As the raw material particles, magnetite particles synthesized by the following method are used. The magnetite particles synthesized by the following method have an alkali metal content reduced to, for example, 0 to 0.02% by mass. In addition, content of an alkali component can be calculated | required by ICP method, atomic absorption method, etc. The average particle size of the raw material particles is preferably 10 nm or more from the viewpoint of preventing sintering and securing the amount of magnetization, and is preferably 30 nm or less in order to obtain fine iron nitride powder.

  Magnetite particles used as raw material particles are formed by neutralizing an iron salt aqueous solution containing iron (II) salt and / or iron (III) salt, and optionally, the formed particles are subjected to oxidation treatment and And / or reducing treatment to obtain magnetite particles, and using the obtained magnetite particles as the iron oxide particles, wherein the neutralization treatment is selected from the group consisting of aqueous ammonia, aqueous ammonium salt and aqueous urea It is produced by a method for synthesizing magnetite particles, which is performed by adding at least one aqueous solution to the aqueous iron salt solution. Hereinafter, a method for synthesizing the magnetite particles will be described.

  As the iron salt aqueous solution, an iron salt containing only one of iron (II) salt (ferrous salt) and iron (III) salt (ferric salt) may be used. ) A salt containing both a salt and an iron (III) salt may be used.

  Examples of the iron salt include sulfate, nitrate, chloride and the like. Moreover, those hydrates can also be used. The iron salt concentration can be, for example, 0.01 to 0.5 mol / L, and preferably 0.02 to 0.3 mol / L. Moreover, when iron (II) salt and iron (III) salt are used together, the mixing ratio is, for example, iron (II) salt: iron (III) salt = 1: 1 to 1: 2. it can.

  In the method for synthesizing the magnetite particles, at least one aqueous solution selected from the group consisting of aqueous ammonia, aqueous ammonium salt solution, and aqueous urea solution is used for the neutralization treatment of the iron salt solution. In this way, magnetite particles free from alkali metal contamination can be obtained by carrying out the neutralization reaction without using an alkali metal hydroxide such as sodium hydroxide. Further, after the neutralization reaction, a known hydrothermal treatment or in-liquid aging reaction may be performed for particle size control or crystallinity improvement.

  What is necessary is just to set the density | concentration of the aqueous solution used for neutralization according to the density | concentration of the said iron salt solution so that pH can be adjusted to about 8-10. For example, when urea is used, it is preferable to add 2.5 to 10 times the iron salt neutralization equivalent. The concentration of the aqueous ammonia and the aqueous ammonium salt solution is preferably 5 to 20% by mass. As the ammonium salt, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphonate, ammonium hydrogen phosphonate, ammonium phosphate, or the like can be used.

If an aqueous solution containing both iron (II) salt and iron (III) salt is used as the iron salt aqueous solution, magnetite particles can be obtained by a neutralization reaction.
On the other hand, when an iron (II) salt aqueous solution is used as the iron salt aqueous solution, ferrous hydroxide is precipitated by the neutralization reaction. In this case, magnetite particles can be obtained by subjecting the obtained ferrous hydroxide to an oxidation treatment. The oxidation treatment can be performed, for example, by introducing air into a suspension in which ferrous hydroxide is precipitated by a neutralization reaction, and heating and holding the suspension for a predetermined time. The heating temperature can be, for example, about 40 to 70 ° C., and the holding time can be about 30 to 180 minutes.
Moreover, when an iron (III) salt is used as the iron salt aqueous solution, ferric hydroxide is precipitated by the neutralization reaction. In this case, magnetite particles can be obtained by subjecting the obtained ferric hydroxide to a reduction treatment. For the reduction treatment in this case, reference can be made to JP-A-8-325098.
In any of the above cases, raw material particles can be obtained by filtering the solution in which the magnetite particles are deposited and subjecting the recovered magnetite particles to a washing treatment such as water washing as necessary.
Next, the sintering prevention process applied to the raw material particles will be described.

Sintering prevention treatment In the method for producing iron nitride powder of the present invention, during the sintering prevention treatment of raw material particles, a sintering inhibitor is added to the solution containing the raw material particles, and the solution after the addition of the sintering inhibitor is neutralized. When neutralizing by adding an agent, at least one selected from the group consisting of ammonia, carbon dioxide and acetic acid is used as the neutralizing agent. Without using sodium hydroxide, which is normally used as a neutralizing agent, by carrying out sintering prevention treatment, it is possible to prevent alkali metal from being mixed into the particles before the reduction treatment, and to effectively prevent sintering. .

As the solution containing the raw material particles, an aqueous solution containing about 2 to 10% by mass of the raw material particles can be used. The aqueous solution is preferably a dispersion in which particles are dispersed by an ultrasonic disperser or the like.

  Any anti-sintering agent added to the solution may be used as long as it exhibits an anti-sintering effect by being deposited on the particle surface, and examples thereof include rare earth elements, aluminum, and silicon. Of these, yttrium and aluminum are preferable. These sintering inhibitors are preferably added in an amount of 1.0 to 40 atomic%, more preferably 4.0 to 30 atomic% with respect to iron. Rare earth elements can be added as nitrates, chlorides and the like, aluminum as chlorides, sodium salts, nitrates and the like, and silicon as sodium silicate salts and the like in the solution containing the raw material particles. Even if the sintering inhibitor is added as a sodium salt, the sodium can be easily removed before the reduction by washing, so that an amount sufficient to promote sintering does not remain in the particles. However, in order to prevent sintering more effectively, it is preferable not to use an alkali component in the production process.

  Next, at least one selected from the group consisting of ammonia, carbon dioxide and acetic acid is added as a neutralizing agent to the solution after the addition of the sintering agent. What is necessary is just to set the addition amount of the said neutralizing agent so that pH can be adjusted. In the case of ammonia, the pH is 7.5 to 9.5, preferably 8.0 to 9.5, and in the case of carbon dioxide, the pH is 5.5 to 6.5, preferably 5.5 to 6. In the case of 0.0 and acetic acid, the pH can be set to, for example, 5.5 to 6.5, preferably 5.5 to 6.0. These neutralizing agents are preferably added while stirring a solution whose temperature is controlled at room temperature or about 35 to 50 ° C.

Reduction treatment, nitriding treatment After performing the above-described sintering treatment, ferromagnetic metal powder can be obtained by performing dehydration and annealing treatment as necessary, followed by hydrogen reduction. If the reduction temperature is 400 ° C. or higher, the inside of the particles can be sufficiently reduced, so that it is possible to avoid a decrease in the nitriding rate due to oxygen remaining in the particles. In order to prevent sintering between particles during reduction, the reduction temperature is preferably 600 ° C. or lower.

Next, nitriding treatment is applied to the obtained ferromagnetic metal powder. To obtain an iron nitride having excellent magnetic properties, it is preferable to form the Fe ₁₆ N ₂ phase is a metastable phase by low-temperature nitriding. If the nitriding temperature is too high, nitriding is excessively promoted, the proportion of Fe ₄ N, Fe ₃ N phase, etc. increases, and it may be difficult to obtain sufficient coercive force and saturation magnetization. However, if the nitriding temperature is too low, nitriding does not proceed sufficiently and the coercive force increasing effect is small. From the above viewpoint, the nitriding temperature is preferably in the range of 100 to 300 ° C. More preferably, it is the range of 120-200 degreeC.
After the nitriding treatment, the target iron nitride powder can be obtained by performing a gradual oxidation treatment as necessary. As conditions for the low-temperature nitridation and the gradual oxidation treatment after nitriding, for example, the conditions shown in JP-A-11-340023, JP-A-2000-277711, and JP-A-2006-196115 can be applied. . The amount of oxygen in the gas used for the nitriding treatment is preferably several ppm or less.

[Iron nitride powder]
Furthermore, the present invention relates to an iron nitride powder mainly composed of Fe ₁₆ N ₂ having an average particle size in the range of 10 to 25 nm and an alkali metal content of 0.02% by mass or less.
The iron nitride powder of the present invention can be obtained by the above-described method for producing the iron nitride powder of the present invention. However, the iron nitride of this invention should just satisfy | fill the above-mentioned average particle diameter and alkali metal ion content, and is not limited to what is manufactured by the said manufacturing method.

The average particle size of the iron nitride powder is in the range of 10 to 25 nm. If the average particle size is less than 10 nm, sufficient magnetic properties cannot be obtained. If the average particle size exceeds 25 nm, it is difficult to obtain a magnetic layer having excellent surface smoothness, and noise is increased, resulting in electromagnetic conversion. Characteristics deteriorate. The surface area of the iron nitride powder is preferably 30 to 90 m ² / g, and more preferably 35 to 80 m ² / g, as a BET specific surface area.
The average particle size in the present invention refers to the average value of the plate diameters of 500 particles measured from a photograph (for example, magnification of 500,000 times) taken with a transmission electron microscope (TEM). In addition, when iron nitride powder has layers, such as an oxide film, on the surface, the said average particle diameter shall mean the size of the whole particle | grains containing an oxide film etc.

  The alkali metal content of the iron nitride powder is 0.02% by mass or less. Iron nitride particles having an alkali metal content exceeding 0.02% by mass are difficult to be finely divided because interparticle sintering occurs during reduction. Furthermore, when applied to a magnetic recording medium, alkali metal binds to a lubricant component such as a fatty acid during storage to form a precipitate such as a fatty acid metal salt, resulting in a decrease in durability after storage. There are also problems such as a large amount of demagnetization. On the other hand, if the iron nitride powder has an alkali metal ion content of 0.02% by mass or less, a magnetic recording medium for high-density recording having good durability and electromagnetic conversion characteristics over a long period of time can be provided. The alkali metal content is preferably in the range of 0 to 0.02, more preferably 0 to 0.018. The content of the alkali metal component can be determined by an ICP method, an atomic absorption method or the like.

Regarding the magnetic properties of the iron nitride powder, the saturation magnetization (σs) is preferably in the range of 55 to 110 A · m ² / kg. If σs is 55 A · m ² / kg or more, a high-intensity signal can be obtained, and if it is 110 A · m ² / kg or less, adjacent recording bits are not affected magnetically during in-plane recording. Recording can be performed satisfactorily. The σs is more preferably in the range of 60 to 105 A · m ² / kg.
The coercive force (Hc) of the iron nitride powder is preferably 143 to 279 kA / m (1800 to 3500 Oe). If Hc is 143 kA / m or more, good recording can be performed without magnetic influence on adjacent recording bits during in-plane recording, and if it is 279 kA / m or less, it is suitable for high-density recording. The Hc is more preferably in the range of 160 to 270 kA / m.

The iron nitride powder is an iron nitride powder containing Fe ₁₆ N ₂ as a main component. The iron nitride powder mainly composed of Fe ₁₆ N ₂ has a large saturation magnetization and is suitable for high density recording. In the present invention, “comprising Fe ₁₆ N ₂ as a main component” means a profile showing the Fe ₁₆ N ₂ phase in X-ray diffraction, and the nitrogen content relative to iron is in the range of 7.0 to 14 atomic%. It means that. The nitrogen content can be measured by fluorescent X-ray analysis, X-ray electron spectroscopy, nitrogen analyzer or the like.
The ratio of nitrogen to iron in Fe ₁₆ N ₂ is 12.5 atomic%, and that the content of nitrogen in iron is 7.0 atomic% or more and less than 12.5 atomic% is not nitrided together with Fe ₁₆ N _2. Of 12.5 atomic% and 14.0 atomic% or less means that a small amount of polynitride is present together with Fe ₁₆ N ₂ . The iron nitride powder preferably has a nitrogen content in the range of 10.0 to 13.0 atomic%, more preferably a composition close to Fe ₁₆ N ₂ . Nitride iron phase contained in the iron nitride powder, it is preferable that a main component Fe ₁₆ N ₂ phase, it is not necessary to be Fe ₁₆ N ₂ phase all, the Fe ₁₆ N ₂ phase α- It may be a mixed phase with the Fe phase, and may include an Fe ₃ N phase and an Fe ₄ N phase. Further, the iron nitride powder may have an iron nitride phase exhibiting ferromagnetism as a core portion (inner layer), and may have a nonmagnetic portion such as an antioxidant layer as an outer layer.

  As described above, the iron nitride powder subjected to the deposition treatment for preventing sintering usually contains one or more elements selected from the group consisting of rare earth metal elements, aluminum and silicon. If the content of the element is too small, the effect of improving dispersibility is small, and the effect of maintaining the shape during reduction is small. On the other hand, if the amount is too large, there are many portions where the above elements remain unreacted, the coercive force and saturation magnetization may be greatly reduced, and there may be problems in the production of media such as the dispersion step and the coating step. Considering the above points, the total content of rare earth elements, aluminum and silicon in the iron nitride powder is preferably 3 to 30 atomic%, more preferably 5 to 25 atomic% with respect to iron. preferable.

[Magnetic recording medium]
Furthermore, the present invention relates to a magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on a nonmagnetic support. The magnetic recording medium of the present invention contains the iron nitride powder produced by the production method of the present invention or the iron nitride powder of the present invention as the ferromagnetic powder. Since the magnetic recording medium of the present invention contains the iron nitride powder, it is excellent in electromagnetic conversion characteristics and running durability over time, and is suitable as a magnetic recording medium for high-density recording.
Hereinafter, the magnetic recording medium of the present invention will be described in more detail.

Binder The magnetic recording medium of the present invention has at least a magnetic layer on a nonmagnetic support, and can further have a nonmagnetic layer between the nonmagnetic support and the magnetic layer. A back coat layer may be provided on the surface opposite to the surface provided with the magnetic layer. The binder, lubricant, dispersant, additive, solvent, dispersion method, and other known techniques for the magnetic layer, nonmagnetic layer, and backcoat layer can be appropriately applied to each other. In particular, known techniques relating to the amount and type of binder, the additive, and the amount and type of dispersant can be applied.

  As the binder, conventionally known thermoplastic resins, thermosetting resins, reactive resins, and mixtures thereof can be used. A thermoplastic resin having a glass transition temperature of −100 to 150 ° C., a number average molecular weight of 1,000 to 200,000, preferably 10,000 to 100,000, and a polymerization degree of about 50 to 1000 is used. can do.

  Examples include vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, There are polymers or copolymers containing vinyl ether as a structural unit, polyurethane resins, and various rubber resins. Thermosetting resins or reactive resins include phenolic resins, epoxy resins, polyurethane curable resins, urea resins, melamine resins, alkyd resins, acrylic reactive resins, formaldehyde resins, silicone resins, epoxy-polyamide resins, polyester resins. And a mixture of an isocyanate prepolymer, a mixture of a polyester polyol and a polyisocyanate, a mixture of a polyurethane and a polyisocyanate, and the like. These resins are described in detail in “Plastic Handbook” published by Asakura Shoten. It is also possible to use a known electron beam curable resin for each layer. These examples and their production methods are described in detail in JP-A No. 62-256219. The above resins can be used alone or in combination, but are preferably selected from vinyl chloride resin, vinyl chloride vinyl acetate copolymer, vinyl chloride vinyl acetate vinyl alcohol copolymer, vinyl chloride vinyl acetate vinyl maleic anhydride copolymer. A combination of at least one selected from the above and a polyurethane resin, or a combination of these with a polyisocyanate.

As the polyurethane resin, those having a known structure such as polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, and polycaprolactone polyurethane can be used. For all binding agents indicated herein, if necessary in order to obtain more excellent dispersibility and _{durability, -COOM, -SO 3 M, -OSO} 3 M, -P = O (OM) 2, - O—P═O (OM) ₂ (wherein M is a hydrogen atom or an alkali metal base), —OH, —NR ₂ , —N ⁺ R ₃ (R is a hydrocarbon group), epoxy group, —SH, — It is preferable to use one in which at least one polar group selected from CN and the like is introduced by copolymerization or addition reaction. The amount of such a polar group is, for example, 10 ⁻¹ to 10 ⁻⁸ mol / g, preferably 10 ⁻² to 10 ⁻⁶ mol / g.

  Specific examples of these binders used in the present invention include VAGH, VYHH, VMCH, VAGF, VAGD, VROH, VYES, VYNC, VMCC, XYHL, XYSG, PKHH, PKHJ, PKHC, PKFE, manufactured by Dow Chemical Co., Ltd. MPR-TA, MPR-TA5, MPR-TAL, MPR-TSN, MPR-TMF, MPR-TS, MPR-TM, MPR-TAO, Denki Kagaku 1000W, DX80, DX81, DX82, manufactured by Nissin Chemical Industry Co., Ltd. DX83, 100FD, Nippon Zeon MR-104, MR-105, MR110, MR100, MR555, 400X-110A, Nippon Polyurethane Nipporan N2301, N2302, N2304, Dainippon Ink, Pandex T-5105, T- R3080, T-5201 Bernock D-400, D-210-80, Crisbon 6109, 7209, Byron UR8200, UR8300, UR-8700, Toyobo Co., Ltd., RV530, RV280, Daiferamin 4020, 5020, 5100, 5300, 9020, 9022 7020, MX5004 manufactured by Mitsubishi Chemical Corporation, Samprene SP-150 manufactured by Sanyo Chemical Co., Ltd., Saran F310, F210 manufactured by Asahi Kasei Corporation, and the like.

For the nonmagnetic layer and the magnetic layer, a binder can be used in the range of, for example, 5 to 50% by mass, and preferably 10 to 30% by mass with respect to the nonmagnetic powder or the magnetic powder. It is preferable to use a combination of 5 to 30% by mass when using a vinyl chloride resin, 2 to 20% by mass when using a polyurethane resin, and 2 to 20% by mass of polyisocyanate. However, for example, when head corrosion occurs due to a small amount of dechlorination, it is possible to use only polyurethane or only polyurethane and isocyanate. The glass transition temperature in the case of using a polyurethane -50 to 150 ° C., preferably from 0 ° C. to 100 ° C., elongation at break from 100 to 2,000% breaking stress 0.05~10kg / mm ² (0.49~98MPa), The yield point is preferably 0.05 to 10 kg / mm ² (0.49 to 98 MPa).

  Examples of polyisocyanates include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate and the like. Moreover, the product of these isocyanates and polyalcohol, the polyisocyanate produced | generated by condensation of isocyanate, etc. can be used. Commercially available product names of these isocyanates include Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate MTL, Takeda Pharmaceutical Taketake D-102, Takenate D-110N, There are Takenet D-200, Takenate D-202, Death Module L, Death Module IL, Death Module N, Death Module HL, etc. manufactured by Sumitomo Bayer Co., Ltd., either alone or by utilizing the difference in curing reactivity. Alternatively, each layer can be used in combination.

Additives can be added to the magnetic layer as necessary. Examples of the additive include an abrasive, a lubricant, a dispersant / dispersion aid, an antifungal agent, an antistatic agent, an antioxidant, a solvent, and carbon black. Examples of these additives include molybdenum disulfide, tungsten disulfide, graphite, boron nitride, graphite fluoride, silicone oil, silicone having a polar group, fatty acid-modified silicone, fluorine-containing silicone, fluorine-containing alcohol, fluorine-containing ester, Polyolefin, polyglycol, polyphenyl ether, phenylphosphonic acid, benzylphosphonic acid, phenethylphosphonic acid, α-methylbenzylphosphonic acid, 1-methyl-1-phenethylphosphonic acid, diphenylmethylphosphonic acid, biphenylphosphonic acid, benzylphenylphosphonic acid , Α-cumylphosphonic acid, toluylphosphonic acid, xylylphosphonic acid, ethylphenylphosphonic acid, cumenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, heptylph Aromatic ring-containing organic phosphonic acids such as enylphosphonic acid, octylphenylphosphonic acid, nonylphenylphosphonic acid and their alkali metal salts, octylphosphonic acid, 2-ethylhexylphosphonic acid, isooctylphosphonic acid, isononylphosphonic acid, isodecylphosphonic acid Acids, isoundecyl phosphonic acid, isododecyl phosphonic acid, isohexadecyl phosphonic acid, isooctadecyl phosphonic acid, isoeicosyl phosphonic acid, alkylphosphonic acids and alkali metal salts thereof, phenyl phosphate, benzyl phosphate, phosphoric acid Phenethyl, α-methylbenzyl phosphate, 1-methyl-1-phenethyl phosphate, diphenylmethyl phosphate, biphenyl phosphate, benzylphenyl phosphate, α-cumyl phosphate, toluyl phosphate, xylyl phosphate, ethyl phosphate Phenyl Aromatic phosphates such as cumenyl phosphate, propylphenyl phosphate, butylphenyl phosphate, heptylphenyl phosphate, octylphenyl phosphate, nonylphenyl phosphate, and alkali metal salts thereof, octyl phosphate, 2-phosphate Alkyl phosphates such as ethylhexyl, isooctyl phosphate, isononyl phosphate, isodecyl phosphate, isoundecyl phosphate, isododecyl phosphate, isohexadecyl phosphate, isooctadecyl phosphate, isoeicosyl phosphate, and alkali metal salts thereof, alkyl sulfones Acid esters and alkali metal salts thereof, fluorine-containing alkyl sulfates and alkali metal salts thereof, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, butyl stearate, oleic acid, linoleic acid, linolenic acid , Monobasic fatty acids which may contain or be branched, such as elaidic acid and erucic acid, and their metal salts, or butyl stearate, octyl stearate, amyl stearate, stearin One or more unsaturated bonds having 10 to 24 carbon atoms such as isooctyl acid, octyl myristate, butyl laurate, butoxyethyl stearate, anhydrosorbitan monostearate, anhydrosorbitan tristearate, etc. A basic fatty acid and a 1 to 6-valent alcohol which may contain or be branched with an unsaturated bond having 2 to 22 carbon atoms, an alkoxy alcohol which may contain or be branched with an unsaturated bond with 12 to 22 carbon atoms, or A module comprising any one of monoalkyl ethers of alkylene oxide polymer Fatty acid esters, difatty acid esters or polyvalent fatty acid esters, fatty acid amides having 2 to 22 carbon atoms, and aliphatic amines having 8 to 22 carbon atoms can be used. In addition to the above hydrocarbon groups, alkyl groups, aryl groups, and aralkyl groups substituted with nitro groups and groups other than hydrocarbon groups such as halogen-containing hydrocarbons such as F, Cl, Br, CF ₃ , CCl ₃ , and CBr ₃ You may have something.

  In addition, nonionic surfactants such as alkylene oxide, glycerin, glycidol, and alkylphenol ethylene oxide adducts, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocycles, phosphonium or sulfoniums, etc. Amphoteric interfaces such as cationic surfactants, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, and sulfate ester groups, amino acids, aminosulfonic acids, sulfuric or phosphate esters of aminoalcohols, and alkylbetaines An activator or the like can also be used. These surfactants are described in detail in “Surfactant Handbook” (published by Sangyo Tosho Co., Ltd.).

  The above-mentioned lubricant, antistatic agent and the like are not necessarily pure and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, oxides, etc. in addition to the main components. These impurities are preferably 30% by mass or less, more preferably 10% by mass or less.

  Specific examples of these additives include, for example, NAF-102, castor oil hardened fatty acid, NAA-42, cation SA, Naimine L-201, Nonion E-208, Anon BF, Anon LG, Takemoto, manufactured by NOF Corporation. Oil and fat: FAL-205, FAL-123, Shin Nippon Chemical Co., Ltd .: NJ Lube OL, Shin-Etsu Chemical Co., Ltd .: TA-3, Lion Corporation: Armido P, Lion Corporation: Duomin TDO, Nisshin Oilio Co., Ltd .: BA-41G, Sanyo Kasei Co., Ltd .: Profan 2012E, New Pole PE61, Ionette MS-400, etc. are mentioned.

Carbon black can be added to the magnetic layer as necessary. Examples of carbon black that can be used in the magnetic layer include rubber furnace, rubber thermal, color black, and acetylene black. Specific surface area is 5 to 500 m ² / g, DBP oil absorption is 10 to 400 ml / 100 g, particle size is 5 to 300 nm, pH is 2 to 10, moisture content is 0.1 to 10%, tap density is 0.1 to 1 g / ml is preferred.

  As specific examples of carbon black, BLACKPEARLS 2000, 1300, 1000, 900, 905, 800, 700, VULCAN XC-72, manufactured by Cabot Corporation, # 80, # 60, # 55, # 50, #, manufactured by Asahi Carbon Co., Ltd. 35, Mitsubishi Chemical Corporation # 2400B, # 2300, # 900, # 1000, # 30, # 40, # 10B, Colombian Carbon Corporation CONDUCTEX SC, RAVEN150, 50, 40, 15, RAVEN-MT-P, Ketjen・ Ketjen Black EC manufactured by Black International, etc. Carbon black may be surface-treated with a dispersant, or may be used after being grafted with a resin, or may be obtained by graphitizing a part of the surface. Carbon black may be dispersed with a binder in advance before being added to the magnetic coating. These carbon blacks can be used alone or in combination. When using carbon black, it is preferable to use 0.1-30 mass% with respect to the mass of a magnetic body. Carbon black functions to prevent the magnetic layer from being charged, reduce the coefficient of friction, impart light-shielding properties, and improve the film strength. These differ depending on the carbon black used. Therefore, these carbon blacks used in the present invention have different types, amounts, and combinations in the magnetic layer and the non-magnetic layer, and are based on the above-mentioned characteristics such as particle size, oil absorption, conductivity, pH, etc. Of course, it is possible to use them properly according to the purpose, but rather they should be optimized in each layer. For the carbon black that can be used in the magnetic layer of the present invention, for example, “Carbon Black Handbook” edited by Carbon Black Association can be referred to.

As abrasives , α-alumina, β-alumina, silicon carbide, chromium oxide, cerium oxide, α-iron oxide, corundum, artificial diamond, silicon nitride, silicon carbide titanium carbide, oxide with an α conversion rate of 90% or more Known materials having a Mohs hardness of 6 or more, such as titanium, silicon dioxide, and boron nitride, can be used alone or in combination. Moreover, you may use the composite_body | complex (what surface-treated the abrasive | polishing agent with the other abrasive | polishing agent) of these abrasive | polishing agents. These abrasives may contain compounds or elements other than the main component, but the effect is not affected if the main component is 90% or more. The particle size of these abrasives is preferably from 0.01 to 2 μm, and in particular, in order to enhance electromagnetic conversion characteristics, it is preferable that the particle size distribution is narrow. Further, in order to improve the durability, it is possible to combine abrasives having different particle sizes as necessary, or to obtain the same effect by widening the particle size distribution even with a single abrasive. The tap density is preferably 0.3 to ² g / cc, the water content is preferably 0.1 to 5%, the pH is 2 to 11, and the specific surface area is preferably 1 to 30 m ² / g. The shape of the abrasive may be any of acicular, spherical, dice, and plate shapes, but those having a corner in a part of the shape are preferable because of high abrasiveness. Specifically, AKP-12, AKP-15, AKP-20, AKP-30, AKP-50, HIT-20, HIT-30, HIT-55, HIT-60, HIT-70, HIT- manufactured by Sumitomo Chemical Co., Ltd. 80, HIT-100, ERC-DBM, HP-DBM, HPS-DBM manufactured by Reynolds, WA10000 manufactured by Fujimi Abrasives, UB20 manufactured by Uemura Kogyo Co., Ltd., G-5 manufactured by Nippon Chemical Industry Co., Ltd., Chromex U2, U1, Toda Kogyo TF100, TF140, Ibiden Beta Random Ultra Fine, Showa Mining B-3, and the like. These abrasives can be added to the nonmagnetic layer as required. By adding to the nonmagnetic layer, the surface shape can be controlled, and the protruding state of the abrasive can be controlled. The particle size and amount of the abrasive added to these magnetic and nonmagnetic layers should of course be set to optimum values.

  Known organic solvents can be used. As the organic solvent, specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone, tetrahydrofuran, etc., methanol, ethanol, propanol, butanol, isobutyl alcohol, isopropyl alcohol, in any ratio Alcohols such as methylcyclohexanol, esters such as methyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, glycol acetate, glycol ethers such as glycol dimethyl ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene , Aromatic hydrocarbons such as cresol, chlorobenzene, methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethyl Nkuroruhidorin, chlorinated hydrocarbons such as dichlorobenzene, N, N- dimethylformamide, may be used hexane.

  These organic solvents are not necessarily 100% pure, and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, oxides, and moisture in addition to the main components. These impurities are preferably 30% by mass or less, more preferably 10% by mass or less. The organic solvent used in the present invention is preferably the same in the magnetic layer and the nonmagnetic layer. The amount added may be changed. Use non-magnetic layers with high surface tension solvents (cyclohexanone, dioxane, etc.) to increase coating stability. Specifically, the arithmetic average value of the upper layer solvent composition may not fall below the arithmetic average value of the nonmagnetic layer solvent composition. It is essential. In order to improve the dispersibility, it is preferable that the polarity is somewhat strong, and it is preferable that 50% by mass or more of the solvent having a dielectric constant of 15 or more is included in the solvent composition. Moreover, it is preferable that a solubility parameter is 8-11.

  These dispersants, lubricants, and surfactants used in the present invention can be properly used in the magnetic layer and further in the nonmagnetic layer described later as needed. For example, of course, the dispersant is not limited to the example shown here, but the dispersant has a property of adsorbing or binding with a polar group, and in the magnetic layer, mainly on the surface of the ferromagnetic metal powder and nonmagnetic. In the layer, it is presumed that the organic phosphorus compound adsorbed or bonded mainly to the surface of the non-magnetic powder with the polar group, for example, is difficult to desorb from the surface of the metal or the metal compound once adsorbed. Therefore, the surface of the ferromagnetic metal or nonmagnetic powder is covered with an alkyl group, aromatic group or the like, so that the affinity of the ferromagnetic metal powder or nonmagnetic powder for the binder component is improved. Furthermore, the dispersion stability of the ferromagnetic powder or nonmagnetic powder can be improved. In addition, since the lubricant exists in a free state, fatty acids with different melting points are used in the nonmagnetic layer and magnetic layer to control the bleeding to the surface, and leaching to the surface using esters with different boiling points and polarities. It is conceivable to improve the coating stability by controlling the amount of the surfactant, to improve the lubrication effect by increasing the additive amount of the lubricant in the nonmagnetic layer. All or a part of the additives used in the present invention may be added in any step during the production of the coating liquid for the magnetic layer or nonmagnetic layer. For example, when mixing with a ferromagnetic powder before the kneading step, when adding at a kneading step with a ferromagnetic powder, a binder and a solvent, when adding at a dispersing step, when adding after dispersing, when adding just before coating, etc. There is.

Non-magnetic layer Next, detailed contents regarding the non-magnetic layer will be described. The magnetic recording medium of the present invention can have a nonmagnetic layer containing a nonmagnetic powder and a binder between the nonmagnetic support and the magnetic layer. The nonmagnetic powder that can be used in the nonmagnetic layer may be an inorganic substance or an organic substance. Carbon black or the like can also be used. Examples of the inorganic substance include metals, metal oxides, metal carbonates, metal sulfates, metal nitrides, metal carbides, and metal sulfides.

Specifically, titanium oxide such as titanium dioxide, cerium oxide, tin oxide, tungsten oxide, ZnO, ZrO ₂ , SiO ₂ , Cr ₂ O ₃ , α-alumina, β-alumina having an α conversion of 90 to 100%, γ-alumina, α-iron oxide, goethite, corundum, silicon nitride, titanium carbide, magnesium oxide, boron nitride, molybdenum disulfide, copper oxide, MgCO ₃ , CaCO ₃ , BaCO ₃ , SrCO ₃ , BaSO ₄ , silicon carbide Titanium carbide or the like can be used alone or in combination of two or more. Preferred are α-iron oxide and titanium oxide.

  The shape of the nonmagnetic powder may be any of acicular, spherical, polyhedral and plate shapes. The crystallite size of the nonmagnetic powder is preferably 4 nm to 500 nm, more preferably 40 to 100 nm. If the crystallite size is in the range of 4 nm to 500 nm, it is preferable because dispersion does not become difficult and it has a suitable surface roughness. The average particle size of these non-magnetic powders is preferably 5 nm to 500 nm. However, if necessary, non-magnetic powders having different average particle sizes may be combined, or a single non-magnetic powder may have a wide particle size distribution. It can also have an effect. The average particle size of the particularly preferred nonmagnetic powder is 10 to 200 nm. The range of 5 nm to 500 nm is preferable because the dispersion is good and the surface roughness is suitable.

The specific surface area of the nonmagnetic powder is, for example, 1 to 150 m ² / g, preferably 20 to 120 m ² / g, and more preferably 50 to 100 m ² / g. A specific surface area in the range of 1 to 150 m ² / g is preferred because it has a suitable surface roughness and can be dispersed with a desired amount of binder. The oil absorption using dibutyl phthalate (DBP) is, for example, 5 to 100 ml / 100 g, preferably 10 to 80 ml / 100 g, and more preferably 20 to 60 ml / 100 g. The specific gravity is, for example, 1 to 12, preferably 3 to 6. The tap density is, for example, 0.05 to 2 g / ml, preferably 0.2 to 1.5 g / ml. When the tap density is in the range of 0.05 to 2 g / ml, there are few particles to be scattered, the operation is easy, and there is a tendency that it is difficult to adhere to the apparatus. The pH of the non-magnetic powder is preferably 2 to 11, and particularly preferably 6 to 9. When the pH is in the range of 2 to 11, it is possible to prevent the friction coefficient from increasing due to high temperature, high humidity, or liberation of fatty acids. The water content of the nonmagnetic powder is, for example, 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.3 to 1.5% by mass. A water content in the range of 0.1 to 5% by mass is preferable because the dispersion is good and the viscosity of the paint after dispersion is stable. The ignition loss is preferably 20% by mass or less, and the ignition loss is preferably small.

When the nonmagnetic powder is an inorganic powder, the Mohs hardness is preferably 4-10. If the Mohs hardness is in the range of 4 to 10, durability can be ensured. The nonmagnetic powder has a stearic acid adsorption amount of, for example, 1 to 20 μmol / m ² , and more preferably ² to 15 μmol / m ² . The heat of wetting of the nonmagnetic powder into water at 25 ° C. is preferably in the range of 200 to 600 erg / cm ² (200 to 600 mJ / m ² ). Moreover, the solvent which exists in the range of this heat of wetting can be used. The amount of water molecules on the surface at 100 to 400 ° C. is suitably 1 to 10 / 100Å. The pH of the isoelectric point in water is preferably between 3 and 9. It is preferable that Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , Sb ₂ O ₃ and ZnO are present on the surface of these nonmagnetic powders by surface treatment. Particularly preferred for dispersibility are Al ₂ O ₃ , SiO ₂ , TiO ₂ and ZrO ₂ , and more preferred are Al ₂ O ₃ , SiO ₂ and ZrO ₂ . These may be used in combination or may be used alone. Further, a surface-treated layer co-precipitated according to the purpose may be used, or a method of treating the surface layer with silica after first treating with alumina, or vice versa may be employed. The surface treatment layer may be a porous layer depending on the purpose, but it is generally preferable that the surface treatment layer is homogeneous and dense.

  Specific examples of the nonmagnetic powder used for the nonmagnetic layer include, for example, Showa Denko Nanotite, Sumitomo Chemical HIT-100, ZA-G1, Toda Kogyo DPN-250, DPN-250BX, and DPN-245. , DPN-270BX, DPB-550BX, DPN-550RX, manufactured by Ishihara Sangyo TTO-51B, TTO-55A, TTO-55B, TTO-55C, TTO-55S, TTO-55D, SN-100, MJ-7, α-iron oxide E270, E271, E300, STT-4D, STT-30D, STT-30, STT-65C, manufactured by Titanium Industry, MT-100S, MT-100T, MT-150W, MT-500B, T-600B manufactured by Teika , T-100F, T-500HD, Sakai Chemical FINEX-25, BF-1, BF-10, BF- 0, ST-M, Dowa Mining Ltd. DEFIC-Y, DEFIC-R, manufactured by Japan Aerosil AS2BM, TiO2P25, manufactured by Ube Industries, Ltd. 100A, 500A, include those fired Titan Kogyo Ltd. Y-LOP and it. Particularly preferred nonmagnetic powders are titanium dioxide and α-iron oxide.

Carbon black can be mixed in the nonmagnetic layer together with nonmagnetic powder to lower the surface electrical resistance, reduce the light transmittance, and obtain a desired micro Vickers hardness. The micro-Vickers hardness of the nonmagnetic layer is generally 25~60kg / mm ² (245~588MPa), preferably in order to adjust the head contact, a 30~50kg / mm ² (294~490MPa), thin film hardness meter ( Using a HMA-400 manufactured by NEC, measurement can be performed using a diamond triangular pyramid needle having a ridge angle of 80 degrees and a tip radius of 0.1 μm at the tip of the indenter. For details, refer to Realize Co., Ltd. It is standardized that the light transmittance is generally 3% or less for absorption of infrared rays having a wavelength of about 900 nm, for example, 0.8% or less for a VHS magnetic tape. For this purpose, rubber furnace, rubber thermal, color black, acetylene black and the like can be used.

The specific surface area of the carbon black employed in the nonmagnetic layer is, for example, 100 to 500 m ² / g, preferably from 150 to 400 m ² / g, DBP oil absorption, for example, 20 to 400 ml / 100 g, preferably 30 to 200 ml / 100 g is there. The particle size of carbon black is, for example, 5 to 80 nm, preferably 10 to 50 nm, and more preferably 10 to 40 nm. Carbon black preferably has a pH of 2 to 10, a water content of 0.1 to 10%, and a tap density of 0.1 to 1 g / ml.

  Specific examples of carbon black that can be used for the nonmagnetic layer include Cabot's BLACKPEARLS 2000, 1300, 1000, 900, 800, 880, 700, VULCAN XC-72, Mitsubishi Chemical Corporation # 3050B, # 3150B. , # 3250B, # 3750B, # 3950B, # 950, # 650B, # 970B, # 850B, MA-600, Columbia Carbon Corporation CONDUCTEX SC, RAVEN8800, 8000, 7000, 5750, 5250, 3500, 2100, 2000, 1800 1500, 1255, 1250, and Ketjen Black EC manufactured by Ketjen Black International.

  Carbon black may be surface-treated with a dispersant, or may be grafted with a resin, or may be obtained by graphitizing a part of the surface. Moreover, before adding carbon black to a coating liquid, you may disperse | distribute with a binder previously. These carbon blacks can be used in a range not exceeding 50% by mass with respect to the inorganic powder and in a range not exceeding 40% of the total mass of the nonmagnetic layer. These carbon blacks can be used alone or in combination. The carbon black that can be used in the nonmagnetic layer of the present invention can be referred to, for example, “Carbon Black Handbook” edited by Carbon Black Association.

  Further, an organic powder can be added to the nonmagnetic layer according to the purpose. Examples of such organic powder include acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, and phthalocyanine pigment, but polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin, and the like. Resin powder and polyfluorinated ethylene resin can also be used. As the production method, those described in JP-A Nos. 62-18564 and 60-255827 can be used.

  As the binder, lubricant, dispersant, additive, solvent, dispersion method and the like of the nonmagnetic layer, those of the magnetic layer can be applied. In particular, known techniques relating to the magnetic layer can be applied to the amount of binder, type, additive, and amount of dispersant added, and type.

  The magnetic recording medium of the present invention may be provided with an undercoat layer. By providing the undercoat layer, the adhesive force between the support and the magnetic layer or the nonmagnetic layer can be improved. As an undercoat layer for improving adhesion, a polyester resin soluble in a solvent can be used. As will be described later, a smoothing layer can be provided as an undercoat layer.

Nonmagnetic support Nonmagnetic support includes polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, cellulose triacetate, polycarbonate, polyamide, polyimide, polyamideimide, polysulfone, polyaramid, aromatic polyamide, polybenzoxazole, etc. Any known film can be used. It is preferable to use a high strength support such as polyethylene naphthalate or polyamide. If necessary, a laminated type support as disclosed in JP-A-3-224127 can be used to change the surface roughness of the magnetic surface and the nonmagnetic support surface. These supports may be subjected in advance to corona discharge treatment, plasma treatment, easy adhesion treatment, heat treatment, dust removal treatment, and the like. It is also possible to apply an aluminum or glass substrate as the support.

Of these, a polyester support (hereinafter simply referred to as polyester) is preferred. The polyester is preferably a polyester composed of a dicarboxylic acid and a diol, such as polyethylene terephthalate and polyethylene naphthalate.
The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid.
Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.

Among the polyesters comprising these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component and ethylene glycol as a diol component from the viewpoint of transparency, mechanical strength, dimensional stability, etc. Polyesters having and / or 1,4-cyclohexanedimethanol as the main constituent are preferred.
Among them, a polyester mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate, a copolymer polyester composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and two or more kinds of these polyesters A polyester having a mixture as a main constituent is preferred. Particularly preferred is a polyester having polyethylene-2,6-naphthalate as a main constituent.
The polyester may be biaxially stretched or a laminate of two or more layers.

  Further, the polyester may be further copolymerized with other copolymerization components, or may be mixed with other polyesters. Examples of these include the dicarboxylic acid components and diol components mentioned above, or polyesters composed thereof.

Polyester has an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof, and a polyoxyalkylene group to make it difficult for delamination during film formation. A diol or the like may be copolymerized.
Of these, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, and the like in terms of polyester polymerization reactivity and film transparency. Compounds in which sodium is substituted with other metals (for example, potassium, lithium, etc.), ammonium salts, phosphonium salts, etc., or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymers and their A compound obtained by oxidizing the hydroxy groups at both ends to form a carboxyl group is preferred. The proportion of copolymerization for this purpose is preferably 0.1 to 10 mol% based on the dicarboxylic acid constituting the polyester.
For the purpose of improving heat resistance, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio is preferably 1 to 20 mol% based on the dicarboxylic acid constituting the polyester.

The polyester can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component. First, a dialkyl ester is used as a dicarboxylic acid component, this is transesterified with the diol component, and this is heated under reduced pressure. A transesterification method of polymerizing by removing excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst can be used, or a heat-resistant stabilizer can be added.
In addition, anti-coloring agents, antioxidants, crystal nucleating agents, slipping agents, stabilizers, anti-blocking agents, UV absorbers, viscosity modifiers, antifoaming and clearing agents, antistatic agents, pH adjustments in each process during synthesis One or more of various additives such as an agent, a dye, a pigment, and a reaction terminator may be added.

Further, a filler may be added to the polyester. Examples of the filler include inorganic powders such as spherical silica, colloidal silica, titanium oxide, and alumina, and organic fillers such as crosslinked polystyrene and silicone resin.
Further, in order to increase the rigidity of the support, these materials can be highly stretched, or a metal, semimetal, or oxide layer thereof can be provided on the surface.

The thickness of the nonmagnetic support is preferably 3 to 80 μm, more preferably 3 to 50 μm, and particularly preferably 3 to 10 μm. Further, it is preferable to use a non-magnetic support having high smoothness. The center surface average roughness (Ra) of the support surface is preferably 6 nm or less, more preferably 4 nm or less, and still more preferably 0.8 nm to 4 nm. Ra is a value measured by HD2000 manufactured by WYKO.
Further, the Young's modulus in the longitudinal direction and the width direction of the nonmagnetic support is preferably 6.0 GPa or more, and more preferably 7.0 GPa or more.

Layer Structure As described above, the thickness structure of the magnetic recording medium of the present invention is such that the thickness of the nonmagnetic support is preferably 3 to 80 μm, more preferably 3 to 50 μm, and particularly preferably 3 to 10 μm. When an undercoat layer is provided between the nonmagnetic support and the nonmagnetic layer or the magnetic layer, the thickness of the undercoat layer is, for example, 0.01 to 0.8 μm, preferably 0.02 to 0.6 μm.

In addition, an intermediate layer for smoothing can be provided between the support and the nonmagnetic layer or magnetic layer, and between the support and the backcoat layer. For example, the surface of the nonmagnetic support contains a polymer. Apply and dry the applied coating solution, or apply a coating solution containing a compound having a radiation curable functional group in the molecule (radiation curable compound), and then irradiate with radiation to cure the coating solution Can be formed.
The number average molecular weight of the radiation curable compound is preferably in the range of 200 to 2,000. When the molecular weight is within this range, the molecular weight is relatively low, so that the coating film is easy to flow in the calendar process, has high moldability, and a smooth coating film can be formed.
Preferred as the radiation curable compound is a bifunctional acrylate compound having a molecular weight of 200 to 2000, and more preferred are acrylics such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and these alkylene oxide adducts. Acid and methacrylic acid are added.

The radiation curable compound may be used in combination with a polymer-type binder. Examples of the binder used in combination include conventionally known thermoplastic resins, thermosetting resins, reactive resins, and mixtures thereof. When ultraviolet rays are used as radiation, it is preferable to use a polymerization initiator in combination. As the polymerization initiator, known radical photopolymerization initiators, cationic photopolymerization initiators, photoamine generators, and the like can be used.
The radiation curable compound can also be used for the nonmagnetic layer.

  The thickness of the magnetic layer is optimized according to the saturation magnetization amount, head gap length, and recording signal band of the magnetic head to be used, but is generally 10 to 150 nm, preferably 20 to 120 nm, and more preferably. Is 30 to 100 nm, particularly preferably 30 to 80 nm. Further, the thickness variation rate (σ / δ) of the magnetic layer is preferably within ± 50%, and more preferably within ± 30%. There may be at least one magnetic layer, and the magnetic layer may be separated into two or more layers having different magnetic characteristics, and a configuration related to a known multilayer magnetic layer can be applied.

  The thickness of the nonmagnetic layer is, for example, 0.1 to 3.0 μm, and preferably 0.3 to 2.0 μm. The non-magnetic layer of the magnetic recording medium of the present invention exhibits its effect if it is substantially non-magnetic. For example, even if it contains a small amount of magnetic material as an impurity or intentionally, This shows the effect of the invention and can be regarded as substantially the same configuration as the magnetic recording medium of the invention. Note that “substantially the same” means that the residual magnetic flux density of the nonmagnetic layer is 10 mT or less or the coercive force is 7.96 kA / m (100 Oe) or less, and preferably has no residual magnetic flux density and coercive force. Means.

Back Coat Layer The magnetic recording medium of the present invention can have a back coat layer on the side opposite to the side having the magnetic layer of the nonmagnetic support. The back coat layer preferably contains carbon black and inorganic powder. For the binder and various additives, the formulation of the magnetic layer and the nonmagnetic layer can be applied. It is particularly preferable to apply the prescription for the nonmagnetic layer. The thickness of the back coat layer is preferably 0.9 μm or less, and more preferably 0.1 to 0.7 μm.

Manufacturing Method The magnetic recording medium of the present invention comprises, for example, a step of applying a nonmagnetic layer coating solution and a magnetic layer coating solution to at least one surface of a nonmagnetic support to obtain a coating raw material, and winding the coating raw material. It can be manufactured by a method having a step of winding around a take-up roll and a step of unwinding and calendering the coating raw material wound up on the take-up roll.

  The steps for producing the magnetic layer coating solution and the nonmagnetic layer coating solution usually comprise at least a kneading step, a dispersing step, and a mixing step provided as necessary before and after these steps. Each process may be divided into two or more stages. All raw materials such as ferromagnetic powder, non-magnetic powder, binder, carbon black, abrasive, antistatic agent, lubricant, and solvent used in the present invention may be added at the beginning or middle of any step. In addition, individual raw materials may be added in two or more steps. For example, polyurethane may be divided and added in a kneading step, a dispersing step, and a mixing step for adjusting the viscosity after dispersion. In order to achieve the object of the present invention, a conventional known manufacturing technique can be used as a partial process. In the kneading step, it is preferable to use a kneading force such as an open kneader, a continuous kneader, a pressure kneader, or an extruder. Details of these kneading treatments are described in JP-A-1-106338 and JP-A-1-79274. In order to disperse the magnetic layer coating solution and the nonmagnetic layer coating solution, glass beads can be used. As such glass beads, zirconia beads, titania beads, and steel beads, which are high specific gravity dispersion media, are suitable. The particle diameter and filling rate of these dispersion media are optimized. A well-known thing can be used for a disperser.

  In the method of manufacturing a magnetic recording medium, for example, a nonmagnetic layer coating solution and a magnetic layer coating solution are applied in multiple layers on the surface of a nonmagnetic support under running. As a coating method, simultaneous multi-layer coating, that is, while the non-magnetic layer coating solution is in a wet state, a method of applying a coating solution for forming a magnetic layer thereon and drying (Wet on wet) may be used. A sequential multilayer coating, that is, a method of applying a coating solution for forming a nonmagnetic layer and drying it, and then applying and drying a coating solution for forming a magnetic layer thereon (Wet on dry) may be used. Sequential multilayer coating is suitable for increasing the density because the interface between the magnetic layer and the non-magnetic layer is uniform, and the variation in thickness of the magnetic layer is reduced and the S / N is improved.

  The coating machines that apply the magnetic layer coating solution or non-magnetic layer coating solution include air doctor coat, blade coat, rod coat, extrusion coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat Kiss coat, cast coat, spray coat, spin coat, etc. can be used. As for these, for example, “Latest Coating Technology” (May 31, 1983) issued by General Technology Center Co., Ltd. can be referred to.

  The magnetic recording medium of the present invention may be a magnetic tape such as a video tape or a computer tape, or may be a magnetic disk such as a flexible disk or a hard disk. In the case of a magnetic tape, the coating layer formed by applying a magnetic layer coating solution may be subjected to a magnetic field orientation treatment using a cobalt magnet or a solenoid on the ferromagnetic powder contained in the coating layer. In the case of a disk, a sufficiently isotropic orientation may be obtained even without non-orientation without using an orientation device, but known random methods such as alternately arranging cobalt magnets obliquely and applying an alternating magnetic field with a solenoid. It is preferable to use an alignment device. In the case of a ferromagnetic metal powder, the isotropic orientation is generally preferably in-plane two-dimensional random, but can also be three-dimensional random with a vertical component. Further, isotropic magnetic characteristics can be imparted in the circumferential direction by using a well-known method such as a counter-polarized magnet and making it vertically oriented. Moreover, circumferential orientation can also be achieved using spin coating. In particular, when performing high density recording, vertical alignment is preferable.

  Moreover, it is preferable to control the drying position of the coating film by controlling the temperature of the drying air, the air volume, and the coating speed. The coating speed is preferably 20 m / min to 1000 m / min, and the temperature of the drying air is preferably 60 ° C. or higher, and appropriate preliminary drying can be performed before entering the magnet zone.

The coating raw material thus obtained is usually wound up once by a winding roll, and then unwound from the winding roll and subjected to a calendar process.
For the calendar process, for example, a super calendar roll or the like is used. Calendering improves surface smoothness and eliminates voids generated by solvent removal during drying and improves the filling rate of the ferromagnetic powder in the magnetic layer. Obtainable. The step of calendering is preferably performed while changing the calendering conditions according to the smoothness of the surface of the coating raw material.

  As the calender treatment conditions, the temperature of the calender roll is preferably in the range of 60 to 100 ° C, more preferably in the range of 70 to 100 ° C, particularly preferably in the range of 80 to 100 ° C, and the pressure is preferably 100. ˜500 kg / cm (98 to 490 kN / m), more preferably 200 to 450 kg / cm (196 to 441 kN / m), and particularly preferably 300 to 400 kg / cm (294 to 392 kN / m). ). In consideration of the characteristics of the coating type medium, it is preferable to control the surface smoothness by the calender roll pressure and the calender roll temperature. Generally, the surface smoothness of the final product is lowered by lowering the calender roll pressure or lowering the calender roll temperature. Conversely, increasing the calender roll pressure or the calender roll temperature increases the surface smoothness of the final product. The surface smoothness can also be controlled by the calendar roll temperature, calendar roll speed, and calendar roll tension.

  Apart from this, the magnetic recording medium obtained after the calendering process can be thermo-processed to allow thermosetting to proceed. What is necessary is just to determine such a thermo process suitably with the mixing | blending prescription of a magnetic layer coating liquid. Thermo treatment temperature is 35-100 degreeC, for example, Preferably it is 50-80 degreeC. The thermo treatment time is 12 to 72 hours, preferably 24 to 48 hours.

  As the calender roll, it is preferable to use a heat-resistant plastic roll such as epoxy, polyimide, polyamide, and polyamideimide. Moreover, it can also process with a metal roll.

  In the magnetic recording medium of the present invention, the surface roughness of the magnetic layer is preferably 1.0 to 3.0 nm, more preferably 1.5 to 2.5 nm, as the center plane average roughness Ra. . The center plane average roughness Ra is a value obtained by measuring a 250 μm square sample area using an optical interference three-dimensional roughness meter “TOPO-3D” manufactured by WYKO (Arizona, US). In calculating the measurement values, corrections such as tilt correction, spherical correction, and cylinder correction are performed in accordance with JIS-B601. Since the iron nitride powder having the particle size described above has good dispersibility and hardly causes orientation aggregation, a magnetic layer having high surface smoothness having a surface roughness in the above range can be obtained.

  The obtained magnetic recording medium can be cut into a desired size using a cutting machine or the like. The cutting machine is not particularly limited, but is preferably provided with a plurality of pairs of rotating upper blades (male blades) and lower blades (female blades). The slitting speed, the engagement depth, and the upper blade (male blade) are appropriately selected. The peripheral speed ratio (upper blade peripheral speed / lower blade peripheral speed) between the blade and the lower blade (female blade), the continuous use time of the slit blade, and the like are selected.

Physical characteristics The saturation magnetic flux density of the magnetic layer of the magnetic recording medium of the present invention is preferably 100 to 400 mT. The coercive force (Hc) of the magnetic layer is preferably 143 to 279 kA / m (1800 to 3500 Oe), more preferably 170 to 250 kA / m. The distribution of coercive force is preferably narrow, and SFD and SFDr are preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.3 to 0.6.

  In the magnetic recording medium of the present invention, Mrδ, which is the product of the remanent magnetization Mr of the magnetic layer and the thickness δ of the magnetic layer, is preferably in the range of 2 to 30 mTμm, and more preferably in the range of 3 to 25 mT · μm. More preferred. If it exceeds 30 mT · μm, the MR head to be used is saturated, and this is not preferred. If it is less than 2 mT · μm, the sensitivity is small and it is difficult to ensure a sufficient S / N.

The coefficient of friction with respect to the head of the magnetic recording medium of the present invention is preferably 0.50 or less, more preferably 0.3 or less, in the temperature range of −10 to 40 ° C. and humidity of 0 to 95%. The surface resistivity is preferably a magnetic surface of 10 ⁴ to 10 ⁸ Ω / sq, and the charged position is preferably within −500 V to +500 V. The elastic modulus at 0.5% elongation of the magnetic layer is preferably 0.98 to 19.6 GPa (100 to 2000 kg / mm ² ) in each in-plane direction, and the breaking strength is preferably 98 to 686 MPa (10 to 70 kg). / Mm ² ), the elastic modulus of the magnetic recording medium is preferably 0.98 to 14.7 GPa (100 to 1500 kg / mm ² ) in each in-plane direction, and the residual spread is preferably 0.5% or less, 100 ° C. The thermal shrinkage at any of the following temperatures is preferably 1% or less, more preferably 0.5% or less, and most preferably 0.1% or less.

The glass transition temperature of the magnetic layer (maximum point of loss tangent of dynamic viscoelasticity measurement measured at 110 Hz) is preferably 50 to 180 ° C, and that of the nonmagnetic layer is preferably 0 to 180 ° C. The loss elastic modulus is preferably in the range of 1 × 10 ⁷ to 8 × 10 ⁸ Pa (1 × 10 ⁸ to 8 × 10 ⁹ dyne / cm ² ), and the loss tangent is preferably 0.2 or less. If the loss tangent is too large, adhesion failure is likely to occur. These thermal characteristics and mechanical characteristics are preferably almost equal within 10% in each in-plane direction of the medium.

The residual solvent contained in the magnetic layer is preferably 100 mg / m ² or less, more preferably 10 mg / m ² or less. The porosity of the coating layer is preferably 30% by volume or less, more preferably 20% by volume or less for both the nonmagnetic layer and the magnetic layer. The porosity is preferably small in order to achieve high output, but it may be better to ensure a certain value depending on the purpose. For example, in the case of a disk medium in which repeated use is important, a larger void ratio is often preferable for running durability.

  In the magnetic recording medium of the present invention, these physical characteristics can be changed between the nonmagnetic layer and the magnetic layer according to the purpose. For example, the elastic modulus of the magnetic layer can be increased to improve running durability, and at the same time, the elastic modulus of the nonmagnetic layer can be made lower than that of the magnetic layer to improve the contact of the magnetic recording medium with the head.

  Normally, two types of fci and bpi are generally used as units representing linear recording density. fci represents the density physically recorded on the medium with the number of bit inversions per inch. On the other hand, bpi depends on the system in terms of the number of bits per inch including signal processing. For this reason, fci is usually used for pure performance evaluation of the medium. The magnetic recording medium of the present invention has good high-density recording characteristics, and can exhibit excellent recording characteristics in a high-density recording area, particularly by being perpendicularly oriented. A preferable range of linear recording density when recording a signal on the magnetic recording medium of the present invention is 100 to 400 kfci. Furthermore, it is 175 kfci-400 kfci. In a system actually used, since it depends on signal processing, it is not uniquely determined, but as a guideline, performance at fci 0.5 to 1 times bpi is reflected. For this reason, the range of 200 kbpi to 800 kbpi, more preferably 350 kbpi to 800 kbpi is particularly preferable. In order to reproduce a magnetic signal recorded at high density with good S / N, it is preferable to use a magnetoresistive head (MR head) as a reproducing head.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the aspect shown in an Example. In addition, the display of "part" in an Example shows "mass part".

[Examples 1-1 to 1-4]
(1) Formation of raw material particles 0.25 mol of FeSO ₄ · 7H ₂ O and 0.50 mol of Fe ₂ (SO ₄ ) ₃ · 9H ₂ O were dissolved in 1500 g of water to prepare an iron salt aqueous solution. Next, a 2.05 mol aqueous ammonia was used as a 1500 g aqueous solution. While stirring the iron salt aqueous solution, an aqueous ammonia solution was added at room temperature (about 25 ° C.), stirred for 20 minutes, and then heated to 60 ° C. to produce Fe ₃ O ₄ particles. The solution was cooled, and the precipitate was filtered and washed with water to recover the generated particles.
The obtained Fe ₃ O ₄ particles were put in an autoclave, hydrothermally treated at the temperature shown in Table 1 for 3 hours, and then washed with water. The obtained Fe ₃ O ₄ particles were almost dice. The average particle size is shown in Table 1.

(2) Formation of iron nitride powder 50 g of the Fe ₃ O ₄ particles formed in the above (1) were dispersed in 1500 ml of pure water using an ultrasonic disperser. To Fe in Fe ₃ O ₄ contained in the dispersion, adding Al equivalent to 5at% aluminum chloride solution (concentration of 10 mass%), an aqueous ammonia solution (concentration 10 mass%) was added with stirring The pH was 7.5. After the Fe ₃ O ₄ particles were settled, the supernatant was removed, and water washing was repeated three times, yttrium corresponding to 8 at% with respect to Fe in Fe ₃ O ₄ was added as an aqueous yttrium nitrate solution (concentration: 10% by mass). While stirring, an aqueous ammonia solution (concentration: 10% by mass) was added to adjust the pH to 7.5, and Al and Y compounds were deposited on the Fe ₃ O ₄ particle surfaces. The Fe ₃ O ₄ particles after the deposition treatment were washed with water, filtered and dried, then heated in nitrogen at 350 ° C. for 60 minutes, and further annealed at 650 ° C. for 2 hours. Thereafter, the temperature was set to 480 ° C. and reduced in a pure hydrogen atmosphere for 4 hours to obtain a ferromagnetic metal powder containing Al and Y. The temperature was lowered to 150 ° C. while flowing hydrogen. Nitriding was performed for 30 hours using ammonia gas while maintaining the temperature at 150 ° C. Subsequently, the ammonia gas was switched to nitrogen gas, the temperature was lowered to 50 ° C., and the particle surface was gradually oxidized with a mixed gas containing about 0.1 to 5 vol% oxygen in nitrogen. At this time, the oxygen concentration was controlled so that the gas temperature did not exceed 90 ° C. As a result of X-ray diffraction, the iron nitride-based magnetic powder thus obtained showed a profile showing the Fe ₁₆ N ₂ phase.

[Example 1-5]
(1) Formation of raw material particles An aqueous iron salt solution was prepared by dissolving 0.25 mol of FeSO ₄ · 7H ₂ O and 0.50 mol of Fe ₂ (SO ₄ ) ₃ · 9H ₂ O in 1000 g of water. Next, 7.5 mol of urea was dissolved in 2000 g of water. While stirring the aqueous iron salt solution, an aqueous urea solution was added at room temperature (about 25 ° C.), heated with stirring, and maintained at 90 ° C. for 60 minutes to generate Fe ₃ O ₄ particles. The reaction liquid was cooled, and the generated particles were recovered by filtering and washing the precipitate.
Part of the obtained particles was dried and observed for shape. It had a granular shape, and the average particle size was 17 nm.

(2) Formation of iron nitride powder 50 g of the Fe ₃ O ₄ particles formed in the above (1) were dispersed in 1500 ml of pure water using an ultrasonic disperser. To the Fe in Fe ₃ O ₄ contained in this dispersion, Al corresponding to 8 at% is added as a sodium aluminate aqueous solution (concentration 10 mass%), and an acetic acid aqueous solution (concentration 10 mass%) is added while stirring. The pH was adjusted to 6.0. After the Fe ₃ O ₄ particles were settled, the supernatant was removed, and washing with water was repeated three times, yttrium corresponding to 3 at% of Fe in Fe ₃ O ₄ was added as an yttrium nitrate aqueous solution (concentration: 10% by mass), While stirring, an aqueous ammonia solution (concentration: 10% by mass) was added to adjust the pH to 7.5, and Al and Y compounds were deposited on the Fe ₃ O ₄ particle surfaces. The Fe ₃ O ₄ particles after the deposition treatment were washed with water, filtered and dried, and then annealed at 650 ° C. for 2 hours in nitrogen. The temperature was reduced to 480 ° C. and reduced in a pure hydrogen atmosphere for 4 hours to obtain a ferromagnetic metal powder containing Al and Y. The temperature was lowered to 150 ° C. while flowing hydrogen. Nitriding was performed for 30 hours using ammonia gas while maintaining the temperature at 150 ° C. The ammonia gas was switched to nitrogen gas, the temperature was lowered to 50 ° C., and the particle surface was gradually oxidized with a mixed gas containing about 0.1 to 5 vol% oxygen in nitrogen. At this time, the oxygen concentration was controlled so that the gas temperature did not exceed 90 ° C. As a result of X-ray diffraction, the iron nitride-based magnetic powder thus obtained showed a profile showing the Fe ₁₆ N ₂ phase.

[Example 1-6]
1.5 mol of FeSO ₄ .7H ₂ O was dissolved in 1500 g of water to prepare an iron salt aqueous solution. Next, 3.2 mol of ammonia water was made into an aqueous solution of 1500 g. While stirring the iron salt aqueous solution, an aqueous ammonia solution was added at room temperature (about 25 ° C.) to produce iron hydroxide. While stirring the iron hydroxide suspension, air was introduced, heated and held at 60 ° C. for 120 minutes to produce Fe ₃ O ₄ particles. After cooling the reaction solution, the precipitate was filtered and washed with water to recover Fe ₃ O ₄ . When a part was dried and observed for shape, it was in a granular shape, and the average particle size was 20 nm.

(2) Formation of iron nitride powder 50 g of the Fe ₃ O ₄ particles formed in the above (1) were dispersed in 1000 ml of pure water using an ultrasonic disperser. To the Fe in the dispersion, Al corresponding to 6 at% was added as a sodium aluminate aqueous solution (concentration 5 mass%), and an acetic acid aqueous solution (concentration 10 mass%) was added while stirring to adjust the pH to 5.8. . After the Fe ₃ O ₄ particles were settled, the supernatant was removed, and washing with water was repeated three times, yttrium corresponding to 3 at% of Fe in Fe ₃ O ₄ was added as an yttrium nitrate aqueous solution (concentration: 10% by mass), While stirring, an aqueous ammonia solution (concentration: 10% by mass) was added to adjust the pH to 7.5, and Al and Y compounds were deposited on the Fe ₃ O ₄ particle surfaces. The Fe ₃ O ₄ particles after the deposition treatment were washed with water, filtered and dried, and then annealed at 650 ° C. for 2 hours in nitrogen. The temperature was reduced to 480 ° C. and reduced in a pure hydrogen atmosphere for 4 hours to obtain a ferromagnetic metal powder containing Al and Y. The temperature was lowered to 150 ° C. while flowing hydrogen. Nitriding was performed for 30 hours using ammonia gas while maintaining the temperature at 150 ° C. The ammonia gas was switched to nitrogen gas, the temperature was lowered to 50 ° C., and the particle surface was gradually oxidized with a mixed gas containing about 0.1 to 5 vol% oxygen in nitrogen. At this time, the oxygen concentration was controlled so that the gas temperature did not exceed 90 ° C. As a result of X-ray diffraction, the iron nitride-based magnetic powder thus obtained showed a profile showing the Fe ₁₆ N ₂ phase.

[Example 1-7]
(1) Formation of raw material particles 0.25 mol of FeSO ₄ .7H ₂ O and 0.50 mol of Fe (NO ₃ ) ₃ .9H ₂ O were dissolved in 1000 g of water to prepare an iron salt aqueous solution. Next, 1.25 mol of ammonium carbonate was dissolved in 1000 g of water. While stirring the iron salt aqueous solution, an ammonium carbonate aqueous solution was added at room temperature (about 25 ° C.), heated with stirring, and held at 70 ° C. for 60 minutes to produce Fe ₃ O ₄ particles. The reaction liquid was cooled, and the generated particles were recovered by filtering and washing the precipitate. When a part was dried and observed for shape, it was in a granular shape, and the average particle size was 14 nm.

(2) The Fe ₃ O ₄ particles 50g formed by iron nitride powder form (1) pure water 1500ml with an ultrasonic disperser to disperse. Al corresponding to 5 at% is added to the Fe in the dispersion with an aluminum chloride aqueous solution (concentration 10 mass%), an aqueous ammonia solution (concentration 10 mass%) is added with stirring, and the pH is set to 7.5. did. After the Fe ₃ O ₄ particles were settled, the supernatant was removed, and water washing was repeated three times, yttrium corresponding to 8 at% with respect to Fe in Fe ₃ O ₄ was added as an aqueous yttrium nitrate solution (concentration: 10% by mass). While stirring, an aqueous ammonia solution (concentration: 10% by mass) was added to adjust the pH to 7.5, and Al and Y compounds were deposited on the Fe ₃ O ₄ particle surfaces. The Fe ₃ O ₄ particles after the deposition treatment were washed with water, filtered and dried, then heated in nitrogen at 400 ° C. for 60 minutes, and further annealed at 650 ° C. for 2 hours. The temperature was reduced to 480 ° C. and reduced in a pure hydrogen atmosphere for 4 hours to obtain a ferromagnetic metal powder containing Al and Y. The temperature was lowered to 150 ° C. while flowing hydrogen. Nitriding was performed for 30 hours using ammonia gas while maintaining the temperature at 150 ° C. The ammonia gas was switched to nitrogen gas, the temperature was lowered to 50 ° C., and the particle surface was gradually oxidized with a mixed gas containing about 0.1 to 5 vol% oxygen in nitrogen. At this time, the oxygen concentration was controlled so that the gas temperature did not exceed 90 ° C. As a result of X-ray diffraction, the iron nitride-based magnetic powder thus obtained showed a profile showing the Fe ₁₆ N ₂ phase.

[Comparative Examples 1-1 to 1-4]
(1) Formation of raw material particles Example 1-1 to Example 1-1 except that 2.05 mol of sodium hydroxide was dissolved in 1,500 g of water to neutralize the iron salt aqueous solution. Fe ₃ O ₄ particles were produced in the same manner as in 1-4. The solution in which the Fe ₃ O ₄ particles were generated was cooled, and the precipitate was filtered and washed with water to recover the generated particles.
The obtained Fe ₃ O ₄ particles were put in an autoclave, and Comparative Examples 1-2 to _1-4 were washed with water after hydrothermal treatment at the temperature shown in Table 1 for 3 hours. For Comparative Example 1-1, no hydrothermal treatment was performed. The obtained Fe ₃ O ₄ particles were almost dice. The average particle size is shown in Table 1.

(2) Formation of iron nitride powder 50 g of the Fe ₃ O ₄ particles formed in the above (1) were dispersed in 1500 ml of pure water using an ultrasonic disperser. An aqueous aluminum chloride solution (concentration of 10% by mass) is added so that Al / Fe is 5 at% with respect to iron in Fe ₃ O ₄ particles contained in the dispersion, and further Y / Fe is 8 at%. An aqueous yttrium nitrate solution (concentration 10% by mass) was added. The mixture was neutralized with sodium hydroxide (concentration: 10% by mass), Al and Y hydroxides were deposited on the magnetite surface, filtered and washed with water to a conductivity of 80 μS / cm, and then dried. Next, it was heated and reduced at 450 ° C. for 2 hours in a state of flowing hydrogen gas to obtain a ferromagnetic metal powder. The temperature was lowered to 150 ° C. while flowing hydrogen gas, the gas was switched to ammonia gas, and a nitriding reaction was performed for 30 hours while maintaining the temperature at 150 ° C. Switching to nitrogen gas, the temperature was lowered to 50 ° C., and the particle surface was gradually oxidized with a mixed gas containing about 0.1 to 5 vol% oxygen in nitrogen. At this time, the oxygen concentration was controlled so that the gas temperature did not exceed 90 ° C. As a result of X-ray diffraction, the iron nitride-based magnetic powder thus obtained showed a profile showing the Fe ₁₆ N ₂ phase.

[Comparative Example 1-5]
(1) Formation of raw material particles 0.25 mol FeSO ₄ .7H ₂ O and 0.50 mol Fe ₂ (SO ₄ ) ₃ · 9H ₂ O were dissolved in 1,500 g of water to prepare an iron salt aqueous solution. . Next, 2.05 mol of sodium hydroxide was dissolved in 1,500 g of water. An aqueous sodium hydroxide solution was added to the iron salt aqueous solution at room temperature, stirred for 20 minutes, and then heated to 60 ° C. to produce Fe ₃ O ₄ particles. The Fe ₃ O ₄ particles were placed in an autoclave, hydrothermally treated at 180 ° C. for 3 hours, and then washed with water. The obtained Fe ₃ O ₄ particles were heat-treated at 400 ° C. for 1 hour in air. The obtained α-Fe ₂ O ₃ particles were spherical or elliptical. The average particle size is shown in Table 1.

(2) Formation of iron nitride powder The same treatment as in Comparative Example 1-1 was performed on α-Fe ₂ O ₃ formed in (1) above. As a result of X-ray diffraction, the obtained iron nitride-based magnetic powder showed a profile showing the Fe ₁₆ N ₂ phase.

Evaluation Method of Iron Nitride Powder (1) Measurement of Average Particle Size The average particle size was measured for 500 iron nitride particles with a high resolution analytical transmission electron microscope (magnification 500000 times).
(2) Measurement of surface area The surface area was determined as a specific surface area by the BET method.
(3) Alkali metal content Iron nitride powder was dissolved in hydrochloric acid, and alkali metal ions were quantified by ICP.
(4) Nitrogen, aluminum and yttrium contents The contents of yttrium, aluminum and nitrogen in the iron nitride powder were measured by fluorescent X-rays. It was confirmed that aluminum and yttrium corresponding to the added amount were contained. The nitrogen content was measured by fluorescent X-rays and confirmed to be in the range of 7.0 to 14 atomic% with respect to iron.
(5) Magnetic characteristics Magnetic characteristics of each iron nitride powder were measured by applying a magnetic field of 796 kA / m (10 kOe).
The results are shown in Table 1.

[Examples 2-1 to 2-7]
(Magnetic layer coating solution)
Iron nitride powder (shown in Table 2) 100 parts Binder resin Vinyl chloride copolymer 14 parts (containing 1 × 10 ⁻⁴ eq / g of —SO ₃ K group, degree of polymerization: 300)
Polyester polyurethane resin 4 parts (Neopentyl glycol / Caprolactone polyol / MDI
= 0.9 / 2.6 / 1, -SO ₃ Na group: 1 × 10 ⁻⁴ eq / g)
α-alumina (average particle diameter: 0.08 μm) 5 parts carbon black 2 parts (average particle diameter: 40 nm, coefficient of variation of particle diameter: 200%)
Phenylphosphonic acid 4 parts Butyl stearate 3 parts Stearic acid 3 parts Methyl ethyl ketone and cyclohexanone 1: 1 mixed solvent 280 parts

  In the above components, magnetic powder, carbon black, phenylphosphonic acid, vinyl chloride copolymer, 130 parts of methyl ethyl ketone and cyclohexanone 1: 1 mixed solvent were kneaded with a kneader, and the remaining components were added and mixed. Disperse with a sand grinder for 1 hour using 5 mmφ zirconia beads. 6 parts of polyisocyanate was added to the obtained dispersion, 20 parts of a 1: 1 mixed solvent of methyl ethyl ketone and cyclohexanone was added, and the mixture was filtered using a filter having an average pore size of 1 μm to prepare a magnetic layer coating solution.

(Non-magnetic layer coating solution)
80 parts of acicular hematite
(Specific surface area by BET method: 65 m ² / g,
Average long axis length: 0.10 μm, average needle ratio: 7,
(pH: 8.8, aluminum treatment: 1% by mass as Al ₂ O ₃ )
20 parts of carbon black
(Average particle size: 17 nm,
DBP and oil amount: 80 ml / 100 g,
(BET surface area: 240 m ^{2 /} g, pH 7.5)
Binder resin Vinyl chloride copolymer 13 parts
(Containing 1 × 10 ⁻⁴ eq / g of —SO ₃ K group, degree of polymerization 300)
Polyester polyurethane resin 5 parts
(Neopentyl glycol / Caprolactone polyol / MDI
= 0.9 / 2.6 / 1, -SO3Na group: 1 x 10-4 eq / g)
Phenylphosphonic acid 4 parts Butyl stearate 3 parts Stearic acid 3 parts Methyl ethyl ketone and cyclohexanone 8: 2 mixed solvent 280 parts

  In the above components, acicular hematite, phenylphosphonic acid, carbon black, vinyl chloride copolymer, methyl ethyl ketone and cyclohexanone 8: 2 mixed solvent 130 parts are kneaded with a kneader, then the above remaining components are added and mixed, 1 mmφ zirconia beads were used and dispersed for 1 hour using a sand grinder. 10 parts of isocyanate and 30 parts of cyclohexanone were added to the obtained dispersion, and the obtained dispersion was filtered using a filter having an average pore diameter of 1 μm to prepare a nonmagnetic layer coating solution.

The obtained nonmagnetic layer coating solution was applied onto a polyethylene naphthalate support having a thickness of 6.5 μm so that the thickness after drying was 2.0 μm and dried to form a nonmagnetic layer. Using a head having another two-slit coating part, the magnetic layer coating solution is supplied and applied from the front slit so that the magnetic layer has a thickness of 250 nm on the formed non-magnetic layer, and the latter slit The coating solution was sucked more so that the thickness of the magnetic layer after drying was 75 nm. While the magnetic layer is still wet, after passing through a rare earth magnet (surface magnetic flux 500 mT) as a longitudinally oriented magnet, it passes through a solenoid magnet (magnetic flux density 500 mT), and the orientation does not return within the solenoid. The magnetic layer was further dried and wound up in the drying section.
Next, a back coat layer coating solution is applied to the side opposite to the surface on which the nonmagnetic underlayer and magnetic layer of the nonmagnetic support are formed, so that the thickness of the backcoat layer after drying and calendering is 700 nm. Applied and dried. The backcoat layer coating solution was prepared by dispersing the following backcoat layer coating solution components using a sand mill with a residence time of 45 minutes, adding 8.5 parts of polyisocyanate, and stirring and filtering.
<Back coat paint component>
Carbon black (average particle size: 25 nm) ... 40.5 parts carbon black (average particle size: 350 nm) ... 0.5 parts barium sulfate ... 4 parts nitrocellulose ... 28 parts polyurethane resin (SO ₃ Na-containing) 20 parts cyclohexanone 100 parts toluene 100 parts methyl ethyl ketone 100 parts

  The magnetic recording medium original sheet thus obtained was mirror-finished with a seven-stage calender (temperature 80 ° C., linear pressure 300 kg / cm), and subjected to thermo treatment at 60 ° C. and 40% RH for 24 hours. Then, the magnetic layer surface was ground with a diamond wheel (rotation measurement + 150%, winding angle 30 °) while being cut at a width of 1/2 inch and running at 100 m / min to produce a magnetic tape.

Measurement Method (1) Electromagnetic Conversion Characteristics Electromagnetic conversion characteristics were measured by the following method.
A composite GMR head having a recording track width of 1.5 μm, a reproduction track width of 0.75 μm, and a distance between shields of 0.15 μm was mounted on the drum tester. The relative recording speed of the tape and the head was 10.2 m / sec, the optimum recording current was determined from the input / output characteristics of λ = 0.15 μm, and a signal (λ = 0.15 μm) was recorded and reproduced with this current. C / N is from the peak of the reproduced carrier to the demagnetizing noise, and the resolution bandwidth of the spectrum analyzer is 100 kHz. The electromagnetic conversion characteristics are shown in Table 2 as relative values with respect to the tape medium of Comparative Example 2-1.
(2) Magnetic properties Magnetic properties were measured using an oscillating sample magnetometer with an applied magnetic field of 796 kA / m.
(3) Magnetic layer average thickness δ
The average thickness δ of the magnetic layer was determined by (i) and (ii) below.
(i) Acquisition of cross-sectional image of magnetic tape A cross-sectional ultrathin section (section thickness, about 80 nm to 100 nm) parallel to the longitudinal direction of the tape was cut out by an ultramicrotome method using an embedding block. Using a transmission electron microscope (TEM H-9000, manufactured by HITACHI), a photograph of the cross section of the magnetic tape in the cut ultra-thin section is taken in the longitudinal direction of the tape, centering on the interface between the magnetic layer and the nonmagnetic layer. Images were continuously taken for 25 to 30 μm to obtain a continuous cross-sectional image of the magnetic tape.
(ii) Calculation of magnetic layer average thickness δ From the continuous photograph obtained in (i) above, the magnetic layer surface and the magnetic layer / nonmagnetic layer interface line were visually drawn to trim the magnetic layer. Next, the trimmed magnetic layer line was captured by a scanner, and the width of the magnetic layer surface and the magnetic layer / nonmagnetic layer interface was subjected to image processing to calculate the average thickness δ of the magnetic layer. For image processing, KS Imaging Systems Ver. 3, the thickness of the magnetic layer at about 2100 points was measured every 12.5 nm in the longitudinal direction of the magnetic layer. Scale correction at the time of image capture from the scanner and image analysis was performed using a line with an actual size of 2 cm. In all of the magnetic tapes of Examples and Comparative Examples, the magnetic layer average thickness δ was 75 nm.
(4) Surface Roughness of Magnetic Layer A 250 μm square sample area was measured using an optical interference three-dimensional roughness meter “TOPO-3D” manufactured by WYKO (US Arizona). In calculating the measurement values, corrections such as tilt correction, spherical correction, and cylindrical correction were performed according to JIS-B601, and the center plane average surface roughness Ra was set as the value of the surface roughness.
(5) Demagnetization factor A magnetic recording medium sheet (magnetization Mo) produced from the same material as the tape whose magnetic properties were evaluated in (2) above was stored in a thermostat at 60 ° C. and 90% RH for 7 days, and then ( The same magnetic measurement as in 2) was performed, and the magnetization (M) of the sample was measured and obtained, and the demagnetization factor was obtained as (M / Mo-1) * 100.
(6) Friction coefficient About each tape medium, the friction coefficient before and behind 60 degreeC90% RH 7 day storage was measured with the following method.
The tape and the stainless steel pole were wound with a tension (T1) of 50 g and contacted at an angle of 180 degrees, and the tension (T2) necessary for running the tape at a speed of 3.3 cm / s was measured. Using these measured values, the friction coefficient was obtained by the following formula.
μ = 1 / π · ln (T2 / T1)
The results are shown in Table 2.

Evaluation Results From the results of Examples 1-1 to 1-7, it was shown that fine iron nitride powder having a small alkali metal content can be obtained by the method for producing iron nitride powder of the present invention. As shown in Table 2, by using the iron nitride powders of these examples, a magnetic recording medium having excellent magnetic properties, running durability and storage stability could be obtained.

  According to the present invention, it is possible to provide a magnetic recording medium that is excellent in high-density recording characteristics and excellent in storage stability and running durability over a long period of time.

Claims (5)

A method for producing an iron nitride powder comprising subjecting iron oxide particles to sintering prevention treatment, reduction treatment and nitriding treatment in this order,
Particles are formed by subjecting an iron salt aqueous solution containing iron (II) salt and / or iron (III) salt to neutralization treatment, and optionally, magnetite by subjecting the formed particles to oxidation treatment and / or reduction treatment. Particles are obtained, the obtained magnetite particles are used as the iron oxide particles, and the neutralization treatment is performed using at least one aqueous solution selected from the group consisting of aqueous ammonia, aqueous ammonium salt solution, and aqueous urea solution as the iron salt. By adding to the aqueous solution,
The sintering prevention treatment includes adding a sintering inhibitor to the solution containing the particles, neutralizing the solution after adding the sintering inhibitor by adding a neutralizing agent, and the neutralization. A method for producing iron nitride powder, which uses at least one selected from the group consisting of ammonia, carbon dioxide and acetic acid as an agent. An iron nitride powder mainly composed of Fe ₁₆ N ₂ having an average particle diameter of 10 to 25 nm and an alkali metal content of 0.02% by mass or less. The iron nitride powder according to claim 2, which has a coercive force in the range of 143 to 279 kA / m. The iron nitride powder according to claim 2 or 3, which has a saturation magnetization in the range of 55 to 110 A · m ² / kg. A magnetic recording medium having a magnetic layer containing a ferromagnetic powder and a binder on a nonmagnetic support,
The magnetic recording medium is an iron nitride powder manufactured by the manufacturing method according to claim 1 or the iron nitride powder according to any one of claims 2 to 4.