WO2016136314A1 - 複合金属酸化物研磨材料の製造方法及び複合金属酸化物研磨材料 - Google Patents

複合金属酸化物研磨材料の製造方法及び複合金属酸化物研磨材料 Download PDF

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WO2016136314A1
WO2016136314A1 PCT/JP2016/050881 JP2016050881W WO2016136314A1 WO 2016136314 A1 WO2016136314 A1 WO 2016136314A1 JP 2016050881 W JP2016050881 W JP 2016050881W WO 2016136314 A1 WO2016136314 A1 WO 2016136314A1
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Prior art keywords
polishing
polishing material
metal oxide
zirconium
composite metal
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PCT/JP2016/050881
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English (en)
French (fr)
Japanese (ja)
Inventor
寿夫 小泉
啓治 小野
高橋　直人
大樹 橋本
加藤　良一
務 山本
勝 見上
瑞穂 和田
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堺化学工業株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives

Definitions

  • the present invention relates to a method for producing a composite metal oxide polishing material and a composite metal oxide polishing material.
  • Cerium oxide-based abrasives are used for polishing precision optical glass products that require high transparency and accuracy, such as lenses and prisms. This abrasive is produced by firing and pulverizing minerals rich in so-called rare earths (rare earths).
  • Patent Literature 1 discloses that a perovskite oxide is suitable as an abrasive
  • Patent Literature 2 discloses an iron-based perovskite-type abrasive
  • Patent Literature 3 discloses.
  • a zirconium-based perovskite-type abrasive is disclosed.
  • the abrasive described in Patent Document 2 is manufactured by spray pyrolysis, and requires special equipment and a great deal of time for manufacturing, so it is not suitable for mass production and uses rare metals such as nickel and cobalt. Therefore, there are problems such as concern about supply insecurity similar to cerium oxide.
  • the abrasive described in Patent Document 3 is also manufactured by spray pyrolysis, and is not suitable for mass production.
  • the inventor of the present invention is a method for producing a cerium-free polishing material at a low cost without introducing a special equipment with a simple manufacturing process, and polishing by mixing and baking a strontium compound and a zirconium compound.
  • a method for obtaining a material has been found, and among the polishing materials obtained by this method, those using zirconium oxide as a raw material zirconium compound have already been found to be remarkably excellent in polishing rate.
  • zirconium oxide is usually produced by firing and pulverizing zirconium hydroxide, there is room for improvement to further reduce production costs and improve production efficiency by omitting this firing and pulverization step. was there.
  • the present invention provides a polishing material that has a good polishing rate in a cerium-free polishing material and that can realize reduction in manufacturing cost and improvement in manufacturing efficiency, and the polishing material in a simple manner.
  • An object of the present invention is to provide a production method for obtaining the above.
  • the present inventor has been diligently studying in order to solve the above-mentioned problems.
  • polishing materials obtained by mixing and baking a strontium compound and a zirconium compound polishing using a zirconium compound other than zirconium oxide as a raw material. Focusing on the fact that the polishing rate of the material is not good, we have newly found that this factor is the content of the sulfur compound contained in the raw zirconium compound.
  • zirconium compounds such as zirconium hydroxide and zirconium carbonate often use substances containing sulfate ions such as sulfuric acid, ammonium sulfate, sodium sulfate, and potassium sulfate at the time of synthesis.
  • the zirconium compound obtained by the usual synthesis method contains a sulfur compound
  • the present inventor has found that the content of this sulfur compound affects the polishing rate of the polishing material after mixing and firing with the strontium compound. I found a new thing.
  • the cause is not certain, for example, it is estimated as one of the causes that the crystallinity of the obtained zirconium compound varies depending on the amount of sulfur compound added when the zirconium compound is produced.
  • the present invention is a method for producing a composite metal oxide polishing material comprising a mixing step of mixing a strontium compound and a zirconium compound, and a firing step of firing the mixture obtained by the mixing step,
  • the SO 3 equivalent of the sulfur compound contained in the zirconium compound is 2.0 parts by weight or less with respect to 100 parts by weight of the zirconium compound in terms of ZrO 2 .
  • the strontium compound in the mixing step is preferably at least one selected from the group consisting of strontium carbonate and strontium hydroxide. Since strontium carbonate and strontium hydroxide easily react with the zirconium compound to easily produce strontium zirconate (SrZrO 3 ), productivity is further improved.
  • the zirconium compound in the mixing step is preferably at least one selected from the group consisting of zirconium carbonate and zirconium hydroxide. Since zirconium carbonate and zirconium hydroxide have high reactivity with the strontium compound, a polishing material with better polishing characteristics can be provided. Moreover, if these are used, reduction of manufacturing cost and improvement of manufacturing efficiency can be realized more.
  • the firing temperature in the firing step is preferably more than 800 ° C. and 1500 ° C. or less. When the firing temperature is within this range, a polishing material with better polishing characteristics can be provided.
  • the present invention also provides a composite metal oxide polishing material comprising:
  • the SO 3 equivalent of the sulfur compound contained in the composite metal oxide polishing material is 1.2 parts by weight or less with respect to 100 parts by weight of the zirconium compound equivalent to ZrO 2 contained in the composite metal oxide polishing material. It is also a composite metal oxide polishing material.
  • a polishing material having a good polishing rate in a cerium-free polishing material can be efficiently produced. Since the production method of the present invention is performed by a solid phase reaction method, the production process is simpler than that of the spray pyrolysis method, and the production can be performed at a low cost without introducing special equipment. In addition, the composite metal oxide polishing material of the present invention can exhibit a good polishing rate, and can sufficiently cope with the recent shortage of rare earth supply, and thus can be said to be an extremely advantageous material industrially.
  • FIG. 1-1 is a graph showing the results of differential heat measurement for each zirconium compound used in Example 1 and Comparative Example 1.
  • 1-2 is a graph showing the results of thermogravimetric measurement for each zirconium compound used in Example 1 and Comparative Example 1.
  • FIG. 2-1 is a graph showing the results of differential heat measurement for each mixed powder (dried product of the mixture) according to Example 1 and Comparative Example 1.
  • FIG. 2-2 is a graph showing the results of thermogravimetric measurements on the mixed powders (dried mixture) according to Example 1 and Comparative Example 1.
  • FIG. 3 is a graph showing the relationship of zeta potential to pH for each abrasive slurry used in the Reference Example or Comparative Reference Example.
  • the method for producing a composite metal oxide polishing material of the present invention includes a mixing step of mixing a strontium compound and a zirconium compound, and a baking for baking the mixture obtained by the mixing step. Process. Therefore, the composite metal oxide polishing material can achieve a high polishing rate. As can be seen from the raw materials used, the production method of the present invention is performed by a solid phase reaction method. Therefore, the manufacturing process is simpler than that of the spray pyrolysis method, and manufacturing at a low cost is possible without introducing special equipment.
  • strontium compound one of the raw materials in the production method of the present invention.
  • the strontium compound is not particularly limited as long as it is a compound containing a strontium atom, but among them, at least one selected from the group consisting of strontium carbonate and strontium hydroxide is preferable.
  • Strontium carbonate and strontium hydroxide easily react with the zirconium compound to easily produce strontium zirconate (SrZrO 3 ).
  • zirconium compound as a raw material
  • SO 3 equivalent amount of sulfur compounds contained in this respect in terms of ZrO 2 per 100 parts by weight of said zirconium compound, using 2.0 or less part by weight compound.
  • the sulfur compound content (SO 3 equivalent) is preferably 1.5 parts by weight or less, more preferably 1.1 parts by weight or less, and even more preferably 0.5 parts by weight or less.
  • the zirconium compound is not particularly limited as long as it is a compound containing a zirconium atom, but among them, zirconium oxide, zirconium carbonate, and zirconium hydroxide are preferable. These can provide a polishing material having high reactivity with a strontium compound and better polishing characteristics. Among them, it is preferable to use a zirconium compound other than zirconium oxide, whereby the firing and pulverization steps during the synthesis of zirconium oxide can be omitted, and the manufacturing cost can be reduced and the manufacturing efficiency can be improved. That is, it is preferably at least one selected from the group consisting of zirconium carbonate and zirconium hydroxide.
  • the zirconium compound preferably has a specific surface area of 0.1 to 250 m 2 / g.
  • a specific surface area is within this range, a moderately crystalline SrZrO 3 phase is easily generated efficiently.
  • the specific surface area of the zirconium compound is 0.1 m 2 / g or more, the reactivity with the strontium compound is further increased, and when it is 250 m 2 / g or less, the reaction control with the strontium compound becomes easy. Therefore, in any case, a composite metal oxide polishing material having a good polishing rate is easily obtained. More preferably, it is 0.3 to 240 m 2 / g, and still more preferably 0.5 to 230 m 2 / g.
  • the specific surface area (also referred to as SSA) means the BET specific surface area.
  • the BET specific surface area refers to a specific surface area obtained by the BET method, which is one method for measuring the specific surface area.
  • the specific surface area refers to the surface area per unit mass of a certain object.
  • the BET method is a gas adsorption method in which gas particles such as nitrogen are adsorbed on solid particles and the specific surface area is measured from the amount adsorbed.
  • the specific surface area is determined by obtaining the monomolecular adsorption amount VM by the BET equation from the relationship between the pressure P and the adsorption amount V.
  • the production method of the present invention includes a mixing step of mixing a strontium compound and a zirconium compound.
  • the mixing method is not particularly limited, and may be wet mixing or dry mixing, but wet mixing is desirable from the viewpoint of mixing properties.
  • the dispersion medium used for wet mixing is not particularly limited, and water or lower alcohol can be used, but water is preferable from the viewpoint of production cost, and ion-exchanged water is more preferable.
  • a ball mill, a paint conditioner, or a sand grinder may be used.
  • the zirconium compound can be used for the mixing step in the form of a cake obtained by synthesis.
  • a drying step may be performed as necessary.
  • the dispersion medium is removed from the slurry obtained in the mixing step and dried.
  • the method for drying the slurry is not particularly limited as long as the solvent used at the time of mixing can be removed, and examples thereof include drying under reduced pressure and drying by heating. Further, the slurry may be dried as it is, or may be dried after being filtered. Note that the dry product of the mixture may be dry-pulverized.
  • the raw material mixture obtained in the mixing step (may be a dried product obtained through a further drying step) is fired. Thereby, a composite metal oxide polishing material can be obtained.
  • the raw material mixture may be fired as it is, or may be fired after being molded into a predetermined shape (for example, a pellet shape).
  • the firing atmosphere is not particularly limited. The firing step may be performed only once or twice or more.
  • the firing temperature in the firing step may be a temperature sufficient for the reaction between the strontium compound and the zirconium compound, but is preferably more than 800 ° C. and 1500 ° C. or less. When the firing temperature exceeds 800 ° C., the reaction proceeds more sufficiently, and the zirconium compound is easily crystallized as zirconium oxide. When the firing temperature is 1500 ° C. or less, the generated strontium zirconate may be vigorously sintered. Since it is sufficiently suppressed, the polishing rate can be further increased in any case.
  • the lower limit of the firing temperature is more preferably 850 ° C. or higher. Thereby, it becomes possible to fully exhibit the effect of this invention.
  • the firing temperature in the firing step means the highest temperature reached in the firing step.
  • a raw material zirconium compound when a compound having a sulfur compound content exceeding the range set in the present invention is used, even if the firing step is performed at the same firing temperature as in the case of using the zirconium compound of the present invention. Since the resulting polishing material does not have sufficient crystallinity, a good polishing rate cannot be obtained. Further, even if the calcination temperature is further increased so that the crystallinity of the polishing material is approximately the same, a sufficient polishing rate cannot be obtained.
  • the holding time at the firing temperature may be a time sufficient for the reaction between the strontium compound and the zirconium compound. For example, it is preferably 5 minutes to 24 hours. When the holding time is within this range, the reaction proceeds more sufficiently, and when the holding time is 24 hours or less, the generated fired product (strontium zirconate) is sufficiently suppressed from being vigorously sintered.
  • the polishing rate can be further increased. More preferably, it is 7 minutes to 22 hours, and further preferably 10 minutes to 20 hours.
  • the rate of temperature rise during the temperature rise until reaching the maximum temperature (firing temperature) is 0.2 to 15 ° C./min. If the rate of temperature increase is 0.2 ° C./min or more, the time required for temperature increase does not become too long, so that waste of energy and time can be sufficiently suppressed, and if it is 15 ° C./min or less.
  • the temperature of the furnace contents can sufficiently follow the set temperature, and firing unevenness is more sufficiently suppressed. More preferably, it is 0.5 to 12 ° C./min, and further preferably 1.0 to 10 ° C./min.
  • a pulverization step may be performed as necessary.
  • the fired product obtained in the firing step is pulverized.
  • the pulverization method and pulverization conditions are not particularly limited, and for example, a ball mill, a reiki machine, a hammer mill, a jet mill, or the like may be used.
  • the composite metal oxide polishing material of the present invention includes a sulfur compound contained in the polishing material (more specifically, a sulfur compound incorporated in the crystal of the polishing material). ) In terms of SO 3 is 1.2 parts by weight or less with respect to 100 parts by weight in terms of ZrO 2 of the zirconium compound contained in the composite metal oxide polishing material. When the content of the sulfur compound is within this range, the polishing material has a very good polishing rate.
  • the content of the sulfur compound is preferably 1.0 part by weight or less, more preferably 0.8 part by weight or less, and still more preferably 0.6 part by weight or less.
  • the abrasive material is preferably obtained by the production method of the present invention described above.
  • the polishing material preferably includes a crystal phase of ZrO 2 and a crystal phase of SrZrO 3 . Since the crystal phase of ZrO 2 contained in the polishing material is responsible for the mechanical polishing action and the crystal phase of SrZrO 3 is responsible for the chemical polishing action, a better polishing rate can be exhibited.
  • the polishing material of the present invention is preferably a composite of ZrO 2 and SrZrO 3 , but this can increase the polishing rate.
  • the composite of SrZrO 3 and ZrO 2 refers to secondary particles formed by partially sintering the primary particles of SrZrO 3 and zirconium oxide. For example, when element mapping is performed on the composite by energy dispersive X-ray spectroscopy (EDS), primary particles from which Sr and Zr are detected and primary particles from which only Zr is detected form secondary particles. The situation is observed.
  • EDS energy dispersive X-ray spectroscopy
  • the polishing material preferably has a half width of a peak derived from the (040) plane of orthorhombic SrZrO 3 in X-ray diffraction using CuK ⁇ rays as a radiation source in a range of 0.1 to 3.0 °.
  • the half width is in this range, the crystallinity of SrZrO 3 that effectively exhibits the chemical polishing action is improved, and thus the chemical polishing action can be sufficiently exhibited.
  • the half width exceeds 3.0 °, the crystallinity of SrZrO 3 is not sufficient, and when the half width is less than 0.1 °, the crystallinity of SrZrO 3 becomes too high. In some cases, the chemical polishing action derived from SrZrO 3 may not be sufficiently obtained.
  • the angle is more preferably 0.1 to 1.0 °, further preferably 0.1 to 0.7 °, and particularly preferably 0.1 to 0.4 °.
  • the polishing material is preferably ratio D 10 of D 90 indicative of sharpness of volume-based particle size distribution (D 90 / D 10) is 1.5 to 50.
  • D 90 / D 10 exceeds 50, the particle size variation is too large, so that sufficient contact between the polishing material and the object to be polished cannot be obtained, and the polishing rate may not be sufficient.
  • D 90 / D 10 is less than 1.5, the variation in particle diameter is too small, so that contact between the polishing material and the object to be polished cannot be obtained sufficiently, and the polishing rate may not be sufficient.
  • D 90 / D 10 is large, it means that the particle size distribution is broad, smaller value means that the particle size distribution is sharp.
  • D 10 and D 90 are values obtained by measuring the particle size distribution, respectively. It means 10% cumulative particle diameter on a volume basis and D 10, and D 90 refers to the 90% cumulative particle diameter on a volume basis.
  • the polishing material preferably contains 10 to 43% by weight of Sr in terms of SrO.
  • Sr content is less than 10% by weight in terms of SrO, the content of SrZrO 3 is lowered and the chemical polishing action may not be sufficiently obtained.
  • Sr content exceeds 43 wt% in terms of SrO, ZrO 2 content is relatively reduced, mechanical polishing action may not be obtained sufficiently. More preferably, it is 11 to 43% by weight, and still more preferably 12 to 43% by weight.
  • the polishing material preferably has a specific surface area of 1.0 to 50 m 2 / g.
  • the specific surface area is less than 1.0 m 2 / g, the specific surface area of the polishing material is too small to sufficiently contact the object to be polished, and may not be sufficiently polished.
  • the specific surface area exceeds 50 m 2 / g, the abrasive grains constituting the polishing material may be too small to obtain a sufficient mechanical polishing action. More preferably, it is 1.0 to 45 m 2 / g, and still more preferably 1.0 to 40 m 2 / g.
  • the polishing material of the present invention can be applied to various polishing objects.
  • the present invention can be applied to a polishing object in which cerium oxide, chromium oxide, bengara (Fe 2 O 3 ), or the like has been conventionally used as a polishing material.
  • the object to be polished is not particularly limited, and examples thereof include a glass substrate, a metal plate, a stone, sapphire, silicon nitride, silicon carbide, silicon oxide, gallium nitride, gallium arsenide, indium arsenide, and indium phosphide.
  • the polishing material may be used by appropriately mixing with other components depending on the application.
  • the polishing material of the present invention may be mixed with a dispersion medium, may be mixed with an additive, or the dispersion medium and the additive may be mixed simultaneously.
  • the form at the time of mixing with a dispersion medium and / or an additive is not specifically limited, For example, it can use in forms, such as a powder form, a paste form, and a slurry form.
  • a dispersion medium For example, water, an organic solvent, a mixture thereof, etc. are mentioned, 1 type (s) or 2 or more types can be used.
  • the organic solvent include alcohol, acetone, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane and the like.
  • the alcohol include monovalent water-soluble alcohols such as methanol, ethanol and propanol; bivalent or more such as ethylene glycol and glycerin. Of water-soluble alcohols.
  • the dispersion medium is preferably water, and more preferably ion-exchanged water.
  • the additive is not particularly limited, and examples thereof include acids, alkalis, pH adjusters, chelating agents, antifoaming agents, dispersants, viscosity modifiers, aggregation inhibitors, lubricants, reducing agents, rust inhibitors, and publicly known.
  • An abrasive material etc. are mentioned. These may be used alone or in combination of two or more, as long as the effects of the present invention are not impaired.
  • polishing method using the composite metal oxide polishing material of the present invention.
  • the composite metal oxide polishing material of the present invention can be applied to various types of polishing targets.
  • the polishing method using the composite metal oxide polishing material of the present invention is not limited only to the following polishing method.
  • a polishing method in which the polishing step b for polishing the negatively chargeable substrate under a condition where the zeta potential is negative is performed at least once each.
  • a silicon carbide substrate is also included.
  • transparent or semi-transparent things such as soda-lime glass, an alkali free glass, borosilicate glass, quartz glass, are mentioned, for example.
  • the polishing step a for polishing the negatively chargeable substrate under a condition where the zeta potential of the abrasive slurry is positive, and the negatively chargeable substrate is polished under a condition where the zeta potential of the abrasive slurry is negative.
  • Each of the polishing steps b is performed at least once.
  • the order of these polishing steps is not particularly limited, and the polishing step b may be performed after the polishing step a, or the polishing step a may be performed after the polishing step b.
  • each polishing step may be performed a plurality of times, or the polishing step a and the polishing step b may be performed alternately.
  • the polishing step a is performed a plurality of times, as long as the zeta potential of the abrasive slurry is positive, the zeta potential may be changed or may be changed.
  • the polishing step b is performed a plurality of times, and as long as the zeta potential of the abrasive slurry is negative, the zeta potential may be changed or may be changed.
  • “the zeta potential of the abrasive slurry” is a value obtained under the measurement conditions described in the examples described later.
  • the action due to electrostatic attraction is exhibited in the polishing step a, and the action due to electrostatic repulsion is exhibited in the polishing step b.
  • a high polishing rate and a negative charge after polishing due to these synergistic effects It is estimated that excellent surface smoothness in the conductive substrate will be realized.
  • the surface of the negatively chargeable substrate before polishing has a recess made of fine scratches or holes.
  • the substrate to be polished is negatively charged, whereas the abrasive slurry is positively charged, so that the abrasive penetrates deep into the recesses by electrostatic attraction and promotes polishing. Therefore, it is considered that the polishing rate is increased.
  • the polishing step b since the substrate to be polished and the abrasive slurry are both negatively charged, the abrasive does not penetrate deep into the recess due to electrostatic repulsion, but is applied between the polishing pad and the substrate. It is considered that a large amount of abrasive is present on the convex portion of the substrate surface due to the pressure, thereby smoothing the substrate surface. Therefore, if the object to be polished is a negatively chargeable substrate, the same working mechanism is obtained. Therefore, the above polishing method can be applied not only to a glass substrate but also to various negatively chargeable substrates.
  • polishing is performed in the presence of an abrasive slurry.
  • the same abrasive slurry may be used, that is, continuously used (reused) to control only the zeta potential of the slurry, and the zeta potential may be positive or negative. It is also possible to prepare each abrasive slurry separately and switch the abrasive slurry in each polishing step. In either case, a slurry containing the composite metal oxide polishing material of the present invention may be used as the abrasive slurry.
  • the abrasive slurry can be used continuously (reused), and even when switching, it is not necessary to prepare abrasive slurry of greatly different types. This eliminates the need for cleaning work and dedicated equipment.
  • the above polishing method can be said to be a very advantageous method compared to the conventional polishing method.
  • the polishing step a is a step of polishing the negatively chargeable substrate using the abrasive slurry under conditions where the zeta potential of the abrasive slurry is positive.
  • this polishing process it is possible to achieve a high polishing rate almost equal to that when using a conventional cerium oxide-based abrasive, and the surface of the negatively charged substrate is higher than when using a cerium oxide-based abrasive. Smoothness can also be improved.
  • the polishing step b is a step of polishing a negatively chargeable substrate using the abrasive slurry under conditions where the zeta potential of the abrasive slurry is negative.
  • this polishing process while achieving a significantly higher polishing speed than the precision polishing process using conventional colloidal silica, it is possible to carry out precise polishing that is almost the same as the precision polishing process using colloidal silica. High surface smoothness can be realized in the conductive substrate.
  • the negatively chargeable substrate is polished under the condition where the zeta potential of the abrasive slurry is positive in the polishing step a and under the condition where the zeta potential of the abrasive slurry is negative in the polishing step b.
  • Each is more preferably 10 mV or more, further preferably 15 mV or more, and particularly preferably 20 mV or more.
  • the upper limit of the absolute value in each step is not particularly limited, for example, ease of control (for example, if the zeta potential is excessively large in the polishing step a, the abrasive may adhere to the glass substrate surface, For example, if the zeta potential is too low in the polishing step b, the electrostatic repulsion between the negatively chargeable substrate and the abrasive slurry may be too strong and the polishing rate may not be sufficiently increased. Therefore, from the viewpoint of preventing this, it is preferable that the voltage is 100 mV or less.
  • the zeta potential of the abrasive slurry can be controlled by adjusting the pH of the abrasive slurry. If the abrasive slurry contains the composite metal oxide abrasive of the present invention, adjusting the pH of the abrasive slurry to less than the isoelectric point of the abrasive slurry, while its zeta potential becomes positive, When the pH of the material slurry is adjusted to a range exceeding the isoelectric point of the abrasive slurry, the zeta potential becomes negative.
  • the abrasives emphasized increasing the polishing rate or increasing the surface smoothness, but the composite metal oxide polishing material of the present invention can easily control the abrasiveness only by pH. In this respect, a unique effect that cannot be conceived from the prior art can be exhibited.
  • the pH may be adjusted by adding a pH adjusting agent to the abrasive slurry, or the pH of the abrasive slurry may be adjusted using a pH buffer solution.
  • pH adjustment may not be performed.
  • An acid or an alkali can be used as the pH adjuster. If an acid is used, the pH of the abrasive slurry can be adjusted to the acidic side, and if an alkali is used, the pH of the abrasive slurry can be adjusted to the alkali side.
  • the acid is preferably, for example, an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, perchloric acid or phosphoric acid; an organic acid such as oxalic acid or citric acid; and the alkali is, for example, an aqueous sodium hydroxide solution or potassium hydroxide.
  • Alkaline aqueous solutions such as aqueous solution, calcium hydroxide aqueous solution, sodium carbonate aqueous solution, ammonia water, sodium hydrogen carbonate aqueous solution, are preferable.
  • the polishing step a is performed under the condition that the pH of the abrasive slurry is larger than the isoelectric point of the negatively chargeable substrate and less than the isoelectric point of the abrasive slurry.
  • the lower limit of the pH of the abrasive slurry in the polishing step a is preferably 2 or more. More preferably, it is 3 or more, More preferably, it is 4 or more.
  • the upper limit of the pH of the abrasive slurry in the polishing step b is preferably 12 or less. More preferably, it is 11 or less.
  • the isoelectric point of the abrasive slurry (and the composite metal oxide polishing material of the present invention) means that the algebraic sum of the charge on the abrasive grains (the composite metal oxide polishing material of the present invention) in the abrasive slurry is zero.
  • a certain point that is, a point at which the positive charge and negative charge on the abrasive grains become equal, can be expressed by the pH of the abrasive slurry at that point.
  • the content of the composite metal oxide polishing material of the present invention in the abrasive slurry is preferably 0.001 to 90% by weight in 100% by weight of the abrasive slurry, for example. More preferably, it is 0.01 to 30% by weight.
  • the abrasive slurry preferably further contains a dispersion medium.
  • the dispersion medium is as described above.
  • Example 1 Zr raw material preparation step Zirconium oxychloride octahydrate (made by Showa Chemical Co., Ltd.) (3.0 kg) was dissolved in 6.7 L of ion-exchanged water with stirring. The solution was adjusted to 25 ° C. with stirring, and while maintaining this temperature, 180 g / L of an aqueous sodium hydroxide solution was added over 1 hour with stirring until pH 9.5, and the mixture was further stirred for 1 hour. . The slurry was washed with filtered water, and washed with water until the electric conductivity of the washing became 100 ⁇ S / cm or less to obtain a zirconium hydroxide cake.
  • Firing step 30 g of the dried product of the mixture obtained in the above (3) drying step is placed in an alumina crucible having an outer diameter of 55 mm and a capacity of 60 mL, and an electric muffle furnace (ADVANTEC, KM-420). Was fired to obtain a fired product.
  • ADVANTEC electric muffle furnace
  • the temperature was raised from room temperature to 950 ° C. over 285 minutes, held at 950 ° C. for 180 minutes, and then the heater was turned off and cooled to room temperature. The firing was performed in the air.
  • Examples 2 and 3 A composite metal oxide polishing material was obtained in the same manner as in Example 1 except that the firing temperature in the firing step was changed to the temperature shown in Table 1.
  • Example 4 Zr raw material preparation process Zirconium oxychloride octahydrate (made by Showa Chemical Co., Ltd.) 3.0 kg and ammonium sulfate (made by Toagosei Co., Ltd.) 0.35 kg are dissolved in 6.7 L of ion-exchanged water while stirring. I let you. The solution was adjusted to 25 ° C. with stirring, and while maintaining this temperature, 180 g / L of an aqueous sodium hydroxide solution was added over 1 hour with stirring until pH 9.5, and the mixture was further stirred for 1 hour. .
  • the slurry was washed with filtered water, and washed with water until the electric conductivity of the washing became 100 ⁇ S / cm or less to obtain a zirconium hydroxide cake.
  • (2) Drying step to (5) Grinding step were performed in the same manner as in Example 1 to obtain a composite metal oxide polishing material.
  • Example 5 A composite metal oxide polishing material was obtained in the same manner as in Example 1 except that 109 g of zirconium carbonate (manufactured by Sakai Kogyo Co., Ltd.) was used as the Zr raw material in the mixing step.
  • Example 6 A composite metal oxide polishing material was obtained in the same manner as in Example 1 except that 69 g of zirconium carbonate (manufactured by Sakai Kogyo Co., Ltd.) was used as the Zr raw material in the mixing step.
  • Comparative Example 1 (1) Zr raw material preparation step Zirconium oxychloride octahydrate (produced by Showa Chemical Co., Ltd.) 3.0 kg and ammonium sulfate (produced by Toagosei Co., Ltd.) 0.70 kg are dissolved in 6.7 L of ion-exchanged water with stirring. I let you. The solution was adjusted to 25 ° C. with stirring, and while maintaining this temperature, 180 g / L of an aqueous sodium hydroxide solution was added over 1 hour with stirring until pH 9.5, and the mixture was further stirred for 1 hour. .
  • the slurry was washed with filtered water, and washed with water until the electric conductivity of the washing became 100 ⁇ S / cm or less to obtain a zirconium hydroxide cake.
  • the (2) drying step to (5) pulverization step were performed in the same manner as in Example 1 to obtain a comparative polishing material.
  • Comparative Example 2 (1) A comparative polishing material was obtained in the same manner as in Example 1 except that the zirconium hydroxide cake obtained in the Zr raw material preparation step was dried at 130 ° C. for 15 hours.
  • Comparative Examples 3 and 4 Except having changed the calcination temperature in a baking process into the temperature of Table 1, it carried out similarly to the comparative example 2, and obtained the abrasive material for a comparison.
  • Example 1 Differential thermal / thermogravimetric measurement of zirconium compound (zirconium hydroxide)
  • zirconium hydroxide zirconium hydroxide
  • TG / DTA differential thermal and thermogravimetric analysis
  • TG / DTA differential heat / thermogravimetry
  • Glass plate used Soda lime glass (manufactured by Matsunami Glass Industry Co., Ltd., size 36 ⁇ 36 ⁇ 1.3 mm, specific gravity 2.5 g / cm 3 )
  • Polishing machine Desktop polishing machine (manufactured by MT Corporation, MAT BC-15C, polishing plate diameter 300 mm ⁇ )
  • Polishing pad Polyurethane foam pad (Nitta Haas, MHN-15A, no ceria impregnation) Polishing pressure: 101 g / cm 2 Plate rotation speed: 70rpm
  • Abrasive composition supply amount 100 mL / min Polishing time: 60 min 3. The weight of the glass plate before and after the glass plate polishing test was measured with an electronic balance.
  • the polishing rate ( ⁇ m / min) was calculated.
  • Three glass plates were polished at the same time, and after polishing for 60 minutes, the glass plate and the abrasive slurry were exchanged. This operation was performed three times, and a value obtained by averaging the polishing rate of a total of 9 sheets was used as the polishing rate value in each example and comparative example.
  • the results are shown in Table 2. Very good ( ⁇ ) when the polishing rate is 0.29 ⁇ m / min or more, good ( ⁇ ) when the polishing rate is 0.22 ⁇ m / min or more and less than 0.29 ⁇ m / min, and defective ( ⁇ ). ).
  • SO 3 * 1 (parts by weight) means the SO 3 equivalent of the sulfur compound contained in the Zr raw material with respect to 100 parts by weight of the Zr raw material (zirconium compound) in terms of ZrO 2.
  • SO 3 * 2 (part by weight) means the SO 3 equivalent of the sulfur compound contained in the polishing material with respect to 100 parts by weight of the zirconium compound equivalent to ZrO 2 contained in the abrasive.
  • the zirconium compound used in Example 1 and the zirconium compound used in Comparative Example 1 are mainly different in content of sulfur compounds. Comparison of the results of differential thermal / thermogravimetric measurement under this difference shows that, from FIGS. 1-1 and 1-2, any zirconium compound (zirconium hydroxide) has an exothermic peak with no weight change. It was done. This indicates that amorphous zirconium hydroxide is a main component at a temperature below the exothermic peak, and that zirconium hydroxide crystallizes as zirconium oxide at the exothermic peak temperature.
  • the exothermic peak of zirconium hydroxide was 416 ° C., and the exothermic peak of zirconium hydroxide used in Comparative Example 1 was 506 ° C. Therefore, it was found that the zirconium hydroxide used in Comparative Example 1 had a higher temperature required for crystallization than the zirconium hydroxide used in Example 1, that is, it was difficult to crystallize at the same firing temperature.
  • FIGS. 2-1 and 2-2 show the dried product (called mixed powder) of a mixture of the zirconium compound (zirconium hydroxide) used in Example 1 or Comparative Example 1 and the strontium compound (strontium carbonate). It is a graph which shows the result of having performed differential heat and thermogravimetry. From FIG. 2, an exothermic peak without any weight change is observed in any of the mixed powders, and the mixed powder of Comparative Example 1 is necessary for crystallization compared to the mixed powder of Example 1 due to the difference in peak temperature. It has been found that crystallization is difficult at higher temperatures, ie, at the same firing temperature.
  • the reason why the temperatures of the exothermic peaks are different is that the amount of the sulfur compound contained in the zirconium hydroxide used in Comparative Example 1 exceeds the range defined in the present invention. It also affects the crystallinity of the resulting abrasive material. From Table 2, the half width of the peak derived from the (040) plane of orthorhombic SrZrO 3 of the polishing material according to Comparative Example 1 and SSA increased as compared with the composite metal oxide polishing material according to Example 1. ing. This indicates that the crystallinity of the polishing material when fired at the same 950 ° C. is low. Further, a significant difference in polishing rate was confirmed between Comparative Example 1 and Example 1. Therefore, when the content of the sulfur compound contained in the zirconium compound exceeds the range specified in the present invention, it is considered that the crystallinity of the polishing material is lowered and the polishing rate is lowered.
  • the polishing materials according to Comparative Examples 3 to 4 have higher crystallinity by increasing the firing temperature compared to Example 1.
  • the full width at half maximum of the peak derived from the (040) plane of orthorhombic SrZrO 3 of the polishing materials according to Comparative Examples 3 and 4 and SSA are those of the composite metal oxide polishing material according to Example 1.
  • the polishing rate is low. This is presumably because the particles were sintered too much, although the crystallinity of the polishing material became comparable by increasing the firing temperature.
  • the polishing material according to Comparative Example 2 was the same as the polishing material according to Example 1 in that the zirconium compound (zirconium hydroxide) was dried at 130 ° C.
  • the production method of the present invention can efficiently provide a polishing material having a good polishing rate in a cerium-free polishing material.
  • an abrasive slurry A was prepared. Specifically, 20.0 g of the abrasive was dispersed in 380.0 g of ion exchange water and stirred at 25 ° C. for 10 minutes. In this way, an abrasive slurry A was obtained.
  • the zeta potential was measured under the following conditions. The relationship of the zeta potential with respect to pH of this abrasive slurry is shown in FIG. Moreover, the isoelectric point of the abrasive slurry A was 6.2.
  • the isoelectric point is the point where the algebraic sum of the charge on the abrasive grains (composite metal oxide polishing material) in the abrasive slurry is zero, that is, the positive and negative charges on the abrasive grains.
  • the point which becomes equal is said and can be represented by the pH of the abrasive slurry at that point.
  • a zeta potential measuring machine was charged with 30 cc of the abrasive slurry for zeta potential measurement thus obtained.
  • the abrasive slurry C using colloidal silica, which will be described later, was dispersed for 1 minute using an ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Seisakusho) for 60 cc of the abrasive slurry C and setting the strength to V-LEVEL3. Went.
  • a zeta potential measuring machine was charged with 30 cc of the abrasive slurry for zeta potential measurement thus obtained.
  • Acid side pH adjustment solution hydrochloric acid aqueous solution, 0.1 mol / L
  • Alkaline side pH adjustment solution sodium hydroxide aqueous solution, 1 mol / L
  • Comparative Reference Example 1 (1) A cerium oxide abrasive for glass polishing as an abrasive for the first polishing process (Showa Denko KK, SHOROX (R) A-10, cerium oxide content: 60% by weight, isoelectric point: 10.4) An abrasive slurry B was prepared in the same manner as in Reference Example 1 except that was used. After adjusting the pH of the slurry so that the zeta potential of this abrasive slurry B becomes the value shown in Table 3, in the presence of this slurry, polishing similar to “(vi) Glass plate polishing test” of Example 1 The glass plate was polished under the conditions, and the polishing rate was measured.
  • Table 3 shows the polishing rate and the pH value of the abrasive slurry B in this step. Furthermore, the surface roughness of the glass substrate after the first polishing step was evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.
  • (2) Second polishing step The abrasive slurry B used in the first polishing step was taken out from the polishing machine, and the polishing machine was cleaned. Separately, 52.2 g of colloidal silica (Fuso Chemical Co., Ltd., Quarton (R) PL-7, isoelectric point: 5.8) was dispersed in 347.8 g of ion-exchanged water and stirred at 25 ° C. for 10 minutes. This was prepared as an abrasive slurry C.
  • the glass is subjected to the same polishing conditions as in the first polishing step in the presence of the abrasive slurry C.
  • the substrate was polished.
  • Table 3 shows the pH value of the abrasive slurry C in this step.
  • the polishing rate in the second polishing step and the surface roughness of the glass substrate after the second polishing step were evaluated in the same manner as in Reference Example 1. The results are shown in Table 3.
  • the relationship of the zeta potential with respect to pH of each of the abrasive slurry B and C is shown in FIG.
  • the preferred polishing method described above that is, the polishing step a for polishing the negatively chargeable substrate under the condition that the zeta potential of the slurry containing the composite metal oxide polishing material of the present invention is positive, and the zeta of the abrasive slurry
  • a polishing method in which the polishing step b for polishing the negatively chargeable substrate under a condition where the potential is negative is performed at least once each in a cerium-free polishing material with a high polishing rate and excellent surface smoothness. It turns out that it can be realized.
  • Comparative Reference Example 1 since a cerium oxide-based abrasive was used in the first polishing step and colloidal silica was used in the second polishing step, it was necessary to perform a cleaning operation of the polishing machine, In Reference Example 1, since the same type of abrasive slurry A is used in the first polishing step and the second polishing step, the cleaning work of the polishing machine is unnecessary, which is very advantageous in terms of work and equipment. It was.

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