WO2012118054A1 - 表面処理皮膜付き硬質粒子の製造方法及び表面処理皮膜付き硬質粒子 - Google Patents

表面処理皮膜付き硬質粒子の製造方法及び表面処理皮膜付き硬質粒子 Download PDF

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WO2012118054A1
WO2012118054A1 PCT/JP2012/054869 JP2012054869W WO2012118054A1 WO 2012118054 A1 WO2012118054 A1 WO 2012118054A1 JP 2012054869 W JP2012054869 W JP 2012054869W WO 2012118054 A1 WO2012118054 A1 WO 2012118054A1
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film
hard particles
metal
surface treatment
hard
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PCT/JP2012/054869
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English (en)
French (fr)
Japanese (ja)
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貴延 斉藤
貴 石川
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日本パーカライジング株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates

Definitions

  • the present invention relates to a method for producing a hard particle with a surface treatment film and an aqueous dispersion thereof, a hard particle with a surface treatment film produced by the production method, and an aqueous dispersion thereof.
  • a surface treatment film may be formed on the surface of these hard particles.
  • Patent Documents 1 and 2 As a technique for forming a surface treatment film on the surface of hard particles, a method of depositing metal, oxide or carbide by vapor phase chemical growth (see Patent Documents 1 and 2), or a metal by electroless plating A method for depositing a film (see Patent Document 3) has been proposed.
  • a method of treating the surface of the hard particles with a silane coupling agent and a method of treating the surface of the hard particles with a silane coupling agent after forming a plating film or a baking film on the surface of the hard particles have been proposed (See Patent Documents 4 and 5).
  • a treatment method using a silane coupling agent a method has been proposed in which hard particles are dipped in a treatment solution containing a silane coupling agent and pulled up, and then dried and fired as it is.
  • JP-A 61-297079 JP-A-1-234166 Japanese Patent Publication No.52-49197 JP-A-62-99082 JP 2004-74330 A JP 59-141441 A JP-A-1-93443 JP-A-3-285822 JP-A-57-196744 Japanese Unexamined Patent Publication No. 64-28376 Japanese Patent Laid-Open No. 64-28377
  • the surface treatment film can be uniformly formed on the surface of the hard particles.
  • the film forming apparatus is expensive or the film forming process is complicated and expensive. There is a problem that.
  • the methods proposed in Patent Documents 4 and 5 are wet surface treatment methods that are expected to be low in cost, but there is a problem in the uniformity of the film formed on the surface of the hard particles.
  • the present invention has been made to solve the above-described problems of the prior art, and its purpose is to form a surface-treated film formed by forming a uniform surface-treated film having good dispersibility and adhesion to the matrix phase.
  • An object of the present invention is to provide a method capable of producing attached hard particles at low cost.
  • Another object of the present invention is to provide a method for producing an aqueous dispersion containing the hard particles with a surface-treated film with good dispersion stability.
  • Another object of the present invention is to provide hard particles with a surface treatment film produced by the method and an aqueous dispersion containing the hard particles with a surface treatment film with good dispersion stability.
  • the method for producing a hard particle with a surface-treated film according to the present invention for solving the above-described problems includes a step of preparing hard particles having a Knoop hardness of 1000 or more (preparation step), and the hard particles as Zr, Ti. , Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V are held in an aqueous solution containing a fluoride complex of one or more metals selected from the surface of the hard particles.
  • a step of forming the metal hydrated oxide-containing film (hydrated oxide-containing film forming step), and a step of drying the hard particles on which the metal hydrated oxide-containing film is formed (drying step). It is characterized by having.
  • the hard particles are held in an aqueous solution containing a metal fluoride complex solution to form a hydrated oxide-containing film of the metal, so that an expensive apparatus and complicated film forming conditions are not required. Furthermore, hard particles with a surface-treated film can be produced, and the production cost can be reduced.
  • the hydrated oxide-containing film is uniformly formed on the surface of the hard particles, has good water dispersibility, and can exhibit good dispersibility and adhesion even when dispersed in a metal or resin. it can.
  • a contact step with an aqueous solution containing a phosphorus compound is provided between the hydrated oxide-containing film forming step and the drying step.
  • the hard particles on which the hydrated oxide-containing film is formed are brought into contact with the phosphorus compound-containing aqueous solution, the phosphorus compound is adsorbed on the hydrated oxide-containing film to form a phosphorus compound-adsorbed film.
  • the hard particles further provided with the phosphorus compound adsorption film can have better water dispersibility, dispersibility in metal or resin, and adhesion. The reason is considered that the surface charge on the surface of the hard particles is strengthened by providing the phosphorus compound adsorption film.
  • a step of heat treatment is provided after the drying step under conditions of an air atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere.
  • the metal hydrated oxide-containing film is formed into a metal oxide or metal nitride. It can be set as the metal compound film containing 1 type, or 2 or more types chosen from a thing, a metal oxynitride, a metal carbide, etc.
  • the heat treatment step is a heat treatment step at a temperature of 400 ° C. or higher in a non-oxidizing atmosphere or a reducing atmosphere having an oxygen partial pressure of 50 Torr or less.
  • the surface treatment film provided on the surface of the hard particles can be made more uniform and more stable, with good water dispersibility and in the metal or resin. Good dispersibility and adhesion can be achieved.
  • a method for producing an aqueous dispersion containing hard particles with a surface-treated film according to the present invention for solving the above-described problems includes a step of preparing hard particles having a Knoop hardness of 1000 or more (preparation step), Holding the hard particles in an aqueous solution containing a fluoride complex of one or more metals selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V; Forming the metal hydrated oxide-containing film on the surface of the hard particles (hydrated oxide-containing film forming process), and using the hard particles formed with the metal hydrated oxide-containing film as an aqueous solvent And a step of suspending (suspension step).
  • the hard particles are held in an aqueous solution containing a metal fluoride complex solution to form a hydrated oxide-containing film of the metal, so that an expensive apparatus and complicated film forming conditions are not required. Furthermore, hard particles with a surface-treated film can be produced, and the production cost can be reduced.
  • the hydrated oxide-containing film is uniformly formed on the surface of the hard particles, has good water dispersibility, and can exhibit good dispersibility and adhesion even when dispersed in a metal or resin. it can.
  • the hard particles are retained in an aqueous solution containing a metal fluoride complex solution to form a hydrated oxide-containing film of the metal, and then suspended in an aqueous solvent, thereby
  • the hydrate oxide film provided on the surface exhibits good compatibility, dispersibility and dispersion stability with an aqueous solvent.
  • the obtained hard particles with a surface-treated film exhibit good dispersibility and dispersion stability in an aqueous solvent. Therefore, when the hard particles with a surface-treated film are used as a dispersion raw material, there are problems such as aggregation. And can be preferably provided as a raw material dispersed in metal or resin.
  • membrane can be manufactured easily and reduction of manufacturing cost can be aimed at.
  • a contact step with an aqueous solution containing a phosphorus compound between the hydrated oxide-containing film forming step and the suspending step is provided.
  • the phosphorus compound on which the hydrated oxide-containing film is formed are brought into contact with the phosphorus compound-containing aqueous solution, the phosphorus compound is adsorbed on the hydrated oxide-containing film to form a phosphorus compound-adsorbed film. Thereafter, the hydrated oxide-containing film provided with the phosphorus compound-adsorbing film exhibits better compatibility and dispersibility with respect to the aqueous solvent by being suspended in the aqueous solvent.
  • the hard particles with a surface treatment film according to the present invention for solving the above-mentioned problems are hard particles having Knoop hardness of 1000 or more, and Zr, Ti, Si, Cr, Ta provided on the surface of the hard particles. And one or more metal compound films selected from Hf, Sn, Mo, W, Zn, In and V.
  • the metal compound film is provided on the surface of the hard particles, the water dispersibility is good, and even when dispersed in a metal or resin, good dispersibility and adhesion can be exhibited. it can.
  • the metal compound film contains at least one or two or more metal compounds selected from oxides, hydroxides, nitrides, and carbides of the metal. Is preferred.
  • the amount of metal element in the metal compound film is preferably 1 to 500 mg / m 2 .
  • the amount of the phosphorus compound in the phosphorus compound film is preferably 1 to 100 mg / m 2 .
  • An aqueous dispersion containing hard particles with a surface-treated film according to the present invention for solving the above-mentioned problems is formed on the surface of hard particles having a Knoop hardness of 1000 or more with Zr, Ti, Si, Cr, Ta,
  • the hard particles with a surface treatment film having a hydrated oxide-containing film of one or more metals selected from Hf, Sn, Mo, W, Zn, In and V, and the hard particles with the surface treatment film are suspended.
  • an aqueous solvent that is cloudy.
  • the present invention is an aqueous dispersion in which hard particles with a surface treatment film having a hydrated oxide-containing film of various metals on the surface of hard particles having a Knoop hardness of 1000 or more are suspended in an aqueous solvent,
  • the hydrate oxide film provided on the surface of the hard particles exhibits good compatibility with an aqueous solvent, dispersibility, and dispersion stability.
  • this aqueous dispersion exhibits good long-term dispersibility in an aqueous solvent. Therefore, when this aqueous dispersion is used as a dispersion raw material, there is no problem such as agglomeration, and the dispersion raw material in a metal or resin Can be preferably provided.
  • the metal compound film is at least one or more selected from oxides, hydroxides, nitrides and carbides of the metal. It is preferable that the metal compound is included. At this time, the amount of metal element in the metal compound film is preferably 1 to 200 mg / m 2 .
  • the amount of the phosphorus compound in the phosphorus compound adsorption film is preferably 1 to 50 mg / m 2 .
  • hard particles with a surface treatment film can be produced without requiring an expensive apparatus or complicated film formation conditions, and the production cost can be reduced. it can.
  • the hydrated oxide-containing film is uniformly formed on the surface of the hard particles, has good water dispersibility, and can exhibit good dispersibility and adhesion even when dispersed in a metal or resin. it can.
  • hard particles with a surface treatment film can be produced without the need for expensive equipment and complicated film formation conditions, and the production cost Can be reduced.
  • the hydrated oxide-containing film is uniformly formed on the surface of the hard particles, has good water dispersibility, and can exhibit good dispersibility and adhesion even when dispersed in a metal or resin. it can.
  • the metal compound film is provided on the surface of the hard particles, the water dispersibility is good, and even when dispersed in a metal or resin, the dispersion is good. Property and adhesion.
  • the hydrate oxide film provided on the surface of the suspended hard particles has good compatibility and dispersibility with an aqueous solvent.
  • the aqueous dispersion exhibits good long-term dispersibility in an aqueous solvent.
  • the method for producing hard particles with a surface-treated film includes a step of preparing hard particles and a step of holding the hard particles in an aqueous solution containing a metal fluoride complex (water The hard oxide particles with a surface-treated film are produced through a step of forming a hydrated oxide-containing film), a washing step, and a drying step. Further, as shown in the process diagram of FIG. 2, a heat treatment process may be provided after the drying process. Further, as shown in the process diagram of FIG.
  • a contact step (phosphorus compound adsorption film forming step) with an aqueous solution containing a phosphorus compound is provided between the forming step of the hydrated oxide-containing film and the drying step. Also good.
  • a heat treatment process similar to that of FIG. 2 may be provided after the drying process.
  • FIG.4 and FIG.5 the example of the manufactured hard particle 1 with a surface treatment film is shown.
  • the prepared hard particles 2 have a Knoop hardness of 1000 or more. If it is such a hard particle, it will not specifically limit, Specific examples of the constituent material include silicon carbide, tungsten carbide, chromium carbide, boron carbide, diamond, CBN, and aluminum oxide (alumina).
  • the Knoop hardness of the hard particles can be measured using a micro Knoop hardness meter according to JIS-Z2251. As an example, the Knoop hardness of diamond is about 6000, the Knoop hardness of CBN is about 4700, and the Knoop hardness of alumina is about 2000. Of these, diamond or CBN having a Knoop hardness of 4000 or more can be preferably used.
  • the particle diameter and shape of the hard particles are not particularly limited, and conventionally known particles can be applied, but a more preferable particle diameter is in the range of 0.1 to 50 ⁇ m in average particle diameter.
  • the average particle size of the hard particles can be measured and evaluated by a sedimentation test method described in JIS-R6002.
  • the prepared hard particles 2 may be subjected to a conventionally known acid treatment such as sulfuric acid, aqua regia, nitric acid or hydrochloric acid, if necessary, before the subsequent hydrated oxide-containing film forming step. Moreover, you may give conventionally well-known pre-processing means, such as washing.
  • the forming step of the hydrated oxide-containing film 3 ′ is a step of holding the hard particles 2 in an aqueous solution containing a metal fluoride complex and forming the hydrated oxide-containing film 3 ′ on the surface of the hard particles 2. is there. Since this film forming method is performed in a liquid phase, it is called a liquid phase precipitation method.
  • the liquid phase precipitation method generally includes immersing the substrate in an aqueous solution containing a complex in which metal ions are coordinated with anions such as fluoride ions and sulfate ions, and further adding an anion scavenger.
  • the anion scavenger destabilizes the metal ions by extracting the anions from the metal complex, and deposits a metal hydrated oxide-containing film on the substrate.
  • a liquid phase precipitation method is proposed in Patent Documents 6 to 11 described above.
  • the metal exists in the form of a fluoride complex in the aqueous solution.
  • the metal constituting the metal fluoride complex include one or more metals selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In, and V. it can.
  • Such a metal fluoride complex can be obtained by adding a fluorine-containing compound into an aqueous solvent to form an aqueous solution of the metal fluoride.
  • fluorine-containing compound examples include zirconium fluoride, zirconium hydrofluoric acid, ammonium zirconium fluoride, zircon potassium fluoride, sodium zircon fluoride, titanium fluoride, titanium hydrofluoric acid, ammonium titanium fluoride, potassium titanium fluoride, sodium titanium fluoride, and fluoride.
  • aqueous solvent As an aqueous solvent, what is necessary is just a solvent containing 50 mass% or more and 100 mass% or less of water, and the organic solvent may be contained as needed. Moreover, other additives, such as surfactant, may be contained.
  • Examples of the solvent that can be contained in the aqueous solvent include lower alcohols such as ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl acetoacetate, and 2-ethoxyethyl acetate.
  • Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran ; Ethylene glycol monomethyl ether acetate Esters of glycol ethers such as propylene glycol monomethyl ether acetate; carbonates such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, isooctane, decane and dodecane; cyclopentane And alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; N, N-dimethyl
  • Examples of a preferable metal constituting the metal fluoride complex include one or more metals selected from Zr, Ti, Cr, Zn, and In.
  • Preferred metal complexes include the above-mentioned metals. It can be obtained by adding a fluorine compound in an aqueous solvent.
  • the aqueous solution containing a metal fluoride complex preferably has a concentration of the fluorine-containing compound in the aqueous solvent in the range of 0.0001 to 1 mol / L.
  • metal fluoride complexes include compounds other than the fluorine-containing compounds described above (for example, hydrated oxides; inorganic acid salts such as nitrates, sulfates, chlorides, and phosphates; organic acids such as acetic acid)
  • One or more compounds selected from acid salts, etc. and one or more fluorine compounds selected from hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, sodium fluoride, and acidic sodium fluoride Can also be added to an aqueous solvent to form an aqueous solution, whereby a metal fluoride complex can be obtained.
  • the adhesion amount of the hydrated oxide-containing film 3 ′ to the hard particles 2 before the heat treatment described later is preferably in the range of 1 to 200 mg / m 2 as the adhesion amount of the metal element.
  • the adhesion amount of the metal element is less than 1 mg / m 2 , when the hard particles 2 with the surface treatment film are dispersed in the metal or resin matrix, the adhesion with the matrix may be lowered.
  • the adhesion amount of the metal element exceeds 200 mg / m 2 , the adhesion with the matrix may be lowered when dispersed in the metal or the resin matrix.
  • the measurement of the adhesion amount of the metal element constituting the hydrated oxide-containing film 3 ′ is performed by dissolving the hydrated oxide-containing film 3 ′ on the surface of the hard particles, as described in the examples described later.
  • Examples of means for bringing the hard particles into contact with an aqueous solution containing a metal fluoride complex include a method in which the hard particles 2 are put into the aqueous solution under stirring and brought into contact with each other.
  • the contact time at this time is preferably a time that allows the predetermined amount of the hydrated oxide-containing film to be deposited, and is usually about 30 seconds to 72 hours.
  • the hard particles described above are immersed in an aqueous solution containing a complex in which an anion is coordinated to a metal ion, and an anion scavenger is added under stirring conditions.
  • a method of holding the film for a predetermined time to form a hydrated oxide-containing film, followed by washing and then heat-treating can also be mentioned.
  • hard particles may be added to an aqueous solution containing an anion scavenger in advance, and then an aqueous solution containing a fluoride complex may be added.
  • the metal complex is a metal fluoride complex
  • boric acid ferrous chloride, ferric chloride, aluminum salt, magnesium salt, calcium salt, sodium hydroxide, ammonia
  • aluminum examples include titanium, iron, nickel, magnesium, copper, zinc, silicon metal; silicon dioxide, calcium oxide, diboron trioxide, aluminum oxide, magnesium oxide; Of these, boric acid is preferable because impurities do not precipitate in the deposited film.
  • a drying process is a process normally applied after the formation process of hydrated oxide containing film
  • this drying process is unnecessary.
  • the drying step is usually performed in an air atmosphere at 100 ° C., but it may be dried at a temperature other than that, for example, a nitrogen gas atmosphere or an argon gas atmosphere other than the air atmosphere.
  • the drying time is not particularly limited.
  • the heat treatment step is a step provided as necessary as shown in FIG. 2, and is a step of heat treating the hard particles 2 on which the metal hydrated oxide-containing film 3 ′ is formed.
  • heat treatment is performed under conditions of an air atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere.
  • the metal hydrated oxide-containing film 3 ′ before heat treatment is changed into the metal compound film 3 by the heat treatment.
  • the metal hydrated oxide-containing film 3 ′ is converted into a metal oxide, metal nitride, metal oxynitride, and metal. It can be set as the metal compound film
  • the pressure of each atmosphere, the atmosphere gas content, the heat treatment temperature, the heat treatment time, and the like can be arbitrarily set according to the metal compound film 3 to be obtained after the heat treatment.
  • an example of the atmospheric pressure can be arbitrarily selected from a range of 0.01 to 760 Torr, and an example of a heat treatment temperature can be set in a range of 150 to 1000 ° C.
  • the oxidation of the metal hydrated oxide-containing film 3 ' can be suppressed or the oxygen can be reduced by performing it in a non-oxidizing atmosphere or reducing atmosphere having an oxygen partial pressure of 50 Torr or less.
  • a metal compound film 3 made of metal carbide or the like In particular, it is preferably performed in a non-oxidizing atmosphere or a reducing atmosphere of 10 Torr or less.
  • the lower limit of the oxygen partial pressure is not particularly limited, but can be about 0.01 Torr.
  • the non-oxidizing atmosphere include a vacuum atmosphere in the pressure range, or an argon atmosphere and a nitrogen gas atmosphere in the pressure range.
  • the reducing atmosphere is the pressure range, and includes a reducing element (hydrogen gas or ammonia). And an argon atmosphere containing a gas etc.) and a nitrogen gas atmosphere.
  • the hydrated oxide-containing film 3 ′ can be made into the metal compound film 3 containing the gas component.
  • the metal in the hydrated oxide-containing film 3 ′ can be nitrided to form the metal compound film 3 containing a metal nitride.
  • heat treatment is performed in a non-oxidizing atmosphere such as a vacuum atmosphere or an argon atmosphere, whereby the hydrated oxide-containing film 3 '
  • the metal compound film 3 containing a metal carbide can be obtained by carbonizing the metal.
  • the heat treatment temperature is preferably 400 ° C. or higher, more preferably 500 ° C. or higher.
  • the upper limit of the heat treatment temperature is not particularly limited, but can be about 1000 ° C.
  • the heat treatment time is arbitrarily set depending on the heat treatment atmosphere and the heat treatment temperature described above, but may be a time sufficient for the hydrated oxide-containing film 3 ′ to become the metal compound film 3. Usually, it is about 10 minutes to 24 hours.
  • the metal compound film 3 includes at least one or two or more metal compounds selected from metal oxides, hydroxides, nitrides, and carbides.
  • the composition of these metal compounds can be arbitrarily adjusted by the heat treatment atmosphere. For example, when heat treatment is performed in an air atmosphere, the metal compound film 3 containing an oxide, a hydroxide, or the like is likely to be obtained.
  • a compound based on the heat treatment atmosphere for example, a metal compound mainly containing metal nitride, metal carbide, or the like can be used.
  • the metal compound film 3 provided on the surface of the hard particles 2 can be formed, and good water dispersibility and good dispersibility and adhesion in a metal or resin can be achieved.
  • the formation process of the phosphorus compound adsorption film 4 ′ is a process added as necessary as shown in FIG. 3, and is performed between the hydrated oxide-containing film formation process and the drying process.
  • the phosphorus compound adsorption film 4 ′ is formed by bringing the hard particles 2 having the hydrated oxide-containing film 3 ′ on the surface into contact with an aqueous solution containing a phosphorus compound.
  • the surface charge of the hard particles 1 with a surface-treated film is strengthened and the dispersibility can be improved.
  • the reason for the “adsorption film” is that the phosphorus compound is adsorbed onto the hydrated oxide-containing film 3 ′ to form a film (phosphorus compound adsorption film 4 ′).
  • a cleaning process is performed, and then contacted with an aqueous solution containing a phosphorus compound. After contacting with the phosphorus compound, it is washed with water and sent to the drying step.
  • Examples of phosphorus compounds include phosphoric acids, phosphate esters, and organic phosphonic acids.
  • metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, and hexametaphosphoric acid
  • polyphosphoric acid is a chain phosphoric acid condensate that includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and the like. To do.
  • it is preferable to use phosphoric acids because they are excellent in dispersibility and dispersion stability.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate 2, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, and dibutyl phosphate.
  • Organic phosphonic acids include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 2-phosphono-1,2,4-butanetricarboxylic acid (PBTC), nitrilotris (methylenephosphonic acid) (NTMP), nitrilotri Carbon number of the same or different alkylene groups such as bis (ethylenephosphonic acid), nitrilotris (propylenephosphonic acid), nitrilobis (ethylenephosphonic acid) mono (methylenephosphonic acid), nitrilobis (methylenephosphonic acid) mono (propylenephosphonic acid) Nitrilotris (alkylenephosphonic acid) which is an alkylene group of 1 to 4; an alkylene group such as ethylenediaminetetramethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, ethylenediaminetetrapropylenephosphonic acid is an alkyl group having 1 to 4 carbon atoms.
  • HEDP 1-hydroxyethylidene-1,
  • Ethylenediaminetetraalkylenephosphonic acid which is an ethylene group; hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid; hydroxymethanediphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, propane-1-hydroxy-1 , 1 diphosphonic acid and the like, and alkane-1-hydroxy-1, 1-diphosphonic acid having 1 to 4 carbon atoms;
  • the aqueous solution containing the phosphorus compound is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of the aqueous solvent.
  • the adhesion amount of the phosphorus compound adsorption film 4 ′ is preferably in the range of 1 to 50 mg / m 2 as the adhesion amount of the phosphorus element. If the adhesion amount of the phosphorus element is less than 1 mg / m 2 , the effect of increasing the surface charge cannot be sufficiently obtained, and the dispersibility when the hard particles 1 with the surface treatment film are dispersed in the metal and the resin matrix is reduced. It cannot be improved further. On the other hand, if the adhesion amount of the phosphorus element exceeds 50 mg / m 2 , the adhesion with the mother phase may be lowered.
  • the measurement of the adhesion amount of the phosphorus element constituting the phosphorus compound adsorbing film 4 ′ is performed by dissolving the adsorbed phosphorus compound adsorbing film 4 ′ and analyzing the liquid by ICP analysis, as will be described in Examples described later.
  • the concentration of the phosphorus element component constituting the phosphorus compound adsorption film 4 ′ was analyzed. From the result, the adhesion amount of the phosphorus element constituting the phosphorus compound adsorption film 4 ′ was calculated.
  • Means for bringing the hard particles 2 provided with the hydrated oxide-containing film 3 ′ into contact with an aqueous solution containing a phosphorus compound is a method in which the hard particles 2 are put in contact with the aqueous solution under stirring. Can be mentioned.
  • the contact time at this time is preferably a time that allows the predetermined amount of the phosphorus compound adsorbing film 4 ′ to be deposited, and is usually about 30 seconds to 24 hours.
  • the cleaning step is (a) after the preparation step of the hard particles 2 and before the formation step of the hydrated oxide-containing film 3 ′, (b) after the formation step of the hydrated oxide-containing film 3 ′ and before the drying step, ) If a process for forming the phosphorus compound adsorption film 4 ′ is added as necessary, after the process for forming the hydrated oxide-containing film 3 ′, before the process for forming the phosphorus compound adsorption film 4 ′, or (d) It can be inserted arbitrarily at the stage after the formation process of the phosphorus compound adsorption film 4 ′ and before the drying process.
  • the washing method is not particularly limited, and a method of repeating the step of adding ion-exchanged water again after concentration by centrifugation, suction filtration, decantation or the like is exemplified.
  • the hard particle 2 is held in an aqueous solution containing a metal fluoride complex solution and the metal hydrated oxide-containing film is contained. Since 3 ′ is formed, the hard particles 1 with a surface-treated film can be manufactured without requiring an expensive apparatus or complicated film forming conditions, and the manufacturing cost can be reduced. Further, the hydrated oxide-containing film 3 ′ is uniformly formed on the surface of the hard particles 2, and has good water dispersibility. Even when dispersed in a metal or resin, it has good dispersibility and adhesion. Can show. Further, the hard particles 1 with a surface treatment film having the phosphorus compound film 4 formed on the surface by drying or heat treatment after forming the phosphorus compound adsorption film 4 ′ can further improve dispersibility and adhesion.
  • the hard particle 1 with a surface treatment film according to the present invention is produced by the above-described method for producing a hard particle with a surface treatment film, and as shown in FIG. And one or more metal compound films 3 selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V provided on the surface of the hard particles 2.
  • metal compound films 3 selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V provided on the surface of the hard particles 2.
  • the hard particles 2, the metal compound film 3 provided on the surface of the hard particles 2, and the phosphorus compound film 4 are included.
  • the metal compound film 3 constituting the hard particle 1 with the surface treatment film contains at least one kind or two or more kinds of metal compounds selected from metal oxides, hydroxides, nitrides and carbides.
  • the adhesion amount of the metal compound film 3 to the surface of the hard particles 2 is preferably in the range of 1 to 200 mg / m 2 as the adhesion amount of the metal element. When the adhesion amount of the metal element is less than 1 mg / m 2 , when the hard particles 2 with the surface treatment film are dispersed in the metal or the resin matrix, the adhesion with the matrix may be lowered.
  • the adhesion amount of the metal element exceeds 200 mg / m 2 , when dispersed in the metal or the resin matrix, the adhesion to the matrix may be lowered.
  • the measurement of the adhesion amount of the metal element constituting the metal compound film 3 is performed by dissolving the metal compound film 3 on the surface of the hard particles and analyzing the liquid by ICP analysis, as will be described in Examples described later. The density
  • the phosphorus compound film 4 constituting the hard particles 1 with the surface treatment film is a compound film containing phosphorus, and the adhesion amount of the phosphorus compound film 4 is in the range of 1 to 50 mg / m 2 as the adhesion amount of the phosphorus element. Is preferred. If the adhesion amount of the phosphorus element is less than 1 mg / m 2 , the effect of increasing the surface charge cannot be sufficiently obtained, and the dispersibility when the hard particles 1 with the surface treatment film are dispersed in the metal and the resin matrix is reduced. It cannot be improved further. On the other hand, if the adhesion amount of the phosphorus element exceeds 50 mg / m 2 , the adhesion with the mother phase may be lowered.
  • the metal compound film 3 and the phosphorus compound film 4 are provided on the surface of the hard particle 2, water dispersibility is good, and in a metal or a resin. Good dispersibility and adhesiveness can be exhibited even if dispersed in the composition.
  • the manufacturing method of the aqueous dispersion which concerns on this invention is a method of manufacturing the aqueous dispersion 11 (refer FIG. 6) which contains the hard particle 1 with a surface treatment film
  • the metal hydrated oxide is not subjected to drying or heat treatment after the formation step of the hydrated oxide-containing film 3 ′.
  • the hard particles 2 on which the containing film 3 ′ is formed are suspended in an aqueous solvent.
  • membrane 3 ', the formation process of phosphorus compound adsorption film 4', a drying process, heat processing A process, a washing process, etc. are the same as each process which constitutes a manufacturing method of an above-mentioned hard particle with a surface treatment coat. Therefore, the description is omitted here.
  • the suspension step is a step of suspending the hard particles 2 formed with the metal hydrated oxide-containing film 3 ′ in the aqueous solvent 12.
  • the aqueous solvent 12 used here is a solvent containing 50% by mass or more and 100% by mass or less of water, and an organic solvent may be included as necessary. Moreover, the other additive may be contained.
  • Solvents that can be blended in the aqueous solvent include, for example, lower alcohols such as ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl acetoacetate, 2-ethoxyethyl acetate, and the like.
  • glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran ; Ethylene glycol monomethyl ether acetate Esters of glycol ethers such as propylene glycol monomethyl ether acetate; carbonates such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, isooctane, decane and dodecane; cyclopentane And alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; N, N-dimethylform
  • additives include surfactants and the like. Such additives can be contained in an aqueous solvent in an amount of 0.01 to 10% by mass within the range not departing from the spirit of the additive.
  • the suspension concentration of the hard particles with a surface-treated film 1 in the aqueous solvent 12 is preferably 0.5 to 90% by mass, and more preferably 1 to 50% by mass. If the suspension concentration is less than 0.5% by mass, the concentration is too low to contain hard particles in the matrix, and the effect of dispersing the hard particles such as improving the hardness may not be obtained. On the other hand, when the suspension concentration exceeds 90% by mass, the viscosity of the dispersion may be too high to be handled.
  • the hard particles 2 on which the hydrated oxide-containing film 3 ′ is formed are brought into contact with the phosphorus compound-containing aqueous solution, so that the phosphorus compound is adsorbed on the hydrated oxide-containing film. It becomes a phosphorus compound adsorption film. Thereafter, by suspending in an aqueous solvent, the hydrated oxide-containing film 3 ′ provided with the phosphorus compound-adsorbing film 4 ′ has better compatibility, dispersibility and dispersion stability with respect to the aqueous solvent. Indicates.
  • membrane 3 'provided in the surface of the hard particle 2 is with respect to the aqueous solvent 12. Therefore, the obtained hard particles 1 with the surface-treated film exhibit good dispersibility and dispersion stability in the aqueous solvent 12.
  • this hard particle 1 with a surface treatment film is used as a dispersion raw material, there is no problem such as aggregation, and it can be preferably provided as a dispersion raw material in a metal or resin.
  • the dispersibility and dispersion stability of the hard particles 1 with the surface treatment film are suspended by suspending the hard particles 1 with the surface treatment film in which the phosphorus compound film 4 is further formed in the aqueous solvent 12 without performing the heat treatment step.
  • the property can be further improved.
  • the aqueous dispersion 11 according to the present invention is manufactured by the above-described aqueous dispersion manufacturing method.
  • the hard particles 2 having a Knoop hardness of 1000 or more, and the hard particles 2
  • One or more metal compound films 3 selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In, and V provided on the surface, and provided as necessary.
  • the hard particles 1 with a surface-treated film having the phosphorus compound-adsorbing film 4 ′ are suspended in an aqueous solvent without being dried or heat-treated.
  • the metal hydrated oxide-containing film 3 ′ constituting the hard particles 1 with the surface treatment film is mainly composed of one or more metal hydroxides selected from the metals described above.
  • the adhesion amount of the hydrated oxide-containing film 3 ′ to the surface of the hard particles 2 is preferably in the range of 1 to 200 mg / m 2 as the adhesion amount of the metal element.
  • the adhesion amount of the metal element is less than 1 mg / m 2
  • the hard particles with a surface treatment film may aggregate after the hard particles with a surface treatment film 1 are dispersed in an aqueous solvent 12. Further, when the hard particles 1 with a surface treatment film contained in the aqueous dispersion 11 are used as particles to be contained in a metal or resin, dispersibility and adhesion to the metal or resin matrix may be lowered. On the other hand, when the adhesion amount of the metal element exceeds 200 mg / m 2 , the adhesion with the metal or the resin matrix may be lowered.
  • the phosphorus compound adsorption film 4 ′ constituting the aqueous dispersion 11 is an adsorption film of a compound containing phosphorus, and the adhesion amount of the phosphorus compound adsorption film 4 ′ is 1 to 50 mg / m 2 as the adhesion amount of phosphorus element.
  • the range of is preferable. If the adhesion amount of the phosphorus element is less than 1 mg / m 2 , the effect of increasing the surface charge cannot be sufficiently obtained, and even if the hard particles 1 with the surface treatment film are dispersed in the aqueous solvent 12, the surface treatment film is attached. The dispersibility and dispersion stability of the hard particles 1 cannot be improved so much. On the other hand, when the adhesion amount of the phosphorus element exceeds 50 mg / m 2 , the adhesion with the metal or the resin matrix may be lowered.
  • the hard particles 2 are held in an aqueous solution containing a metal fluoride complex solution to form the metal hydrated oxide-containing film 3 ′. Thereafter, by suspending in an aqueous solvent, the hydrate oxide film 3 ′ provided on the surface of the hard particles 2 exhibits good compatibility, dispersibility, and dispersion stability with respect to the aqueous solvent.
  • the hard particles 1 with a surface-treated film suspended in the aqueous dispersion 11 exhibit good dispersibility and dispersion stability in the aqueous solvent 12, so that the hard particles 1 with a surface-treated film are used as a dispersion raw material.
  • there is no problem such as agglomeration and it can be preferably provided as a raw material dispersed in a metal or resin.
  • Example 1 Diamond particles (hard particles, manufactured by Tomei Diamond Co., Ltd.) were added to 50 mL of a 0.06 mol / L zinc fluoride aqueous solution (fluoride aqueous solution) heated to 40 ° C. and adjusted to pH 6.4 with aqueous ammonia under stirring conditions. 1 g of an average particle diameter: 16.0 ⁇ m) was added. Further, a 0.6 mol / L boric acid aqueous solution (anion scavenger) adjusted to pH 6.4 with aqueous ammonia was added to the aqueous solution at 40 ° C. and 50 mL was added. Subsequently, the mixture was stirred for 5 hours while maintaining the liquid temperature at 40 ° C.
  • a 0.06 mol / L zinc fluoride aqueous solution fluoride aqueous solution
  • pH 6.4 aqueous ammonia
  • Example 1 After concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing.
  • the washed particles were heated at 100 ° C. until they were dried in an air atmosphere, and then further heated at 300 ° C. in an air atmosphere for 1 hour. In this way, hard particles (diamond particles) A with a surface treatment film according to Example 1 were produced.
  • Example 2 1 g of silicon carbide particles (hard particles, manufactured by Shinano Denki Co., Ltd., average particle size: 20 ⁇ m) was added to 48 mL of 0.41 mol / L boric acid aqueous solution (anion supplement) heated to 40 ° C. under stirring conditions. did. Furthermore, 52 mL of 0.19 mol / L chromium (III) fluoride aqueous solution (fluoride aqueous solution) heated to 40 ° C. was added to the aqueous solution. Subsequently, the mixture was stirred for 3 hours while maintaining the liquid temperature at 40 ° C. Then, after concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing. The washed particles were heated at 100 ° C. until they were dried in an air atmosphere. In this way, hard particles (silicon carbide particles) B with a surface treatment film according to Example 2 were produced.
  • silicon carbide particles hard particles, manufactured by Shinano Denki Co.,
  • Example 3 Boron carbide particles (hard particles, New Metals End Co., Ltd.) under stirring conditions were added to 100 mL of a 0.06 mol / L zircon hydrofluoric acid aqueous solution (fluoride aqueous solution) heated to 40 ° C. and adjusted to pH 2.0 with aqueous ammonia. 2 g of Chemicals, average particle size: 15 to 16 ⁇ m) was added. Further, an aluminum plate (A1050P) was added to the aqueous solution as an anion scavenger and stirred for 4 hours while maintaining the liquid temperature at 40 ° C. Thereafter, the aluminum plate was taken out and concentrated by decantation, and then the operation of adding ion exchange water again was repeated 10 times for washing. The washed particles were heated at 100 ° C. until they were dried in an air atmosphere. In this way, hard particles (boron carbide particles) C with a surface treatment film according to Example 3 were produced.
  • Example 4 To 70 mL of a mixed aqueous solution (fluoride aqueous solution) of 0.04 mol / L indium nitrate and 0.12 mol / L hydrofluoric acid, heated to 40 ° C. and adjusted to pH 6.5 with aqueous ammonia, 2 g of boron carbide particles (hard particles, manufactured by New Metals End Chemicals Co., Ltd., average particle size: 15 to 16 ⁇ m) was added. Further, 0.4 mL / L boric acid aqueous solution (anion scavenger) adjusted to pH 6.4 with ammonia water was heated to 40 ° C. and 30 mL was added to the aqueous solution.
  • a mixed aqueous solution fluoride aqueous solution
  • 2 g of boron carbide particles hard particles, manufactured by New Metals End Chemicals Co., Ltd., average particle size: 15 to 16 ⁇ m
  • Example 5 3 g of diamond particles (hard particles, manufactured by Tomei Dia Co., Ltd., average particle size: 16.0 ⁇ m) in 80 mL of a 0.25 mol / L boric acid aqueous solution (anion scavenger) heated to 40 ° C. Added. Furthermore, 20 mL of 0.55 mol / L ammonium titanium fluoride aqueous solution (fluoride aqueous solution) heated to 40 ° C. was added to the aqueous solution. Subsequently, the mixture was stirred for 3 hours while maintaining the liquid temperature at 40 ° C. Then, after concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing. The washed particles were heated at 100 ° C. until they were dried in an air atmosphere. In this way, hard particles (diamond particles) E with a surface treatment film according to Example 5 were produced.
  • a 0.25 mol / L boric acid aqueous solution anion a
  • Example 6 The hard particles (boron carbide particles) C with a surface-treated film produced in Example 3 were heated at 700 ° C. for 2 hours under a vacuum with an oxygen partial pressure of 5 Torr. In this way, hard particles (boron carbide particles) F with a surface treatment film according to Example 6 were produced.
  • Example 7 The hard particles (diamond particles) E with a surface treatment film prepared in Example 5 were heated at 500 ° C. for 3 hours in a nitrogen atmosphere having an oxygen partial pressure of 1 Torr. In this manner, hard particles (diamond particles) G with a surface treatment film according to Example 7 were produced.
  • Example 8 After adding the surface-treated film-coated hard particles (boron carbide particles) C prepared in Example 3 to a 1.0 mass% tripolyphosphoric acid aqueous solution (25 ° C.), the mixture was stirred for 1 hour. Then, after concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing. Then, it heated until it dried in air
  • Example 9 The surface-treated coated hard particles (silicon carbide particles) A prepared in Example 2 were added to a 0.1 mass% tripolyphosphoric acid aqueous solution (25 ° C.) and stirred for 10 minutes. Then, after concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing. Then, it heated until it dried in air
  • Example 10 CBN particles (hard particles, New Metals End Chemicals Co., Ltd.) under stirring conditions were added to 100 mL of 0.06 mol / L zircon hydrofluoric acid aqueous solution (fluoride aqueous solution) heated to 40 ° C. and adjusted to pH 2.0 with aqueous ammonia. Manufactured, average particle size: 15 to 16 ⁇ m) was added. Further, an aluminum plate (A1050P) was added to the aqueous solution as an anion scavenger and stirred for 4 hours while maintaining the liquid temperature at 40 ° C. Thereafter, the aluminum plate was taken out and concentrated by decantation, and then the operation of adding ion exchange water again was repeated 10 times for washing.
  • A1050P aluminum plate
  • the washed particles are concentrated again by decantation, and then ion-exchanged water is added to the aqueous disperse containing hard particles with surface treatment film (CBN particles) according to Example 10 having a solid content concentration of 50.0% by mass. John J was made.
  • CBN particles hard particles with surface treatment film
  • Example 11 The surface-treated coated hard particles (silicon carbide particles) A prepared in Example 2 were added to a 1.0 mass% tripolyphosphoric acid aqueous solution (25 ° C.) and stirred for 1 hour. Then, after concentrating by decantation, the operation of adding ion exchange water again was repeated 10 times for washing. Then, after concentrating again by decantation, ion-exchange water was added, and aqueous dispersion K containing hard particles (silicon carbide particles) with a surface treatment film according to Example 11 having a solid content concentration of 20.0% by mass was obtained. Produced.
  • Comparative Example 5 Hard particles according to Comparative Example 5 were formed without forming a surface treatment film on diamond particles (hard particles, manufactured by New Metals End Chemicals Co., Ltd., average particle size: 30 ⁇ m).
  • Examples 1 to 11 and Comparative Examples 1 to 5 were placed in nickel plating baths containing nickel sulfate 0.53M, nickel chloride 0.09M, and sodium citrate 1.24M, and adjusted to pH 8 with sodium hydroxide. 5 g / L of the hard particles with a surface-treated film obtained in 1 were added. After stirring for 10 minutes, stirring was stopped, and after standing for 1 minute, a pure copper plate (C1020P, thickness 0.1 mm, length 40 mm, width 30 mm) as a base material and a nickel anode were set to a distance of 50 mm between the electrodes. Installed facing each other. Thereafter, electrolysis was performed at a liquid temperature of 50 ° C.
  • the surface treatment film of the hard particles with the surface treatment film of Examples 1 to 5 was made of each metal. It was estimated to be a hydrated oxide-containing film. In Example 6, it was estimated that zirconium carbide was formed in addition to zirconium hydrated oxide. In Example 7, it was estimated that titanium nitride was formed in addition to titanium hydrated oxide. In Example 8, it was estimated that the surface treatment film was made of zirconium hydrated oxide, and the phosphorus compound was adsorbed on the surface. In Example 9, it was estimated that the surface treatment film was composed of chromium hydrated oxide, and the phosphorus compound was adsorbed on the surface.
  • Comparative Example 1 it was estimated that the surface treatment film was formed of calcium carbonate.
  • Comparative Example 2 metallic Ni was detected, in Comparative Example 3, metallic Ti was detected, and in Comparative Example 4, it was estimated that the surface treatment film was composed of a hydrated oxide of silicon.
  • Examples 1 to 7 had two points for both adhesion and dispersibility.
  • the adhesion was 2 points and the dispersibility was 3 points, which resulted in further excellent dispersibility.
  • the dispersibility was 3 points, and the dispersibility was excellent.
  • Comparative Examples 1 to 3 and 5 all had one point of adhesion and one point of dispersibility, resulting in poor adhesion and dispersibility. Further, in Comparative Example 4, the adhesion was 2 points, but the dispersibility was 1 point, resulting in poor dispersibility.
  • EPMA analysis was performed on the hard particles (diamond particles) E with the surface treatment coating obtained in Example 5 and the hard particles (diamond particles) not formed with the surface treatment coating of Comparative Example 5 under the following conditions.
  • the method for producing hard particles with a surface treatment film according to the present invention and the obtained hard particles with a surface treatment film are used as hard particles for surface hardening used for dispersion plating of metals such as aluminum. Available for use. Moreover, it can utilize suitably also for abrasive grains for cutting, such as a cutting wheel and a wire saw.

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PCT/JP2012/054869 2011-03-01 2012-02-28 表面処理皮膜付き硬質粒子の製造方法及び表面処理皮膜付き硬質粒子 WO2012118054A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1018083A (ja) * 1996-07-01 1998-01-20 Nippon Parkerizing Co Ltd 酸化チタン被覆金属材料の製造方法
JP2923047B2 (ja) * 1988-11-07 1999-07-26 ノートン カンパニー 多重金属被覆超研摩グリット及びその製造方法
JP2007217258A (ja) * 2006-02-20 2007-08-30 Futaba Corp ナノ炭素粒子分散液及びその製造方法とコア・シェル型ナノ炭素粒子及びその製造方法
JP2010527802A (ja) * 2007-05-22 2010-08-19 エレメント シックス リミテッド コーティングされたダイヤモンド
JP2010540759A (ja) * 2007-10-05 2010-12-24 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 改善された炭化ケイ素粒子、ならびにその製造方法および使用方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2923047B2 (ja) * 1988-11-07 1999-07-26 ノートン カンパニー 多重金属被覆超研摩グリット及びその製造方法
JPH1018083A (ja) * 1996-07-01 1998-01-20 Nippon Parkerizing Co Ltd 酸化チタン被覆金属材料の製造方法
JP2007217258A (ja) * 2006-02-20 2007-08-30 Futaba Corp ナノ炭素粒子分散液及びその製造方法とコア・シェル型ナノ炭素粒子及びその製造方法
JP2010527802A (ja) * 2007-05-22 2010-08-19 エレメント シックス リミテッド コーティングされたダイヤモンド
JP2010540759A (ja) * 2007-10-05 2010-12-24 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 改善された炭化ケイ素粒子、ならびにその製造方法および使用方法

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