WO2012118054A1 - Process of producing hard particle provided with surface treatment coating, and hard particle provided with surface treatment coating - Google Patents

Process of producing hard particle provided with surface treatment coating, and hard particle provided with surface treatment coating 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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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

Abstract

[Problem] To provide: a process of producing a hard particle provided with a surface treatment coating, which can be produced by forming a uniform surface treatment coating on the surface of an inert hard particle such as a diamond particle and a CBN particle employing a wet-mode technique that can be achieved at low cost, and which has good dispersibility; and others. [Solution] A hard particle (1) provided with a surface treatment coating is produced by a process comprising: a step of preparing a hard particle (2) having a Knoop hardness of 1000 or more; a step of holding the hard particle (2) in an aqueous solution containing a fluoride complex of at least one metal selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V to form a film (3') containing a hydrated oxide of the metal on the surface of the hard particle (2); and a step of drying the hard particle on which the film (3') containing the hydrated oxide of the metal has been formed. It is preferred that a step of bringing the particle into contact with an aqueous solution containing a phosphorus compound is provided between the hydrated-oxide-containing film formation step and the drying step.

Description

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Method for producing hard particles with surface treatment film and hard particles with surface treatment film
　本発明は、表面処理皮膜付き硬質粒子及びその水性ディスパージョンの製造方法、並びにその製造方法で製造された表面処理皮膜付き硬質粒子及びその水性ディスパージョンに関する。 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.
　炭化ケイ素、炭化タングステン、炭化クロム、炭化ホウ素、ダイヤモンド、又はＣＢＮ等の硬質粒子を金属又は樹脂等の母相中に分散させる場合、それら硬質粒子の分散性や母相との間の密着性が不十分なことがある。そのため、分散性や母相との密着性を向上させるため、それら硬質粒子の表面に表面処理皮膜を形成することがある。 When hard particles such as silicon carbide, tungsten carbide, chromium carbide, boron carbide, diamond, or CBN are dispersed in a parent phase such as metal or resin, the dispersibility of these hard particles and the adhesion between the hard particles is It may be insufficient. Therefore, in order to improve the dispersibility and the adhesion with the matrix, a surface treatment film may be formed on the surface of these hard particles.
　硬質粒子の表面に表面処理皮膜を形成するための技術として、気相化学成長法で金属、酸化物又は炭化物等を析出させる方法（特許文献１，２を参照）や、無電解めっき法で金属膜を析出させる方法（特許文献３を参照）が提案されている。また、硬質粒子の表面をシランカップリング剤で処理する方法や、硬質粒子の表面にめっき皮膜や焼付皮膜を形成した後、さらにその表面をシランカップリング剤で処理する方法が提案されている（特許文献４，５を参照）。シランカップリング剤による処理方法として、シランカップリング剤を含む処理液中に硬質粒子を浸漬して引き上げ、その後そのまま乾燥し焼成する方法が提案されている。 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. In addition, 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). As 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.
特開昭６１－２９７０７９号公報JP-A 61-297079 特開平１－２３４１６６号公報JP-A-1-234166 特公昭５２－４９１９７号公報Japanese Patent Publication No.52-49197 特開昭６２－９９０８２号公報JP-A-62-99082 特開２００４－７４３３０号公報JP 2004-74330 A 特開昭５９－１４１４４１号公報JP 59-141441 A 特開平１－９３４４３号公報JP-A-1-93443 特開平３－２８５８２２号公報JP-A-3-285822 特開昭５７－１９６７４４号公報JP-A-57-196744 特開昭６４－２８３７６号公報Japanese Unexamined Patent Publication No. 64-28376 特開昭６４－２８３７７号公報Japanese Patent Laid-Open No. 64-28377
　特許文献１～３で提案された方法では、硬質粒子の表面に均一に表面処理皮膜を成膜できるとされているが、成膜装置が高価であったり成膜プロセスが複雑で高コストであったりするという問題がある。また、特許文献４，５で提案された方法は、低コストが期待される湿式法による表面処理方法であるが、硬質粒子の表面に生成した皮膜の均一性に問題がある。 In the methods proposed in Patent Documents 1 to 3, the surface treatment film can be uniformly formed on the surface of the hard particles. However, the film forming apparatus is expensive or the film forming process is complicated and expensive. There is a problem that. Further, 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.
　本発明は、上記した従来技術の問題を解決するためになされたものであって、その目的は、均一で母相に対する分散性と密着性の良い表面処理皮膜を成膜してなる表面処理皮膜付き硬質粒子を低コストで製造できる方法を提供することにある。また、その表面処理皮膜付き硬質粒子を分散安定性よく含有する水性ディスパージョンの製造方法を提供することにある。 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.
　本発明の他の目的は、その方法で製造された表面処理皮膜付き硬質粒子、及びその表面処理皮膜付き硬質粒子を分散安定性よく含有する水性ディスパージョンを提供することにある。 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.
　（１）上記課題を解決するための本発明に係る表面処理皮膜付き硬質粒子の製造方法は、ヌープ硬度が１０００以上の硬質粒子を準備する工程（準備工程）と、該硬質粒子をＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属のフッ化物錯体を含む水溶液中に保持して、前記硬質粒子の表面に前記金属の水和酸化物含有膜を形成する工程（水和酸化物含有膜形成工程）と、前記金属の水和酸化物含有膜が形成された硬質粒子を乾燥させる工程（乾燥工程）とを有することを特徴とする。 (1) 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.
　この発明によれば、硬質粒子を金属のフッ化物錯体溶液を含む水溶液中に保持して該金属の水和酸化物含有膜を形成するので、高価な装置や複雑な成膜条件を必要とせずに、表面処理皮膜付き硬質粒子を製造でき、製造コストの低減を図ることができる。また、水和酸化物含有膜は硬質粒子の表面に均一に形成されており、水分散性も良好であり、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the present invention, 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. In addition, 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.
　本発明に係る表面処理皮膜付き硬質粒子の製造方法において、前記水和酸化物含有膜形成工程と前記乾燥工程との間に、リン化合物を含有する水溶液への接触工程を設ける。 In the method for producing hard particles with a surface treatment film according to the present invention, 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.
　この発明によれば、水和酸化物含有膜を形成した硬質粒子をリン化合物含有水溶液に接触させるので、水和酸化物含有膜上にリン化合物が吸着してリン化合物吸着膜となる。リン化合物吸着膜をさらに設けた硬質粒子は、水分散性と、金属中や樹脂中への分散性及び密着性とをより良好なものとすることができる。この理由は、リン化合物吸着膜を設けることにより、硬質粒子表面の表面電荷が強まったためであろうと考えられる。 According to the present invention, since 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.
　本発明に係る表面処理皮膜付き硬質粒子の製造方法において、前記乾燥工程後に、大気雰囲気、非酸化雰囲気又は還元雰囲気の条件下で熱処理する工程（熱処理工程）を設ける。 In the method for producing hard particles with a surface-treated film according to the present invention, a step of heat treatment (heat treatment step) is provided after the drying step under conditions of an air atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere.
　この発明によれば、前記乾燥工程後の熱処理工程を、大気雰囲気、非酸化雰囲気又は還元雰囲気のいずれの条件下で行うかによって、金属の水和酸化物含有膜を、金属酸化物、金属窒化物、金属酸窒化物、及び金属炭化物等から選ばれる１種又は２種以上を含む金属化合物膜とすることができる。 According to the present invention, depending on whether the heat treatment step after the drying step is performed in 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.
　本発明に係る表面処理皮膜付き硬質粒子の製造方法において、前記熱処理工程が、酸素分圧５０Ｔｏｒｒ以下の非酸化雰囲気下又は還元雰囲気下で、４００℃以上の温度で熱処理する工程である。 In the method for producing hard particles with a surface treatment film according to the present invention, 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.
　この発明によれば、上記条件で熱処理するので、硬質粒子表面に設けた表面処理皮膜をより均一且つより安定なものとすることができ、良好な水分散性と、金属中や樹脂中への良好な分散性と密着性を達成することができる。 According to the present invention, since the heat treatment is performed under the above-described conditions, 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.
　（２）上記課題を解決するための本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの製造方法は、ヌープ硬度が１０００以上の硬質粒子を準備する工程（準備工程）と、該硬質粒子をＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属のフッ化物錯体を含む水溶液中に保持して、前記硬質粒子の表面に前記金属の水和酸化物含有膜を形成する工程（水和酸化物含有膜形成工程）と、前記金属の水和酸化物含有膜が形成された硬質粒子を水性溶媒に懸濁する工程（懸濁工程）とを有することを特徴とする。 (2) 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).
　この発明によれば、硬質粒子を金属のフッ化物錯体溶液を含む水溶液中に保持して該金属の水和酸化物含有膜を形成するので、高価な装置や複雑な成膜条件を必要とせずに、表面処理皮膜付き硬質粒子を製造でき、製造コストの低減を図ることができる。また、水和酸化物含有膜は硬質粒子の表面に均一に形成されており、水分散性も良好であり、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the present invention, 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. In addition, 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.
　この発明によれば、硬質粒子を金属のフッ化物錯体溶液を含む水溶液中に保持して該金属の水和酸化物含有膜を形成し、その後に水性溶媒に懸濁することにより、硬質粒子の表面に設けられた水和物酸化物膜が水性溶媒に対して良好な相溶性と分散性及び分散安定性とを示す。その結果、得られた表面処理皮膜付き硬質粒子は、水性溶媒中で良好な分散性及び分散安定性を示すので、この表面処理皮膜付き硬質粒子を分散原料として用いる場合に、凝集等の不具合がなく、金属中や樹脂中への分散原料として好ましく提供できる。また、水和酸化物含有膜の形成に、高価な装置や複雑な成膜条件を必要としないので、表面処理皮膜付き硬質粒子を容易に製造でき、製造コストの低減を図ることができる。 According to this invention, 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. As a result, 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. Moreover, since an expensive apparatus and complicated film-forming conditions are not required for formation of a hydrated oxide containing film | membrane, the hard particle with a surface treatment film | membrane can be manufactured easily and reduction of manufacturing cost can be aimed at.
　本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの製造方法において、前記水和酸化物含有膜形成工程と前記懸濁工程との間に、リン化合物を含有する水溶液への接触工程を設ける。 In the method for producing an aqueous dispersion containing hard particles with a surface-treated film according to the present invention, 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.
　この発明によれば、水和酸化物含有膜を形成した硬質粒子をリン化合物含有水溶液に接触させるので、水和酸化物含有膜上にリン化合物が吸着してリン化合物吸着膜となる。その後に水性溶媒中に懸濁することにより、リン化合物吸着膜が設けられた水和酸化物含有膜は、水性溶媒に対してより良好な相溶性と分散性を示す。 According to the present invention, since 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. 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.
　（３）上記課題を解決するための本発明に係る表面処理皮膜付き硬質粒子は、ヌープ硬度が１０００以上の硬質粒子と、該硬質粒子の表面に設けられたＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属化合物膜とを有することを特徴とする。 (3) 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.
　この発明によれば、上記金属化合物膜が硬質粒子の表面に設けられているので、水分散性が良好で、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the present invention, since 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.
　本発明に係る表面処理皮膜付き硬質粒子において、前記金属化合物膜が、前記金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種又は２種以上の金属化合物を含むことが好ましい。このとき、金属化合物膜中の金属元素量は１～５００ｍｇ／ｍ２であることが好ましい。 In the hard particles with a surface-treated film according to the present invention, 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. At this time, the amount of metal element in the metal compound film is preferably 1 to 500 mg / m 2 .
　本発明に係る表面処理皮膜付き硬質粒子において、前記金属化合物膜の表面にリン化合物膜が形成されていることが好ましい。このとき、リン化合物膜中のリン化合物量が１～１００ｍｇ／ｍ２であることが好ましい。 In the hard particles with a surface treatment film according to the present invention, it is preferable that a phosphorus compound film is formed on the surface of the metal compound film. At this time, the amount of the phosphorus compound in the phosphorus compound film is preferably 1 to 100 mg / m 2 .
　（４）上記課題を解決するための本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンは、ヌープ硬度が１０００以上の硬質粒子の表面に、Ｚｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属の水和酸化物含有膜を有する表面処理皮膜付き硬質粒子と、該表面処理皮膜付き硬質粒子が懸濁されている水性溶媒とを有することを特徴とする。 (4) 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. And an aqueous solvent that is cloudy.
　この発明は、ヌープ硬度が１０００以上の硬質粒子の表面に各種金属の水和酸化物含有膜を有する表面処理皮膜付き硬質粒子を、水性溶媒に懸濁してなる水性ディスパージョンであるので、懸濁した硬質粒子の表面に設けられた水和物酸化物膜が水性溶媒に対して良好な相溶性と分散性及び分散安定性とを示す。その結果、この水性ディスパージョンは、水性溶媒中で良好な長期分散性を示すので、この水性ディスパージョンを分散原料として用いる場合に、凝集等の不具合がなく、金属中や樹脂中への分散原料として好ましく提供できる。 Since 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. As a result, 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.
　本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンにおいて、前記金属化合物膜が、前記金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種又は２種以上の金属化合物を含むことが好ましい。このとき、金属化合物膜中の金属元素量は１～２００ｍｇ／ｍ２であることが好ましい。 In the aqueous dispersion containing hard particles with a surface-treated film according to the present invention, 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 .
　本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンにおいて、前記金属化合物膜の表面にリン化合物吸着膜が形成されていることが好ましい。このとき、リン化合物吸着膜中のリン化合物量が１～５０ｍｇ／ｍ２であることが好ましい。 In the aqueous dispersion containing hard particles with a surface-treated film according to the present invention, it is preferable that a phosphorus compound adsorption film is formed on the surface of the metal compound film. At this time, the amount of the phosphorus compound in the phosphorus compound adsorption film is preferably 1 to 50 mg / m 2 .
　本発明に係る表面処理皮膜付き硬質粒子の製造方法によれば、高価な装置や複雑な成膜条件を必要とせずに、表面処理皮膜付き硬質粒子を製造でき、製造コストの低減を図ることができる。また、水和酸化物含有膜は硬質粒子の表面に均一に形成されており、水分散性も良好であり、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the method for producing hard particles with a surface treatment film according to the present invention, 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. In addition, 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.
　本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの製造方法によれば、高価な装置や複雑な成膜条件を必要とせずに、表面処理皮膜付き硬質粒子を製造でき、製造コストの低減を図ることができる。また、水和酸化物含有膜は硬質粒子の表面に均一に形成されており、水分散性も良好であり、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the method for producing an aqueous dispersion containing hard particles with a surface treatment film according to the present invention, 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. In addition, 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.
　本発明に係る表面処理皮膜付き硬質粒子によれば、上記金属化合物膜が硬質粒子の表面に設けられているので、水分散性が良好で、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the hard particles with a surface-treated film according to the present invention, since 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.
　本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンによれば、懸濁した硬質粒子の表面に設けられた水和物酸化物膜が水性溶媒に対して良好な相溶性と分散性及び分散安定性とを示すので、この水性ディスパージョンは、水性溶媒中で良好な長期分散性を示す。その結果、この水性ディスパージョンを分散原料として用いる場合に、凝集等の不具合がなく、金属中や樹脂中への分散原料として好ましく提供できる。 According to the aqueous dispersion containing hard particles with a surface-treated film according to the present invention, 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. As a result, when this aqueous dispersion is used as a dispersion raw material, there is no problem such as agglomeration, and it can be preferably provided as a dispersion raw material in a metal or resin.
本発明に係る表面処理皮膜付き硬質粒子の製造方法の一例を示す工程図である。It is process drawing which shows an example of the manufacturing method of the hard particle with a surface treatment film | membrane which concerns on this invention. 本発明に係る表面処理皮膜付き硬質粒子の製造方法の他の一例を示す工程図である。It is process drawing which shows another example of the manufacturing method of the hard particle with a surface treatment film concerning the present invention. 本発明に係る表面処理皮膜付き硬質粒子の製造方法のさらに他の一例を示す工程図である。It is process drawing which shows another example of the manufacturing method of the hard particle with a surface treatment film concerning the present invention. 本発明に係る表面処理皮膜付き硬質粒子の一例を示す模式的な断面図である。It is typical sectional drawing which shows an example of the hard particle with a surface treatment film | membrane which concerns on this invention. 本発明に係る表面処理皮膜付き硬質粒子の他の一例を示す模式的な断面図である。It is typical sectional drawing which shows another example of the hard particle with a surface treatment film | membrane which concerns on this invention. 本発明に係る表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの一例を示す説明図である。It is explanatory drawing which shows an example of the aqueous dispersion containing the hard particle with a surface treatment film | membrane which concerns on this invention.
　以下、本発明に係る表面処理皮膜付き硬質粒子及び水性ディスパージョン、並びにそれらの製造方法について詳細に説明する。 Hereinafter, the hard particles with a surface treatment film and the aqueous dispersion according to the present invention and the production methods thereof will be described in detail.
　［表面処理皮膜付き硬質粒子の製造方法］
　本発明に係る表面処理皮膜付き硬質粒子の製造方法は、図１の工程図に示すように、硬質粒子の準備工程、その硬質粒子を金属のフッ化物錯体を含む水溶液中に保持する工程（水和酸化物含有膜の形成工程）、洗浄工程、及び乾燥工程を順次経て、表面処理皮膜付き硬質粒子が製造される。また、図２の工程図に示すように、乾燥工程の後に熱処理工程を設けてもよい。また、図３の工程図に示すように、水和酸化物含有膜の形成工程と乾燥工程との間に、リン化合物を含有する水溶液への接触工程（リン化合物吸着膜形成工程）を設けてもよい。なお、図３の製造工程において、乾燥工程の後には図２と同様の熱処理工程を設けてもよい。また、図４及び図５には、製造された表面処理皮膜付き硬質粒子１の例を示す。 [Method for producing hard particles with surface treatment film]
As shown in the process diagram of FIG. 1, the method for producing hard particles with a surface-treated film according to the present invention 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. 3, 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. In the manufacturing process of FIG. 3, a heat treatment process similar to that of FIG. 2 may be provided after the drying process. Moreover, in FIG.4 and FIG.5, the example of the manufactured hard particle 1 with a surface treatment film is shown.
　以下、図１～図３に示す各工程について順に説明する。 Hereinafter, each process shown in FIGS. 1 to 3 will be described in order.
　（準備工程）
　準備される硬質粒子２は、ヌープ硬度が１０００以上である。こうした硬質粒子であれば特に限定されず、その構成材料の具体例としては、炭化ケイ素、炭化タングステン、炭化クロム、炭化ホウ素、ダイヤモンド、ＣＢＮ、及び酸化アルミニウム（アルミナ）等が挙げられる。硬質粒子のヌープ硬度は、ＪＩＳ－Ｚ２２５１に準拠してマイクロヌープ硬度計を用いて測定できる。一例としては、ダイヤモンドのヌープ硬さは約６０００であり、ＣＢＮのヌープ硬さは約４７００であり、アルミナのヌープ硬さは約２０００である。これらのうち、ヌープ硬さが４０００以上のダイヤモンドやＣＢＮを好ましく採用することができる。また、硬質粒子の粒径及び形状は特に限定されず、従来公知のものを適用できるが、より好ましい粒径としては、平均粒径で０．１～５０μｍの範囲である。硬質粒子の平均粒径は、ＪＩＳ－Ｒ６００２に記載の沈降試験方法によって測定して評価できる。 (Preparation process)
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 μm 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.
　なお、準備した硬質粒子２は、その後の水和酸化物含有膜形成工程の前に、必要に応じて、硫酸、王水、硝酸又は塩酸等の従来公知の酸処理を行ってもよい。また、水洗等の従来公知の前処理手段を施してもよい。 Note that 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.
　（水和酸化物含有膜の形成工程）
　水和酸化物含有膜３’の形成工程は、硬質粒子２を金属のフッ化物錯体を含む水溶液中に保持して、硬質粒子２の表面に水和酸化物含有膜３’を形成する工程である。この膜形成方法は、液相中で行われることから、液相析出法と呼ばれる。なお、液相析出法とは、一般的に、金属イオンにフッ化物イオンや硫酸イオン等のアニオンを配位させた錯体を含む水溶液中に基材を浸漬し、さらにアニオン捕捉剤を添加することで、アニオン捕捉剤が金属錯体からアニオンを引き抜くことにより金属イオンを不安定化させ、基材上に金属水和酸化物含有膜を析出させる手法である。こうした液相析出法は、上記した特許文献６～１１で提案されている。 (Formation process of hydrated oxide-containing film)
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. In addition, 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. In this method, 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. Such a liquid phase precipitation method is proposed in Patent Documents 6 to 11 described above.
　本発明に係る製造方法では、水溶液中には、金属はフッ化物錯体の状態で存在する。金属のフッ化物錯体を構成する金属としては、Ｚｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属を挙げることができる。こうした金属のフッ化物錯体は、フッ素含有化合物を水性溶媒中に添加して、水溶液化した金属フッ化物錯体を得ることができる。フッ素含有化合物としては、例えば、フッ化ジルコニウム、ジルコニウムフッ酸、ジルコニウムフッ化アンモニウム、ジルコンフッ化カリウム、ジルコンフッ化ナトリウム、フッ化チタン、チタンフッ酸、チタンフッ化アンモニウム、チタンフッ化カリウム、チタンフッ化ナトリウム、フッ化ケイ素、ケイフッ酸、ケイフッ化アンモニウム、ケイフッ化カリウム、ケイフッ化ナトリウム、フッ化クロム（III）、クロム（III）フッ酸、クロム（III）フッ化アンモニウム、クロム（III）フッ化カリウム、クロム（III）フッ化ナトリウム、フッ化タンタル、タンタルフッ酸、タンタルフッ化アンモニウム、タンタルフッ化カリウム、タンタルフッ化ナトリウム、フッ化ハフニウム、ハフニウムフッ酸、ハフニウムフッ化アンモニウム、ハフニウムフッ化カリウム、ハフニウムフッ化ナトリウム、フッ化錫、錫フッ酸、錫フッ化アンモニウム、錫フッ化カリウム、錫フッ化ナトリウム、モリブデンフッ酸、モリブデンフッ化アンモニウム、モリブデンフッ化カリウム、モリブデンフッ化ナトリウム、タングステンフッ酸、タングステンフッ化アンモニウム、タングステンフッ化カリウム、タングステンフッ化ナトリウム、フッ化亜鉛、亜鉛フッ酸、亜鉛フッ化アンモニウム、亜鉛フッ化カリウム、亜鉛フッ化ナトリウム、フッ化インジウム、インジウムフッ酸、インジウムフッ化アンモニウム、インジウムフッ化カリウム、インジウムフッ化ナトリウム、フッ化バナジウム、バナジウムフッ酸、バナジウムフッ化アンモニウム、バナジウムフッ化カリウム、及びバナジウムフッ化ナトリウムから選ばれる１種又は２種以上のフッ素化合物を挙げることができる。 In the production method according to the present invention, the metal exists in the form of a fluoride complex in the aqueous solution. Examples of 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. Examples of the fluorine-containing compound 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. Silicon, silicofluoric acid, ammonium silicofluoride, potassium silicofluoride, sodium silicofluoride, chromium (III) fluoride, chromium (III) hydrofluoric acid, chromium (III) ammonium fluoride, chromium (III) potassium fluoride, chromium (III ) Sodium fluoride, tantalum fluoride, tantalum hydrofluoric acid, tantalum ammonium fluoride, potassium tantalum fluoride, sodium tantalum fluoride, hafnium fluoride, hafnium hydrofluoric acid, hafnium ammonium fluoride, hafnium fu Potassium fluoride, hafnium sodium fluoride, tin fluoride, tin hydrofluoric acid, ammonium tin fluoride, potassium tin fluoride, sodium tin fluoride, molybdenum hydrofluoric acid, molybdenum ammonium fluoride, potassium molybdenum fluoride, sodium molybdenum fluoride, Tungsten hydrofluoric acid, tungsten ammonium fluoride, tungsten potassium fluoride, sodium tungsten fluoride, zinc fluoride, zinc hydrofluoric acid, zinc ammonium fluoride, potassium zinc fluoride, sodium zinc fluoride, indium fluoride, indium hydrofluoric acid, Indium ammonium fluoride, indium potassium fluoride, indium sodium fluoride, vanadium fluoride, vanadium hydrofluoric acid, vanadium ammonium fluoride, vanadium potassium fluoride, and sodium vanadium fluoride It can be exemplified al one or more fluorine compounds selected.
　水性溶媒としては、５０質量％以上１００質量％以下の水を含有する溶媒であればよく、必要に応じて有機溶媒が含まれていてもよい。また、界面活性剤等その他の添加剤が含まれていてもよい。 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.
　水性溶媒に含有可能な溶媒としては、例えば、エタノール、イソプロパノール等の低級アルコール；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン；酢酸エチル、酢酸ブチル、アセト酢酸エチル、２－エトキシエチルアセテート等のエステル；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル；エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフラン等のエーテル；エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテルのエステル；エチレンカーボネート、プロピレンカーボネート等のカーボネート；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ヘキサン、イソオクタン、デカン、ドデカン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、テルペン類等を挙げることができる。これらの溶媒は、単独で用いてもよいし、任意の２種以上の混合溶媒として配合して用いてもよい。 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. Esters: 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-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and terpenes. These solvents may be used alone or in combination as any two or more mixed solvents.
　金属のフッ化物錯体を構成する好ましい金属としては、Ｚｒ、Ｔｉ、Ｃｒ、Ｚｎ及びＩｎから選ばれる１種又は２種以上の金属を挙げることができ、好ましいフッ化物錯体としては、これら金属の上記フッ素化合物を水性溶媒中に添加して得ることができる。 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.
　金属のフッ化物錯体を含む水溶液は、水性溶媒中のフッ素含有化合物の濃度として、０．０００１～１ｍｏｌ/Ｌの範囲であることが好ましい。 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.
　金属のフッ化物錯体を得る他の方法としては、上記したフッ素含有化合物以外の化合物（例えば、水和酸化物；硝酸塩、硫酸塩、塩化物、リン酸塩等の無機酸塩；酢酸等の有機酸塩、等）から選ばれる１種又は２種以上の化合物と、フッ酸、フッ化アンモニウム、酸性フッ化アンモニウム、フッ化ナトリウム及び酸性フッ化ナトリウムから選ばれる１種又は２種以上のフッ素化合物とを、水性溶媒中に添加して水溶液化することによっても、金属のフッ化物錯体を得ることができる。 Other methods for obtaining 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.
　後述する熱処理を施す前における硬質粒子２への水和酸化物含有膜３’の付着量は、金属元素の付着量として１～２００ｍｇ／ｍ２の範囲であることが好ましい。金属元素の付着量として１ｍｇ／ｍ２未満では、表面処理皮膜付き硬質粒子２を金属や樹脂母相中に分散させる際、母相との密着性が低下することがある。一方、金属元素の付着量として２００ｍｇ／ｍ２を超えると、金属や樹脂母相中に分散させる際、母相との密着性が低下することがある。なお、水和酸化物含有膜３’を構成する金属元素の付着量の測定は、後述する実施例で説明するように、硬質粒子表面の水和酸化物含有膜３’を溶解し、その液をＩＣＰ分析して、水和酸化物含有膜３’を構成する金属元素成分の濃度を分析した。その結果から、水和酸化物含有膜３’を構成する金属元素の付着量を算出した。 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. 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 resin matrix, the adhesion with the 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 matrix may be lowered when dispersed in the metal or the resin matrix. In addition, 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. Was analyzed by ICP to analyze the concentration of the metal element component constituting the hydrated oxide-containing film 3 ′. From the result, the adhesion amount of the metal element constituting the hydrated oxide-containing film 3 ′ was calculated.
　金属のフッ化物錯体を含む水溶液に硬質粒子を接液させる手段としては、その水溶液中に硬質粒子２を攪拌状態下で投入して接触させる方法等を挙げることができる。このときの接触時間としては、水和酸化物含有膜を上記した所定量付着できるだけの時間であることが好ましく、通常、３０秒～７２時間程度である。 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.
　また、水和酸化物含有膜を形成する効果的な方法として、金属イオンにアニオンを配位させた錯体を含む水溶液中に前記した硬質粒子を浸漬し、攪拌条件下でアニオン捕捉剤を添加し、所定時間保持して水和酸化物含有膜を形成し、洗浄した後に熱処理する方法も挙げることができる。なお、予めアニオン補足剤を含有する水溶液に硬質粒子を加え、その後にフッ化物錯体を含む水溶液を配合させてもよい。ここで用いるアニオン捕捉剤としては、金属錯体が金属フッ化物錯体の場合は、ホウ酸、塩化第一鉄、塩化第二鉄、アルミニウム塩、マグネシウム塩、カルシウム塩、水酸化ナトリウム、アンモニア；アルミニウム、チタン、鉄、ニッケル、マグネシウム、銅、亜鉛、シリコン金属；二酸化ケイ素、酸化カルシウム、三酸化二ホウ素、酸化アルミニウム、酸化マグネシウム；等が例示される。中でも、ホウ酸は、析出皮膜中に不純物が析出することが無いことから好ましい。 In addition, as an effective method for forming a hydrated oxide-containing film, 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. Note that 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. As an anion scavenger used here, when 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.
　（乾燥工程）
　乾燥工程は、水和酸化物含有膜３’の形成工程後に通常適用される工程である。なお、水和酸化物含有膜３’を形成した後に、洗浄工程を経てそのまま水性溶媒中に入れて水性ディスパージョンとする場合には、この乾燥工程は不要である。 (Drying process)
A drying process is a process normally applied after the formation process of hydrated oxide containing film | membrane 3 '. In addition, after forming hydrated oxide containing film | membrane 3 ', when putting in an aqueous solvent as it is through an washing | cleaning process and making it an aqueous dispersion, this drying process is unnecessary.
　乾燥工程は、通常、１００℃で大気雰囲気中で行うが、それ以外の温度で乾燥させてもよいし、大気雰囲気以外の例えば窒素ガス雰囲気やアルゴンガス雰囲気等であってもよい。乾燥時間も特に限定されない。 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.
　（熱処理工程）
　熱処理工程は、図２に示すように必要に応じて設けられる工程であって、金属の水和酸化物含有膜３’が形成された硬質粒子２を熱処理する工程である。通常は、乾燥工程後に、大気雰囲気、非酸化雰囲気又は還元雰囲気の条件下で熱処理する。この熱処理工程により、熱処理前の金属の水和酸化物含有膜３’は、熱処理によって金属化合物膜３へと変化する。 (Heat treatment process)
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. Usually, after the drying step, heat treatment is performed under conditions of an air atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere. By this heat treatment step, the metal hydrated oxide-containing film 3 ′ before heat treatment is changed into the metal compound film 3 by the heat treatment.
　熱処理工程を、大気雰囲気、非酸化雰囲気又は還元雰囲気のいずれの条件下で行うかによって、金属の水和酸化物含有膜３’を、金属酸化物、金属窒化物、金属酸窒化物、及び金属炭化物等からから選ばれる１種又は２種以上を含む金属化合物膜３とすることができる。各雰囲気の圧力、雰囲気ガス含量、熱処理温度、及び熱処理時間等は、熱処理後に得ようとする金属化合物膜３に応じて任意に設定することができる。例えば雰囲気圧力の例としては、０．０１～７６０Ｔｏｒｒの範囲から任意に選択することができ、熱処理温度の例としては、１５０～１０００℃の範囲内とすることができる。 Depending on whether the heat treatment step is performed in an air atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere, 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 | membrane 3 containing 1 type, or 2 or more types chosen from carbide | carbonized_material etc. 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. For example, 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.
　この熱処理工程において、酸素分圧が５０Ｔｏｒｒ以下の非酸化雰囲気下又は還元雰囲気下で行えば、金属の水和酸化物含有膜３’の酸化を抑制し又は酸素を還元できるので、例えば金属窒化物や金属炭化物等からなる金属化合物膜３とすることができる。特に１０Ｔｏｒｒ以下の非酸化雰囲気下又は還元雰囲気下で行うことが好ましい。酸素分圧の下限は特に限定されないが、０．０１Ｔｏｒｒ程度とすることができる。非酸化雰囲気としては、前記圧力範囲の真空雰囲気、又は前記圧力範囲のアルゴン雰囲気や窒素ガス雰囲気等を挙げることができ、還元雰囲気としては、前記圧力範囲であって、還元元素（水素ガスやアンモニアガス等）を含有するアルゴン雰囲気や窒素ガス雰囲気等を挙げることができる。 In this heat treatment step, 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. Or 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. Examples of 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.
　雰囲気中のガス成分によって、水和酸化物含有膜３’をそのガス成分を含む金属化合物膜３とすることができる。例えば、窒素ガス雰囲気下で熱処理することにより、水和酸化物含有膜３’中の金属を窒化させて、金属窒化物を含む金属化合物膜３とすることができる。また、ダイヤモンドや炭化珪素等のように、硬質粒子２が炭素を含む場合には、真空雰囲気下又はアルゴン雰囲気下等の非酸化雰囲気下で熱処理することにより、水和酸化物含有膜３’中の金属を炭化させて、金属炭化物を含む金属化合物膜３とすることができる。 Depending on the gas component in the atmosphere, the hydrated oxide-containing film 3 ′ can be made into the metal compound film 3 containing the gas component. For example, by performing a heat treatment in a nitrogen gas atmosphere, the metal in the hydrated oxide-containing film 3 ′ can be nitrided to form the metal compound film 3 containing a metal nitride. Further, when the hard particles 2 contain carbon, such as diamond and silicon carbide, 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.
　熱処理温度としては、４００℃以上の温度が好ましく、５００℃以上の温度がより好ましい。また、熱処理温度の上限も特に限定されないが、１０００℃程度とすることができる。 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.
　熱処理時間は、前記した熱処理雰囲気や熱処理温度によって任意に設定されるが、水和酸化物含有膜３’が金属化合物膜３となるに足る時間であればよい。通常、１０分～２４時間程度である。 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.
　金属化合物膜３は、金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種又は２種以上の金属化合物を含む。これらの金属化合物の組成は、熱処理雰囲気によって任意に調整できる。例えば、大気雰囲気下で熱処理した場合は、酸化物や水酸化物等を含有する金属化合物膜３となり易い。一方、非酸化雰囲気下又は還元雰囲気下で熱処理した場合には、その熱処理雰囲気に基づいた化合物、例えば金属窒化物や金属炭化物等を主に含む金属化合物とすることができる。しかし、こうした雰囲気下で熱処理を行う場合であっても、還元により金属として含まれていたり、金属酸化物として残っていたり、金属水酸化物として残っていたりする場合も含む。また、非酸化や還元の程度が低い場合には、金属の酸化物や水酸化物を主に含む金属化合物とすることができる。 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. On the other hand, when heat treatment is performed in a non-oxidizing atmosphere or a reducing atmosphere, 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. However, even when the heat treatment is performed in such an atmosphere, the case where it is included as a metal by reduction, remains as a metal oxide, or remains as a metal hydroxide is included. Further, when the degree of non-oxidation or reduction is low, a metal compound mainly containing a metal oxide or hydroxide can be obtained.
　こうした熱処理工程により、硬質粒子２の表面に設けられた金属化合物膜３を形成させ、良好な水分散性と、金属中や樹脂中への良好な分散性と密着性を達成することができる。 By such a heat treatment step, 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.
　（リン化合物吸着膜の形成工程）
　リン化合物吸着膜４’の形成工程は、図３に示すように必要に応じて付加される工程であって、水和酸化物含有膜形成工程と乾燥工程との間で行われる。この工程では、水和酸化物含有膜３’を表面に形成した硬質粒子２をリン化合物を含有する水溶液に接触させることにより、リン化合物吸着膜４’を形成する。水和酸化物含有膜３’の表面にリン化合物を吸着させることにより、表面処理皮膜付き硬質粒子１の表面電荷が強まり、分散性を向上させることができる。「吸着膜」としたのは、水和酸化物含有膜３’上にリン化合物が吸着して膜（リン化合物吸着膜４’）となるからである。 (Formation process of phosphorus compound adsorption film)
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. In this step, 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. By adsorbing a phosphorus compound on the surface of the hydrated oxide-containing film 3 ′, 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 ′).
　具体的には、金属の水和酸化物含有膜３’の形成工程後に洗浄工程を経て、リン化合物を含有する水溶液と接液させる。リン化合物に接触させた後においては、水洗し、乾燥工程に送られる。 Specifically, after the formation process of the metal hydrated oxide-containing film 3 ′, 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.
　リン化合物としては、リン酸類、リン酸エステル、及び有機ホスホン酸等が挙げられる。リン酸類としては、リン酸（＝オルトリン酸）、メタリン酸及びポリリン酸を包含する縮合リン酸、及びその塩（アンモニウム塩、ナトリウム塩、カルシウム塩、及びマグネシウム塩等）を挙げることができ、より具体的には、メタリン酸はトリメタリン酸、テトラメタリン酸、及びヘキサメタリン酸等を包含し、ポリリン酸は鎖状のリン酸縮合物であって、ピロリン酸、トリポリリン酸、及びテトラポリリン酸等を包含する。特に、リン酸類を用いた場合は、分散性と分散安定性に優れているので好ましい。 Examples of phosphorus compounds include phosphoric acids, phosphate esters, and organic phosphonic acids. Examples of phosphoric acids include phosphoric acid (= orthophosphoric acid), condensed phosphoric acid including metaphosphoric acid and polyphosphoric acid, and salts thereof (such as ammonium salt, sodium salt, calcium salt, and magnesium salt). Specifically, metaphosphoric acid includes trimetaphosphoric acid, tetrametaphosphoric acid, and hexametaphosphoric acid, and polyphosphoric acid is a chain phosphoric acid condensate that includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and the like. To do. In particular, it is preferable to use phosphoric acids because they are excellent in dispersibility and dispersion stability.
　リン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェー２ト、モノメチルホスフェート、ジメチルホスフェート、エチルホスフェート、ジエチルホスフェート、モノブチルホスフェート、及びジブチルホスフェート等を挙げることができる。 Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate 2, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate, and dibutyl phosphate.
　有機ホスホン酸としては、１－ヒドロキシエチリデン－１，１－ジホスホン酸（ＨＥＤＰ）、２－ホスホノ－１，２，４－ブタントリカルボン酸（ＰＢＴＣ）、ニトリロトリス（メチレンホスホン酸）（ＮＴＭＰ）、ニトリロトリス（エチレンホスホン酸）、ニトリロトリス（プロピレンホスホン酸）、ニトリロビス（エチレンホスホン酸）モノ（メチレンホスホン酸）、ニトリロビス（メチレンホスホン酸）モノ（プロピレンホスホン酸）等のアルキレン基が同一又は異なる炭素数１～４のアルキレン基であるニトリロトリス（アルキレンホスホン酸）；エチレンジアミンテトラメチレンホスホン酸、エチレンジアミンテトラエチレンホスホン酸、エチレンジアミンテトラプロピレンホスホン酸等のアルキレン基が炭素数１～４のアルキレン基であるエチレンジアミンテトラアルキレンホスホン酸；ヘキサメチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸；ヒドロキシメタンジホスホン酸、エタン－１－ヒドロキシ－１、１－ジホスホン酸、プロパン－１－ヒドロキシ－１，１ジホスホン酸等の炭素数１～４のアルカン－１－ヒドロキシ－１、１－ジホスホン酸；等を挙げることができる。 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. 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;
　リン化合物を含有する水溶液は、水溶媒１００質量部に対するリン化合物の添加量として、０．０１～５０質量部の範囲であることが好ましい。 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.
　リン化合物吸着膜４’の付着量は、リン元素の付着量として１～５０ｍｇ／ｍ２の範囲が好ましい。リン元素の付着量として１ｍｇ／ｍ２未満では、表面電荷を高めるという効果を十分に得ることができず、表面処理皮膜付き硬質粒子１を金属及び樹脂母相中に分散させる際の分散性をより向上させることができない。一方、リン元素の付着量として５０ｍｇ／ｍ２を超えると、母相との密着性が低下することがある。なお、リン化合物吸着膜４’を構成するリン元素の付着量の測定は、後述する実施例で説明するように、吸着させたリン化合物吸着膜４’を溶解し、その液をＩＣＰ分析して、リン化合物吸着膜４’を構成するリン元素成分の濃度を分析した。その結果から、リン化合物吸着膜４’を構成するリン元素の付着量を算出した。 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. In addition, 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.
　リン化合物を含有する水溶液に、水和酸化物含有膜３’が設けられた硬質粒子２を接液させる手段としては、その水溶液中に硬質粒子２を攪拌状態下で投入して接触させる方法等を挙げることができる。このときの接触時間としては、リン化合物吸着膜４’を上記した所定量付着できるだけの時間であることが好ましく、通常、３０秒～２４時間程度である。 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.
　（洗浄工程）
　洗浄工程は、（ア）硬質粒子２の準備工程後で水和酸化物含有膜３’の形成工程前、（イ）水和酸化物含有膜３’の形成工程後で乾燥工程前、（ウ）必要に応じてリン化合物吸着膜４’の形成工程が付加された場合には、水和酸化物含有膜３’の形成工程後でリン化合物吸着膜４’の形成工程前、又は（エ）リン化合物吸着膜４’の形成工程後で乾燥工程前、の段階で、任意に挿入できる。 (Washing process)
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.
　洗浄方法としては、特に限定されないが、遠心分離、吸引濾過、又はデカンテーション等による濃縮後に再度イオン交換水を加えるといった工程を反復する手法が例示される。 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.
　以上説明したように、本発明に係る表面処理皮膜付き硬質粒子の製造方法によれば、硬質粒子２を金属のフッ化物錯体溶液を含む水溶液中に保持して該金属の水和酸化物含有膜３’を形成するので、高価な装置や複雑な成膜条件を必要とせずに、表面処理皮膜付き硬質粒子１を製造でき、製造コストの低減を図ることができる。また、水和酸化物含有膜３’は硬質粒子２の表面に均一に形成されており、水分散性も良好であり、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。また、リン化合物吸着膜４’を形成した後に乾燥又は熱処理してなるリン化合物膜４を表面に有する表面処理皮膜付き硬質粒子１は、分散性や密着性をより向上させることができる。 As described above, according to the method for producing a hard particle with a surface treatment film according to the present invention, 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.
　（表面処理皮膜付き硬質粒子）
　本発明に係る表面処理皮膜付き硬質粒子１は、上記した表面処理皮膜付き硬質粒子の製造方法で製造されたものであって、図４に示すように、ヌープ硬度が１０００以上の硬質粒子２と、その硬質粒子２の表面に設けられたＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属化合物膜３とを有する。また、図５に示すように、硬質粒子２と、その硬質粒子２の表面に設けられた上記した金属化合物膜３と、リン化合物膜４とを有する。 (Hard particles with surface treatment film)
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. Have. Further, as shown in FIG. 5, 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.
　この表面処理皮膜付き硬質粒子１を構成する金属化合物膜３は、金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種又は２種以上の金属化合物を含む。その金属化合物膜３の硬質粒子２の表面への付着量は、金属元素の付着量として１～２００ｍｇ／ｍ２の範囲であることが好ましい。金属元素の付着量として１ｍｇ／ｍ２未満では、表面処理皮膜付き硬質粒子２を金属中や樹脂母相中に分散させる際、母相との密着性が低下することがある。一方、金属元素の付着量として２００ｍｇ／ｍ２を超えると、金属中や樹脂母相中に分散させる際、逆に母相との密着性が低下することがある。なお、金属化合物膜３を構成する金属元素の付着量の測定は、後述する実施例で説明するように、硬質粒子表面の金属化合物膜３を溶解し、その液をＩＣＰ分析して、金属化合物膜３を構成する金属元素成分の濃度を分析した。その結果から、金属化合物膜３を構成する金属元素の付着量を算出した。 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. On the other hand, when 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. In addition, 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 | concentration of the metal element component which comprises the film | membrane 3 was analyzed. From the result, the adhesion amount of the metal element constituting the metal compound film 3 was calculated.
　この表面処理皮膜付き硬質粒子１を構成するリン化合物膜４は、リンを含有する化合物膜であり、そのリン化合物膜４の付着量は、リン元素の付着量として１～５０ｍｇ／ｍ２の範囲が好ましい。リン元素の付着量として１ｍｇ／ｍ２未満では、表面電荷を高めるという効果を十分に得ることができず、表面処理皮膜付き硬質粒子１を金属及び樹脂母相中に分散させる際の分散性をより向上させることができない。一方、リン元素の付着量として５０ｍｇ／ｍ２を超えると、母相との密着性が低下することがある。なお、リン化合物膜４を構成するリン元素の付着量の測定は、後述する実施例で説明するように、吸着させたリン化合物膜４を溶解し、その液をＩＣＰ分析して、リン化合物膜４を構成するリン元素成分の濃度を分析した。その結果から、リン化合物膜４を構成するリン元素の付着量を算出した。 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. In addition, the measurement of the adhesion amount of the phosphorus element which comprises the phosphorus compound film | membrane 4 melt | dissolves the adsorbed phosphorus compound film | membrane 4 and ICP analyzes the liquid so that it may demonstrate in the Example mentioned later, and a phosphorus compound film | membrane 4 was analyzed for the concentration of phosphorus element components. From the result, the adhesion amount of the phosphorus element constituting the phosphorus compound film 4 was calculated.
　本発明に係る表面処理皮膜付き硬質粒子１によれば、上記金属化合物膜３やリン化合物膜４が硬質粒子２の表面に設けられているので、水分散性が良好で、金属中や樹脂中に分散させても良好な分散性と密着性を示すことができる。 According to the hard particle 1 with a surface treatment film according to the present invention, since 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.
　［水性ディスパージョンの製造方法］
　本発明に係る水性ディスパージョンの製造方法は、表面処理皮膜付き硬質粒子１を含有し、懸濁状態とした水性ディスパージョン１１（図６を参照）を製造する方法である。具体的には、上記した本発明に係る表面処理皮膜付き硬質粒子１の製造方法において、水和酸化物含有膜３’の形成工程後に、乾燥も熱処理も行わずに、金属の水和酸化物含有膜３’が形成された硬質粒子２を水性溶媒に懸濁させる工程により製造する方法である。なお、水和酸化物含有膜３’の形成工程と、懸濁工程との間に、リン化合物を含有する水溶液への接触工程を設けてもよい。 [Method for producing aqueous dispersion]
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 | membrane, and was made into the suspended state. Specifically, in the method for producing the hard particle 1 with a surface treatment film according to the present invention described above, the metal hydrated oxide is not subjected to drying or heat treatment after the formation step of the hydrated oxide-containing film 3 ′. In this method, the hard particles 2 on which the containing film 3 ′ is formed are suspended in an aqueous solvent. In addition, you may provide the contact process to the aqueous solution containing a phosphorus compound between the formation process of hydrated oxide containing film | membrane 3 ', and a suspension process.
　なお、水性ディスパージョンの製造方法を構成する各工程、すなわち、硬質粒子の準備工程、金属の水和酸化物含有膜３’の形成工程、リン化合物吸着膜４’の形成工程、乾燥工程、熱処理工程、及び洗浄工程等は、上記した表面処理皮膜付き硬質粒子の製造方法を構成する各工程と同じである。そのため、ここではその説明を省略する。 In addition, each process which comprises the manufacturing method of aqueous dispersion, ie, the preparation process of a hard particle, the formation process of metal hydrated oxide containing film | 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.
　（懸濁工程）
　懸濁工程は、金属の水和酸化物含有膜３’が形成された硬質粒子２を水性溶媒１２に懸濁させる工程である。ここで用いる水性溶媒１２は、５０質量％以上１００質量％以下の水を含有する溶媒のことであり、必要に応じて有機溶媒が含まれていてもよい。また、その他の添加剤が含まれていてもよい。 (Suspension process)
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.
　水性溶媒に配合可能な溶媒としては、例えば、エタノール、イソプロパノール等の低級アルコール；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン；酢酸エチル、酢酸ブチル、アセト酢酸エチル、２－エトキシエチルアセテート等のエステル；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル；エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフラン等のエーテル；エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエーテルのエステル；エチレンカーボネート、プロピレンカーボネート等のカーボネート；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ヘキサン、イソオクタン、デカン、ドデカン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、テルペン類等を挙げることができる。これらの溶媒は、単独で用いてもよいし、任意の２種以上の混合溶剤を配合して用いてもよい。 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. Esters; 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-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and terpenes. These solvents may be used alone or in combination with any two or more kinds of mixed solvents.
　その他の添加剤としては、界面活性剤等を挙げることができる。なお、こうした添加剤は、その趣旨に反しない範囲で、水性溶媒中に０．０１～１０質量％含有させることができる。 Other 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.
　水性溶媒１２中への表面処理皮膜付き硬質粒子１の懸濁濃度は、０．５～９０質量％であることが好ましく、１～５０質量％であることがより好ましい。懸濁濃度が０．５質量％未満では、濃度が低すぎて母相中に硬質粒子を含有させられず、硬度向上等、硬質粒子を分散させることによる効果が得られなくなることがある。一方、懸濁濃度が９０質量％を超えると、ディスパージョンの粘度が高くなりすぎて扱いずらくなることがある。 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.
　こうした水性ディスパージョン１１の製造方法によれば、水和酸化物含有膜３’を形成した硬質粒子２をリン化合物含有水溶液に接触させるので、水和酸化物含有膜上にリン化合物が吸着してリン化合物吸着膜となる。その後に水性溶媒中に懸濁することにより、リン化合物吸着膜４’が設けられた水和酸化物含有膜３’は、水性溶媒に対してより良好な相溶性と分散性及び分散安定性とを示す。 According to such a method for producing the aqueous dispersion 11, 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.
　以上、本発明に係る表面処理皮膜付き硬質粒子１を含有する水性ディスパージョン１１の製造方法によれば、硬質粒子２の表面に設けられた水和物酸化物膜３’が水性溶媒１２に対して良好な相溶性と分散性及び分散安定性とを示すので、得られた表面処理皮膜付き硬質粒子１は、水性溶媒１２中で良好な分散性及び分散安定性とを示す。その結果、この表面処理皮膜付き硬質粒子１を分散原料として用いる場合に、凝集等の不具合がなく、金属中や樹脂中への分散原料として好ましく提供できる。また、リン化合物膜４をさらに形成した表面処理皮膜付き硬質粒子１を、熱処理工程を実施せずに水性溶媒１２中に懸濁させることにより、表面処理皮膜付き硬質粒子１の分散性及び分散安定性をさらに向上させることができる。 As mentioned above, according to the manufacturing method of the aqueous dispersion 11 containing the hard particle 1 with the surface treatment film | membrane which concerns on this invention, the hydrate oxide film | 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. As a result, when 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. Moreover, 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.
　（水性ディスパージョン）
　本発明に係る水性ディスパージョン１１は、上記した水性ディスパージョンの製造方法で製造されたものであって、図６に示すように、ヌープ硬度が１０００以上の硬質粒子２と、その硬質粒子２の表面に設けられたＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属化合物膜３と、必要に応じて設けられたリン化合物吸着膜４’とを有する表面処理皮膜付き硬質粒子１を、乾燥も熱処理もせずに、水性溶媒中に懸濁してなるものである。 (Aqueous dispersion)
The aqueous dispersion 11 according to the present invention is manufactured by the above-described aqueous dispersion manufacturing method. As shown in FIG. 6, 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.
　この表面処理皮膜付き硬質粒子１を構成する金属の水和酸化物含有膜３’は、上記した金属の中から選ばれるいずれか１又は２以上金属の水酸化物で主に構成されている。その水和酸化物含有膜３’の硬質粒子２の表面への付着量は、金属元素の付着量として１～２００ｍｇ／ｍ２の範囲であることが好ましい。 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.
　金属元素の付着量として１ｍｇ／ｍ２未満では、表面処理皮膜付き硬質粒子１を水性溶媒１２中に分散させた後に、表面処理皮膜付き硬質粒子が凝集することがある。また、水性ディスパージョン１１が含む表面処理皮膜付き硬質粒子１を、金属や樹脂に含有させる粒子として用いる場合に、金属や樹脂母相への分散性や密着性が低下することがある。一方、金属元素の付着量として２００ｍｇ／ｍ２を超えると、金属や樹脂母相との密着性が低下することがある。 When 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.
　水性ディスパージョン１１を構成するリン化合物吸着膜４’は、リンを含有する化合物の吸着膜であり、そのリン化合物吸着膜４’の付着量は、リン元素の付着量として１～５０ｍｇ／ｍ２の範囲が好ましい。リン元素の付着量として１ｍｇ／ｍ２未満では、表面電荷を高めるという効果を十分に得ることができず、表面処理皮膜付き硬質粒子１を水性溶媒１２中に分散させても、表面処理皮膜付き硬質粒子１の分散性や分散安定性をさほど高めることはできない。一方、リン元素の付着量として５０ｍｇ／ｍ２を超えると、金属や樹脂母相との密着性が低下することがある。 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.
　以上、本発明に係る水性ディスパージョン１１の製造方法によれば、硬質粒子２を金属のフッ化物錯体溶液を含む水溶液中に保持して該金属の水和酸化物含有膜３’を形成し、その後に水性溶媒に懸濁することにより、硬質粒子２の表面に設けられた水和物酸化物膜３’が水性溶媒に対して良好な相溶性と分散性及び分散安定性とを示す。その結果、水性ディスパージョン１１中で懸濁する表面処理皮膜付き硬質粒子１は、水性溶媒１２中で良好な分散性及び分散安定性を示すので、この表面処理皮膜付き硬質粒子１を分散原料として用いる場合に、凝集等の不具合がなく、金属中や樹脂中への分散原料として好ましく提供できる。 As described above, according to the method for producing the aqueous dispersion 11 according to the present invention, 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. As a result, 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. When used, there is no problem such as agglomeration, and it can be preferably provided as a raw material dispersed in a metal or resin.
　以下、実施例により本発明を具体的に説明する。ただし、本発明は下記の実施例に限られるものではない。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.
　［実施例１］
　４０℃に加温し、アンモニア水によってｐＨを６．４に調整した０．０６ｍｏｌ／Ｌフッ化亜鉛水溶液（フッ化物水溶液）５０ｍＬに、攪拌条件下でダイヤモンド粒子（硬質粒子、トーメイダイヤ株式会社製、平均粒径：１６．０μｍ）を１ｇ添加した。さらにその水溶液に、アンモニア水によってｐＨを６．４に調整した０．６ｍｏｌ／Ｌホウ酸水溶液（アニオン補足剤）を４０℃に加温して５０ｍＬ添加した。引き続き、液温を４０℃に保持しながら５時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、１００℃で大気雰囲気中で乾燥するまで加熱し、その後さらに３００℃で大気雰囲気中で１時間加熱した。こうして、実施例１に係る表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ａを作製した。 [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 μm) 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. 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, 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.
　［実施例２］
　４０℃に加温した０．４１ｍｏｌ／Ｌホウ酸水溶液（アニオン補足剤）４８ｍＬ中に、攪拌条件下で炭化ケイ素粒子（硬質粒子、信濃電気精錬株式会社製、平均粒径：２０μｍ）を１ｇ添加した。さらにその水溶液に、４０℃に加温した０．１９ｍｏｌ／Ｌフッ化クロム（III）水溶液（フッ化物水溶液）５２ｍＬを添加した。引き続き、液温を４０℃に保持しながら３時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例２に係る表面処理皮膜付き硬質粒子（炭化ケイ素粒子）Ｂを作製した。 [Example 2]
1 g of silicon carbide particles (hard particles, manufactured by Shinano Denki Co., Ltd., average particle size: 20 μm) 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.
　［実施例３］
　４０℃に加温し、アンモニア水によってｐＨを２．０に調整した０．０６ｍｏｌ／Ｌジルコンフッ酸水溶液（フッ化物水溶液）１００ｍＬに、攪拌条件下で炭化ホウ素粒子（硬質粒子、株式会社ニューメタルスエンドケミカルス製、平均粒径：１５～１６μｍ）を２ｇ添加した。さらにその水溶液に、アルミニウム板（Ａ１０５０Ｐ）をアニオン補足剤として投入し、液温を４０℃に保持しながら４時間攪拌した。その後、アルミニウム板を取り出し、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例３に係る表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｃを作製した。 [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 μm) 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.
　［実施例４］
　４０℃に加温し、アンモニア水によってｐＨを６．５に調整した０．０４ｍｏｌ／Ｌ硝酸インジウムと０．１２ｍｏｌ／Ｌフッ化水素酸との混合水溶液（フッ化物水溶液）７０ｍＬに、攪拌条件下で炭化ホウ素粒子（硬質粒子、株式会社ニューメタルスエンドケミカルス製、平均粒径：１５～１６μｍ）２ｇ添加した。さらにその水溶液に、アンモニア水でｐＨを６．４に調整した０．４ｍｏｌ／Ｌホウ酸水溶液（アニオン補足剤）を４０℃に加温して３０ｍＬ添加した。引き続き、液温を４０℃に保持しながら３５時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例４に係る表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｄを作製した。 [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 μm) 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. Then, it stirred for 35 hours, hold | maintaining liquid temperature at 40 degreeC. 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 (boron carbide particles) D with a surface treatment film according to Example 4 were produced.
　［実施例５］
　４０℃に加温し、０．２５ｍｏｌ／Ｌホウ酸水溶液（アニオン補足剤）８０ｍＬ中に、攪拌条件下でダイヤモンド粒子（硬質粒子、トーメイダイヤ株式会社製、平均粒径：１６．０μｍ）を３ｇ添加した。さらにその水溶液に、４０℃に加温した０．５５ｍｏｌ／Ｌチタンフッ化アンモニウム水溶液（フッ化物水溶液）２０ｍＬを添加した。引き続き、液温を４０℃に保持しながら３時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例５に係る表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｅを作製した。 [Example 5]
3 g of diamond particles (hard particles, manufactured by Tomei Dia Co., Ltd., average particle size: 16.0 μm) 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.
　［実施例６］
　実施例３で作製した表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｃを、酸素分圧５Ｔｏｒｒの真空下で７００℃で２時間加熱した。こうして、実施例６に係る表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｆを作製した。 [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.
　［実施例７］
　実施例５で作製した表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｅを、酸素分圧１Ｔｏｒｒの窒素雰囲気下で５００℃で３時間加熱した。こうして、実施例７に係る表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｇを作製した。 [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.
　［実施例８］
　実施例３で作製した表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｃを、１．０質量％トリポリリン酸水溶液（２５℃）に添加した後、１時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。その後、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例１０に係る表面処理皮膜付き硬質粒子（炭化ホウ素粒子）Ｈを作製した。 [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 | atmosphere atmosphere at 100 degreeC. In this way, hard particles (boron carbide particles) H with a surface treatment film according to Example 10 were produced.
　［実施例９］
　実施例２で作製した表面処理皮膜付き硬質粒子（炭化ケイ素粒子）Ａを、０．１質量％トリポリリン酸水溶液（２５℃）に添加した後、１０分間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。その後、１００℃で大気雰囲気中で乾燥するまで加熱した。こうして、実施例９に係る表面処理皮膜付き硬質粒子（炭化ケイ素粒子）Ｉを作製した。 [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 | atmosphere atmosphere at 100 degreeC. In this way, hard particles (silicon carbide particles) I with a surface treatment film according to Example 9 were produced.
　［実施例１０］
　４０℃に加温し、アンモニア水によってｐＨを２．０に調整した０．０６ｍｏｌ／Ｌジルコンフッ酸水溶液（フッ化物水溶液）１００ｍＬに、攪拌条件下でＣＢＮ粒子（硬質粒子、株式会社ニューメタルスエンドケミカルス製、平均粒径：１５～１６μｍ）を２ｇ添加した。さらにその水溶液に、アルミニウム板（Ａ１０５０Ｐ）をアニオン補足剤として投入し、液温を４０℃に保持しながら４時間攪拌した。その後、アルミニウム板を取り出し、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。洗浄後の粒子を、再度デカンテーションにより濃縮した後、イオン交換水を添加して、固形分濃度５０．０質量％の実施例１０に係る表面処理皮膜付き硬質粒子（ＣＢＮ粒子）を含む水性ディスパージョンＪを作製した。 [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 μm) 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 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.
　［実施例１１］
　実施例２で作製した表面処理皮膜付き硬質粒子（炭化ケイ素粒子）Ａを、１．０質量％トリポリリン酸水溶液（２５℃）中に添加した後、１時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。その後、再度デカンテーションにより濃縮した後、イオン交換水を添加して、固形分濃度２０．０質量％の実施例１１に係る表面処理皮膜付き硬質粒子（炭化ケイ素粒子）を含む水性ディスパージョンＫを作製した。 [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.
　［比較例１］
　０．２ｍｏｌ／Ｌ炭酸水素ナトリウム水溶液２０ｍＬ中に、攪拌条件下で炭化ケイ素粒子（硬質粒子、信濃電気精錬株式会社製、平均粒径：２０μｍ）を１ｇ添加した。さらにその水溶液に、３０℃に加温した０．２ｍｏｌ／Ｌ水酸化カルシウム水溶液２０ｍＬを添加した。引き続き、液温を４０℃に保持しながら２４時間攪拌した。その後、デカンテーションにより濃縮した後、再度イオン交換水を加える作業を１０回繰り返して洗浄した。こうして、比較例１に係る表面処理皮膜付き硬質粒子（炭化ケイ素粒子）Ｌを作製した。 [Comparative Example 1]
1 g of silicon carbide particles (hard particles, manufactured by Shinano Denki Co., Ltd., average particle size: 20 μm) were added to 20 mL of a 0.2 mol / L sodium hydrogen carbonate aqueous solution under stirring conditions. Furthermore, 20 mL of 0.2 mol / L calcium hydroxide aqueous solution heated to 30 ° C. was added to the aqueous solution. Subsequently, the mixture was stirred for 24 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. Thus, hard particles (silicon carbide particles) L with a surface treatment film according to Comparative Example 1 were produced.
　［比較例２］
　ダイヤモンド粒子（硬質粒子、トーメイダイヤ株式会社製、平均粒径：１６．０μｍ）に金属ニッケルを真空蒸着して、比較例２に係る表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｍを作製した。 [Comparative Example 2]
Metal nickel was vacuum-deposited on diamond particles (hard particles, manufactured by Tomei Diamond Co., Ltd., average particle size: 16.0 μm) to prepare hard particles (diamond particles) M with a surface treatment film according to Comparative Example 2.
　［比較例３］
　ＣＢＮ粒子（硬質粒子、株式会社ニューメタルスエンドケミカルス製、平均粒径：１５～１６μｍ）に金属チタンをスパッタリングして、比較例３に係る表面処理皮膜付き硬質粒子（ＣＢＮ粒子）Ｎを作製した。 [Comparative Example 3]
Metal titanium was sputtered onto CBN particles (hard particles, manufactured by New Metals End Chemicals Co., Ltd., average particle size: 15 to 16 μm) to produce hard particles (CBN particles) N with a surface treatment film according to Comparative Example 3.
　［比較例４］
　ダイヤモンド粒子（硬質粒子、トーメイダイヤ株式会社製、平均粒径：１６．０μｍ）にＳｉＯ２を高周波励起イオンプレーティングして、比較例３に係る表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｏを作製した。 [Comparative Example 4]
High-frequency excitation ion plating of SiO 2 is applied to diamond particles (hard particles, manufactured by Tomei Dia Co., Ltd., average particle size: 16.0 μm) to produce hard particles (diamond particles) O with a surface treatment film according to Comparative Example 3. did.
　［比較例５］
　ダイヤモンド粒子（硬質粒子、株式会社ニューメタルスエンドケミカルス製、平均粒径：３０μｍ）に表面処理皮膜を形成しないで、比較例５に係る硬質粒子とした。 [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 μm).
　［表面処理皮膜付き硬質粒子の評価］
　実施例１～１１及び比較例１～５で得られた表面処理皮膜付き硬質粒子について、以下のようにして各種の評価を行った。 [Evaluation of hard particles with surface treatment film]
Various evaluations were performed on the hard particles with a surface-treated film obtained in Examples 1 to 11 and Comparative Examples 1 to 5 as follows.
　（表面処理皮膜の組成分析）
　実施例１～１１及び比較例１～４で得られた表面処理皮膜付き硬質粒子をカーボンテープに貼り付け、それをサンプルホルダに取り付けて測定試料とした。以下に示す条件でＸＰＳ分析を行い、表面処理皮膜の構成元素の定性分析を行った。その結果を表１に示す。 (Surface treatment film composition analysis)
The hard particles with a surface-treated film obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were attached to a carbon tape and attached to a sample holder to obtain a measurement sample. XPS analysis was performed under the following conditions, and qualitative analysis of the constituent elements of the surface treatment film was performed. The results are shown in Table 1.
　ＸＰＳ分析条件；
　・使用装置：島津製作所株式会社製、ＥＳＣＡ８５０
　・励起Ｘ線：Ｍｇ－Ｋα
　・測定面積：約５０ｍｍ２
　・測定領域：０～１１００ｅＶ
　・１ｓｅｃスパッタリングした後に分析（ＳｉＯ２換算でのスパッタリング速度：８０ｎｍ／ｍｉｎ） XPS analysis conditions;
-Equipment used: ESCA850, manufactured by Shimadzu Corporation
Excitation X-ray: Mg-Kα
・ Measurement area: Approximately 50mm 2
・ Measurement area: 0 to 1100eV
・ Analysis after sputtering for 1 sec (Sputtering rate in terms of SiO 2 : 80 nm / min)
　（表面処理皮膜の付着量の分析）
　実施例１～１１及び比較例１～４で得られた表面処理皮膜付き硬質粒子１ｇを、５質量％フッ化水素酸水溶液１００ｍＬ（２５℃）に添加し、１時間攪拌した。その後、遠心分離により表面処理皮膜を除去し、硬質粒子を沈降させた。ろ液をＩＣＰ分析して、表面処理皮膜を構成する金属元素成分の濃度分析と吸着リン化合物由来のＰの濃度分析とを行った。その分析結果を換算して、表面処理皮膜を構成する金属元素としての付着量と吸着リン化合物を構成するリン元素としての付着量を算出した。その結果を表１に示す。なお、表１には示さないが、水和酸化物含有膜中には水和物を構成する水素原子も含まれる。 (Analysis of amount of surface treatment film)
1 g of hard particles with a surface-treated film obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were added to 100 mL (25 ° C.) of 5 mass% hydrofluoric acid aqueous solution and stirred for 1 hour. Thereafter, the surface treatment film was removed by centrifugation, and the hard particles were allowed to settle. The filtrate was subjected to ICP analysis, and concentration analysis of metal element components constituting the surface treatment film and concentration analysis of P derived from the adsorbed phosphorus compound were performed. The analysis result was converted to calculate the adhesion amount as a metal element constituting the surface treatment film and the adhesion amount as a phosphorus element constituting the adsorbed phosphorus compound. The results are shown in Table 1. Although not shown in Table 1, the hydrated oxide-containing film also contains hydrogen atoms constituting the hydrate.
　（密着性評価）
　実施例１～１１及び比較例１～５で得られた表面処理皮膜付き硬質粒子７０質量％と、フェノール樹脂塗料（昭和高分子株式会社製、ＢＲＰ－５４１７）３０質量％とを均一に混合した。そこにクレゾールを加えて、硬質粒子の分散溶液中の溶剤量を５０質量％とした。次に、この分散溶解液を１０×５０ｍｍの黄銅板に塗布した後、その塗布膜を炉内温度３００℃の焼成炉で熱硬化させた。次いで、室温まで放冷したのち、セロハン粘着テープを貼り付けて垂直に引き剥がし、硬質粒子の脱落の有無を実体顕微鏡（１０００倍）で表面観察した。密着性の評価は、硬質粒子の脱落が認められるものを１点、脱落が認められないものを２点とした。その結果を表１に示す。 (Adhesion evaluation)
70% by mass of the hard particles with a surface treatment film obtained in Examples 1 to 11 and Comparative Examples 1 to 5 and 30% by mass of phenol resin paint (BRP-5417, manufactured by Showa Polymer Co., Ltd.) were uniformly mixed. . Cresol was added thereto to adjust the amount of solvent in the hard particle dispersion to 50% by mass. Next, this dispersion solution was applied to a 10 × 50 mm brass plate, and then the coating film was thermally cured in a baking furnace having a furnace temperature of 300 ° C. Next, after allowing to cool to room temperature, a cellophane adhesive tape was applied and peeled off vertically, and the presence or absence of the hard particles was observed with a stereomicroscope (1000 times). For the evaluation of adhesion, one point was obtained when hard particles were removed, and two points were obtained when no removal was observed. The results are shown in Table 1.
　（分散性評価）
　硫酸ニッケル０．５３Ｍ、塩化ニッケル０．０９Ｍ、及びクエン酸ナトリウム１．２４Ｍを含有し、水酸化ナトリウムでｐＨを８に調整したニッケルめっき浴中に、実施例１～１１及び比較例１～５で得られた表面処理皮膜付き硬質粒子を５ｇ／Ｌ添加した。１０分間スターラー攪拌した後、攪拌を止め、１分静置した後に、基材としての純銅板（Ｃ１０２０Ｐ、厚さ０．１ｍｍ、縦４０ｍｍ、横３０ｍｍ）とニッケル陽極とを、極間距離５０ｍｍとして対向させて設置した。その後、液温５０℃、電流密度２０Ａ／ｄｍ２で電解を行い、めっき膜厚約１０μｍのニッケルめっき銅板を得た。その後、得られたニッケルめっき銅板を実体顕微鏡（１０００倍）で表面観察した。硬質粒子が僅かしか析出していないものを１点、硬質粒子が析出するが不均一なものを２点、硬質粒子が均一に析出しているものを３点とした。その結果を表１に示す。 (Dispersibility evaluation)
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. and a current density of 20 A / dm 2 to obtain a nickel-plated copper plate having a plating film thickness of about 10 μm. Thereafter, the surface of the obtained nickel-plated copper plate was observed with a stereomicroscope (1000 times). A point where only a few hard particles were deposited was assigned 1 point, a hard particle was precipitated but 2 points were non-uniform, and a case where hard particles were deposited uniformly was assigned 3 points. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果から明らかなように、実施例１～５の表面処理皮膜付き硬質粒子の表面処理皮膜からは、それぞれの金属元素と酸素が検出されたことから、その表面処理皮膜は各金属の水和酸化物含有膜であることが推定された。なお、実施例６では、ジルコニウムの水和酸化物に加え、ジルコニウム炭化物が形成していることが推定された。また、実施例７では、チタンの水和酸化物に加え、チタン窒化物が形成していることが推定された。また、実施例８では、表面処理皮膜がジルコニウムの水和酸化物からなり、その表面にリン化合物が吸着していることが推定された。また、実施例９では、表面処理皮膜がクロムの水和酸化物からなり、その表面にリン化合物が吸着していることが推定された。一方、比較例１では、表面処理皮膜がカルシウムの炭酸塩で形成されていることが推定された。また、比較例２では金属Ｎｉが検出され、比較例３では金属Ｔｉが検出され、比較例４では、表面処理皮膜がケイ素の水和酸化物からなることが推定された。 As is apparent from the results in Table 1, since the respective metal elements and oxygen were detected from the surface treatment film of the hard particles with the surface treatment film of Examples 1 to 5, the surface treatment film 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. On the other hand, in Comparative Example 1, it was estimated that the surface treatment film was formed of calcium carbonate. In 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.
　密着性と分散性に関しては、実施例１～７では密着性及び分散性とも２点であった。また、実施例８，９では、密着性が２点で分散性は３点であり、分散性がさらに優れる結果となった。また、実施例１０，１１の水性ディスパージョンでは、分散性がいずれも３点であり、分散性に優れる結果になった。一方、比較例１～３，５では、いずれも密着性が１点で分散性も１点であり、密着性と分散性のいずれも劣る結果となった。また、比較例４では、密着性は２点であったが分散性は１点であり、分散性に劣る結果となった。 Regarding adhesion and dispersibility, Examples 1 to 7 had two points for both adhesion and dispersibility. In Examples 8 and 9, the adhesion was 2 points and the dispersibility was 3 points, which resulted in further excellent dispersibility. Moreover, in the aqueous dispersions of Examples 10 and 11, the dispersibility was 3 points, and the dispersibility was excellent. On the other hand, 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.
　（表面処理皮膜の均一成膜性評価）
　実施例５で得られた表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｅ及び比較例５の表面処理被膜を形成していない硬質粒子（ダイヤモンド粒子）について、以下の条件でＥＰＭＡ分析を実施した。 (Evaluation of uniform film formability of surface treatment film)
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.
　ＥＰＭＡ分析条件；
　・使用装置：日本電子株式会社製、ＪＸＡ－８２３０
　・加速電圧：１５．０ｋＶ
　・照射電流：５×１０－８Ａ
　・測定元素：Ｔｉ，Ｏ，Ｃ
　・測定倍率：３０００倍 EPMA analysis conditions;
-Device used: JXA-8230, manufactured by JEOL Ltd.
・ Acceleration voltage: 15.0kV
・ Irradiation current: 5 × 10 −8 A
・ Measurement elements: Ti, O, C
・ Measurement magnification: 3000 times
　その結果、表面処理被膜を形成していないダイヤモンド粒子の表面からは、Ｔｉが検出されず、ＣとＯのみが検出された。しかし、表面処理皮膜付き硬質粒子（ダイヤモンド粒子）Ｃの表面にはＴｉが検出され、且つＯの検出強度が高くなっていた。その結果、ＴｉとＯが、ダイヤモンド粒子表面の全面で、ほぼ同強度で検出されており、表面処理皮膜が均一に形成されていることが確認できた。 As a result, Ti was not detected and only C and O were detected from the surface of the diamond particles on which the surface treatment film was not formed. However, Ti was detected on the surface of the hard particles (diamond particles) C with a surface treatment film, and the detection intensity of O was high. As a result, Ti and O were detected with almost the same intensity on the entire surface of the diamond particle, and it was confirmed that the surface treatment film was uniformly formed.
　用途は特に限定されないが、本発明に係る表面処理皮膜付き硬質粒子の製造方法及び得られた表面処理皮膜付き硬質粒子は、アルミニウム等の金属の分散めっきに使用される表面硬化用硬質粒子としての用途に利用できる。また、切削ホイール、ワイヤーソー等の切削用砥粒等にも好適に利用できる。 Although the use is not particularly limited, 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.
　１　表面処理皮膜付き硬質粒子
　２　硬質粒子
　３　金属化合物膜
　３’　金属水和酸化物含有膜
　４　リン化合物膜
　４’　リン化合物吸着膜
　１１　水性ディスパージョン
　１２　水性溶媒 DESCRIPTION OF SYMBOLS 1 Hard particle with surface treatment film 2 Hard particle 3 Metal compound film 3 'Metal hydrated oxide containing film 4 Phosphorus compound film 4' Phosphorus compound adsorption film 11 Aqueous dispersion 12 Aqueous solvent

Claims (12)

  1. 　ヌープ硬度が１０００以上の硬質粒子を準備する工程と、
    　前記硬質粒子をＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属のフッ化物錯体を含む水溶液中に保持して、前記硬質粒子の表面に前記金属の水和酸化物含有膜を形成する工程と、
    　前記金属の水和酸化物含有膜が形成された硬質粒子を乾燥させる工程と、を有することを特徴とする表面処理皮膜付き硬質粒子の製造方法。     Preparing hard particles having Knoop hardness of 1000 or more;
    The hard particles are held in an aqueous solution containing one or more metal fluoride complexes selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V. Forming a hydrated oxide-containing film of the metal on the surface of the hard particles;
    And a step of drying the hard particles on which the metal hydrated oxide-containing film is formed.
  2. 　前記水和酸化物含有膜形成工程と前記乾燥工程との間に、リン化合物を含有する水溶液への接触工程を設ける、請求項１に記載の表面処理皮膜付き硬質粒子の製造方法。 The method for producing hard particles with a surface-treated film according to claim 1, wherein 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.
  3. 　前記乾燥工程後に、大気雰囲気、非酸化雰囲気又は還元雰囲気の条件下で熱処理する工程を設ける、請求項１又は２に記載の表面処理皮膜付き硬質粒子。 The hard particle with a surface-treated film according to claim 1 or 2, wherein a heat treatment step is performed after the drying step under conditions of an air atmosphere, a non-oxidizing atmosphere or a reducing atmosphere.
  4. 　前記熱処理工程が、酸素分圧５０Ｔｏｒｒ以下の非酸化雰囲気下又は還元雰囲気下で、４００℃以上の温度で熱処理する工程である、請求項３に記載の表面処理皮膜付き硬質粒子の製造方法。 The method for producing hard particles with a surface-treated film according to claim 3, wherein the heat treatment step is a step of heat treatment 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.
  5. 　ヌープ硬度が１０００以上の硬質粒子を準備する工程と、
    　前記硬質粒子をＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属のフッ化物錯体を含む水溶液中に保持して、前記硬質粒子の表面に前記金属の水和酸化物含有膜を形成する工程と、
    　前記金属の水和酸化物含有膜が形成された硬質粒子を水性溶媒に懸濁する工程と、を有することを特徴とする表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの製造方法。     Preparing hard particles having Knoop hardness of 1000 or more;
    The hard particles are held in an aqueous solution containing one or more metal fluoride complexes selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V. Forming a hydrated oxide-containing film of the metal on the surface of the hard particles;
    Suspending the hard particles on which the metal hydrated oxide-containing film is formed in an aqueous solvent, and a method for producing an aqueous dispersion containing hard particles with a surface-treated film.
  6. 　前記水和酸化物含有膜形成工程と前記懸濁工程との間に、リン化合物を含有する水溶液への接触工程を設ける、請求項５に記載の表面処理皮膜付き硬質粒子を含有する水性ディスパージョンの製造方法。 The aqueous dispersion containing hard particles with a surface-treated film according to claim 5, wherein a contact step with an aqueous solution containing a phosphorus compound is provided between the hydrated oxide-containing film forming step and the suspending step. Manufacturing method.
  7. 　ヌープ硬度が１０００以上の硬質粒子と、該硬質粒子の表面に設けられたＺｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属化合物膜と、を有することを特徴とする表面処理皮膜付き硬質粒子。 Hard particles having Knoop hardness of 1000 or more, and one or two selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V provided on the surface of the hard particles A hard particle with a surface-treated film, characterized by comprising the above metal compound film.
  8. 　前記金属化合物膜は、前記金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種の金属化合物を含む、請求項７に記載の表面処理皮膜付き硬質粒子。 The hard particle with a surface-treated film according to claim 7, wherein the metal compound film includes at least one metal compound selected from the metal oxide, hydroxide, nitride, and carbide.
  9. 　前記金属化合物膜の表面にリン化合物膜が形成されている、請求項７又は８に記載の表面処理皮膜付き硬質粒子。 The hard particles with a surface-treated film according to claim 7 or 8, wherein a phosphorus compound film is formed on a surface of the metal compound film.
  10. 　ヌープ硬度が１０００以上の硬質粒子の表面に、Ｚｒ、Ｔｉ、Ｓｉ、Ｃｒ、Ｔａ、Ｈｆ、Ｓｎ、Ｍｏ、Ｗ、Ｚｎ、Ｉｎ及びＶから選ばれる１種又は２種以上の金属の水和酸化物含有膜を有する表面処理皮膜付き硬質粒子と、該表面処理皮膜付き硬質粒子が懸濁されている水性溶媒と、を有することを特徴とする表面処理皮膜付き硬質粒子を含有する水性ディスパージョン。 Hydration oxidation of one or more metals selected from Zr, Ti, Si, Cr, Ta, Hf, Sn, Mo, W, Zn, In and V on the surface of hard particles having Knoop hardness of 1000 or more An aqueous dispersion containing hard particles with a surface-treated film, comprising: hard particles with a surface-treated film having an object-containing film; and an aqueous solvent in which the hard particles with the surface-treated film are suspended.
  11. 　前記金属化合物膜が、前記金属の酸化物、水酸化物、窒化物及び炭化物の中から選ばれる少なくとも１種の金属化合物を含む、請求項８に記載の表面処理皮膜付き硬質粒子を含有する水性ディスパージョン。 The aqueous solution containing hard particles with a surface-treated film according to claim 8, wherein the metal compound film contains at least one metal compound selected from oxides, hydroxides, nitrides and carbides of the metal. Dispersion.
  12. 　前記金属化合物膜の表面にリン化合物吸着膜が形成されている、請求項１０又は１１に記載の表面処理皮膜付き硬質粒子を含有する水性ディスパージョン。 The aqueous dispersion containing hard particles with a surface treatment film according to claim 10 or 11, wherein a phosphorus compound adsorption film is formed on the surface of the metal compound film.
PCT/JP2012/054869 2011-03-01 2012-02-28 Process of producing hard particle provided with surface treatment coating, and hard particle provided with surface treatment coating WO2012118054A1 (en)

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JPH1018083A (en) * 1996-07-01 1998-01-20 Nippon Parkerizing Co Ltd Production of metal material coated with titanium oxide
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