WO2010137652A1 - Ceramic for decorative parts, and decorative parts - Google Patents

Ceramic for decorative parts, and decorative parts Download PDF

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Publication number
WO2010137652A1
WO2010137652A1 PCT/JP2010/059001 JP2010059001W WO2010137652A1 WO 2010137652 A1 WO2010137652 A1 WO 2010137652A1 JP 2010059001 W JP2010059001 W JP 2010059001W WO 2010137652 A1 WO2010137652 A1 WO 2010137652A1
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WO
WIPO (PCT)
Prior art keywords
mass
cobalt
chromium
ceramic
titanium carbide
Prior art date
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PCT/JP2010/059001
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French (fr)
Japanese (ja)
Inventor
邦英 四方
一英 草野
Original Assignee
京セラ株式会社
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Priority claimed from JP2009127291A external-priority patent/JP2010275576A/en
Priority claimed from JP2009149381A external-priority patent/JP2011006272A/en
Application filed by 京セラ株式会社 filed Critical 京セラ株式会社
Publication of WO2010137652A1 publication Critical patent/WO2010137652A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; CARE OF BIRDS, FISHES, INSECTS; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K87/00—Fishing rods
    • A01K87/04—Fishing-line guides on rods, e.g. tips
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/405—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour

Definitions

  • the present invention relates to ceramics for decorative parts and decorative parts using the same.
  • Patent Document 1 70 to 95% of a hard phase composed of titanium carbonitride and 4a, 5a, and 6a group carbides, nitrides, and carbonitrides, 5 to 30% of a binder phase composed of an iron group metal, and a bond
  • a super-hard alloy composed of 1 to 5% (more than weight percent) of group 4a, 5a and 6a elements dispersed and dissolved in the phase and unavoidable impurities is disclosed.
  • Patent Document 2 one or more of tungsten carbide, tantalum carbide, and titanium carbide are used as a main component, and one or two of Ni and Co are added at 5 to 30%, Cr and Cemented carbide containing 1 to 2 or more of Cr carbides in terms of Cr in an amount of 2 to 15% (more than weight%).
  • Ni and Co one or more of Ni and Co as the main component
  • Patent Document 3 discloses a titanium carbide-based cermet alloy composed of a hard phase mainly composed of titanium carbide and a binder phase mainly composed of one or two of Co and Ni, and includes Ti and Mo in the binder phase.
  • a titanium carbide-based cermet alloy whose content satisfies the conditions 0.85 ⁇ Mo (wt.%) / Ti (wt.%), 6 wt.% ⁇ Ti + Mo is disclosed.
  • Patent Document 4 discloses a silver sintered alloy having titanium carbide as a dispersed particle phase and chromium, molybdenum, nickel as a binder phase, and 58.1 to 90% by weight of the titanium converted into carbides in the total amount.
  • Chromium is 1 to 15% by weight in terms of carbides
  • molybdenum is 3 to 32% by weight in terms of carbides
  • nickel is 1 to 20% by weight
  • 1% by weight or less in terms of conversion Nb being 1.7% by weight or less in terms of carbide in the total amount
  • Co being 1% by weight or less in the total amount are disclosed.
  • the super-hard alloy described in Patent Document 1 has a very wide range of compositions, and thus may have a color tone other than silver. Furthermore, since the composition shown in the examples is only when the hard phase is TiCN and WC and the binder phase is Co and Ni, it becomes a blackish tone due to the influence of WC exhibiting black, and has a beautiful silver color. There was a problem that it was not a color tone.
  • the composition shown in the example has a hard phase composed of TiC and WC, and thus has a blackish tone due to the influence of WC that exhibits a black color. There was a problem that it was not a ceramic having a color tone.
  • the present invention has been devised to solve the above-mentioned problems, and has a silvery color tone, which provides high-quality feeling, aesthetic satisfaction and mental comfort, and has excellent corrosion resistance and ceramics for decorative parts.
  • An object of the present invention is to provide a decorative part for fishing line guide used.
  • the ceramic for decorative parts of the present invention is a ceramic for decorative parts comprising a titanium carbide sintered body, wherein zirconia is 9% by mass to 30% by mass, and at least one of cobalt and nickel is 5% by mass to 25% by mass. % Or less, chromium is contained in an amount of 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is dissolved in cobalt or nickel. It is a feature.
  • the ceramic for decorative parts of the present invention is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, and niobium is 2 mass%.
  • the chromium and niobium are contained in a solid solution with cobalt in a content of not less than 10% by mass and not more than 10% by mass.
  • the fishing line guiding decorative part of the present invention is characterized by comprising the ceramics for decorative part of the present invention having any one of the above-mentioned configurations.
  • the ceramic for decorative parts of the present invention made of a titanium carbide sintered body, wherein zirconia is 9% by mass or more and 30% by mass or less, and at least one of cobalt and nickel is 5% by mass or more. 25% by mass or less, chromium is 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is in solid solution with cobalt or nickel. Therefore, since zirconia suppresses oxidation and wear of titanium carbide, even when used for sliding parts, wear marks are not noticeable and can be used for a long period of time, and it becomes easy to provide a stable and preferable silver sintered body.
  • the ceramic for decorative parts of the present invention is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, niobium Since the chromium and niobium are in solid solution with cobalt, the wettability between the binder phase and titanium carbide is improved and the sinterability is improved. Shattering and chipping are less likely to occur during ceramic processing.
  • the fishing line guiding decorative part of the present invention when it is made of the ceramic for decorative part of the present invention, it is possible to obtain mental comfort through sight such as luxury and aesthetic satisfaction.
  • a fishing line guide ring that guides the fishing line even if it is rubbed against fine sand adhered to the fishing line, it has high hardness, so the surface is not easily scratched and the silver color tone is maintained. However, it becomes easy to endure long-term use.
  • FIG. 1 An example of a fishing line guide ring and a fishing line guide provided with the fishing line guide ring, which are decorative parts for guiding a fishing line of the present embodiment, is shown.
  • (A) is a plan view of the fishing line guide ring. It is a perspective view of the guide for fishing lines provided with the guide ring for fishing lines of (a).
  • An example of a watch case which is a decorative part for watch of the present embodiment is shown, (a) is a perspective view of the watch case seen from the front side, and (b) is a watch case of (a) seen from the back side. It is a perspective view.
  • the ceramic for decorative parts of the first embodiment is a ceramic for decorative parts made of a titanium carbide sintered body, wherein zirconia is 9% by mass to 30% by mass, and at least one of cobalt and nickel is 5% by mass. 25% by mass or less, chromium 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is dissolved in cobalt or nickel. Yes.
  • the titanium carbide sintered body is a sintered body containing titanium carbide (TiC) as a main component, and the main component referred to here is all the components 100 constituting the ceramic for decorative parts. It is a component occupying 50% by mass or more with respect to mass%. Titanium carbide, which is the main component, exhibits a good silver color as a decorative product and has high mechanical properties such as strength and hardness, so that the titanium carbide sintered material of the first embodiment is used. In the ceramic for decorative parts made of a body, it is preferable to contain titanium carbide in a content of 70% by mass or more.
  • zirconia makes it easy to suppress the problem that when the fishing line or the like moves while contacting the surface of the ceramic, the titanium carbide and the binder phase in the contact portion are oxidized and volume expansion occurs, causing cracks and wear.
  • the content of zirconia is 9% by mass or more and 30% by mass or less because the temperature of the contact surface rises due to friction when the fishing line moves while contacting the ceramic surface. This is to suppress the problem that when the moisture is present in the surface, the titanium carbide and the binder phase on the contact surface are gradually oxidized to expand in volume, causing cracks in the surrounding structure and progressing wear. Even if the fishing line moves while contacting the surface of the ceramic and the titanium carbide or binder phase wears, the zirconia crystal particles remain on the surface as protrusions, which come into contact with the fishing line. Oxidation proceeds slowly and wear is suppressed.
  • the amount of zirconia is less than 9% by mass, the number of zirconia crystal particles present on the surface of the ceramic decreases, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase tends to be reduced.
  • it exceeds 30% by mass the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic increases, and cracks tend to remain in the sintered ceramic. There is a tendency.
  • the content of at least one of cobalt and nickel is 5% by mass or more and 25% by mass or less because at least one of cobalt and nickel is present uniformly as a binder among the crystal grains of titanium carbide. It is possible to maintain the strength of the resin and to maintain the hardness and to prevent scratches.
  • at least one of cobalt and nickel is less than 5% by mass, at least one of cobalt and nickel is insufficient among the titanium carbide crystal particles, and the structure becomes non-uniform and the strength tends to decrease. If it exceeds 25% by mass, the hardness of the ceramic will be reduced and scratches will easily occur.
  • the chromium content of 1% by mass or more and 10% by mass or less increases the wettability of at least one of cobalt and nickel with titanium carbide, improves the sinterability, and improves the surface of the binder phase.
  • a chromium oxide film is formed by combining with oxygen in the air to increase the corrosion resistance, and it is possible to maintain the strength by appropriately dissolving in at least one of cobalt and nickel. If the chromium content is less than 1% by mass, the wettability between cobalt and titanium carbide decreases and the sinterability deteriorates, so voids are likely to occur, and it is difficult to form a chromium oxide film on the surface of the binder phase.
  • Chromium is mainly dissolved in at least one of cobalt and nickel in the binder phase, but a part thereof may exist as a carbide.
  • the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, the remaining titanium carbide content is 50% by mass or more, high hardness can be maintained, and the surface is scratched. This is because it is difficult.
  • the total content of zirconia, cobalt, nickel and chromium is 50% by mass or more, the content of the remaining titanium carbide tends to be reduced, and the surface cannot be maintained, and the surface tends to be damaged.
  • chromium when chromium is in solid solution with at least one of cobalt and nickel, a chromium oxide film is formed on the surface of the binder phase, and the problem of corrosion or discoloration of the ceramic surface is suppressed. be able to.
  • chromium may partially exist in the form of another compound such as chromium carbide or chromium nitride.
  • the sample is analyzed by X-ray diffraction and the peak positions of cobalt and nickel are shifted in the direction of the chromium peak. What is necessary is just to confirm with the image of a result, or printing on chart paper.
  • the decorative surface in the ceramic for decorative parts of the first embodiment refers to a surface where the decorative value of the decorative component is required, and does not indicate all surfaces.
  • the outer surface of the watch case is also an object of appreciation and requires a decorative value. is there.
  • the contents of titanium, zirconium, cobalt, nickel and chromium can be measured using a fluorescent X-ray analysis (XRF) method.
  • XRF fluorescent X-ray analysis
  • at least two types of mixed powders having different concentrations of each element of titanium carbide, zirconium, cobalt, nickel, and chromium are prepared in advance, and are each molded by a pressing method to obtain a standard sample.
  • each of these standard samples is irradiated with X-rays, and a calibration curve is created using the least square method from the relationship between the intensity of the fluorescent X-rays and the known concentration.
  • the ceramics for decorative parts of 1st Embodiment are grind
  • This measurement sample is irradiated with X-rays, the intensity of fluorescent X-rays is measured, and the concentration content is obtained from the calibration curve.
  • the contents of titanium, cobalt, nickel, zirconium and chromium can also be measured using ICP (Inductively-Coupled-Plasma) emission spectroscopy.
  • the produced ceramics are vaporized and vaporized with discharge plasma and excited, and when the excited atoms return to a low energy level, the type of atoms is identified and the emission intensity is used to identify each type of atom. Quantitative analysis of atoms. Further, nitrogen can be measured with an oxygen / nitrogen analyzer, and carbon can be measured with a carbon analyzer.
  • the ceramic for decorative parts of the first embodiment preferably contains molybdenum in a content of 35% by mass or less with respect to cobalt.
  • molybdenum When molybdenum is contained in a content of 35% by mass or less with respect to cobalt, the firing temperature can be lowered and the growth of crystal grains is suppressed, so that the graining and chipping are less likely to occur during processing, and the decoration has a beautiful surface.
  • a member can be produced.
  • Molybdenum forms a eutectic alloy with at least one of cobalt and nickel, but when the content exceeds 35% by mass with respect to at least one of cobalt and nickel, a molybdenum-rich phase precipitates in the binder phase. When the product is processed, graining and chipping are likely to occur, and the surface may be rough and cause variations in color tone.
  • chromium when chromium is contained in a metal element other than titanium in a content of 10% by mass or more and less than 40% by mass, chromium is present at the crystal grain boundary between cobalt and titanium carbide. Solid solution improves the wettability of the binder phase and titanium carbide to improve the sinterability. If the chromium content is less than 10% by mass, the effect of improving the wettability tends to be small and the sinterability tends to be reduced. If the chromium content exceeds 40% by mass, a chromium-rich phase appears and the particles are easily degranulated. It tends to be difficult to form a uniform and beautiful ceramic surface.
  • the ceramic for decorative parts of the second embodiment is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, Niobium is contained in a content of 2% by mass or more and 10% by mass or less, and chromium and niobium are in solid solution with cobalt.
  • the titanium carbide sintered body is a sintered body containing titanium carbide (TiC) as a main component, and the main component referred to here is all the components 100 constituting the ceramic for decorative parts. It is a component occupying 50% by mass or more with respect to mass%. Titanium carbide, which is the main component, exhibits a good silver color as a decorative product and has high mechanical properties such as strength and hardness, so that the titanium carbide sintered material of the second embodiment is used. In the ceramic for decorative parts made of a body, it is preferable to contain titanium carbide in a content of 70% by mass or more.
  • the content of cobalt is set to 5% by mass or more and 25% by mass or less because cobalt can exist uniformly as a binder among the titanium carbide crystal particles to maintain the strength of the ceramic and maintain the hardness. It can be made difficult to scratch.
  • cobalt is less than 5% by mass, cobalt is insufficient between the titanium carbide crystal grains, and the structure becomes non-uniform and the strength tends to decrease.
  • it exceeds 25% by mass the hardness of the ceramic decreases. And become easily scratched.
  • the chromium content of 1% by mass or more and 10% by mass or less improves the wettability of cobalt and titanium carbide, improves the sinterability, and improves the oxygen content in the air on the surface of the binder phase. This is because the film is bonded to form a chromium oxide film and the corrosion resistance is increased. If the chromium content is less than 1% by mass, the wettability between cobalt and titanium carbide decreases and the sinterability deteriorates, so voids are likely to occur, and it is difficult to form a chromium oxide film on the surface of the binder phase. If the corrosion resistance decreases and exceeds 10% by mass, the binder phase becomes too hard and the strength tends to decrease. Chromium is mainly dissolved in cobalt in the binder phase, but a part thereof may exist as a carbide.
  • chromium when chromium is in solid solution with cobalt, it is possible to suppress the problem that the surface of the ceramic is corroded or discolored by forming a chromium oxide film on the surface of the binder phase.
  • chromium may partially exist in the form of another compound such as chromium carbide or chromium nitride.
  • the state in which chromium is in solid solution with cobalt is determined by analyzing the sample by X-ray diffraction and confirming that the peak position of cobalt is shifted in the direction of the peak of chromium in the analysis result image or chart. You can check by printing on paper.
  • Niobium acts as a color tone adjusting agent. In addition to the metal niobium, it also has an effect of increasing wettability, and includes a niobium compound having a composition formula represented by, for example, NbCo 3 or NbC.
  • the content of niobium is 2% by mass or more and 10% by mass or less because niobium is mainly dissolved in cobalt to improve the action as a color adjusting agent and the wettability between titanium carbide and cobalt.
  • the content of niobium is large, the liquidus temperature of the binder phase becomes high, so that the sinterability may be lowered.
  • the niobium content is more preferably 4% by mass or more and 8% by mass or less. This is because niobium works to suppress grain growth, so the crystal grain boundary increases, and the incident light is strongly influenced by diffuse reflection by the crystal grain boundary in addition to the specular reflection by the crystal forming the decorative surface. In addition, the color tone of the decorative surface increases the glossy color tone, and further, a high-class feeling and aesthetic satisfaction can be obtained. As a result, mental comfort can be obtained through vision.
  • the binder phase is strong against corrosion against sweat and saliva, so the surface of the ceramic is maintained in a stable state and the color tone is also stable. Color unevenness between products can be reduced.
  • niobium can be replaced with tantalum, in which case the amount of tantalum added is 3% by mass or more and 20% by mass or less. Tantalum has the same effect as niobium, and the binder phase is strong against corrosion. However, since the material is expensive, it is preferably used according to the cost.
  • niobium is preferable that they are precipitated as cobalt niobium, for example NBCO 3 combines with cobalt by precipitation of NBCO 3, brightness drifting dignity exude.
  • This cobalt niobium such as NbCo 3 can be detected by an X-ray diffraction method.
  • the decorative surface in the ceramic for decorative parts of the second embodiment refers to a surface where the decorative value of the decorative component is required, and does not indicate all surfaces.
  • the outer surface of the watch case is also an object of appreciation and requires a decorative value. is there.
  • the contents of titanium, cobalt, chromium and niobium can be measured using a fluorescent X-ray analysis (XRF) method.
  • XRF fluorescent X-ray analysis
  • at least two kinds of mixed powders having different concentrations of each element of titanium, cobalt, chromium, and niobium are prepared in advance, and are each molded by a pressing method to obtain a standard sample.
  • each of these standard samples is irradiated with X-rays, and a calibration curve is created using the least square method from the relationship between the intensity of the fluorescent X-rays and the known concentration.
  • the ceramics for decorative parts of 2nd Embodiment are grind
  • This measurement sample is irradiated with X-rays, the intensity of fluorescent X-rays is measured, and the concentration content is obtained from the calibration curve.
  • the contents of titanium, cobalt, chromium and niobium can also be measured using ICP (Inductively-Coupled-Plasma) emission spectroscopy. Specifically, the produced ceramics are vaporized and vaporized with discharge plasma and excited, and when the excited atoms return to a low energy level, the type of atoms is identified and the emission intensity is used to identify each type of atom. Quantitative analysis of atoms. Furthermore, carbon can be measured with a carbon analyzer.
  • the ceramic for decorative parts of the second embodiment preferably contains molybdenum in a content of 35% by mass or less with respect to cobalt.
  • molybdenum When molybdenum is contained in a content of 35% by mass or less with respect to cobalt, the firing temperature can be lowered and the growth of crystal grains is suppressed, so that the graining and chipping are less likely to occur during processing, and the decoration has a beautiful surface.
  • a member can be produced.
  • Molybdenum forms a eutectic alloy with at least one of cobalt and nickel, but when the content exceeds 35% by mass with respect to at least one of cobalt and nickel, a molybdenum-rich phase precipitates in the binder phase. When the product is processed, graining and chipping are likely to occur, and the surface may be rough and cause variations in color tone.
  • chromium when chromium is contained in a metal element other than titanium in a content of 10% by mass or more and less than 40% by mass, chromium is present at the crystal grain boundary between cobalt and titanium carbide. Solid solution improves the wettability of the binder phase and titanium carbide to improve the sinterability. If the chromium content is less than 10% by mass, the effect of improving the wettability will be reduced and the sinterability will be reduced. If it exceeds 40% by mass, a chromium-rich phase will appear and it will be easy to degranulate, resulting in voids. It is difficult to form a uniform and beautiful ceramic surface.
  • the ceramic for decorative parts of the second embodiment includes zirconia in a content of 9% by mass to 30% by mass, and the total of zirconia, cobalt, chromium, niobium, and molybdenum is less than 50% by mass. preferable.
  • Zirconia suppresses the problem that when a fishing line or the like moves while being in contact with the surface of the ceramic, the titanium carbide and the binder phase in the contact portion are oxidized and volume-expanded to cause cracks and wear.
  • the content of zirconia is set to 9% by mass or more and 30% by mass or less because the temperature of the contact surface rises due to friction when the fishing line moves while contacting the ceramic surface. This is to suppress the problem that when the moisture is present there, the titanium carbide and the binder phase on the contact surface gradually oxidize and expand in volume, causing cracks with the surrounding structure and progressing wear. . Even if the fishing line moves while contacting the surface of the ceramic and the titanium carbide or binder phase wears, the zirconia crystal particles remain on the surface as protrusions, which come into contact with the fishing line. Oxidation slows down and wear is suppressed.
  • the amount of zirconia is less than 9% by mass, the number of zirconia crystal particles present on the surface of the ceramic decreases, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase tends to be reduced.
  • it exceeds 30% by mass the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic increases, and cracks tend to remain in the sintered ceramic. .
  • the total content of zirconia, cobalt, chromium, niobium and molybdenum is less than 50% by mass because the content of the remaining titanium carbide can be increased, so that high hardness can be maintained, This is because the surface is hardly damaged.
  • the total content of zirconia, cobalt, chromium, niobium and molybdenum is 50% by mass or more, the content of the remaining titanium carbide decreases, and the surface cannot be maintained, and the surface is easily damaged. is there.
  • the fishing line guiding decorative parts of the first and second embodiments are made of the ceramics for decorative products of the first and second embodiments having the above-described configuration, and specific examples thereof include a fishing line guide.
  • a fishing line guide with a ring and this fishing line guide ring.
  • the ceramics for decorative parts of the first and second embodiments are used for a fishing line guide ring and a fishing line guide provided with the fishing line guide ring, when assembled as a fishing line guide on a fishing rod, the color variation between the guides It does not impair the aesthetic appearance, has a unified sense of color, can provide a high-class feeling as a fishing rod, aesthetic satisfaction, and can provide mental comfort through vision.
  • the decorative component for fishing line guide according to the first embodiment has high corrosion resistance. There is no change in color and the sense of quality is not reduced.
  • the fishing line guiding decorative part of the second embodiment has high corrosion resistance because the main component of the ceramic binder phase is cobalt, chromium, niobium, molybdenum and zirconia. The product is not discolored and the quality is not reduced.
  • zirconia when the ceramics for decorative parts of the first and second embodiments contain zirconia, zirconia is expanded in volume due to oxidation of titanium carbide and the binder phase at the contact portion between the fishing line and the ceramic, and cracks and wear are caused. Reduce the problem of progress.
  • FIG. 1 shows an example of a fishing line guide ring, which is a decorative part for fishing line guides of the first and second embodiments, and a fishing line guide provided with the fishing line guide ring.
  • FIG. 1 (a) is a plan view of the fishing line guide ring. It is a figure and (b) is a perspective view of the guide for fishing lines provided with the guide ring for fishing lines of (a).
  • the fishing line guide ring 1 of the example shown in FIG. 1 is for guiding a fishing line (not shown) through the inner periphery thereof, and the fishing line guide 6 is a holding portion 2 that holds the fishing line guide ring 1.
  • the fishing line guide ring 1 is provided on a frame 5 integrally formed with a support portion 3 of the holding portion 2 and a fixing portion 4 that is fixed to a fishing rod (not shown).
  • the silver-colored fishing line guide ring 1 and the fishing line guide 6 and the color of the fishing rod are in good harmony, it can be suitably used for fishing gear.
  • it since it exhibits a silvery color tone, it can be used as a fishing tackle preferred by those who want a high-class feeling as a luxury item.
  • the surface of the fishing line guide ring 1 may be covered with a transparent film having high wear resistance, for example, a film made of amorphous hard carbon to further improve the wear resistance.
  • the wear resistance of the ceramics for decorative parts of the first and second embodiments can be evaluated by producing a wear resistance evaluation apparatus having the following configuration and using it.
  • FIG. 2 is a schematic configuration diagram of an abrasion resistance evaluation apparatus used for evaluating the abrasion resistance of the ceramics for decorative parts according to the first and second embodiments.
  • the wear resistance evaluation apparatus 10 is connected to a nylon thread 12, a plurality of pulleys 13 that apply tension to the thread 12 at a predetermined position, and a pulley 13a that is one of the pulleys 13, and the thread 12 is indicated by an arrow. It consists of a motor (not shown) that travels in the direction and a water tank 14 that attaches muddy water to the thread 12, and a load corresponding to the mass of the weight 15 is applied. It is structured to slide on the outer peripheral surface of a cylindrical decorative part ceramic 11 fixed with a jig (not shown) or the like, and the number of nylon threads 12 may be, for example, 3 .
  • Conditions for evaluating the wear resistance of the ceramic 11 for decorative parts using this wear resistance evaluation apparatus 10 are, for example, that the mass of the weight 15 is 500 g and the thread 12 is a cylindrical ceramic 11 for decorative parts.
  • the speed of sliding on the outer periphery of the thread 12 may be set to 60 m / min, and the traveling distance of the yarn 12 may be set to 3000 m or more.
  • the deepest part of the scratches caused by the wear of the cylindrical ceramics 11 for decorative parts was measured with a surface shape measuring microscope (measurement part VF-7510 / controller VF made by Keyence). -7500), and the wear resistance can be evaluated by comparing the measured values.
  • the ceramic for decorative parts of the embodiment is characterized by comprising ceramics for decorative parts of the first and second embodiments, and examples thereof include a watch case and a watch band piece.
  • the ceramics for decorative parts of the first and second embodiments have a small color difference between products. Therefore, when used in a watch case or a watch band piece, the aesthetics of the parts due to color variations between parts when assembled. There is no loss, it has a sense of unity in color, it can fully obtain a high-class feeling and aesthetic satisfaction as a watch, and can obtain mental comfort through vision. Furthermore, in the case of the ceramic for decorative parts of the first embodiment, since the main component of the ceramic binder phase is zirconia, cobalt, nickel and chromium, it can be worn for a long period of time because of its high corrosion resistance. The product is not discolored and the quality is not reduced. Further, when the binder phase does not contain nickel, nickel allergy is less likely to occur.
  • the main component of the ceramic binder phase is cobalt, chromium, niobium, molybdenum and zirconia, it has high corrosion resistance, so it can be worn for a long time. However, the product does not change color and the sense of quality does not deteriorate.
  • FIG. 3 shows an example of a watch case which is a ceramic for decorative parts according to the first and second embodiments
  • (a) is a perspective view of the watch case as viewed from the front side
  • (b) It is the perspective view which looked at the case for timepieces of (a) from the back side.
  • FIG. 4 is a schematic view showing an example of the configuration of a watch band that is a decorative part for watch of the present invention.
  • symbol is attached
  • a watch case 20A shown in FIG. 3 includes a recess 21 for housing a movement (drive mechanism) (not shown) and a foot 22 for fixing a watch band (not shown) for mounting the watch on an arm.
  • the concave portion 21 includes a thin bottom portion 23 and a thick trunk portion 24.
  • the band piece which comprises the band 50 for timepieces shown in FIG. 4 is arrange
  • the pin 40 is inserted into the through hole 31 of the middle piece 30 and both ends of the inserted pin 40 are inserted into the pin holes 32 of the outer piece 33,
  • the piece 30 and the outer piece 33 are sequentially connected to form a watch band 50.
  • the watch decorative parts of the present invention used as the band pieces constituting the watch cases 20A and 20B and the watch band 50 are made of the ceramics for decorative parts of the present invention, a high-class feeling as a watch. , You can get enough aesthetic satisfaction and you can get mental comfort through vision.
  • titanium carbide which is a main component in the sintered body, and at least one of zirconium, cobalt and nickel and chromium powder is weighed.
  • Pulverized and mixed to prepare a blended raw material More specifically, titanium carbide powder having an average particle diameter of 10 to 30 ⁇ m, zirconium oxide (zirconia) powder having an average particle diameter of 0.2 ⁇ m to 2 ⁇ m, and cobalt and nickel having an average particle diameter of 1 to 20 ⁇ m.
  • the grinding / mixing time may be 50 hours or more. At this time, silicon, phosphorus, sulfur, manganese, iron, and the like are listed as inevitable impurities in the blended raw material, but these may have an adverse effect on the color of the decorative surface. Is preferred.
  • the titanium carbide powder may be TiC having a stoichiometric composition or TiC 1-x N x (0 ⁇ x ⁇ 0.2) having a non-stoichiometric composition. From the viewpoint of color tone with high quality and decorative value, the purity of each powder is preferably 99% or more, and titanium carbide powder partially reacts with cobalt powder to produce a small amount of compounds such as Co 3 Ti It doesn't matter what. In particular, in order to satisfy 0 ⁇ x ⁇ 0.2 when the composition formula is TiC 1-x N x for the titanium carbide sintered body constituting the ceramic for decorative parts, the titanium carbide powder has the composition formula of TiC 1-x When N x , 0 ⁇ x ⁇ 0.3 may be used.
  • a predetermined amount of paraffin wax is added as a binder, and a desired molding method such as dry pressure molding method, cold static It is formed into a desired shape such as a disk, flat plate, or torus by a hydraulic pressure molding method, extrusion molding method, or the like.
  • the molding pressure affects the open porosity and Vickers hardness (Hv) on the decorative surface, so that the molding pressure is preferably 49 to 196 MPa.
  • the molding pressure is set to 49 to 196 MPa because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and a Vickers hardness (Hv) can be set to 8 GPa or more. It is.
  • the life of the mold can be extended.
  • the obtained molded body is degreased in a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary, and then fired in an inert gas atmosphere or a vacuum, and the relative density with respect to the theoretical density is 95%.
  • a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary
  • fired in an inert gas atmosphere or a vacuum and the relative density with respect to the theoretical density is 95%.
  • the above sintered body is obtained.
  • firing in an inert gas atmosphere or in a vacuum is because, when firing in an oxidizing atmosphere, titanium carbide is oxidized and most of the titanium oxide is represented by the composition formula TiO 2. This is because the overall color tone of the ceramic for decorative parts is whitish.
  • the degree of vacuum is preferably 5 Pa or less.
  • the reason why the degree of vacuum is 5 Pa or less is that titanium carbide does not oxidize during firing, and thus a silver-colored ceramic for decorative parts is obtained.
  • the firing temperature is preferably 1200 to 1600 ° C. This is because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and the firing cost can be reduced.
  • the surface of the sintered body is subjected to grinding using a grinder on the surface where the decorative value of the sintered body is required, and then the barrel is polished so that the surface of the sintered body has a silver color tone.
  • the ceramic for decorative parts of the first embodiment can be obtained.
  • the pores appearing on such a decorative surface have a maximum diameter of 30 ⁇ m or less, and by setting this range, adhesion of germs, foreign matters, contaminants, etc. into the pores is possible. Can be reduced.
  • a rotating barrel polishing machine In barrel polishing, a rotating barrel polishing machine is used. Alumina, green carborundum (GC), or the like as media is introduced into the rotating barrel polishing machine together with an appropriate amount of water, and the wet polishing is performed for 24 to 150 hours.
  • GC green carborundum
  • titanium carbide which is a main component in the sintered body and each powder of cobalt, chromium and niobium are weighed, pulverized and mixed. Use as a blended raw material. More specifically, titanium carbide powder having an average particle diameter of 10 to 30 ⁇ m, cobalt powder having an average particle diameter of 1 to 20 ⁇ m, chromium powder having an average particle diameter of 3 to 70 ⁇ m, or a composition formula of Cr 3 Chromium carbide powder having an average particle size of 3 to 60 ⁇ m expressed as C 2 and niobium powder having an average particle size of 20 to 50 ⁇ m are prepared.
  • Cobalt powder is 5 to 25% by mass, chromium or chromium carbide. These powders may be weighed, pulverized and mixed so that the powder is 1 to 10% by mass, the niobium powder is 2 to 10% by mass, and the balance is titanium carbide.
  • the grinding / mixing time may be 50 hours or more. At this time, silicon, phosphorus, sulfur, manganese, iron, and the like are listed as inevitable impurities in the blended raw material, but these may have an adverse effect on the color of the decorative surface. Is preferred.
  • the titanium carbide powder may be TiC having a stoichiometric composition or TiC 1-x N x (0 ⁇ x ⁇ 0.2) having a non-stoichiometric composition. From the viewpoint of color tone with high quality and decorative value, the purity of each powder is preferably 99% or more, and titanium carbide powder partially reacts with cobalt powder to produce a small amount of compounds such as Co 3 Ti It doesn't matter what. In particular, in order to satisfy 0 ⁇ x ⁇ 0.2 when the composition formula is TiC 1-x N x for the titanium carbide sintered body constituting the ceramic for decorative parts, the titanium carbide powder has the composition formula of TiC 1-x When N x , 0 ⁇ x ⁇ 0.3 may be used.
  • a predetermined amount of paraffin wax is added as a binder, and a desired molding method such as dry pressure molding method, cold static It is formed into a desired shape such as a disk, flat plate, or torus by a hydraulic pressure molding method, extrusion molding method, or the like.
  • the molding pressure affects the open porosity and Vickers hardness (Hv) on the decorative surface, so that the molding pressure is preferably 49 to 196 MPa.
  • the molding pressure is set to 49 to 196 MPa because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and a Vickers hardness (Hv) can be set to 8 GPa or more. It is.
  • the life of the mold can be extended.
  • the obtained molded body is degreased in a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary, and then fired in an inert gas atmosphere or a vacuum, and the relative density with respect to the theoretical density is 95%.
  • a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary
  • fired in an inert gas atmosphere or a vacuum and the relative density with respect to the theoretical density is 95%.
  • the above sintered body is obtained.
  • firing in an inert gas atmosphere or in a vacuum is because, when firing in an oxidizing atmosphere, titanium carbide is oxidized and most of the titanium oxide is represented by the composition formula TiO 2. This is because the overall color tone of the ceramics for decorative parts becomes whitish.
  • the degree of vacuum is preferably 5 Pa or less.
  • the reason why the degree of vacuum is 5 Pa or less is that titanium carbide does not oxidize during firing, and thus a silver-colored ceramic for decorative parts is obtained.
  • the firing temperature is preferably 1200 to 1600 ° C. This is because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and the firing cost can be reduced.
  • the surface of the sintered body is subjected to grinding using a grinder on the surface where the decorative value of the sintered body is required, and then the barrel is polished so that the surface of the sintered body has a silver color tone.
  • the ceramic for decorative parts of the second embodiment can be obtained.
  • the pores appearing on such a decorative surface have a maximum diameter of 30 ⁇ m or less, and by setting this range, adhesion of germs, foreign matters, contaminants, etc. into the pores is possible. Can be reduced.
  • a rotating barrel polishing machine In barrel polishing, a rotating barrel polishing machine is used. Alumina, green carborundum (GC), or the like as media is introduced into the rotating barrel polishing machine together with an appropriate amount of water, and the wet polishing is performed for 24 to 150 hours.
  • GC green carborundum
  • the decorative part ceramic of the second embodiment contains molybdenum, titanium carbide powder having an average particle diameter of 10 to 30 ⁇ m, cobalt powder having an average particle diameter of 1 to 20 ⁇ m, and an average particle diameter 3 to 70 ⁇ m chromium powder or chromium carbide powder having an average particle size of 3 to 60 ⁇ m represented by the composition formula Cr 3 C 2 , niobium powder having an average particle size of 20 to 50 ⁇ m, and an average particle size 1 to 10 ⁇ m of molybdenum powder, cobalt powder 5 to 25% by mass, chromium or chromium carbide powder 1 to 10% by mass, niobium powder 2 to 10% by mass, molybdenum based on cobalt What is necessary is just to weigh and grind
  • the ceramic for decorative parts of the second embodiment contains zirconia, titanium carbide powder having an average particle diameter of 10 to 30 ⁇ m, cobalt powder having an average particle diameter of 1 to 20 ⁇ m, and an average particle diameter 3 to 70 ⁇ m chromium powder or chromium carbide powder having an average particle size of 3 to 60 ⁇ m represented by the composition formula Cr 3 C 2 , niobium powder having an average particle size of 20 to 50 ⁇ m, and an average particle size 1-10 ⁇ m molybdenum powder and zirconia powder having an average particle size of 0.2-2 ⁇ m, cobalt powder 5-25% by mass, chromium or chromium carbide powder 1-10% by mass, niobium 2 to 10% by weight of the powder, the ratio of molybdenum to cobalt is 35% or less, the powder of 9 to 30% by weight of zirconia, the balance being titanium carbide powder, and the total of cobalt, chromium, niobium, zir
  • the ceramics for decorative parts of the first and second embodiments obtained as described above exhibit a highly evaluated silver color as a particularly beautiful color tone, have a high-class feeling, and can obtain aesthetic satisfaction, and as a result.
  • fishing line guide decorative parts such as fishing line guides
  • operation buttons such as number keys
  • Living items such as decorative parts for mobile terminals such as frame parts for fixing cases and displays, faucets and toiletries in bathrooms or washrooms, spoons, forks, butter knives, fountain pen stationery, stamps, business cards, cremation accessory Clasps for decorative parts, brooches, necklaces, earrings, rings, tie pins, tie tacks, buttons, initial logos, bags, etc.
  • Decorative parts for accessories such as PDAs (Personal Digital Assistants: Personal Information Equipment) such as operation buttons such as number keys and various input keys, frame parts for fixing the display, etc.
  • Operation buttons such as input keys, cases, decorative parts for portable music players such as frame parts that fix the display, decorative parts for casings of portable data storage devices, tiles, handles, garden stones, display boards, roads
  • Decorative parts for building materials such as guide markers for fishing, decorative parts such as fishing equipment, golf clubs, poker chips, shogi pieces, sports equipment such as shoji stones, and entertainment items, string pieces, protective plates for guitars, violins
  • Decoration parts such as musical instrument parts such as bow handles, earphones, and speaker boxes or audio equipment parts, and parts included in the mouth such as crowns and mouthpieces for musical instruments
  • it can also be suitably used as a ceramic for decorative parts that produces a beautiful silver color tone used for decorative parts for automobiles such as disc brake pads, handles, and emblems.
  • Example 1 First, titanium carbide powder (purity 99%, average particle size 22.3 ⁇ m), zirconia powder (purity 99% or more, average particle size 1.5 ⁇ m), cobalt powder (purity 99% or more, average particle size 1.3 ⁇ m) or nickel powder ( Weigh 99% or more of purity, average particle size 12.8 ⁇ m) and chromium powder (purity 99%, average particle size 55 ⁇ m) so that the ratio (content) in the sintered body is the ratio shown in Table 1, It mixed and it was set as the preparation raw material.
  • titanium carbide powder purity 99%, average particle size 22.3 ⁇ m
  • zirconia powder purity 99% or more, average particle size 1.5 ⁇ m
  • cobalt powder purity 99% or more, average particle size 1.3 ⁇ m
  • nickel powder Weigh 99% or more of purity, average particle size 12.8 ⁇ m
  • chromium powder purity 99%, average particle size 55 ⁇ m
  • an isopropanol solution is added to each of the prepared raw materials, pulverized and mixed for 72 to 96 hours using a vibration mill, and then 3 parts by weight of paraffin wax as a binder is added to the prepared raw materials. Were dried into granules. And the obtained granule was pressure-molded with the pressure of 98 Mpa, and the molded object was produced. Next, this molded body was degreased at 400 ° C. in a vacuum atmosphere and then fired by holding at 1300-1600 ° C. for 2 hours to obtain a cylindrical sintered body having a diameter of 10 mm and a height of 10 mm. It was.
  • First Embodiment Sample No. which is a ceramic for decorative parts. Samples 3-6, 9-12, 15-18, 21-24, 27-30, 32 and 33, and 1, 2, 7, 8, 13, 14, 19, 20, 25, 26 as comparative examples , 31 and 34 ceramics for decorative parts made of sintered titanium carbide were obtained.
  • a questionnaire survey was conducted on 40 monitors, 5 men and women for each age group in their 20s and 50s, to see if they felt color irregularities by arranging samples on a black table, and 3 people felt color irregularities. ⁇ if the number of people is less than one name, ⁇ if the number of people who feel uneven color is 4-10 people, can be used and judged as acceptable, and ⁇ if the number of people who feel uneven color is more than 11 people, cannot be used It was rejected.
  • chipping when lapping of 10 samples is finished, if there are 2 or less chippings with a length of 0.5mm or more on the front and back edges, 2 is a total. When the number was 4 or less, it was judged as “good” as “good” and judged as acceptable.
  • a watch case shown in FIG. 1 assembled with the watch band shown in FIG. 3 was manufactured, and a total of 40 men and women of each age group in their 20s to 50s. After the monitor has been worn for 300 hours (about 30 days), place the watch case and watch band at a position 30 to 40 cm away from the eyes. Is marked ⁇ , and when 6 or more and 10 or less monitors visually found a flaw, it was marked as ⁇ , and each was judged acceptable and passed, and 11 or more monitors found a flaw visually. As unusable and rejected.
  • sample No. 1 was used using the wear resistance evaluation apparatus shown in FIG. Place a cylindrical ceramics for decorative component of 1-24 (in FIG. 2, the position of the ceramics for decorative component 11) was fixed by a jig, the semi-porcelain earth in water 0.001 m 3 (in clay 10 g of clay mixed with porcelain earth) was added and mixed to prepare muddy water in the water tank 14.
  • the mass of the weight 15 is set to 500 g
  • the speed at which the thread 12 slides on the outer peripheral side of the cylindrical ceramic for decorative parts is set to 60 m / min
  • the traveling distance of the thread 12 is set to 3000 m.
  • the adhered nylon thread 12 (Toray made silver scale ⁇ 3) was slid on the outer peripheral side of the cylindrical ceramic for decorative parts. Then, using the surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF-7500), the deepest part of the flaw caused by the wear of the cylindrical ceramics for decorative parts by sliding the thread 12 was measured, and the average value of 6 samples was calculated as the wear depth. And if the wear depth is less than 10 ⁇ m, the wear mark is inconspicuous, so it can be used as ⁇ , and it is judged as acceptable, and if the wear depth exceeds 10 ⁇ m, the wear mark is conspicuous and cannot be used as x. did. The results are shown in Table 1.
  • sample No. 1,2,7,8,13,14,19,20,25,26,31 and 34 are rated as x for color unevenness, chipping, scratch resistance, and abrasion resistance. It was not possible to form a beautiful silver decorative surface that would provide aesthetic satisfaction and mental comfort.
  • the sample No. which is a sample within the range of the first embodiment. 3 to 6, 9 to 12, 15 to 18, 21 to 24, 27 to 30, 32, and 33 are ⁇ or ⁇ for color unevenness, chipping, scratch resistance, and abrasion resistance, and a sense of luxury, aesthetic satisfaction, and It was possible to form a beautiful silver-colored decorative surface that provides mental comfort.
  • sample No. 1 and 2 have a low cobalt content of less than 5% by mass, and it is difficult to wet the surface of the titanium carbide crystal particles uniformly during sintering. It can be seen that the color unevenness has increased because the mirror surface has become rough due to shedding. In addition, because the crystal grains of titanium carbide are easy to fall off, the corners of the sample become brittle and chipping is likely to occur. It turns out that it fell. Sample No. No. 7 has a cobalt content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increased and scratch resistance decreased, resulting in a rough mirror surface and increased color unevenness. I understand.
  • sample No. which is an example of the first embodiment is used.
  • the cobalt content is in the range of 5 to 25% by mass, titanium carbide is less likely to be crushed, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that no degranulation marks remained and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
  • sample No. 8 has a chromium content of less than 1% by mass, so that a chromium oxide film cannot be sufficiently formed on the surface of the ceramic, resulting in a decrease in corrosion resistance. For this reason, the surface of the sample reacts with a grinding liquid or a cleaning liquid. It is thought that the color unevenness became large due to the adhesion of water scale during drying.
  • Sample No. No. 13 has a chromium content exceeding 10% by mass, so that the binder phase becomes too hard and the titanium carbide crystal particles are easily grained, the mirror surface becomes rough and the color unevenness is large. It can be seen that the corner portion of the sample becomes brittle and chipping is likely to occur, and the degranulation trace remains in a streak shape even in the flat portion of the sample, and the scratch resistance is lowered.
  • sample No. which is the sample of the first embodiment.
  • the chromium content is in the range of 1 to 10% by mass, it can be seen that a chromium oxide film was formed on the ceramic surface and the color tone was stabilized.
  • the binder phase is kept at an appropriate hardness, it can be seen that titanium carbide degranulation was suppressed, and that chipping and scratch resistance were evaluated favorably.
  • Sample No. which is a comparative example for zirconia. 14 has a low zirconia content of less than 9% by mass, so there are not enough zirconia particles on the surface of the ceramics, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase when the fishing line slides. It is thought that the amount of wear increased because of this.
  • Sample No. 19 since the content of zirconia exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic becomes large. It can be seen that cracks remained in the ceramic and chipping, scratch resistance, and wear resistance were lowered.
  • sample No. which is the sample of the first embodiment. 15 to 18, since the content of zirconia is in the range of 9 to 30% by mass, even if titanium carbide and the binder phase are worn when the fishing line slides, the zirconia crystal particles are projected on the surface. From the remaining contact with the fishing line, it can be seen that the oxidation of titanium carbide and the binder phase slowed down and the wear was suppressed.
  • sample No. 20 has a nickel content of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. Therefore, densification does not proceed and the titanium carbide crystal particles are shattered during processing. It can be seen that the color unevenness increased because the mirror surface was rough. In addition, because the titanium carbide crystal grains are easy to shed, the corners of the sample became brittle and chipping was likely to occur, so the degranulation traces remained streaks even in the flat part of the sample, resulting in scratch resistance and wear resistance. It can be seen that and decreased. Sample No. No. 25 has a nickel content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increases and scratch resistance decreases, resulting in a rough mirror surface and uneven color. I understand that.
  • sample No. which is an example of the first embodiment is used.
  • the nickel content is in the range of 5 to 25% by mass, titanium carbide is less likely to be granulated, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that no degranulation marks remained and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
  • sample No. 26 has a total content of at least one of cobalt and nickel of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. It can be seen that the color unevenness has increased because the crystal grains of titanium carbide have fallen and the mirror surface has become rough. In addition, because the crystal grains of titanium carbide are easy to shed, the corners of the sample became brittle and chipping was likely to occur, so the degranulation traces remained streaks even in the flat part of the sample, resulting in scratch resistance and wear resistance. It can be seen that and decreased. Sample No. Since the total content of cobalt and nickel exceeds 25% by mass, the proportion of the binder phase on the ceramic surface increases and scratch resistance decreases, resulting in a rough mirror surface and large color unevenness. You can see that
  • sample No. which is an example of the first embodiment is used.
  • the total content of cobalt and nickel is in the range of 5-25% by mass, so that titanium carbide is less likely to fall apart, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that there was no degranulation trace in the flat part, and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
  • the total content of zirconia, cobalt, nickel and chromium is 50% by mass or more, so the amount of titanium carbide on the surface is reduced, the surface is easily scratched, and the wear resistance is also reduced. .
  • sample No. which is an example of the first embodiment is used.
  • sample No. which is an example of the first embodiment is used.
  • the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass
  • the content of titanium carbide is 50% by mass or more
  • the hardness is maintained, and scratch resistance and abrasion resistance are maintained. It turns out that it became ceramics excellent in property.
  • Example 2 A test was conducted to confirm the change in characteristics by changing the ratio of molybdenum to cobalt.
  • titanium carbide powder (purity 99%, average particle size 22.3 ⁇ m), zirconia powder (purity 99% or more, average particle size 1.5 ⁇ m), cobalt powder (purity 99% or more, average particle size 1.3 ⁇ m) and nickel powder ( Purity 99% or more, average particle size 12.8 ⁇ m), chromium powder (purity 99%, average particle size 55 ⁇ m) and molybdenum powder (purity 99% or more, average particle size 3.3 ⁇ m) ratio in sintered body (content) Were weighed so that the ratio shown in Table 2 was obtained, and pulverized and mixed to prepare a blended raw material.
  • sample No. 1 was manufactured by the same manufacturing method as in Example 1. Ceramics for decorative parts made of 35-50 sintered titanium carbide were obtained.
  • sample no. In 40, 45, and 50 since the ratio of molybdenum to at least one of cobalt and nickel exceeds 35%, a molybdenum-rich phase precipitates in the binder phase, resulting in a partially non-uniform structure. It can be seen that it became difficult to process the entire surface uniformly, and that the degranulation and chipping increased.
  • sample No. which is an example of the first embodiment is used.
  • the content ratio of molybdenum to cobalt is 35% or less, so that in addition to small color unevenness, the firing temperature is lowered and crystal grain growth occurs. It can be seen that degranulation and chipping are less likely to occur during processing.
  • the ratio of molybdenum to cobalt is 35% or less, it is possible to form a beautiful silver-colored decorative surface that can provide a higher-class feeling, aesthetic satisfaction, and mental comfort, and less uneven color. It can be seen that degranulation and chipping during mechanical processing were suppressed and the mechanical strength was maintained.
  • Example of the second embodiment (Example 3) First, titanium carbide powder (purity 99%, average particle size 22.3 ⁇ m), cobalt powder (purity 99% or more, average particle size 1.3 ⁇ m), chromium powder (purity 99%, average particle size 55 ⁇ m), niobium powder (purity 99.5) %, Average particle size 33 ⁇ m) was weighed so that the ratio (content) in the sintered body would be the ratio shown in Table 1, and pulverized and mixed to prepare a blended raw material.
  • an isopropanol solution is added to each of the prepared raw materials, pulverized and mixed for 72 to 96 hours using a vibration mill, and then 3 parts by weight of paraffin wax as a binder is added to the prepared raw materials. Were dried into granules. And the obtained granule was pressure-molded with the pressure of 98 Mpa, and the molded object was produced. Next, this molded body was degreased at 400 ° C. in a vacuum atmosphere and then fired by holding at 1300-1600 ° C. for 2 hours to obtain a cylindrical sintered body having a diameter of 10 mm and a height of 10 mm. It was.
  • Second Embodiment Sample No. which is a ceramic for decorative parts. Samples 53 to 56, 59 to 62, and 65 to 68, and ceramics for decorative parts made of titanium carbide sintered bodies 51, 52, 57, 58, 63, 64, and 69 were obtained as comparative examples.
  • titanium, cobalt, chromium and niobium constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide.
  • a questionnaire survey was conducted on 40 monitors, 5 men and women for each age group in their 20s and 50s, to see if they felt color irregularities by arranging samples on a black table, and 3 people felt color irregularities. ⁇ if the number of people is less than one name, ⁇ if the number of people who feel uneven color is 4-10 people, can be used and judged as acceptable, and ⁇ if the number of people who feel uneven color is more than 11 people, cannot be used It was rejected.
  • chipping when lapping of 10 samples is finished, if there are 2 or less chippings with a length of 0.5mm or more on the front and back edges, 2 is a total. When the number was 4 or less, it was judged as “good” as “good” and judged as acceptable.
  • a watch case shown in FIG. 1 assembled with the watch band shown in FIG. 3 was manufactured, and a total of 40 men and women of each age group in their 20s to 50s. After the monitor has been worn for 300 hours (about 30 days), place the watch case and watch band at a position 30 to 40 cm away from the eyes. ⁇ if there are 6 or more and 10 or less monitors visually found scratches, ⁇ if each is acceptable and judged to be acceptable, and 11 or more monitors find scratches visually As x, it was unusable and rejected. The results are shown in Table 3.
  • sample No. which is a comparative example. 51, 52, 57, 58, 63, 64, and 69 are rated as x for uneven color, chipping, and scratch resistance, and have beautiful silver color that gives a sense of luxury, aesthetic satisfaction, and mental comfort. A decorative surface could not be formed.
  • sample No. which is a sample within the range of the second embodiment. 3 to 6, 9 to 12, 15 to 18 are ⁇ or ⁇ in terms of color unevenness, chipping and scratch resistance, and form a beautiful silver decorative surface that gives a sense of luxury, aesthetic satisfaction and mental comfort. I was able to.
  • sample No. 51 and 52 have a cobalt content of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. Therefore, densification does not proceed, and the titanium carbide crystal particles are not processed during processing. It can be seen that the color unevenness has increased because the mirror surface has become rough due to shedding. In addition, because the crystal grains of titanium carbide are easy to shed, the corners of the sample became brittle and chipping was likely to occur. I understand. Sample No. No. 7 has a cobalt content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increased and scratch resistance decreased, resulting in a rough mirror surface and increased color unevenness. I understand.
  • sample No. which is an example of the second embodiment is used.
  • the cobalt content is in the range of 5 to 25% by mass, titanium carbide is less likely to be crushed, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that there was no degranulation trace and the ceramic was excellent in scratch resistance. Therefore, it can be seen that the color unevenness can be prevented from worsening due to mechanical factors such as grain separation and scarring of titanium carbide.
  • sample No. as a comparative example. 58 has a low chromium content of less than 1% by mass, so that a sufficient chromium oxide film cannot be formed on the ceramic surface, resulting in a decrease in corrosion resistance, and the surface of the sample reacts with grinding or cleaning liquid. It is thought that the color unevenness became large due to the adhesion of water scale during drying.
  • Sample No. No. 63 has a chromium content of over 10% by mass, so that the binder phase becomes too hard and the titanium carbide crystal particles are easily grained, the mirror surface is rough, and the color unevenness is large. It can be seen that the corner portion of the sample becomes brittle and chipping is likely to occur, and the degranulation trace remains in a streak shape even in the flat portion of the sample, and the scratch resistance is lowered.
  • sample No. which is the sample of the second embodiment.
  • the chromium content is in the range of 1 to 10% by mass, so that it can be seen that a chromium oxide film is formed on the ceramic surface and the color tone is stabilized.
  • the binder phase is kept at an appropriate hardness, it can be seen that titanium carbide degranulation is suppressed, and that chipping and scratch resistance are evaluated well.
  • sample No. as a comparative example.
  • the niobium content is less than 2% by mass, the chemical stability of the surface of the binder phase is lowered and the color is liable to be discolored, and the color tone of the ceramic varies and the color unevenness increases.
  • Sample No. 19 has a niobium content of more than 10% by mass, which increases the liquidus temperature of the binder phase, lowers the sinterability, and makes it easy for the grains of titanium carbide to fall. It can be seen that the surface becomes rough and uneven color occurs.
  • sample No. which is the sample of the second embodiment.
  • niobium content is in the range of 2 to 10% by mass
  • niobium is mainly dissolved in cobalt as the binder phase, so that the binder phase is maintained in a stable state on the ceramic surface.
  • the color tone was stable and no color unevenness occurred.
  • the bonding force between cobalt and titanium carbide is kept high, and it is understood that the titanium carbide is prevented from degranulating and the chipping and scratch resistance are evaluated well.
  • Example 4 A test was conducted to confirm the change in characteristics by changing the ratio of molybdenum to cobalt.
  • titanium carbide powder (purity 99%, average particle size 22.3 ⁇ m), cobalt powder (purity 99% or more, average particle size 1.3 ⁇ m), chromium powder (purity 99%, average particle size 55 ⁇ m), niobium powder (purity 99.5) %, Average particle size 33 ⁇ m) and molybdenum powder (purity 99% or more, average particle size 3.3 ⁇ m) are weighed, pulverized and mixed so that the ratio (content) in the sintered body is the ratio shown in Table 2. And used as a blended raw material.
  • sample No. 1 was manufactured by the same manufacturing method as in Example 3. Ceramics for decorative parts made of 70 to 75 titanium carbide sintered bodies were obtained.
  • Example 3 Thereafter, as in Example 3, the contents of titanium, cobalt, chromium and molybdenum constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide.
  • the sample No. In 75 since the ratio of molybdenum to cobalt exceeds 35%, a molybdenum-rich phase precipitates in the binder phase, resulting in a partially non-uniform structure, and the ceramic is processed uniformly throughout. It can be seen that threshing and chipping increased.
  • the firing temperature is lowered to suppress grain growth of the crystal grains. It can be seen that chipping is less likely to occur.
  • the ratio of molybdenum to cobalt is 35% or less, it is possible to form a beautiful silver-colored decorative surface that can provide a higher-class feeling, aesthetic satisfaction, and mental comfort, and less uneven color. It can be seen that degranulation and chipping during mechanical processing were suppressed and the mechanical strength was maintained.
  • Example 5 A test was conducted to confirm the change in characteristics due to the inclusion of zirconia.
  • titanium carbide powder (purity 99%, average particle size 22.3 ⁇ m), zirconia powder (purity 99% or more, average particle size 1.5 ⁇ m), cobalt powder (purity 99% or more, average particle size 1.3 ⁇ m), chromium powder ( Purity 99%, average particle size 55 ⁇ m), niobium powder (purity 99.5%, average particle size 33 ⁇ m) and molybdenum powder (purity 99% or more, average particle size 3.3 ⁇ m) ratio (content) in the sintered body 3 was weighed so as to have the ratio shown in FIG.
  • Example 3 the sample No. 1 was manufactured by the same manufacturing method as in Example 3. Ceramics for decorative parts made of 76 to 88 sintered titanium carbide were obtained.
  • Example 1 Thereafter, as in Example 1, the contents of titanium, zirconium, cobalt, chromium, niobium and molybdenum constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide, and zirconium was converted as zirconia (zirconium oxide).
  • sample No. 1 was used using the wear resistance evaluation apparatus shown in FIG. (2, positions of the ceramics for decorative component 11) 76 predetermined position a cylindrical ceramics for decorative component of ⁇ 88 was fixed by a jig, the semi-porcelain earth in water 0.001 m 3 (in clay 10 g of clay mixed with porcelain earth) was added and mixed to prepare muddy water in the water tank 14.
  • the mass of the weight 15 is set to 500 g
  • the speed at which the thread 12 slides on the outer peripheral side of the cylindrical ceramic for decorative parts is set to 60 m / min
  • the traveling distance of the thread 12 is set to 3000 m.
  • the adhered nylon thread 12 (Toray made silver scale ⁇ 3) was slid on the outer peripheral side of the cylindrical ceramic for decorative parts. Then, using the surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF-7500), the deepest part of the flaw caused by the wear of the cylindrical ceramics for decorative parts by sliding the thread 12 was measured, and the average value of 6 samples was calculated as the wear depth. And if the wear depth is less than 10 ⁇ m, the wear mark is inconspicuous, so it can be used as ⁇ , and it is judged as acceptable, and if the wear depth exceeds 10 ⁇ m, the wear mark is conspicuous and cannot be used as x. did. The results are shown in Table 5.
  • the sample No. In 76, 77 and 84 since the content of zirconia is as low as less than 9% by mass, there are not enough zirconia particles on the surface of the ceramic, and oxidation of titanium carbide and the binder phase occurs when the fishing line slides. It is thought that the effect of suppressing wear and wear decreased, and the amount of wear increased. Further, among the examples of the second embodiment, the sample No. In 82, since the content of zirconia exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic becomes large.
  • sample No. which is an example of the second embodiment is used. Since 78 to 81 and 85 to 87 have a zirconia content in the range of 9 to 30% by mass, the zirconia crystal particles remain on the surface even if the titanium carbide or the binder phase wears when the fishing line slides. Since this remains in the shape of a protrusion and comes into contact with the fishing line, it can be seen that the oxidation of titanium carbide and the binder phase slows down and wear is suppressed.
  • a fishing line guide ring that is a fishing line guide decorative part, and a fishing line guide and a watch decorative part provided with the fishing line guide ring.
  • a watch case or watch band piece When a watch case or watch band piece was made, it has excellent wear resistance and high hardness, so the surface is not easily scratched and the silver color can be maintained for a long time. It has been found that if decorative parts are used, it is possible to construct an attractive product that continues to give luxury, aesthetic satisfaction and mental comfort for a long time.
  • the ceramics for decorative parts using the first and second embodiments as described above are used as decorative parts for fishing line guides and decorative parts for watches, they exhibit a highly evaluated silver color as a beautiful color tone, and have a high-class feeling. Therefore, aesthetic satisfaction can be obtained, and as a result, mental comfort can be obtained through vision.

Abstract

Disclosed is a ceramic for decorative parts which has a silver color tone and can impart a sense of luxury, a feeling of aesthetic satisfaction and spiritual comfort, and which has excellent mechanical characteristics such as a high hardness and a high toughness and shows little color difference. Specifically disclosed is a ceramic for decorative parts comprising sintered titanium carbide, which contains 9 to 30 mass% inclusive of zirconia, 5 to 25 mass% inclusive of at least one of cobalt and nickel and 1 to 10 mass% inclusive of chromium, and in which the sum of the contents of zirconia, cobalt, nickel and chromium is less than 50 mass%, characterized in that chromium is dissolved together with cobalt or nickel to form a solid solution. Since zirconia inhibits the oxidation and abrasion of titanium carbide, it is possible to easily provide a sintered body having a high stability and a favorable silver color which can be used, even in sliding parts, over a long period of time without causing marked abrasion flaws.

Description

装飾部品用セラミックスおよび装飾部品Ceramics and decorative parts for decorative parts
　本発明は、装飾部品用セラミックスおよびこれを用いた装飾部品に関する。 The present invention relates to ceramics for decorative parts and decorative parts using the same.
　従来、銀色を呈する装飾部品用としてセラミック材料を用いたものが知られている。 Conventionally, one using a ceramic material for a decorative part having a silver color is known.
　しかしながら、銀やその合金、あるいは銀色を呈するメッキを施した金属材料は、いずれも硬度が低いことから、硬質物質との接触により、表面に傷が生じたり変形したりするという問題があった。最近では、このような問題を解決するために、種々の装飾部品用セラミックスが提案されている。 However, since silver, its alloys, or silver-plated metallic materials all have low hardness, there is a problem that the surface is scratched or deformed by contact with a hard substance. Recently, in order to solve such problems, various ceramics for decorative parts have been proposed.
　例えば、特許文献１では、炭窒化チタンと４ａ，５ａ，６ａ族の炭化物，窒化物，炭窒化物からなる硬質相が70～95％、鉄族金属からなる結合相が５～30％および結合相中に分散・固溶する４ａ，５ａ，６ａ族元素１～５％（以上、重量パーセント）および不可避不純物からなる超硬質合金が開示されている。 For example, in Patent Document 1, 70 to 95% of a hard phase composed of titanium carbonitride and 4a, 5a, and 6a group carbides, nitrides, and carbonitrides, 5 to 30% of a binder phase composed of an iron group metal, and a bond A super-hard alloy composed of 1 to 5% (more than weight percent) of group 4a, 5a and 6a elements dispersed and dissolved in the phase and unavoidable impurities is disclosed.
　また、特許文献２では、炭化タングステン、炭化タンタルおよび炭化チタンのうち１種または２種以上を主成分とし、これに、ＮｉおよびＣｏのうち１種もしくは２種を５～30％と、ＣｒおよびＣｒの炭化物のうち１種もしくは２種以上をＣｒ換算で２～15％（以上、重量％）とを含有させてなる超硬合金において、ＮｉおよびＣｏのうち１種もしくは２種を主成分とした結合相のＸ線回折における（１１１）面のピーク強度をＩ（111）、（２００）面のピーク強度をＩ（200）としたときに、次式
ＩＡ＝Ｉ（111）／Ｉ（200）
で表されるＩＡ値が5.0以上である装飾用超硬合金が開示されている。 In Patent Document 2, one or more of tungsten carbide, tantalum carbide, and titanium carbide are used as a main component, and one or two of Ni and Co are added at 5 to 30%, Cr and Cemented carbide containing 1 to 2 or more of Cr carbides in terms of Cr in an amount of 2 to 15% (more than weight%). One or more of Ni and Co as the main component When the peak intensity of the (111) plane in the X-ray diffraction of the bonded phase is I (111) and the peak intensity of the (200) plane is I (200), the following formula I A = I (111) / I ( 200)
A decorative cemented carbide having an IA value of 5.0 or more is disclosed.
　また、特許文献３では、炭化チタンを主体とする硬質相とＣｏおよびＮｉの１種または２種を主体とする結合相とからなる炭化チタン基サーメット合金であって、結合相中のＴｉおよびＭｏ含有量が0.85≦Ｍｏ(wt.%)／Ｔｉ(wt.%)、６wt.%≦Ｔｉ＋Ｍｏの条件を満足する炭化チタン基サーメット合金が開示されている。 Patent Document 3 discloses a titanium carbide-based cermet alloy composed of a hard phase mainly composed of titanium carbide and a binder phase mainly composed of one or two of Co and Ni, and includes Ti and Mo in the binder phase. A titanium carbide-based cermet alloy whose content satisfies the conditions 0.85 ≦ Mo (wt.%) / Ti (wt.%), 6 wt.% ≦ Ti + Mo is disclosed.
　さらに、特許文献４では、炭化チタンを分散粒子相とし、クロム，モリブデン，ニッケルを結合相とする銀色焼結合金であって、前記チタンを全量中炭化物に換算して58.1～90重量％、前記クロムを全量中炭化物に換算して１～15重量％、前記モリブデンを全量中炭化物に換算して３～32重量％、前記ニッケルを全量中１～20重量％からなるとともに、ＡＮＳＩ／ＡＳＴＭ　Ｂ276－54で規定される有孔度がＡ－２クラス以上である銀色焼結合金や、この銀色焼結合金がＷ、Ｎｂ、Ｃｏの１種又は２種以上を含むとともに、Ｗが全量中炭化物に換算して１重量％以下、Ｎｂが全量中炭化物に換算して1.7重量％以下、Ｃｏが全量中１重量％以下であるものが開示されている。 Further, Patent Document 4 discloses a silver sintered alloy having titanium carbide as a dispersed particle phase and chromium, molybdenum, nickel as a binder phase, and 58.1 to 90% by weight of the titanium converted into carbides in the total amount. Chromium is 1 to 15% by weight in terms of carbides, molybdenum is 3 to 32% by weight in terms of carbides, nickel is 1 to 20% by weight, and ANSI / ASTM B276- A silver sintered alloy having a porosity of A-2 class or higher as defined in 54, and this silver sintered alloy contains one or more of W, Nb and Co, and W is a total amount of carbides. 1% by weight or less in terms of conversion, Nb being 1.7% by weight or less in terms of carbide in the total amount, and Co being 1% by weight or less in the total amount are disclosed.
特開平７－173568号公報Japanese Unexamined Patent Publication No. 7-173568 特開平５－287432号公報Japanese Patent Laid-Open No. 5-287432 特開平６－172914号公報JP-A-6-172914 特許第3231873号公報Japanese Patent No. 3321873
　しかしながら、特許文献１に記載された超硬質合金では、その組成は非常に広範囲に示されているため、銀色以外の色調を有する材料になる場合がある。さらに、実施例に示された組成は硬質相がＴｉＣＮとＷＣとであり、結合相がＣｏとＮｉとの場合のみであるため、黒色を呈するＷＣの影響で黒みがかった色調となり、美しい銀色の色調ではないという問題があった。 However, the super-hard alloy described in Patent Document 1 has a very wide range of compositions, and thus may have a color tone other than silver. Furthermore, since the composition shown in the examples is only when the hard phase is TiCN and WC and the binder phase is Co and Ni, it becomes a blackish tone due to the influence of WC exhibiting black, and has a beautiful silver color. There was a problem that it was not a color tone.
　また、特許文献２に記載された超硬合金では、炭化チタンを主成分とする実施例は１種類しか示されていないため、美しい銀色の色調を有するセラミックスの組成の範囲が不明確であるという問題があった。 In addition, in the cemented carbide described in Patent Document 2, since only one type of example mainly composed of titanium carbide is shown, the range of the composition of ceramics having a beautiful silver color tone is unclear. There was a problem.
　また、特許文献３に記載された炭化チタン基サーメット合金では、実施例に示された組成は硬質相がＴｉＣとＷＣからなるため、黒色を呈するＷＣの影響で黒みがかった色調となり、美しい銀色の色調を有するセラミックスにはならないという問題があった。 In addition, in the titanium carbide-based cermet alloy described in Patent Document 3, the composition shown in the example has a hard phase composed of TiC and WC, and thus has a blackish tone due to the influence of WC that exhibits a black color. There was a problem that it was not a ceramic having a color tone.
　さらに、特許文献４に記載された銀色焼結合金では、近年の海洋での大物釣りブームによって、より優れた耐摩耗特性を有する釣り具に用いることができる銀色焼結合金が求められているという問題があった。 Furthermore, in the silver-colored sintered alloy described in Patent Document 4, a silver-colored sintered alloy that can be used for fishing gear having more excellent wear resistance characteristics is demanded by a large fishing boom in the recent ocean. There was a problem.
　本発明は、上記課題を解決すべく案出されたものであり、銀色の色調を有し、高級感，美的満足感および精神的安らぎが得られるとともに、耐食性に優れる装飾部品用セラミックスおよびこれを用いた釣糸案内用装飾部品を提供することを目的とする。 The present invention has been devised to solve the above-mentioned problems, and has a silvery color tone, which provides high-quality feeling, aesthetic satisfaction and mental comfort, and has excellent corrosion resistance and ceramics for decorative parts. An object of the present invention is to provide a decorative part for fishing line guide used.
　本発明の装飾部品用セラミックスは、炭化チタン質焼結体からなる装飾部品用セラミックスであって、ジルコニアが９質量％以上30質量％以下、コバルトおよびニッケルの少なくとも１種が５質量％以上25質量％以下、クロムが１質量％以上10質量％以下、ジルコニア、コバルト、ニッケルおよびクロムの合計が50質量％未満の含有量で含まれており、クロムがコバルトまたはニッケルと固溶していることを特徴とするものである。 The ceramic for decorative parts of the present invention is a ceramic for decorative parts comprising a titanium carbide sintered body, wherein zirconia is 9% by mass to 30% by mass, and at least one of cobalt and nickel is 5% by mass to 25% by mass. % Or less, chromium is contained in an amount of 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is dissolved in cobalt or nickel. It is a feature.
　本発明の装飾部品用セラミックスは、炭化チタン質焼結体からなる装飾部品用セラミックスであって、コバルトを５質量％以上２５質量％以下、クロムを１質量％以上１０質量％以下、ニオブを２質量％以上１０質量％以下の含有量で含み、クロムおよびニオブがコバルトと固溶していることを特徴とするものである。 The ceramic for decorative parts of the present invention is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, and niobium is 2 mass%. The chromium and niobium are contained in a solid solution with cobalt in a content of not less than 10% by mass and not more than 10% by mass.
　また、本発明の釣糸案内用装飾部品は、上記いずれかの構成の本発明の装飾部品用セラミックスからなることを特徴とするものである。 Further, the fishing line guiding decorative part of the present invention is characterized by comprising the ceramics for decorative part of the present invention having any one of the above-mentioned configurations.
　本発明の装飾部品用セラミックスによれば、炭化チタン質焼結体からなる装飾部品用セラミックスであって、ジルコニアが９質量％以上30質量％以下、コバルトおよびニッケルの少なくとも１種が５質量％以上25質量％以下、クロムが１質量％以上10質量％以下、ジルコニア、コバルト、ニッケルおよびクロムの合計が50質量％未満の含有量で含まれており、クロムがコバルトまたはニッケルと固溶していることから、ジルコニアが炭化チタンの酸化や磨耗を抑制するため、摺動部品に用いても磨耗痕が目立たず長期間使用することができ安定して好ましい銀色の焼結体が提供し易くなる。 According to the ceramic for decorative parts of the present invention, the ceramic for decorative parts made of a titanium carbide sintered body, wherein zirconia is 9% by mass or more and 30% by mass or less, and at least one of cobalt and nickel is 5% by mass or more. 25% by mass or less, chromium is 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is in solid solution with cobalt or nickel. Therefore, since zirconia suppresses oxidation and wear of titanium carbide, even when used for sliding parts, wear marks are not noticeable and can be used for a long period of time, and it becomes easy to provide a stable and preferable silver sintered body.
　本発明の装飾部品用セラミックスによれば、炭化チタン質焼結体からなる装飾部品用セラミックスであって、コバルトを５質量％以上25質量％以下、クロムを１質量％以上10質量％以下、ニオブを２質量％以上10質量％以下の含有量で含み、クロムおよびニオブがコバルトと固溶していることから、結合相と炭化チタンとの濡れ性が改善されて焼結性が向上するため、セラミックスの加工時に脱粒やチッピングが発生しにくくなる。 According to the ceramic for decorative parts of the present invention, it is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, niobium Since the chromium and niobium are in solid solution with cobalt, the wettability between the binder phase and titanium carbide is improved and the sinterability is improved. Shattering and chipping are less likely to occur during ceramic processing.
　また、本発明の釣糸案内用装飾部品によれば、本発明の装飾部品用セラミックスからなるときには、高級感や美的満足感といった視覚を通じた精神的安らぎを得ることができる。さらに、釣糸を案内する釣糸用ガイドリングに用いた場合に、釣糸に付着した細かい砂等に擦られても、高い硬度を有しているので表面に傷が付きにくく、銀色の色調を維持しつつ、長期間の使用に耐え易くなる。 Further, according to the fishing line guiding decorative part of the present invention, when it is made of the ceramic for decorative part of the present invention, it is possible to obtain mental comfort through sight such as luxury and aesthetic satisfaction. In addition, when used for a fishing line guide ring that guides the fishing line, even if it is rubbed against fine sand adhered to the fishing line, it has high hardness, so the surface is not easily scratched and the silver color tone is maintained. However, it becomes easy to endure long-term use.
本実施形態の釣糸案内用装飾部品である釣糸用ガイドリングおよびこの釣糸用ガイドリングを備えた釣糸用ガイドの一例を示し、（ａ）は釣糸用ガイドリングの平面図であり、（ｂ）は（ａ）の釣糸用ガイドリングを備えた釣糸用ガイドの斜視図である。An example of a fishing line guide ring and a fishing line guide provided with the fishing line guide ring, which are decorative parts for guiding a fishing line of the present embodiment, is shown. (A) is a plan view of the fishing line guide ring. It is a perspective view of the guide for fishing lines provided with the guide ring for fishing lines of (a). 本実施形態の装飾部品用セラミックスの耐磨耗性の評価に用いる耐磨耗性評価装置の概略構成図である。It is a schematic block diagram of the abrasion resistance evaluation apparatus used for evaluation of the abrasion resistance of the ceramics for decorative parts of this embodiment. 本実施形態の時計用装飾部品である時計用ケースの一例を示す、（ａ）は時計用ケースを表側から見た斜視図であり、（ｂ）は（ａ）の時計用ケースを裏側からみた斜視図である。An example of a watch case which is a decorative part for watch of the present embodiment is shown, (a) is a perspective view of the watch case seen from the front side, and (b) is a watch case of (a) seen from the back side. It is a perspective view. 本実施形態の時計用装飾部品である時計用バンドの構成の一例を示す模式図である。It is a schematic diagram which shows an example of a structure of the timepiece band which is the decorative component for timepieces of this embodiment.
　以下、本発明の装飾部品用セラミックスの実施の形態について説明する。
［第１の実施形態］
　第１の実施形態の装飾部品用セラミックスは、炭化チタン質焼結体からなる装飾部品用セラミックスであって、ジルコニアが９質量％以上30質量％以下、コバルトおよびニッケルの少なくとも１種が５質量％以上25質量％以下、クロムが１質量％以上10質量％以下、ジルコニア、コバルト、ニッケルおよびクロムの合計が50質量％未満の含有量で含まれており、クロムがコバルトまたはニッケルと固溶している。 Hereinafter, embodiments of the ceramic for decorative parts of the present invention will be described.
[First Embodiment]
The ceramic for decorative parts of the first embodiment is a ceramic for decorative parts made of a titanium carbide sintered body, wherein zirconia is 9% by mass to 30% by mass, and at least one of cobalt and nickel is 5% by mass. 25% by mass or less, chromium 1% by mass or more and 10% by mass or less, and the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, and chromium is dissolved in cobalt or nickel. Yes.
　第１の実施形態において、炭化チタン質焼結体とは、炭化チタン（ＴｉＣ）を主成分とする焼結体であり、ここでいう主成分とは、装飾部品用セラミックスを構成する全成分100質量％に対して、50質量％以上を占める成分である。この主成分である炭化チタンは、装飾品として良好な銀色を呈するとともに、強度や硬度等の機械的特性が高いという特徴を有していることから、第１の実施形態の炭化チタン質焼結体からなる装飾部品用セラミックスにおいては、炭化チタンを70質量％以上の含有量で含有させることが好適である。 In the first embodiment, the titanium carbide sintered body is a sintered body containing titanium carbide (TiC) as a main component, and the main component referred to here is all the components 100 constituting the ceramic for decorative parts. It is a component occupying 50% by mass or more with respect to mass%. Titanium carbide, which is the main component, exhibits a good silver color as a decorative product and has high mechanical properties such as strength and hardness, so that the titanium carbide sintered material of the first embodiment is used. In the ceramic for decorative parts made of a body, it is preferable to contain titanium carbide in a content of 70% by mass or more.
　また、ジルコニアは、釣糸などがセラミックスの表面に接触しながら移動したとき接触部の炭化チタンや結合相が酸化されて体積膨張しクラックや磨耗が進行するという問題を抑制しやすくなる。 Also, zirconia makes it easy to suppress the problem that when the fishing line or the like moves while contacting the surface of the ceramic, the titanium carbide and the binder phase in the contact portion are oxidized and volume expansion occurs, causing cracks and wear.
　第１の実施形態の装飾部品用セラミックスにおいて、ジルコニアの含有量を９質量％以上30質量％以下としたのは、釣糸などがセラミックスの表面に接触しながら移動すると摩擦により接触面の温度が上昇する場合があり、そこに水分が介在すると、接触面の炭化チタンや結合相が徐々に酸化して体積膨張し周囲の組織とクラックを生じて磨耗が進行するという問題を抑制するためである。釣糸などがセラミックスの表面を接触しながら移動して炭化チタンや結合相が磨耗しても、ジルコニアの結晶粒子は表面に突起状に残り、これが釣糸と接触することから、炭化チタンや結合相の酸化は進行が遅くなり磨耗も抑制される。ジルコニアが９質量％未満になると、セラミックスの表面に存在するジルコニアの結晶粒子の数が少なくなり、炭化チタンや結合相の酸化や磨耗を抑える効果が低下する傾向がある。一方、30質量％を超えると、焼結時のジルコニアの相変態に伴う体積膨張や体積収縮の変化量のセラミックス全体の体積に対する比率が大きくなり、焼結後のセラミックスにクラックが残留しやすくなるという傾向がある。 In the ceramic for decorative parts of the first embodiment, the content of zirconia is 9% by mass or more and 30% by mass or less because the temperature of the contact surface rises due to friction when the fishing line moves while contacting the ceramic surface. This is to suppress the problem that when the moisture is present in the surface, the titanium carbide and the binder phase on the contact surface are gradually oxidized to expand in volume, causing cracks in the surrounding structure and progressing wear. Even if the fishing line moves while contacting the surface of the ceramic and the titanium carbide or binder phase wears, the zirconia crystal particles remain on the surface as protrusions, which come into contact with the fishing line. Oxidation proceeds slowly and wear is suppressed. When the amount of zirconia is less than 9% by mass, the number of zirconia crystal particles present on the surface of the ceramic decreases, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase tends to be reduced. On the other hand, if it exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic increases, and cracks tend to remain in the sintered ceramic. There is a tendency.
　またコバルトおよびニッケルの少なくとも１種の含有量を５質量％以上25質量％以下としたのは、コバルトおよびニッケルの少なくとも１種が炭化チタンの結晶粒子の間で結合剤として均一に存在してセラミックスの強度を保つことができるとともに、硬度を保ち傷が付きにくいものとすることができる。コバルトおよびニッケルの少なくとも１種が５質量％未満になると、コバルトおよびニッケルの少なくとも１種が炭化チタンの結晶粒子の間で不足して組織が不均一となって強度が低下しやすくなり、他方で25質量％を超えると、セラミックスの硬度が低下して傷が付きやすくなる。 In addition, the content of at least one of cobalt and nickel is 5% by mass or more and 25% by mass or less because at least one of cobalt and nickel is present uniformly as a binder among the crystal grains of titanium carbide. It is possible to maintain the strength of the resin and to maintain the hardness and to prevent scratches. When at least one of cobalt and nickel is less than 5% by mass, at least one of cobalt and nickel is insufficient among the titanium carbide crystal particles, and the structure becomes non-uniform and the strength tends to decrease. If it exceeds 25% by mass, the hardness of the ceramic will be reduced and scratches will easily occur.
　特に、コバルトは耐食性が高いことに加えて、近年ヨーロッパなどの諸外国では金属アレルギー対策として特にニッケルの溶出が少ない材料が要望されていることから、その動向にも対応することができる。 In particular, in addition to the high corrosion resistance of cobalt, in recent years, there has been a demand for a material with low nickel elution as a countermeasure against metal allergies in other countries such as Europe.
　また、クロムの含有量を１質量％以上10質量％以下としたのは、コバルトおよびニッケルの少なくとも１種と炭化チタンとの濡れ性が高まり、焼結性が改善されるとともに、結合相の表面では空気中の酸素と結合して酸化クロムの皮膜が形成されて耐食性が増加し、コバルトおよびニッケルの少なくとも１種に適度に固溶して強度を保つことができるためである。クロムが１質量％未満になると、コバルトと炭化チタンとの濡れ性が低下して焼結性が悪くなることからボイドが発生しやすくなり、結合相の表面に酸化クロムの皮膜が形成されにくいため耐食性が低下する傾向があり、10質量％を超えると、結合相が硬くなりすぎるため強度が低下する傾向がある。クロムは、主に結合相の中でコバルトおよびニッケルの少なくとも１種に固溶しているが、一部が炭化物として存在してもよい。 In addition, the chromium content of 1% by mass or more and 10% by mass or less increases the wettability of at least one of cobalt and nickel with titanium carbide, improves the sinterability, and improves the surface of the binder phase. In this case, a chromium oxide film is formed by combining with oxygen in the air to increase the corrosion resistance, and it is possible to maintain the strength by appropriately dissolving in at least one of cobalt and nickel. If the chromium content is less than 1% by mass, the wettability between cobalt and titanium carbide decreases and the sinterability deteriorates, so voids are likely to occur, and it is difficult to form a chromium oxide film on the surface of the binder phase. There exists a tendency for corrosion resistance to fall, and when it exceeds 10 mass%, since a binder phase becomes hard too much, there exists a tendency for intensity | strength to fall. Chromium is mainly dissolved in at least one of cobalt and nickel in the binder phase, but a part thereof may exist as a carbide.
　また、ジルコニア、コバルト、ニッケルおよびクロムの含有量の合計を50質量％未満としたのは、残部の炭化チタンの含有量が50質量％以上となり、高硬度を保つことができ、表面が傷付きにくいためである。ジルコニア、コバルト、ニッケルおよびクロムの含有量の合計が50質量％以上になると、残部の炭化チタンの含有量が少なくなり硬度を保つことができずに表面が傷付きやすくなるという傾向がある。 Also, the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, the remaining titanium carbide content is 50% by mass or more, high hardness can be maintained, and the surface is scratched. This is because it is difficult. When the total content of zirconia, cobalt, nickel and chromium is 50% by mass or more, the content of the remaining titanium carbide tends to be reduced, and the surface cannot be maintained, and the surface tends to be damaged.
　また、クロムは、コバルトおよびニッケルの少なくとも１種と固溶していると、結合相の表面で酸化クロムの被膜を形成して、セラミックスの表面が腐食したり変色したりするという問題を抑制することができる。また、クロムは、一部が炭化クロムや窒化クロムなど他の化合物の状態で存在しても構わない。そして、クロムがコバルトおよびニッケルの少なくとも１種と固溶している状態は、試料をＸ線回折で分析して、コバルトおよびニッケルのピーク位置がクロムのピークの方向にシフトしていることを分析結果の画像にて、あるいはチャート紙に印刷して確認すればよい。 In addition, when chromium is in solid solution with at least one of cobalt and nickel, a chromium oxide film is formed on the surface of the binder phase, and the problem of corrosion or discoloration of the ceramic surface is suppressed. be able to. Further, chromium may partially exist in the form of another compound such as chromium carbide or chromium nitride. And when chromium is in solid solution with at least one of cobalt and nickel, the sample is analyzed by X-ray diffraction and the peak positions of cobalt and nickel are shifted in the direction of the chromium peak. What is necessary is just to confirm with the image of a result, or printing on chart paper.
　なお、第１の実施形態の装飾部品用セラミックスにおける装飾面とは、装飾部品の装飾的価値が要求される面を指し、全ての面を指すものではない。例えば、第１の実施形態の装飾部品用セラミックスを時計用ケースに用いる場合では、この時計用ケースの外側の面は、鑑賞の対象となるものでもあり装飾的価値が要求されるので装飾面である。 In addition, the decorative surface in the ceramic for decorative parts of the first embodiment refers to a surface where the decorative value of the decorative component is required, and does not indicate all surfaces. For example, in the case where the ceramic for decorative parts of the first embodiment is used for a watch case, the outer surface of the watch case is also an object of appreciation and requires a decorative value. is there.
　チタン，ジルコニウム，コバルト，ニッケルおよびクロムの含有量は、蛍光Ｘ線分析（ＸＲＦ）法を用いて測定することができる。具体的には、予め炭化チタン，ジルコニウム，コバルト，ニッケルおよびクロムの各元素の濃度の異なる混合粉末を少なくとも２種類以上用意して、それぞれプレス法により成形して標準試料とする。次に、これら各標準試料にＸ線を照射して、蛍光Ｘ線の強度と既知の濃度との関係から最小二乗法を用いて検量線を作成する。そして、第１の実施形態の装飾部品用セラミックスを粉砕して粉末とし、プレス法により成形して測定試料とする。この測定試料にＸ線を照射して、蛍光Ｘ線の強度を測定し、検量線より濃度である含有率を求める。また、チタン，コバルト，ニッケル，ジルコニウムおよびクロムの含有量は、ＩＣＰ（Inductively Coupled Plasma）発光分光分析法を用いて測定することもできる。具体的には、作製したセラミックスを放電プラズマで蒸発気化して励起し、励起した原子が低いエネルギー順位に戻るとき発する固有のスペクトルを測定することで原子の種類を特定し、その発光強度から各原子の定量分析をする。さらに、窒素については酸素・窒素分析装置で測定することができ、炭素は炭素分析装置で測定することができる。 The contents of titanium, zirconium, cobalt, nickel and chromium can be measured using a fluorescent X-ray analysis (XRF) method. Specifically, at least two types of mixed powders having different concentrations of each element of titanium carbide, zirconium, cobalt, nickel, and chromium are prepared in advance, and are each molded by a pressing method to obtain a standard sample. Next, each of these standard samples is irradiated with X-rays, and a calibration curve is created using the least square method from the relationship between the intensity of the fluorescent X-rays and the known concentration. And the ceramics for decorative parts of 1st Embodiment are grind | pulverized to make a powder, and it shape | molds by the press method to make a measurement sample. This measurement sample is irradiated with X-rays, the intensity of fluorescent X-rays is measured, and the concentration content is obtained from the calibration curve. The contents of titanium, cobalt, nickel, zirconium and chromium can also be measured using ICP (Inductively-Coupled-Plasma) emission spectroscopy. Specifically, the produced ceramics are vaporized and vaporized with discharge plasma and excited, and when the excited atoms return to a low energy level, the type of atoms is identified and the emission intensity is used to identify each type of atom. Quantitative analysis of atoms. Further, nitrogen can be measured with an oxygen / nitrogen analyzer, and carbon can be measured with a carbon analyzer.
　また、第１の実施形態の装飾部品用セラミックスは、モリブデンをコバルトに対して35質量％以下の含有量で含むことが好ましい。モリブデンがコバルトに対して35質量％以下の含有量で含まれると、焼成温度を下げることができて結晶粒の成長を抑制するため、加工時には脱粒やチッピングが生じにくくなり、美しい表面を有する装飾部材を作製することができる。また、モリブデンはコバルトおよびニッケルの少なくとも１種と共晶合金を形成するが、コバルトおよびニッケルの少なくとも１種に対して35質量％以上の含有量になると、結合相にモリブデンリッチな相が析出して製品を加工する時に脱粒やチッピングが生じやすくなり、表面が荒れて色調ばらつきの原因となる場合もある。 Moreover, the ceramic for decorative parts of the first embodiment preferably contains molybdenum in a content of 35% by mass or less with respect to cobalt. When molybdenum is contained in a content of 35% by mass or less with respect to cobalt, the firing temperature can be lowered and the growth of crystal grains is suppressed, so that the graining and chipping are less likely to occur during processing, and the decoration has a beautiful surface. A member can be produced. Molybdenum forms a eutectic alloy with at least one of cobalt and nickel, but when the content exceeds 35% by mass with respect to at least one of cobalt and nickel, a molybdenum-rich phase precipitates in the binder phase. When the product is processed, graining and chipping are likely to occur, and the surface may be rough and cause variations in color tone.
　また、第１の実施形態の装飾部品用セラミックスは、チタンを除く金属元素中にクロムを10質量％以上40質量％未満の含有量で含むときには、クロムはコバルトと炭化チタンとの結晶粒界に固溶して、結合相と炭化チタンとの濡れ性を改善して焼結性を向上する。クロムが10質量％未満であると、濡れ性を改善する効果が小さくなって焼結性が低下する傾向があり、40質量％を超えるとクロムリッチな相が現れて脱粒しやすくなり、ボイドが発生してセラミックスの表面を均一に美しく形成することが困難となりやすい。
［第２の実施形態］
　第２の実施形態の装飾部品用セラミックスは、炭化チタン質焼結体からなる装飾部品用セラミックスであって、コバルトを５質量％以上25質量％以下、クロムを１質量％以上10質量％以下、ニオブを２質量％以上10質量％以下の含有量で含み、クロムおよびニオブがコバルトと固溶していることを特徴とするものである。 Further, in the ceramic for decorative parts of the first embodiment, when chromium is contained in a metal element other than titanium in a content of 10% by mass or more and less than 40% by mass, chromium is present at the crystal grain boundary between cobalt and titanium carbide. Solid solution improves the wettability of the binder phase and titanium carbide to improve the sinterability. If the chromium content is less than 10% by mass, the effect of improving the wettability tends to be small and the sinterability tends to be reduced. If the chromium content exceeds 40% by mass, a chromium-rich phase appears and the particles are easily degranulated. It tends to be difficult to form a uniform and beautiful ceramic surface.
[Second Embodiment]
The ceramic for decorative parts of the second embodiment is a ceramic for decorative parts made of a titanium carbide sintered body, wherein cobalt is 5 mass% to 25 mass%, chromium is 1 mass% to 10 mass%, Niobium is contained in a content of 2% by mass or more and 10% by mass or less, and chromium and niobium are in solid solution with cobalt.
　第２の実施形態において、炭化チタン質焼結体とは、炭化チタン（ＴｉＣ）を主成分とする焼結体であり、ここでいう主成分とは、装飾部品用セラミックスを構成する全成分100質量％に対して、50質量％以上を占める成分である。この主成分である炭化チタンは、装飾品として良好な銀色を呈するとともに、強度や硬度等の機械的特性が高いという特徴を有していることから、第２の実施形態の炭化チタン質焼結体からなる装飾部品用セラミックスにおいては、炭化チタンを70質量％以上の含有量で含有させることが好適である。 In the second embodiment, the titanium carbide sintered body is a sintered body containing titanium carbide (TiC) as a main component, and the main component referred to here is all the components 100 constituting the ceramic for decorative parts. It is a component occupying 50% by mass or more with respect to mass%. Titanium carbide, which is the main component, exhibits a good silver color as a decorative product and has high mechanical properties such as strength and hardness, so that the titanium carbide sintered material of the second embodiment is used. In the ceramic for decorative parts made of a body, it is preferable to contain titanium carbide in a content of 70% by mass or more.
　またコバルトの含有量を５質量％以上25質量％以下としたのは、コバルトが炭化チタンの結晶粒子の間で結合剤として均一に存在してセラミックスの強度を保つことができるとともに、硬度を保ち傷が付きにくいものとすることができる。コバルトが５質量％未満になると、コバルトが炭化チタンの結晶粒子の間で不足して組織が不均一となって強度が低下しやすくなり、他方で25質量％を超えると、セラミックスの硬度が低下して傷が付きやすくなる。 In addition, the content of cobalt is set to 5% by mass or more and 25% by mass or less because cobalt can exist uniformly as a binder among the titanium carbide crystal particles to maintain the strength of the ceramic and maintain the hardness. It can be made difficult to scratch. When cobalt is less than 5% by mass, cobalt is insufficient between the titanium carbide crystal grains, and the structure becomes non-uniform and the strength tends to decrease. On the other hand, when it exceeds 25% by mass, the hardness of the ceramic decreases. And become easily scratched.
　特に、コバルトは耐食性が高いことに加えて、近年ヨーロッパなどの諸外国では金属アレルギー対策として特にニッケルの溶出が少ない材料が要望されていることから、その動向にも対応することができる。 In particular, in addition to the high corrosion resistance of cobalt, in recent years, there has been a demand for a material with low nickel elution as a countermeasure against metal allergies in other countries such as Europe.
　また、クロムの含有量を１質量％以上10質量％以下としたのは、コバルトと炭化チタンとの濡れ性が高まり、焼結性が改善されるとともに、結合相の表面では空気中の酸素と結合して酸化クロムの皮膜が形成されて耐食性が増加し、コバルトに適度に固溶して強度を保つことができるためである。クロムが１質量％未満になると、コバルトと炭化チタンとの濡れ性が低下して焼結性が悪くなることからボイドが発生しやすくなり、結合相の表面に酸化クロムの皮膜が形成されにくいため耐食性が低下し、10質量％を超えると、結合相が硬くなりすぎるため強度が低下しやすくなる。クロムは、主に結合相の中でコバルトに固溶しているが、一部が炭化物として存在してもよい。 The chromium content of 1% by mass or more and 10% by mass or less improves the wettability of cobalt and titanium carbide, improves the sinterability, and improves the oxygen content in the air on the surface of the binder phase. This is because the film is bonded to form a chromium oxide film and the corrosion resistance is increased. If the chromium content is less than 1% by mass, the wettability between cobalt and titanium carbide decreases and the sinterability deteriorates, so voids are likely to occur, and it is difficult to form a chromium oxide film on the surface of the binder phase. If the corrosion resistance decreases and exceeds 10% by mass, the binder phase becomes too hard and the strength tends to decrease. Chromium is mainly dissolved in cobalt in the binder phase, but a part thereof may exist as a carbide.
　また、クロムは、コバルトと固溶していると、結合相の表面で酸化クロムの被膜を形成して、セラミックスの表面が腐食したり変色したりするという問題を抑制することができる。また、クロムは、一部が炭化クロムや窒化クロムなど他の化合物の状態で存在しても構わない。そして、クロムがコバルトと固溶している状態は、試料をＸ線回折で分析して、コバルトのピーク位置がクロムのピークの方向にシフトしていることを分析結果の画像にて、あるいはチャート紙に印刷して確認すればよい。 Further, when chromium is in solid solution with cobalt, it is possible to suppress the problem that the surface of the ceramic is corroded or discolored by forming a chromium oxide film on the surface of the binder phase. Further, chromium may partially exist in the form of another compound such as chromium carbide or chromium nitride. The state in which chromium is in solid solution with cobalt is determined by analyzing the sample by X-ray diffraction and confirming that the peak position of cobalt is shifted in the direction of the peak of chromium in the analysis result image or chart. You can check by printing on paper.
　また、ニオブは、色調調整剤として作用する。また濡れ性を高める作用をするものであって、金属ニオブ以外に組成式が例えばＮｂＣｏ３あるいはＮｂＣで示されるニオブ化合物として存在するものも含む。 Niobium acts as a color tone adjusting agent. In addition to the metal niobium, it also has an effect of increasing wettability, and includes a niobium compound having a composition formula represented by, for example, NbCo 3 or NbC.
　また、ニオブの含有量を２質量％以上10質量％以下としたのは、ニオブが主にコバルトに固溶することによって、色調調整剤としての作用や炭化チタンとコバルトとの濡れ性を改善する作用がある反面、ニオブの含有量が多いと結合相の液相温度が高くなるため焼結性が低下するおそれがあるからである。 In addition, the content of niobium is 2% by mass or more and 10% by mass or less because niobium is mainly dissolved in cobalt to improve the action as a color adjusting agent and the wettability between titanium carbide and cobalt. On the other hand, if the content of niobium is large, the liquidus temperature of the binder phase becomes high, so that the sinterability may be lowered.
　また、ニオブの含有量は４質量％以上８質量％以下であることがより望ましい。これは、ニオブは粒成長を抑制するように働くので、結晶粒界は増加し、入射した光は装飾面を形成する結晶による鏡面反射と併せて結晶粒界による拡散反射の影響を強く受ける結果、装飾面の色調は光沢のある色調感が増し、さらに高級感，美的満足感を得ることができる。その結果、視覚を通じて精神的安らぎが得られるからである。 Further, the niobium content is more preferably 4% by mass or more and 8% by mass or less. This is because niobium works to suppress grain growth, so the crystal grain boundary increases, and the incident light is strongly influenced by diffuse reflection by the crystal grain boundary in addition to the specular reflection by the crystal forming the decorative surface. In addition, the color tone of the decorative surface increases the glossy color tone, and further, a high-class feeling and aesthetic satisfaction can be obtained. As a result, mental comfort can be obtained through vision.
　さらに、ニオブが主に結合相のコバルトの中に存在することにより、結合相が汗や唾液などに対する腐食に対して強くなるため、セラミックスの表面が安定した状態に維持されて色調も安定し、製品間の色むらを少なくすることができる。 Furthermore, since niobium is mainly present in the cobalt of the binder phase, the binder phase is strong against corrosion against sweat and saliva, so the surface of the ceramic is maintained in a stable state and the color tone is also stable. Color unevenness between products can be reduced.
　また、ニオブはタンタルに置換することも可能であり、その場合、タンタルの添加量は３質量％以上20質量％以下である。タンタルもニオブと同様の効果を有しており、結合相は腐食に対して強くなるが、材料が高価であることからコストに応じて用いることが好ましい。 Also, niobium can be replaced with tantalum, in which case the amount of tantalum added is 3% by mass or more and 20% by mass or less. Tantalum has the same effect as niobium, and the binder phase is strong against corrosion. However, since the material is expensive, it is preferably used according to the cost.
　さらに、ニオブはコバルトと化合してコバルトニオブ、例えばＮｂＣｏ３として析出していることが好適で、ＮｂＣｏ３の析出により、気品漂う明るさが醸し出される。このＮｂＣｏ３等のコバルトニオブは、Ｘ線回折法で検出することができる。 Furthermore, niobium is preferable that they are precipitated as cobalt niobium, for example NBCO 3 combines with cobalt by precipitation of NBCO 3, brightness drifting dignity exude. This cobalt niobium such as NbCo 3 can be detected by an X-ray diffraction method.
　なお、第２の実施形態の装飾部品用セラミックスにおける装飾面とは、装飾部品の装飾的価値が要求される面を指し、全ての面を指すものではない。例えば、第２の実施形態の装飾部品用セラミックスを時計用ケースに用いる場合では、この時計用ケースの外側の面は、鑑賞の対象となるものでもあり装飾的価値が要求されるので装飾面である。 In addition, the decorative surface in the ceramic for decorative parts of the second embodiment refers to a surface where the decorative value of the decorative component is required, and does not indicate all surfaces. For example, when the ceramic for decorative parts of the second embodiment is used for a watch case, the outer surface of the watch case is also an object of appreciation and requires a decorative value. is there.
　また、チタン，コバルト，クロムおよびニオブの含有量は、蛍光Ｘ線分析（ＸＲＦ）法を用いて測定することができる。具体的には、予めチタン，コバルト，クロムおよびニオブの各元素の濃度の異なる混合粉末を少なくとも２種類以上用意して、それぞれプレス法により成形して標準試料とする。次に、これら各標準試料にＸ線を照射して、蛍光Ｘ線の強度と既知の濃度との関係から最小二乗法を用いて検量線を作成する。そして、第２の実施形態の装飾部品用セラミックスを粉砕して粉末とし、プレス法により成形して測定試料とする。この測定試料にＸ線を照射して、蛍光Ｘ線の強度を測定し、検量線より濃度である含有率を求める。また、チタン，コバルト，クロムおよびニオブの含有量は、ＩＣＰ（Inductively Coupled Plasma）発光分光分析法を用いて測定することもできる。具体的には、作製したセラミックスを放電プラズマで蒸発気化して励起し、励起した原子が低いエネルギー順位に戻るとき発する固有のスペクトルを測定することで原子の種類を特定し、その発光強度から各原子の定量分析をする。さらに、炭素は炭素分析装置で測定することができる。 Further, the contents of titanium, cobalt, chromium and niobium can be measured using a fluorescent X-ray analysis (XRF) method. Specifically, at least two kinds of mixed powders having different concentrations of each element of titanium, cobalt, chromium, and niobium are prepared in advance, and are each molded by a pressing method to obtain a standard sample. Next, each of these standard samples is irradiated with X-rays, and a calibration curve is created using the least square method from the relationship between the intensity of the fluorescent X-rays and the known concentration. And the ceramics for decorative parts of 2nd Embodiment are grind | pulverized into powder, and it shape | molds by the press method, and is set as a measurement sample. This measurement sample is irradiated with X-rays, the intensity of fluorescent X-rays is measured, and the concentration content is obtained from the calibration curve. The contents of titanium, cobalt, chromium and niobium can also be measured using ICP (Inductively-Coupled-Plasma) emission spectroscopy. Specifically, the produced ceramics are vaporized and vaporized with discharge plasma and excited, and when the excited atoms return to a low energy level, the type of atoms is identified and the emission intensity is used to identify each type of atom. Quantitative analysis of atoms. Furthermore, carbon can be measured with a carbon analyzer.
　また、第２の実施形態の装飾部品用セラミックスは、モリブデンをコバルトに対して35質量％以下の含有量で含むことが好ましい。モリブデンがコバルトに対して35質量％以下の含有量で含まれると、焼成温度を下げることができて結晶粒の成長を抑制するため、加工時には脱粒やチッピングが生じにくくなり、美しい表面を有する装飾部材を作製することができる。また、モリブデンはコバルトおよびニッケルの少なくとも１種と共晶合金を形成するが、コバルトおよびニッケルの少なくとも１種に対して35質量％以上の含有量になると、結合相にモリブデンリッチな相が析出して製品を加工する時に脱粒やチッピングが生じやすくなり、表面が荒れて色調ばらつきの原因となる場合もある。 The ceramic for decorative parts of the second embodiment preferably contains molybdenum in a content of 35% by mass or less with respect to cobalt. When molybdenum is contained in a content of 35% by mass or less with respect to cobalt, the firing temperature can be lowered and the growth of crystal grains is suppressed, so that the graining and chipping are less likely to occur during processing, and the decoration has a beautiful surface. A member can be produced. Molybdenum forms a eutectic alloy with at least one of cobalt and nickel, but when the content exceeds 35% by mass with respect to at least one of cobalt and nickel, a molybdenum-rich phase precipitates in the binder phase. When the product is processed, graining and chipping are likely to occur, and the surface may be rough and cause variations in color tone.
　また、第２の実施形態の装飾部品用セラミックスは、チタンを除く金属元素中にクロムを10質量％以上40質量％未満の含有量で含むときには、クロムはコバルトと炭化チタンとの結晶粒界に固溶して、結合相と炭化チタンとの濡れ性を改善して焼結性を向上する。クロムが10質量％未満であると、濡れ性を改善する効果が小さくなって焼結性が低下し、40質量％を超えるとクロムリッチな相が現れて脱粒しやすくなり、ボイドが発生してセラミックスの表面を均一に美しく形成することが困難となりやすい。 Further, in the ceramic for decorative parts of the second embodiment, when chromium is contained in a metal element other than titanium in a content of 10% by mass or more and less than 40% by mass, chromium is present at the crystal grain boundary between cobalt and titanium carbide. Solid solution improves the wettability of the binder phase and titanium carbide to improve the sinterability. If the chromium content is less than 10% by mass, the effect of improving the wettability will be reduced and the sinterability will be reduced. If it exceeds 40% by mass, a chromium-rich phase will appear and it will be easy to degranulate, resulting in voids. It is difficult to form a uniform and beautiful ceramic surface.
　また、第２の実施形態の装飾部品用セラミックスは、ジルコニアを９質量％以上30質量％以下の含有量で含み、ジルコニア，コバルト，クロム，ニオブおよびモリブデンの合計が50質量％未満であることが好ましい。ジルコニアは、釣糸などがセラミックスの表面に接触しながら移動したとき、接触部の炭化チタンや結合相が酸化されて体積膨張してクラックや磨耗が進行するという問題を抑制する。 Moreover, the ceramic for decorative parts of the second embodiment includes zirconia in a content of 9% by mass to 30% by mass, and the total of zirconia, cobalt, chromium, niobium, and molybdenum is less than 50% by mass. preferable. Zirconia suppresses the problem that when a fishing line or the like moves while being in contact with the surface of the ceramic, the titanium carbide and the binder phase in the contact portion are oxidized and volume-expanded to cause cracks and wear.
　第２の実施形態の装飾部品用セラミックスにおいて、ジルコニアの含有量を９質量％以上30質量％以下としたのは、釣糸などがセラミックスの表面に接触しながら移動すると摩擦により接触面の温度が上昇する場合があり、そこに水分が介在すると、接触面の炭化チタンや結合相が徐々に酸化して体積膨張し、周囲の組織とクラックを生じて磨耗が進行するという問題を抑制するためである。釣糸などがセラミックスの表面を接触しながら移動して炭化チタンや結合相が磨耗しても、ジルコニアの結晶粒子は表面に突起状に残り、これが釣糸と接触することから、炭化チタンや結合相の酸化は進行が遅くなり、磨耗も抑制される。ジルコニアが９質量％未満になると、セラミックスの表面に存在するジルコニアの結晶粒子の数が少なくなり、炭化チタンや結合相の酸化や磨耗を抑える効果が低下する傾向がある。一方、30質量％を超えると、焼結時のジルコニアの相変態に伴う体積膨張や体積収縮の変化量のセラミックス全体の体積に対する比率が大きくなり、焼結後のセラミックスにクラックが残留しやすくなる。 In the ceramic for decorative parts of the second embodiment, the content of zirconia is set to 9% by mass or more and 30% by mass or less because the temperature of the contact surface rises due to friction when the fishing line moves while contacting the ceramic surface. This is to suppress the problem that when the moisture is present there, the titanium carbide and the binder phase on the contact surface gradually oxidize and expand in volume, causing cracks with the surrounding structure and progressing wear. . Even if the fishing line moves while contacting the surface of the ceramic and the titanium carbide or binder phase wears, the zirconia crystal particles remain on the surface as protrusions, which come into contact with the fishing line. Oxidation slows down and wear is suppressed. When the amount of zirconia is less than 9% by mass, the number of zirconia crystal particles present on the surface of the ceramic decreases, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase tends to be reduced. On the other hand, if it exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic increases, and cracks tend to remain in the sintered ceramic. .
　また、ジルコニア，コバルト，クロム，ニオブおよびモリブデンの含有量の合計を50質量％未満としたのは、残部の炭化チタンの含有量を多くすることができことから、高硬度を保つことができ、表面が傷付きにくいためである。ジルコニア，コバルト，クロム，ニオブおよびモリブデンの含有量の合計が50質量％以上になると、残部の炭化チタンの含有量が少なくなり、硬度を保つことができずに表面が傷付きやすくなるという問題がある。 In addition, the total content of zirconia, cobalt, chromium, niobium and molybdenum is less than 50% by mass because the content of the remaining titanium carbide can be increased, so that high hardness can be maintained, This is because the surface is hardly damaged. When the total content of zirconia, cobalt, chromium, niobium and molybdenum is 50% by mass or more, the content of the remaining titanium carbide decreases, and the surface cannot be maintained, and the surface is easily damaged. is there.
　次に、第１，第２の実施形態を用いた釣糸案内用装飾部品について説明する。 Next, the fishing line guiding decorative parts using the first and second embodiments will be described.
　第１，第２の実施形態の釣糸案内用装飾部品は、上記構成の第１，第２の実施形態の装飾品用セラミックスからなることを特徴とし、その具体的な例としては、釣糸用ガイドリングおよびこの釣糸用ガイドリングを備えた釣糸用ガイドがある。 The fishing line guiding decorative parts of the first and second embodiments are made of the ceramics for decorative products of the first and second embodiments having the above-described configuration, and specific examples thereof include a fishing line guide. There is a fishing line guide with a ring and this fishing line guide ring.
　第１，第２の実施形態の装飾部品用セラミックスは、釣糸用ガイドリングおよびこの釣糸用ガイドリングを備えた釣糸用ガイドに用いると、釣竿に釣糸用ガイドとして組み付けたときガイド間の色調バラツキによって美観を損ねることがなく、色調に統一感を有しており、釣竿としての高級感，美的満足感を十分に得ることができ、視覚を通じて精神的安らぎを得ることができる。 When the ceramics for decorative parts of the first and second embodiments are used for a fishing line guide ring and a fishing line guide provided with the fishing line guide ring, when assembled as a fishing line guide on a fishing rod, the color variation between the guides It does not impair the aesthetic appearance, has a unified sense of color, can provide a high-class feeling as a fishing rod, aesthetic satisfaction, and can provide mental comfort through vision.
　さらに、第１の実施形態の釣糸案内用装飾部品は、セラミックスの結合相の主成分がジルコニア，コバルト，ニッケルおよびクロムであることから、耐食性も高いため、長期間釣竿に使用しても製品が変色して高級感が低下することはない。また、第２の実施形態の釣糸案内用装飾部品は、セラミックスの結合相の主成分がコバルト，クロム，ニオブ，モリブデンおよびジルコニアであることから、耐食性も高いため、長期間釣竿に使用しても製品が変色して高級感が低下することはない。特に、第１，第２の実施形態の装飾部品用セラミックスがジルコニアを含有するときには、ジルコニアが、釣糸とセラミックスとの接触部で炭化チタンや結合相が酸化されて体積膨張し、クラックや磨耗が進行するという問題を抑制する。 Furthermore, since the main component of the ceramic binder phase is zirconia, cobalt, nickel and chromium, the decorative component for fishing line guide according to the first embodiment has high corrosion resistance. There is no change in color and the sense of quality is not reduced. In addition, the fishing line guiding decorative part of the second embodiment has high corrosion resistance because the main component of the ceramic binder phase is cobalt, chromium, niobium, molybdenum and zirconia. The product is not discolored and the quality is not reduced. In particular, when the ceramics for decorative parts of the first and second embodiments contain zirconia, zirconia is expanded in volume due to oxidation of titanium carbide and the binder phase at the contact portion between the fishing line and the ceramic, and cracks and wear are caused. Reduce the problem of progress.
　図１は第１，第２の実施形態の釣糸案内用装飾部品である釣糸用ガイドリングおよびこの釣糸用ガイドリングを備えた釣糸用ガイドの一例を示し、（ａ）は釣糸用ガイドリングの平面図であり、（ｂ）は（ａ）の釣糸用ガイドリングを備えた釣糸用ガイドの斜視図である。 FIG. 1 shows an example of a fishing line guide ring, which is a decorative part for fishing line guides of the first and second embodiments, and a fishing line guide provided with the fishing line guide ring. FIG. 1 (a) is a plan view of the fishing line guide ring. It is a figure and (b) is a perspective view of the guide for fishing lines provided with the guide ring for fishing lines of (a).
　図１に示す例の釣糸用ガイドリング１は、その内周側に釣糸（図示しない）を挿通して案内するものであり、釣糸用ガイド６は、釣糸用ガイドリング１を保持する保持部２を備え、この保持部２の支持部３および釣竿（図示しない）に固定する固定部４が一体的に形成された枠体５に釣糸用ガイドリング１を備えたものである。この釣糸用ガイドリング１を第１，第２の実施形態の装飾部品用セラミックスで形成することにより、需要者に高級感，美的満足感および精神的安らぎを与えることができる。 The fishing line guide ring 1 of the example shown in FIG. 1 is for guiding a fishing line (not shown) through the inner periphery thereof, and the fishing line guide 6 is a holding portion 2 that holds the fishing line guide ring 1. The fishing line guide ring 1 is provided on a frame 5 integrally formed with a support portion 3 of the holding portion 2 and a fixing portion 4 that is fixed to a fishing rod (not shown). By forming this fishing line guide ring 1 with the ceramics for decorative parts of the first and second embodiments, it is possible to give the consumer a sense of luxury, aesthetic satisfaction and mental comfort.
　また、銀色の色調の釣糸用ガイドリング１と、釣糸用ガイド６や釣竿の色調との調和がよいので釣具に好適に用いることができる。特に、銀色の色調を呈することから、嗜好品に高級感を求める人の好む釣具とすることができる。なお、釣糸用ガイドリング１の表面を透明な耐磨耗性の高い膜、例えば、非晶質硬質炭素からなる膜で被覆して、耐磨耗性をさらに向上させてもよい。 Further, since the silver-colored fishing line guide ring 1 and the fishing line guide 6 and the color of the fishing rod are in good harmony, it can be suitably used for fishing gear. In particular, since it exhibits a silvery color tone, it can be used as a fishing tackle preferred by those who want a high-class feeling as a luxury item. The surface of the fishing line guide ring 1 may be covered with a transparent film having high wear resistance, for example, a film made of amorphous hard carbon to further improve the wear resistance.
　また、第１，第２の実施形態の装飾部品用セラミックスの耐磨耗性は、以下に示す構成の耐磨耗性評価装置を作製し、これを用いることにより評価することができる。 Further, the wear resistance of the ceramics for decorative parts of the first and second embodiments can be evaluated by producing a wear resistance evaluation apparatus having the following configuration and using it.
　図２は、第１，第２の実施形態の装飾部品用セラミックスの耐磨耗性の評価に用いる耐磨耗性評価装置の概略構成図である。この耐磨耗性評価装置10は、ナイロン製の糸12と、所定位置で糸12に張力を与える複数のプーリー13と、プーリー13の１つであるプーリー13ａに連結して糸12を矢印の向きに走行させるモーター（図示しない）と、糸12に泥水を付着させる水槽14とからなり、おもり15の質量分の荷重が与えられ、水槽14を通って泥水が付着した糸12が、所定位置に治具（図示しない）等で固定された円柱状の装飾部品用セラミックス11の外周面を摺動する構造となっており、ナイロン製の糸12の号数は、例えば３号とすればよい。 FIG. 2 is a schematic configuration diagram of an abrasion resistance evaluation apparatus used for evaluating the abrasion resistance of the ceramics for decorative parts according to the first and second embodiments. The wear resistance evaluation apparatus 10 is connected to a nylon thread 12, a plurality of pulleys 13 that apply tension to the thread 12 at a predetermined position, and a pulley 13a that is one of the pulleys 13, and the thread 12 is indicated by an arrow. It consists of a motor (not shown) that travels in the direction and a water tank 14 that attaches muddy water to the thread 12, and a load corresponding to the mass of the weight 15 is applied. It is structured to slide on the outer peripheral surface of a cylindrical decorative part ceramic 11 fixed with a jig (not shown) or the like, and the number of nylon threads 12 may be, for example, 3 .
　この耐磨耗性評価装置10を用いて装飾部品用セラミックス11の耐磨耗性を評価する際の条件は、例えば、おもり15の質量を500ｇとし、糸12が円柱状の装飾部品用セラミックス11の外周を摺動する速度を60ｍ／分とし、糸12の走行距離が3000ｍ以上になるように設定すればよい。そして、モーターを駆動し糸12を摺動させた後に、円柱状の装飾部品用セラミックス11が磨耗して生じた傷の最も深い部分を表面形状測定顕微鏡（キーエンス製　測定部ＶＦ－7510／コントローラＶＦ－7500）を用いて測定し、この測定値を比較することにより耐磨耗性を評価することができる。 Conditions for evaluating the wear resistance of the ceramic 11 for decorative parts using this wear resistance evaluation apparatus 10 are, for example, that the mass of the weight 15 is 500 g and the thread 12 is a cylindrical ceramic 11 for decorative parts. The speed of sliding on the outer periphery of the thread 12 may be set to 60 m / min, and the traveling distance of the yarn 12 may be set to 3000 m or more. Then, after driving the motor and sliding the thread 12, the deepest part of the scratches caused by the wear of the cylindrical ceramics 11 for decorative parts was measured with a surface shape measuring microscope (measurement part VF-7510 / controller VF made by Keyence). -7500), and the wear resistance can be evaluated by comparing the measured values.
　また、実施形態の装飾部品用セラミックスは、第１，第２の実施形態の装飾部品用セラミックスからなることを特徴とし、その例としては、時計用ケースや時計用バンド駒がある。 Further, the ceramic for decorative parts of the embodiment is characterized by comprising ceramics for decorative parts of the first and second embodiments, and examples thereof include a watch case and a watch band piece.
　次に、第１，第２の実施形態を用いた時計用ケースや時計用バンド駒について説明する。 Next, a watch case and a watch band piece using the first and second embodiments will be described.
　第１，第２の実施形態の装飾部品用セラミックスは、製品間の色差が小さいため、時計用ケースや時計用バンド駒に用いると、個々の部品を組み付けたとき部品間の色調バラツキによって美観を損ねることがなく、色調に統一感を有しており、時計としての高級感，美的満足感を十分に得ることができ、視覚を通じて精神的安らぎを得ることができる。さらに、第１の実施形態の装飾部品用セラミックスの場合には、セラミックスの結合相の主成分がジルコニア，コバルト，ニッケルおよびクロムであることから、耐食性も高いため長期間身につけて使用しても製品が変色して高級感が低下することはない。また、結合相にニッケルを含まない場合には、ニッケルアレルギーが生じにくくなる。第２の実施形態の装飾部品用セラミックスの場合には、セラミックスの結合相の主成分がコバルト，クロム，ニオブ，モリブデンおよびジルコニアであることから、耐食性も高いため、長期間身につけて使用しても製品が変色して高級感が低下することはない。 The ceramics for decorative parts of the first and second embodiments have a small color difference between products. Therefore, when used in a watch case or a watch band piece, the aesthetics of the parts due to color variations between parts when assembled. There is no loss, it has a sense of unity in color, it can fully obtain a high-class feeling and aesthetic satisfaction as a watch, and can obtain mental comfort through vision. Furthermore, in the case of the ceramic for decorative parts of the first embodiment, since the main component of the ceramic binder phase is zirconia, cobalt, nickel and chromium, it can be worn for a long period of time because of its high corrosion resistance. The product is not discolored and the quality is not reduced. Further, when the binder phase does not contain nickel, nickel allergy is less likely to occur. In the case of the ceramic for decorative parts of the second embodiment, since the main component of the ceramic binder phase is cobalt, chromium, niobium, molybdenum and zirconia, it has high corrosion resistance, so it can be worn for a long time. However, the product does not change color and the sense of quality does not deteriorate.
　図３は、第１，第２の実施形態の装飾部品用セラミックスである時計用ケースの一例を示しており、（ａ）は時計用ケースを表側から見た斜視図であり、（ｂ）は（ａ）の時計用ケースを裏側から見た斜視図である。また、図４は本発明の時計用装飾部品である時計用バンドの構成の一例を示す模式図である。なお、これらの図において同じ部位を示す場合は同じ符号を付してある。 FIG. 3 shows an example of a watch case which is a ceramic for decorative parts according to the first and second embodiments, (a) is a perspective view of the watch case as viewed from the front side, and (b) It is the perspective view which looked at the case for timepieces of (a) from the back side. FIG. 4 is a schematic view showing an example of the configuration of a watch band that is a decorative part for watch of the present invention. In addition, when showing the same site | part in these figures, the same code | symbol is attached | subjected.
　図３に示す時計用ケース20Ａは、図示しないムーブメント（駆動機構）を収容する凹部21と、腕に時計を装着するための時計用バンド（図示しない）を固定する足部22とを備えており、凹部21は厚みの薄い底部23と厚みの厚い胴部24とからなる。 A watch case 20A shown in FIG. 3 includes a recess 21 for housing a movement (drive mechanism) (not shown) and a foot 22 for fixing a watch band (not shown) for mounting the watch on an arm. The concave portion 21 includes a thin bottom portion 23 and a thick trunk portion 24.
　そして、図４に示す時計用バンド50を構成するバンド駒は、ピン40が挿入される貫通孔31を有する中駒30と、中駒30を挟むようにして配置され、ピン40の両端が差し込まれるピン穴32を有する外駒33とから構成されており、中駒30の貫通孔31にピン40が挿入され、挿入されたピン40の両端が外駒33のピン穴32に差し込まれることにより、中駒30と外駒33とが順次連結されて時計用バンド50が構成されている。 And the band piece which comprises the band 50 for timepieces shown in FIG. 4 is arrange | positioned so that the intermediate piece 30 which has the through-hole 31 in which the pin 40 is inserted, and the intermediate piece 30 may be pinched | interposed, and the pin into which both ends of the pin 40 are inserted The pin 40 is inserted into the through hole 31 of the middle piece 30 and both ends of the inserted pin 40 are inserted into the pin holes 32 of the outer piece 33, The piece 30 and the outer piece 33 are sequentially connected to form a watch band 50.
　これら、時計用ケース20Ａ，20Ｂおよび時計用バンド50を構成するバンド駒として用いられる本発明の時計用装飾部品は、本発明の装飾部品用セラミックスからなるものであることから、時計としての高級感，美的満足感を十分に得ることができ、視覚を通じて精神的安らぎを得ることができる。 Since the watch decorative parts of the present invention used as the band pieces constituting the watch cases 20A and 20B and the watch band 50 are made of the ceramics for decorative parts of the present invention, a high-class feeling as a watch. ， You can get enough aesthetic satisfaction and you can get mental comfort through vision.
　次に、第１の実施形態の装飾部品用セラミックスの製造方法について説明する。 Next, a method for manufacturing the ceramic for decorative parts of the first embodiment will be described.
　第１の実施形態の装飾部品用セラミックスを得るには、まず、焼結体中で主成分となる炭化チタンと、ジルコニウム，コバルトおよびニッケルの少なくとも１種ならびにクロムの各粉末とを所定量秤量し、粉砕・混合して調合原料とする。より具体的には、平均粒径が10～30μｍの炭化チタンの粉末と、平均粒径が0.2μｍ以上２μｍ以下の酸化ジルコニウム（ジルコニア）の粉末と、平均粒径が１～20μｍのコバルトおよびニッケルの少なくとも１種の粉末と、平均粒径が３μｍ以上10μｍ以下のクロムの粉末または組成式がＣｒ３Ｃ２として表される平均粒径が３μｍ以上60μｍ以下の炭化クロムの粉末とを準備し、コバルトおよびニッケルの少なくとも１種の粉末が５～25質量％、クロムまたは炭化クロムの粉末が１～10質量％、ジルコニアの粉末が９～30質量％、残部が炭化チタンの粉末、そして、コバルト，ニッケル，クロムおよびジルコニアの合計が50質量％未満の含有量となるように秤量して粉砕・混合すればよい。 In order to obtain the ceramic for decorative parts of the first embodiment, first, a predetermined amount of titanium carbide, which is a main component in the sintered body, and at least one of zirconium, cobalt and nickel and chromium powder is weighed. , Pulverized and mixed to prepare a blended raw material. More specifically, titanium carbide powder having an average particle diameter of 10 to 30 μm, zirconium oxide (zirconia) powder having an average particle diameter of 0.2 μm to 2 μm, and cobalt and nickel having an average particle diameter of 1 to 20 μm. And a chromium powder having an average particle size of 3 μm or more and 10 μm or less, or a chromium carbide powder having an average particle size of 3 μm or more and 60 μm or less represented by a composition formula of Cr 3 C 2 , 5 to 25% by mass of at least one powder of cobalt and nickel, 1 to 10% by mass of chromium or chromium carbide powder, 9 to 30% by mass of zirconia powder, the balance of titanium carbide powder, and cobalt, What is necessary is just to weigh, grind | pulverize and mix so that the sum total of nickel, chromium, and zirconia may become less than 50 mass% content.
　なお、粉砕・混合時間は50時間以上にすればよい。このとき、この調合原料における不可避不純物としては珪素，リン，イオウ，マンガン，鉄等が挙げられるが、これらは装飾面の色調に悪影響を及ぼすおそれがあるので、各々0.5質量％未満であることが好適である。 The grinding / mixing time may be 50 hours or more. At this time, silicon, phosphorus, sulfur, manganese, iron, and the like are listed as inevitable impurities in the blended raw material, but these may have an adverse effect on the color of the decorative surface. Is preferred.
　また、炭化チタンの粉末は化学量論的組成のＴｉＣであっても、あるいは非化学量論的組成のＴｉＣ１－ｘＮｘ（０≦ｘ≦0.2）であってもいいが、耐磨耗性および装飾的価値が高い色調という観点からは、各粉末の純度は99％以上であることが好ましく、炭化チタンの粉末が一部コバルトの粉末と反応してＣｏ３Ｔｉなどの化合物を微量生成しても何等差し支えない。特に、装飾部品用セラミックスを成す炭化チタン質焼結体について組成式をＴｉＣ１－ｘＮｘとしたときに０≦ｘ≦0.2とするには、炭化チタンの粉末は組成式をＴｉＣ１－ｘＮｘとしたときに０≦ｘ≦0.3のものを用いればよい。 The titanium carbide powder may be TiC having a stoichiometric composition or TiC 1-x N x (0 ≦ x ≦ 0.2) having a non-stoichiometric composition. From the viewpoint of color tone with high quality and decorative value, the purity of each powder is preferably 99% or more, and titanium carbide powder partially reacts with cobalt powder to produce a small amount of compounds such as Co 3 Ti It doesn't matter what. In particular, in order to satisfy 0 ≦ x ≦ 0.2 when the composition formula is TiC 1-x N x for the titanium carbide sintered body constituting the ceramic for decorative parts, the titanium carbide powder has the composition formula of TiC 1-x When N x , 0 ≦ x ≦ 0.3 may be used.
　次いで、調合原料に有機溶媒として、例えばイソプロパノールを加え、ミルを用いて混合粉砕した後、結合剤としてパラフィンワックスを所定量添加し、所望の成形法、例えば、乾式加圧成形法，冷間静水圧加圧成形法，押し出し成形法等により円板，平板，円環体等の所望形状に成形する。 Next, after adding, for example, isopropanol as an organic solvent to the blended raw material, mixing and grinding using a mill, a predetermined amount of paraffin wax is added as a binder, and a desired molding method such as dry pressure molding method, cold static It is formed into a desired shape such as a disk, flat plate, or torus by a hydraulic pressure molding method, extrusion molding method, or the like.
　また、成形法として乾式加圧を選択した場合は、成形圧力は装飾面における開気孔率およびビッカース硬度（Ｈｖ）に影響を与えることから、成形圧力を49～196ＭＰａとすることが好適である。成形圧力を49～196ＭＰａとするのは、相対密度が95％以上で開気孔率が2.5％以下の焼結体を得ることができるとともに、ビッカース硬度（Ｈｖ）を８ＧＰａ以上にすることができるからである。また、金型の寿命を長くすることもできる。 Also, when dry press is selected as the molding method, the molding pressure affects the open porosity and Vickers hardness (Hv) on the decorative surface, so that the molding pressure is preferably 49 to 196 MPa. The molding pressure is set to 49 to 196 MPa because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and a Vickers hardness (Hv) can be set to 8 GPa or more. It is. In addition, the life of the mold can be extended.
　そして、得られた成形体を必要に応じて真空雰囲気または不活性ガス雰囲気等の非酸化性雰囲気中で脱脂した後、不活性ガス雰囲気または真空中で焼成し、理論密度に対する相対密度が95％以上の焼結体を得る。なお、不活性ガス雰囲気中または真空中で焼成するのは、酸化性雰囲気中で焼成すると、炭化チタンが酸化してそのほとんどが組成式ＴｉＯ２で表される酸化チタンとなり、この酸化チタンが本質的に備えている白色の色調の影響を受けてしまい、装飾部品用セラミックスの全体の色調が白っぽくかすむからである。 Then, the obtained molded body is degreased in a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary, and then fired in an inert gas atmosphere or a vacuum, and the relative density with respect to the theoretical density is 95%. The above sintered body is obtained. In addition, firing in an inert gas atmosphere or in a vacuum is because, when firing in an oxidizing atmosphere, titanium carbide is oxidized and most of the titanium oxide is represented by the composition formula TiO 2. This is because the overall color tone of the ceramic for decorative parts is whitish.
　また、真空中で焼成して装飾部品用セラミックスを得る場合は、その真空度が５Ｐａ以下であることが好適である。真空度を５Ｐａ以下とするのは、炭化チタンが焼成中に酸化することがなく、銀色の装飾部品用セラミックスを得るためである。さらに、焼成温度を1200～1600℃とすることが好適である。これにより、相対密度が95％以上で開気孔率が2.5％以下の焼結体を得ることができるとともに、焼成コストも下げられるからである。 Moreover, when obtaining ceramics for decorative parts by firing in a vacuum, the degree of vacuum is preferably 5 Pa or less. The reason why the degree of vacuum is 5 Pa or less is that titanium carbide does not oxidize during firing, and thus a silver-colored ceramic for decorative parts is obtained. Further, the firing temperature is preferably 1200 to 1600 ° C. This is because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and the firing cost can be reduced.
　そして得られた焼結体の装飾的価値が求められる面に、研削盤を用いて研削加工を行なった後、バレル研磨を行なうことにより、焼結体のその表面は銀色の色調を有する装飾面となって、第１の実施形態の装飾部品用セラミックスを得ることができる。なお、このような装飾面に現れる気孔は、その開口部の最大径を30μｍ以下にすることが好適で、この範囲にすることで、気孔内への雑菌，異物や汚染物等の凝着を低減することができる。 Then, the surface of the sintered body is subjected to grinding using a grinder on the surface where the decorative value of the sintered body is required, and then the barrel is polished so that the surface of the sintered body has a silver color tone. Thus, the ceramic for decorative parts of the first embodiment can be obtained. In addition, it is preferable that the pores appearing on such a decorative surface have a maximum diameter of 30 μm or less, and by setting this range, adhesion of germs, foreign matters, contaminants, etc. into the pores is possible. Can be reduced.
　装飾部品用セラミックスからなる製品の形状が複雑な形状の場合には、予め乾式加圧成形法，冷間静水圧加圧成形法，押し出し成形法，射出成形法等によってブロック形状または製品形状に近い形状に成形し、焼結した後に、製品形状になるように研削加工を施した後、バレル研磨を行なってもよく、あるいは最初から射出成形法によって製品形状とし、焼成後にバレル研磨を行なってもよい。 When the shape of the product made of ceramics for decorative parts is complex, close to the block shape or product shape by dry pressure molding method, cold isostatic pressing method, extrusion molding method, injection molding method, etc. After shaping into a shape and sintering, after grinding to give a product shape, barrel polishing may be performed, or product shape may be formed by injection molding from the beginning, and barrel polishing may be performed after firing Good.
　また、バレル研磨では、回転バレル研磨機を用い、メディアとしてアルミナやグリーンカーボランダム（ＧＣ）などを適量の水とともに回転バレル研磨機に投入し、湿式で24～150時間行なえばよい。 In barrel polishing, a rotating barrel polishing machine is used. Alumina, green carborundum (GC), or the like as media is introduced into the rotating barrel polishing machine together with an appropriate amount of water, and the wet polishing is performed for 24 to 150 hours.
　次に、第２の実施形態の装飾部品用セラミックスの製造方法について説明する。 Next, a method for manufacturing the ceramic for decorative parts of the second embodiment will be described.
　第２の実施形態の装飾部品用セラミックスを得るには、まず、焼結体中で主成分となる炭化チタンと、コバルト，クロムおよびニオブの各粉末とを所定量秤量し、粉砕・混合して調合原料とする。より具体的には、平均粒径が10～30μｍの炭化チタンの粉末と、平均粒径が１～20μｍのコバルトの粉末と、平均粒径が３～70μｍのクロムの粉末または組成式がＣｒ３Ｃ２として表される平均粒径が３～60μｍの炭化クロムの粉末と、平均粒径が20～50μｍのニオブの粉末とを準備し、コバルトの粉末が５～25質量％、クロムまたは炭化クロムの粉末が１～10質量％、ニオブの粉末が２～10質量％、残部が炭化チタンの粉末となるように秤量して粉砕・混合すればよい。 In order to obtain the ceramic for decorative parts of the second embodiment, first, titanium carbide which is a main component in the sintered body and each powder of cobalt, chromium and niobium are weighed, pulverized and mixed. Use as a blended raw material. More specifically, titanium carbide powder having an average particle diameter of 10 to 30 μm, cobalt powder having an average particle diameter of 1 to 20 μm, chromium powder having an average particle diameter of 3 to 70 μm, or a composition formula of Cr 3 Chromium carbide powder having an average particle size of 3 to 60 μm expressed as C 2 and niobium powder having an average particle size of 20 to 50 μm are prepared. Cobalt powder is 5 to 25% by mass, chromium or chromium carbide. These powders may be weighed, pulverized and mixed so that the powder is 1 to 10% by mass, the niobium powder is 2 to 10% by mass, and the balance is titanium carbide.
　なお、粉砕・混合時間は50時間以上にすればよい。このとき、この調合原料における不可避不純物としては珪素，リン，イオウ，マンガン，鉄等が挙げられるが、これらは装飾面の色調に悪影響を及ぼすおそれがあるので、各々0.5質量％未満であることが好適である。 The grinding / mixing time may be 50 hours or more. At this time, silicon, phosphorus, sulfur, manganese, iron, and the like are listed as inevitable impurities in the blended raw material, but these may have an adverse effect on the color of the decorative surface. Is preferred.
　また、炭化チタンの粉末は化学量論的組成のＴｉＣであっても、あるいは非化学量論的組成のＴｉＣ１－ｘＮｘ（０≦ｘ≦0.2）であってもいいが、耐磨耗性および装飾的価値が高い色調という観点からは、各粉末の純度は99％以上であることが好ましく、炭化チタンの粉末が一部コバルトの粉末と反応してＣｏ３Ｔｉなどの化合物を微量生成しても何等差し支えない。特に、装飾部品用セラミックスを成す炭化チタン質焼結体について組成式をＴｉＣ１－ｘＮｘとしたときに０≦ｘ≦0.2とするには、炭化チタンの粉末は組成式をＴｉＣ１－ｘＮｘとしたときに０≦ｘ≦0.3のものを用いればよい。 The titanium carbide powder may be TiC having a stoichiometric composition or TiC 1-x N x (0 ≦ x ≦ 0.2) having a non-stoichiometric composition. From the viewpoint of color tone with high quality and decorative value, the purity of each powder is preferably 99% or more, and titanium carbide powder partially reacts with cobalt powder to produce a small amount of compounds such as Co 3 Ti It doesn't matter what. In particular, in order to satisfy 0 ≦ x ≦ 0.2 when the composition formula is TiC 1-x N x for the titanium carbide sintered body constituting the ceramic for decorative parts, the titanium carbide powder has the composition formula of TiC 1-x When N x , 0 ≦ x ≦ 0.3 may be used.
　次いで、調合原料に有機溶媒として、例えばイソプロパノールを加え、ミルを用いて混合粉砕した後、結合剤としてパラフィンワックスを所定量添加し、所望の成形法、例えば、乾式加圧成形法，冷間静水圧加圧成形法，押し出し成形法等により円板，平板，円環体等の所望形状に成形する。 Next, after adding, for example, isopropanol as an organic solvent to the blended raw material, mixing and grinding using a mill, a predetermined amount of paraffin wax is added as a binder, and a desired molding method such as dry pressure molding method, cold static It is formed into a desired shape such as a disk, flat plate, or torus by a hydraulic pressure molding method, extrusion molding method, or the like.
　また、成形法として乾式加圧を選択した場合は、成形圧力は装飾面における開気孔率およびビッカース硬度（Ｈｖ）に影響を与えることから、成形圧力を49～196ＭＰａとすることが好適である。成形圧力を49～196ＭＰａとするのは、相対密度が95％以上で開気孔率が2.5％以下の焼結体を得ることができるとともに、ビッカース硬度（Ｈｖ）を８ＧＰａ以上にすることができるからである。また、金型の寿命を長くすることもできる。 Also, when dry press is selected as the molding method, the molding pressure affects the open porosity and Vickers hardness (Hv) on the decorative surface, so that the molding pressure is preferably 49 to 196 MPa. The molding pressure is set to 49 to 196 MPa because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and a Vickers hardness (Hv) can be set to 8 GPa or more. It is. In addition, the life of the mold can be extended.
　そして、得られた成形体を必要に応じて真空雰囲気または不活性ガス雰囲気等の非酸化性雰囲気中で脱脂した後、不活性ガス雰囲気または真空中で焼成し、理論密度に対する相対密度が95％以上の焼結体を得る。なお、不活性ガス雰囲気中または真空中で焼成するのは、酸化性雰囲気中で焼成すると、炭化チタンが酸化してそのほとんどが組成式ＴｉＯ２で表される酸化チタンとなり、この酸化チタンが本質的に備えている白色の色調の影響を受けてしまい、装飾部品用セラミックスの全体の色調が白っぽくかすむからである。 Then, the obtained molded body is degreased in a non-oxidizing atmosphere such as a vacuum atmosphere or an inert gas atmosphere as necessary, and then fired in an inert gas atmosphere or a vacuum, and the relative density with respect to the theoretical density is 95%. The above sintered body is obtained. In addition, firing in an inert gas atmosphere or in a vacuum is because, when firing in an oxidizing atmosphere, titanium carbide is oxidized and most of the titanium oxide is represented by the composition formula TiO 2. This is because the overall color tone of the ceramics for decorative parts becomes whitish.
　また、真空中で焼成して装飾部品用セラミックスを得る場合は、その真空度が５Ｐａ以下であることが好適である。真空度を５Ｐａ以下とするのは、炭化チタンが焼成中に酸化することがなく、銀色の装飾部品用セラミックスを得るためである。さらに、焼成温度を1200～1600℃とすることが好適である。これにより、相対密度が95％以上で開気孔率が2.5％以下の焼結体を得ることができるとともに、焼成コストも下げられるからである。 Moreover, when obtaining ceramics for decorative parts by firing in a vacuum, the degree of vacuum is preferably 5 Pa or less. The reason why the degree of vacuum is 5 Pa or less is that titanium carbide does not oxidize during firing, and thus a silver-colored ceramic for decorative parts is obtained. Further, the firing temperature is preferably 1200 to 1600 ° C. This is because a sintered body having a relative density of 95% or more and an open porosity of 2.5% or less can be obtained, and the firing cost can be reduced.
　そして得られた焼結体の装飾的価値が求められる面に、研削盤を用いて研削加工を行なった後、バレル研磨を行なうことにより、焼結体のその表面は銀色の色調を有する装飾面となって、第２の実施形態の装飾部品用セラミックスを得ることができる。なお、このような装飾面に現れる気孔は、その開口部の最大径を30μｍ以下にすることが好適で、この範囲にすることで、気孔内への雑菌，異物や汚染物等の凝着を低減することができる。 Then, the surface of the sintered body is subjected to grinding using a grinder on the surface where the decorative value of the sintered body is required, and then the barrel is polished so that the surface of the sintered body has a silver color tone. Thus, the ceramic for decorative parts of the second embodiment can be obtained. In addition, it is preferable that the pores appearing on such a decorative surface have a maximum diameter of 30 μm or less, and by setting this range, adhesion of germs, foreign matters, contaminants, etc. into the pores is possible. Can be reduced.
　装飾部品用セラミックスからなる製品の形状が複雑な形状の場合には、予め乾式加圧成形法，冷間静水圧加圧成形法，押し出し成形法，射出成形法等によってブロック形状または製品形状に近い形状に成形し、焼結した後に、製品形状になるように研削加工を施した後、バレル研磨を行なってもよく、あるいは最初から射出成形法によって製品形状とし、焼成後にバレル研磨を行なってもよい。 When the shape of the product made of ceramics for decorative parts is complex, close to the block shape or product shape by dry pressure molding method, cold isostatic pressing method, extrusion molding method, injection molding method, etc. After shaping into a shape and sintering, after grinding to give a product shape, barrel polishing may be performed, or product shape may be formed by injection molding from the beginning, and barrel polishing may be performed after firing Good.
　また、バレル研磨では、回転バレル研磨機を用い、メディアとしてアルミナやグリーンカーボランダム（ＧＣ）などを適量の水とともに回転バレル研磨機に投入し、湿式で24～150時間行なえばよい。 In barrel polishing, a rotating barrel polishing machine is used. Alumina, green carborundum (GC), or the like as media is introduced into the rotating barrel polishing machine together with an appropriate amount of water, and the wet polishing is performed for 24 to 150 hours.
　さらに、第２の実施形態の装飾部品用セラミックスがモリブデンを含有する場合は、平均粒径が10～30μｍの炭化チタンの粉末と、平均粒径が１～20μｍのコバルトの粉末と、平均粒径が３～70μｍのクロムの粉末または組成式がＣｒ３Ｃ２として表される平均粒径が３～60μｍの炭化クロムの粉末と、平均粒径が20～50μｍのニオブの粉末と、平均粒径が１μｍ～10μｍのモリブデンの粉末とを準備し、コバルトの粉末が５～25質量％、クロムまたは炭化クロムの粉末が１～10質量％、ニオブの粉末が２～10質量％、モリブデンのコバルトに対する割合が35％以下、残部が炭化チタンの粉末となるように秤量して粉砕・混合すればよい。そして、成形、焼成、加工は上記と同様に行なえばよい。 Further, when the decorative part ceramic of the second embodiment contains molybdenum, titanium carbide powder having an average particle diameter of 10 to 30 μm, cobalt powder having an average particle diameter of 1 to 20 μm, and an average particle diameter 3 to 70 μm chromium powder or chromium carbide powder having an average particle size of 3 to 60 μm represented by the composition formula Cr 3 C 2 , niobium powder having an average particle size of 20 to 50 μm, and an average particle size 1 to 10 μm of molybdenum powder, cobalt powder 5 to 25% by mass, chromium or chromium carbide powder 1 to 10% by mass, niobium powder 2 to 10% by mass, molybdenum based on cobalt What is necessary is just to weigh and grind | pulverize and mix so that a ratio may be 35% or less and the remainder becomes a powder of titanium carbide. Molding, firing, and processing may be performed in the same manner as described above.
　さらに、第２の実施形態の装飾部品用セラミックスがジルコニアを含有する場合は、平均粒径が10～30μｍの炭化チタンの粉末と、平均粒径が１～20μｍのコバルトの粉末と、平均粒径が３～70μｍのクロムの粉末または組成式がＣｒ３Ｃ２として表される平均粒径が３～60μｍの炭化クロムの粉末と、平均粒径が20～50μｍのニオブの粉末と、平均粒径が１～10μｍのモリブデンの粉末と、平均粒径が0.2～２μｍのジルコニアの粉末とを準備し、コバルトの粉末が５～25質量％、クロムまたは炭化クロムの粉末が１～10質量％、ニオブの粉末が２～10質量％、モリブデンのコバルトに対する割合が35％以下、ジルコニアの粉末が９～30質量％、残部が炭化チタンの粉末、そして、コバルト，クロム，ニオブ，ジルコニアおよびモリブデンの合計が50質量％未満の含有量となるように秤量して粉砕・混合すればよい。このとき、モリブデンは含有しなくてもよい。そして、成形、焼成、加工は上記と同様に行なえばよい。 Further, when the ceramic for decorative parts of the second embodiment contains zirconia, titanium carbide powder having an average particle diameter of 10 to 30 μm, cobalt powder having an average particle diameter of 1 to 20 μm, and an average particle diameter 3 to 70 μm chromium powder or chromium carbide powder having an average particle size of 3 to 60 μm represented by the composition formula Cr 3 C 2 , niobium powder having an average particle size of 20 to 50 μm, and an average particle size 1-10 μm molybdenum powder and zirconia powder having an average particle size of 0.2-2 μm, cobalt powder 5-25% by mass, chromium or chromium carbide powder 1-10% by mass, niobium 2 to 10% by weight of the powder, the ratio of molybdenum to cobalt is 35% or less, the powder of 9 to 30% by weight of zirconia, the balance being titanium carbide powder, and the total of cobalt, chromium, niobium, zirconia and molybdenum 50 mass May be pulverized and mixed were weighed such that the content of less than. At this time, molybdenum may not be contained. Molding, firing, and processing may be performed in the same manner as described above.
　以上のようにして得られる第１，第２の実施形態の装飾部品用セラミックスは、特に美しい色調として評価の高い銀色を呈し、高級感があって、美的満足感を得ることができ、その結果、視覚を通じて精神的安らぎを得ることができるので、時計ケース，バンド駒，バックルなどの時計用装飾部品や、釣糸用ガイド等の釣糸案内用装飾部品，ナンバーキー，各種入力キー等の操作ボタン，ケース，ディスプレイを固定する枠状部品等の携帯端末機用装飾部品や、浴室または洗面室の蛇口や洗面具，スプーン，フォーク，バターナイフ，万年筆ステーショナリー，印材，名刺，火葬用副葬品などの生活用品用装飾部品や、ブローチ，ネックレス，イヤリング，リング，ネクタイピン，タイタック，ボタン，イニシャルロゴ，バッグ等の止め金具などの装身具用装飾部品や、ナンバーキー，各種入力キー等の操作ボタン，ケース，ディスプレイを固定する枠状部品等のＰＤＡ（Personal Digital Assistants：個人用情報機器）用装飾部品や、ナンバーキー，各種入力キー等の操作ボタン，ケース，ディスプレイを固定する枠状部品等の携帯音楽再生装置用装飾部品や、携帯型データ記憶装置の筐体用装飾部品や、タイル，取っ手，庭石，表示板，道路用誘導マーカーなどの建材用装飾部品や、釣り具用品，ゴルフクラブ，ポーカーチップ，将棋の駒，碁石などのスポーツ用品または娯楽用品等の装飾部品や、弦楽器用駒，ギター用保護板，バイオリン用弓取っ手，イヤホン，スピーカボックスなどの楽器部品または音響機器部品等の装飾部品や、歯冠，楽器用マウスピースなどの口に含む部品や、ディスクブレーキパッド，取っ手，エンブレムなどの自動車用装飾部品などに用いられる、美しい銀色の色調を醸し出す装飾部品用セラミックスとしても好適に用いることができる。 The ceramics for decorative parts of the first and second embodiments obtained as described above exhibit a highly evaluated silver color as a particularly beautiful color tone, have a high-class feeling, and can obtain aesthetic satisfaction, and as a result. , So that you can get mental comfort through vision, such as watch case, band piece, buckle and other watch decorative parts, fishing line guide decorative parts such as fishing line guides, operation buttons such as number keys, various input keys, Living items such as decorative parts for mobile terminals such as frame parts for fixing cases and displays, faucets and toiletries in bathrooms or washrooms, spoons, forks, butter knives, fountain pen stationery, stamps, business cards, cremation accessory Clasps for decorative parts, brooches, necklaces, earrings, rings, tie pins, tie tacks, buttons, initial logos, bags, etc. Decorative parts for accessories such as PDAs (Personal Digital Assistants: Personal Information Equipment) such as operation buttons such as number keys and various input keys, frame parts for fixing the display, etc. Operation buttons such as input keys, cases, decorative parts for portable music players such as frame parts that fix the display, decorative parts for casings of portable data storage devices, tiles, handles, garden stones, display boards, roads Decorative parts for building materials such as guide markers for fishing, decorative parts such as fishing equipment, golf clubs, poker chips, shogi pieces, sports equipment such as shoji stones, and entertainment items, string pieces, protective plates for guitars, violins Decoration parts such as musical instrument parts such as bow handles, earphones, and speaker boxes or audio equipment parts, and parts included in the mouth such as crowns and mouthpieces for musical instruments In addition, it can also be suitably used as a ceramic for decorative parts that produces a beautiful silver color tone used for decorative parts for automobiles such as disc brake pads, handles, and emblems.
　以下、本発明の実施例を具体的に説明するが、本実施形態はこれらの実施例に限定されるものではない。 Examples of the present invention will be specifically described below, but the present embodiment is not limited to these examples.
　第１の実施形態についての実施例
　（実施例１）
　まず、炭化チタン粉末（純度99％，平均粒径22.3μｍ），ジルコニア粉末（純度99％以上，平均粒径1.5μｍ），コバルト粉末（純度99％以上，平均粒径1.3μｍ）またはニッケル粉末（純度99％以上，平均粒径12.8μｍ），クロム粉末（純度99％，平均粒径55μｍ）を焼結体での比率（含有量）が表１に示す比率になるように秤量し、粉砕・混合して調合原料とした。 Example of the first embodiment (Example 1)
First, titanium carbide powder (purity 99%, average particle size 22.3μm), zirconia powder (purity 99% or more, average particle size 1.5μm), cobalt powder (purity 99% or more, average particle size 1.3μm) or nickel powder ( Weigh 99% or more of purity, average particle size 12.8μm) and chromium powder (purity 99%, average particle size 55μm) so that the ratio (content) in the sintered body is the ratio shown in Table 1, It mixed and it was set as the preparation raw material.
　次に、得られた各調合原料にイソプロパノール溶液を加えて、振動ミルを用いて72～96時間粉砕・混合した後、バインダとしてパラフィンワックスを調合原料に対し３質量部添加して、噴霧乾燥法により乾燥させて顆粒とした。そして、得られた顆粒を98ＭＰａの圧力で加圧成形して、成形体を作製した。次に、この成形体を真空雰囲気中にて400℃で脱脂した後、1300～1600℃で２時間保持して焼成して、直径が10ｍｍで高さが10ｍｍの円柱状の焼結体を得た。 Next, an isopropanol solution is added to each of the prepared raw materials, pulverized and mixed for 72 to 96 hours using a vibration mill, and then 3 parts by weight of paraffin wax as a binder is added to the prepared raw materials. Were dried into granules. And the obtained granule was pressure-molded with the pressure of 98 Mpa, and the molded object was produced. Next, this molded body was degreased at 400 ° C. in a vacuum atmosphere and then fired by holding at 1300-1600 ° C. for 2 hours to obtain a cylindrical sintered body having a diameter of 10 mm and a height of 10 mm. It was.
　そして、錫製のラップ盤に平均粒径が１μｍのダイヤモンド砥粒を供給して焼結体の端面をラップ加工した。引き続き、回転バレル研磨機を用いて、水と主成分がアルミナのメディアとグリーンカーボランダム（ＧＣ）とを入れて、70時間バレル研磨を行ない端面および外周面を鏡面に仕上げ、第１の実施形態の装飾部品用セラミックスである試料No．３～６，９～12，15～18，21～24，27～30，32および33の試料と、比較例として、１，２，７，８，13，14，19，20，25，26，31および34の炭化チタン質焼結体からなる装飾部品用セラミックスを得た。 Then, diamond abrasive grains having an average particle diameter of 1 μm were supplied to a tin lapping machine to lapping the end face of the sintered body. Subsequently, using a rotating barrel polishing machine, water, a medium whose main component is alumina, and green carborundum (GC) are added, barrel polishing is performed for 70 hours, and the end surface and outer peripheral surface are finished to be mirror surfaces. First Embodiment Sample No., which is a ceramic for decorative parts. Samples 3-6, 9-12, 15-18, 21-24, 27-30, 32 and 33, and 1, 2, 7, 8, 13, 14, 19, 20, 25, 26 as comparative examples , 31 and 34 ceramics for decorative parts made of sintered titanium carbide were obtained.
　その後、各試料を構成するチタン，ジルコニウム，コバルト，ニッケルおよびクロムの含有量はＩＣＰ発光分光分析装置を用いて測定した。 Thereafter, the contents of titanium, zirconium, cobalt, nickel and chromium constituting each sample were measured using an ICP emission spectroscopic analyzer.
　そして、20歳代～50歳代の各年代について男女５名ずつ計40名のモニターに、試料を黒色の台に並べて色むらを感じるかのアンケート調査を実施し、色むらを感じる人数が３名以下の場合は◎とし、色むらを感じる人数が４～10名の場合は○として、使用可能で合格と判定し、色むらを感じる人数が11名以上の場合は×として、使用不可能で不合格とした。 Then, a questionnaire survey was conducted on 40 monitors, 5 men and women for each age group in their 20s and 50s, to see if they felt color irregularities by arranging samples on a black table, and 3 people felt color irregularities. ◎ if the number of people is less than one name, ◯ if the number of people who feel uneven color is 4-10 people, can be used and judged as acceptable, and × if the number of people who feel uneven color is more than 11 people, cannot be used It was rejected.
　また、チッピングについては、各試料10個のラップ加工が終了した時点で表裏の端部に長さが0.5ｍｍ以上のチッピングが試料１個につき計２個以下である場合は◎とし、計２個以上４個以下の場合は○として、それぞれ使用可能であり合格と判定し、計５個以上である場合は×として、使用不可能であり不合格とした。 As for chipping, when lapping of 10 samples is finished, if there are 2 or less chippings with a length of 0.5mm or more on the front and back edges, 2 is a total. When the number was 4 or less, it was judged as “good” as “good” and judged as acceptable.
　また、耐傷性については、図１に示す時計用ケースに図３に示す時計用バンドを組み付けたものを製作して、20歳代～50歳代の各年代について男女５名ずつ計40名のモニターが300時間（約30日間）身に付けた後、時計用ケースおよび時計用バンドを目から30～40ｃｍ離した位置に置き、蛍光灯で照らして５人以下のモニターが目視で傷を見つけた場合は◎とし、６人以上10人以下のモニターが目視で傷を見つけた場合は○として、それぞれ使用可能であり合格と判定し、11以上のモニターが目視で傷を見つけた場合は×として、使用不可能であり不合格とした。 In addition, regarding scratch resistance, a watch case shown in FIG. 1 assembled with the watch band shown in FIG. 3 was manufactured, and a total of 40 men and women of each age group in their 20s to 50s. After the monitor has been worn for 300 hours (about 30 days), place the watch case and watch band at a position 30 to 40 cm away from the eyes. Is marked ◎, and when 6 or more and 10 or less monitors visually found a flaw, it was marked as ◯, and each was judged acceptable and passed, and 11 or more monitors found a flaw visually. As unusable and rejected.
　また、耐磨耗性の評価については、図２に示す例の耐磨耗性評価装置を用いて、試料Ｎｏ．１～24の円柱状の装飾部品用セラミックスを所定位置（図２において、装飾部品用セラミックス11の位置）に治具で固定した後、水0.001ｍ３に対して半磁器土（粘土の中に磁器土を配合した粘土）を10ｇ投入し混合して水槽14中に泥水を準備した。そして、おもり15の質量を500ｇに、糸12が円柱状の装飾部品用セラミックスの外周側を摺動する速度を60ｍ／分に、糸12の走行距離を3000ｍとなるように設定し、泥水が付着したナイロン製（東レ製　銀鱗Σ３号）の糸12を、円柱状の装飾部品用セラミックスの外周側で摺動させた。その後、表面形状測定顕微鏡（キーエンス製　測定部ＶＦ－7510／コントローラＶＦ－7500）を用いて、糸12を摺動させることによって円柱状の装飾部品用セラミックスが磨耗して生じた傷の最も深い部分を測定し、各試料６個の平均値を磨耗深さとして算出した。そして、磨耗深さが10μｍ以下の場合は磨耗痕が目立たないため○として使用可能で合格と判定し、磨耗深さが10μｍを超える場合は磨耗痕が目立つため×として使用不可能で不合格とした。結果を表１に示す。 For the evaluation of wear resistance, sample No. 1 was used using the wear resistance evaluation apparatus shown in FIG. Place a cylindrical ceramics for decorative component of 1-24 (in FIG. 2, the position of the ceramics for decorative component 11) was fixed by a jig, the semi-porcelain earth in water 0.001 m 3 (in clay 10 g of clay mixed with porcelain earth) was added and mixed to prepare muddy water in the water tank 14. The mass of the weight 15 is set to 500 g, the speed at which the thread 12 slides on the outer peripheral side of the cylindrical ceramic for decorative parts is set to 60 m / min, and the traveling distance of the thread 12 is set to 3000 m. The adhered nylon thread 12 (Toray made silver scale Σ3) was slid on the outer peripheral side of the cylindrical ceramic for decorative parts. Then, using the surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF-7500), the deepest part of the flaw caused by the wear of the cylindrical ceramics for decorative parts by sliding the thread 12 Was measured, and the average value of 6 samples was calculated as the wear depth. And if the wear depth is less than 10μm, the wear mark is inconspicuous, so it can be used as ○, and it is judged as acceptable, and if the wear depth exceeds 10μm, the wear mark is conspicuous and cannot be used as x. did. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す通り、比較例である試料Ｎｏ．１，２，７，８，13，14，19，20，25，26，31および34は、色むら，チッピング，耐傷性，耐磨耗性について各評価が×のものもあり、高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができなかった。それに比べて、第１の実施形態の範囲内の試料である試料Ｎｏ．３～６，９～12，15～18，21～24，27～30，32，33は、色むら，チッピング，耐傷性，耐磨耗性について○または◎となり、高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができた。 As shown in Table 1, sample No. 1,2,7,8,13,14,19,20,25,26,31 and 34 are rated as x for color unevenness, chipping, scratch resistance, and abrasion resistance. It was not possible to form a beautiful silver decorative surface that would provide aesthetic satisfaction and mental comfort. Compared to that, the sample No. which is a sample within the range of the first embodiment. 3 to 6, 9 to 12, 15 to 18, 21 to 24, 27 to 30, 32, and 33 are ○ or ◎ for color unevenness, chipping, scratch resistance, and abrasion resistance, and a sense of luxury, aesthetic satisfaction, and It was possible to form a beautiful silver-colored decorative surface that provides mental comfort.
　まず、コバルトについて、比較例である試料Ｎｏ．１，２は、コバルトの含有量が５質量％未満と少なく、焼結時には炭化チタン結晶粒子の表面を均一に濡らすことが困難なため、緻密化が進まず、加工時に炭化チタンの結晶粒子が脱粒して鏡面が荒れた状態となったために色むらが大きくなったことが分かる。また、炭化チタンの結晶粒子が脱粒しやすいため試料の角部は脆くなりチッピングが発生しやすくなったために、試料の平面部でも脱粒痕が筋状に残って耐傷性と耐磨耗性とが低下したことが分かる。また、試料Ｎｏ．７はコバルトの含有量が25質量％を超えていることから、セラミックスの表面で結合相の占める割合が大きくなって耐傷性が低下したため、鏡面が荒れた状態となり、色むらが大きくなったことが分かる。 First, for cobalt, sample No. 1 and 2 have a low cobalt content of less than 5% by mass, and it is difficult to wet the surface of the titanium carbide crystal particles uniformly during sintering. It can be seen that the color unevenness has increased because the mirror surface has become rough due to shedding. In addition, because the crystal grains of titanium carbide are easy to fall off, the corners of the sample become brittle and chipping is likely to occur. It turns out that it fell. Sample No. No. 7 has a cobalt content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increased and scratch resistance decreased, resulting in a rough mirror surface and increased color unevenness. I understand.
　これに対して、第１の実施形態の実施例である試料Ｎｏ．３～６は、コバルトの含有量が５～25質量％の範囲であることから、炭化チタンが脱粒しにくく、試料の角部の強度が保たれてチッピングが生じにくいため、試料の平面部では脱粒痕が残らず、耐傷性と耐磨耗性とに優れたセラミックスになったことが分かる。従って、炭化チタンの脱粒や傷跡などの機械的な因子により、色差が大きくなったり色むらが悪化したりすることを抑制できたことが分かる。 On the other hand, sample No. which is an example of the first embodiment is used. In Nos. 3 to 6, since the cobalt content is in the range of 5 to 25% by mass, titanium carbide is less likely to be crushed, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that no degranulation marks remained and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
　次に、クロムについて、比較例である試料Ｎｏ．８は、クロムの含有量が１質量％未満と少ないことから、セラミックスの表面に酸化クロムの被膜を十分に形成できず耐食性が低下し、そのために試料の表面が研削液や洗浄液などと反応したり乾燥時に水垢が付着しやすくなったりして、色むらが大きくなったと考えられる。また、試料Ｎｏ．13は、クロムの含有量が10質量％を超えているため、結合相が硬くなり過ぎて炭化チタンの結晶粒子が脱粒しやすくなり、鏡面が荒れた状態となって色むらが大きく、さらに試料の角部は脆くなりチッピングが発生しやすく、試料の平面部でも脱粒痕が筋状に残って耐傷性が低下したことが分かる。 Next, with respect to chromium, sample No. as a comparative example. No. 8 has a chromium content of less than 1% by mass, so that a chromium oxide film cannot be sufficiently formed on the surface of the ceramic, resulting in a decrease in corrosion resistance. For this reason, the surface of the sample reacts with a grinding liquid or a cleaning liquid. It is thought that the color unevenness became large due to the adhesion of water scale during drying. Sample No. No. 13 has a chromium content exceeding 10% by mass, so that the binder phase becomes too hard and the titanium carbide crystal particles are easily grained, the mirror surface becomes rough and the color unevenness is large. It can be seen that the corner portion of the sample becomes brittle and chipping is likely to occur, and the degranulation trace remains in a streak shape even in the flat portion of the sample, and the scratch resistance is lowered.
　これに対して、第１の実施形態の試料である試料Ｎｏ．９～12は、クロムの含有量が１～10質量％の範囲であることから、セラミックスの表面に酸化クロムの被膜が形成されて色調が安定したことが分かる。また、結合相が適度な硬さに保たれるため、炭化チタンの脱粒が抑制されて、チッピングや耐傷性は良好な評価となったことが分かる。 On the other hand, sample No. which is the sample of the first embodiment. In Nos. 9 to 12, since the chromium content is in the range of 1 to 10% by mass, it can be seen that a chromium oxide film was formed on the ceramic surface and the color tone was stabilized. Moreover, since the binder phase is kept at an appropriate hardness, it can be seen that titanium carbide degranulation was suppressed, and that chipping and scratch resistance were evaluated favorably.
　次に、ジルコニアについて比較例である試料Ｎｏ．14は、ジルコニアの含有量が９質量％未満と少ないことから、セラミックスの表面にジルコニアの粒子が十分に存在せず、釣糸が摺動したときに炭化チタンや結合相の酸化や磨耗を抑える効果が低下し、そのために磨耗量が増加したと考えられる。また、試料Ｎｏ．19は、ジルコニアの含有量が30質量％を超えているため、焼結時のジルコニアの相変態に伴う体積膨張や体積収縮の変化量のセラミックス全体の体積に対する比率が大きくなり、焼結後のセラミックスにクラックが残留して、チッピング、耐傷性、耐磨耗性が低下したことが分かる。 Next, Sample No. which is a comparative example for zirconia. 14 has a low zirconia content of less than 9% by mass, so there are not enough zirconia particles on the surface of the ceramics, and the effect of suppressing oxidation and wear of titanium carbide and the binder phase when the fishing line slides. It is thought that the amount of wear increased because of this. Sample No. 19, since the content of zirconia exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic becomes large. It can be seen that cracks remained in the ceramic and chipping, scratch resistance, and wear resistance were lowered.
　また、表１には記載していないが、特許文献４に記載されたジルコニアを含有しない組成でセラミックスを作製し、同じ方法で耐摩耗性の評価を行なったところ、第１の実施形態の実施例のうちでジルコニアの一番少ない試料Ｎｏ．15よりも磨耗量が増加しており、第１の実施形態の装飾部品用セラミックスの方が耐磨耗性について改善されていることが分かった。 Although not described in Table 1, ceramics were produced with a composition not containing zirconia described in Patent Document 4, and the wear resistance was evaluated by the same method. As a result, the first embodiment was carried out. Sample No. with the fewest zirconia among the examples. The amount of wear increased more than 15, and it was found that the ceramic for decorative parts of the first embodiment was improved in wear resistance.
　これに対して、第１の実施形態の試料である試料Ｎｏ．15～18は、ジルコニアの含有量が９～30質量％の範囲であることから、釣糸が摺動したときに炭化チタンや結合相が磨耗しても、ジルコニアの結晶粒子が表面に突起状に残り、これが釣糸と接触することから炭化チタンや結合相の酸化は進行が遅くなり、磨耗が抑制されたことが分かる。 On the other hand, sample No. which is the sample of the first embodiment. 15 to 18, since the content of zirconia is in the range of 9 to 30% by mass, even if titanium carbide and the binder phase are worn when the fishing line slides, the zirconia crystal particles are projected on the surface. From the remaining contact with the fishing line, it can be seen that the oxidation of titanium carbide and the binder phase slowed down and the wear was suppressed.
　次に、ニッケルについて、比較例である試料Ｎｏ．20は、ニッケルの含有量が５質量％未満と少なく、焼結時には炭化チタン結晶粒子の表面を均一に濡らすことが困難なため、緻密化が進まず、加工時に炭化チタンの結晶粒子が脱粒して鏡面が荒れた状態となったために、色むらが大きくなったことが分かる。また、炭化チタンの結晶粒子が脱粒しやすいため、試料の角部は脆くなり、チッピングが発生しやすくなったために、試料の平面部でも脱粒痕が筋状に残って耐傷性と耐磨耗性とが低下したことが分かる。また、試料Ｎｏ．25は、ニッケルの含有量が25質量％を超えていることから、セラミックスの表面で結合相の占める割合が大きくなって耐傷性が低下したため、鏡面が荒れた状態となり、色むらが大きくなったことが分かる。 Next, for nickel, sample No. as a comparative example. No. 20 has a nickel content of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. Therefore, densification does not proceed and the titanium carbide crystal particles are shattered during processing. It can be seen that the color unevenness increased because the mirror surface was rough. In addition, because the titanium carbide crystal grains are easy to shed, the corners of the sample became brittle and chipping was likely to occur, so the degranulation traces remained streaks even in the flat part of the sample, resulting in scratch resistance and wear resistance. It can be seen that and decreased. Sample No. No. 25 has a nickel content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increases and scratch resistance decreases, resulting in a rough mirror surface and uneven color. I understand that.
　これに対して、第１の実施形態の実施例である試料Ｎｏ．21～24は、ニッケルの含有量が５～25質量％の範囲であることから、炭化チタンが脱粒しにくく、試料の角部の強度が保たれてチッピングが生じにくいため、試料の平面部では脱粒痕が残らず、耐傷性と耐磨耗性とに優れたセラミックスになったことが分かる。従って、炭化チタンの脱粒や傷跡などの機械的な因子により、色差が大きくなったり色むらが悪化したりすることを抑制できたことが分かる。 On the other hand, sample No. which is an example of the first embodiment is used. In Nos. 21 to 24, since the nickel content is in the range of 5 to 25% by mass, titanium carbide is less likely to be granulated, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that no degranulation marks remained and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
　次に、コバルトとニッケルについて、比較例である試料Ｎｏ．26は、コバルトおよびニッケルの少なくとも１種の合計の含有量が５質量％未満と少なく、焼結時には炭化チタン結晶粒子の表面を均一に濡らすことが困難なため、緻密化が進まず、加工時に炭化チタンの結晶粒子が脱粒して鏡面が荒れた状態となったために色むらが大きくなったことが分かる。また、炭化チタンの結晶粒子が脱粒しやすいことから試料の角部が脆くなりチッピングが発生しやすくなったために、試料の平面部でも脱粒痕が筋状に残って、耐傷性と耐磨耗性とが低下したことが分かる。また、試料Ｎｏ．31はコバルトおよびニッケルの合計の含有量が25質量％を超えていることから、セラミックスの表面で結合相の占める割合が大きくなって耐傷性が低下したため、鏡面が荒れた状態となり色むらが大きくなったことが分かる。 Next, for cobalt and nickel, sample No. as a comparative example. No. 26 has a total content of at least one of cobalt and nickel of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. It can be seen that the color unevenness has increased because the crystal grains of titanium carbide have fallen and the mirror surface has become rough. In addition, because the crystal grains of titanium carbide are easy to shed, the corners of the sample became brittle and chipping was likely to occur, so the degranulation traces remained streaks even in the flat part of the sample, resulting in scratch resistance and wear resistance. It can be seen that and decreased. Sample No. Since the total content of cobalt and nickel exceeds 25% by mass, the proportion of the binder phase on the ceramic surface increases and scratch resistance decreases, resulting in a rough mirror surface and large color unevenness. You can see that
　これに対して、第１の実施形態の実施例である試料Ｎｏ．27～30は、コバルトおよびニッケルの合計の含有量が５～25質量％の範囲であることから、炭化チタンが脱粒しにくく、試料の角部の強度が保たれてチッピングが生じにくいため、試料の平面部では脱粒痕が残らず、耐傷性と耐磨耗性とに優れたセラミックスになったことが分かる。従って、炭化チタンの脱粒や傷跡などの機械的な因子により、色差が大きくなったり色むらが悪化したりすることを抑制できたことが分かる。 On the other hand, sample No. which is an example of the first embodiment is used. In 27-30, the total content of cobalt and nickel is in the range of 5-25% by mass, so that titanium carbide is less likely to fall apart, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that there was no degranulation trace in the flat part, and the ceramic was excellent in scratch resistance and wear resistance. Therefore, it can be seen that it was possible to suppress the increase in color difference and the deterioration of color unevenness due to mechanical factors such as titanium carbide degranulation and scars.
　次に、ジルコニア、コバルト、ニッケルおよびクロムの合計の含有量について、比較例である試料Ｎｏ．34は、ジルコニア、コバルト、ニッケルおよびクロムの合計の含有量が50質量％以上であることから、表面の炭化チタンの量が少なくなり、表面が傷付きやすく、耐摩耗性も低下したことが分かる。 Next, for the total content of zirconia, cobalt, nickel and chromium, Sample No. as a comparative example. 34, the total content of zirconia, cobalt, nickel and chromium is 50% by mass or more, so the amount of titanium carbide on the surface is reduced, the surface is easily scratched, and the wear resistance is also reduced. .
　これに対して、第１の実施形態の実施例である試料Ｎｏ．32，33は、ジルコニア、コバルト、ニッケルおよびクロムの合計の含有量が50質量％未満であることから、炭化チタンの含有量が50質量％以上となり、硬度が保たれて、耐傷性および耐摩耗性に優れたセラミックスになったことが分かる。 On the other hand, sample No. which is an example of the first embodiment is used. For 32 and 33, since the total content of zirconia, cobalt, nickel and chromium is less than 50% by mass, the content of titanium carbide is 50% by mass or more, the hardness is maintained, and scratch resistance and abrasion resistance are maintained. It turns out that it became ceramics excellent in property.
　（実施例２）
　モリブデンのコバルトに対する割合を変化させることによる特性の変化を確認する試験を行なった。 (Example 2)
A test was conducted to confirm the change in characteristics by changing the ratio of molybdenum to cobalt.
　まず、炭化チタン粉末（純度99％，平均粒径22.3μｍ），ジルコニア粉末（純度99％以上，平均粒径1.5μｍ），コバルト粉末（純度99％以上，平均粒径1.3μｍ）およびニッケル粉末（純度99％以上，平均粒径12.8μｍ），クロム粉末（純度99％，平均粒径55μｍ）およびモリブデン粉末（純度99％以上，平均粒径3.3μｍ）を焼結体での比率（含有量）が表２に示す比率になるように秤量し、粉砕・混合して調合原料とした。 First, titanium carbide powder (purity 99%, average particle size 22.3 μm), zirconia powder (purity 99% or more, average particle size 1.5 μm), cobalt powder (purity 99% or more, average particle size 1.3 μm) and nickel powder ( Purity 99% or more, average particle size 12.8μm), chromium powder (purity 99%, average particle size 55μm) and molybdenum powder (purity 99% or more, average particle size 3.3μm) ratio in sintered body (content) Were weighed so that the ratio shown in Table 2 was obtained, and pulverized and mixed to prepare a blended raw material.
　次に、実施例１と同様の製造方法にて試料Ｎｏ．35～50の炭化チタン質焼結体からなる装飾部品用セラミックスを得た。 Next, sample No. 1 was manufactured by the same manufacturing method as in Example 1. Ceramics for decorative parts made of 35-50 sintered titanium carbide were obtained.
　その後、実施例１と同様に各試料を構成するチタン，コバルト，ニッケル，クロム，ジルコニウムおよびモリブデンの含有量はＩＣＰ発光分光分析装置を用いて測定した。 Thereafter, the contents of titanium, cobalt, nickel, chromium, zirconium, and molybdenum constituting each sample were measured using an ICP emission spectroscopic analyzer in the same manner as in Example 1.
　その後、実施例１と同様に、色むら，チッピングおよび耐傷性のテストを行なった。結果を表２に示す。 Thereafter, in the same manner as in Example 1, tests for uneven color, chipping and scratch resistance were performed. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示す通り、試料Ｎｏ．40，45，50は、モリブデンのコバルトおよびニッケルの少なくとも１種に対する割合が35％を超えているため、結合相にモリブデンリッチな相が析出して組織が部分的に不均一な状態となり、セラミックスを全体的に均一に加工することが難しくなって、脱粒やチッピングが増加したことが分かる。これに対して、第１の実施形態の実施例である試料Ｎｏ．35～39，41～44，46～49は、モリブデンのコバルトに対する含有量の割合が35％以下であることから、色むらが小さいことに加えて、焼成温度が下がって結晶粒の粒成長を抑制し、加工時には脱粒やチッピングが生じにくくなったことが分かる。このことから、モリブデンのコバルトに対する割合が35％以下であれば、より高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができるとともに、色むらも少なく、機械的加工時の脱粒やチッピングが抑制され、機械的強度が保たれたことが分かる。 As shown in Table 2, sample no. In 40, 45, and 50, since the ratio of molybdenum to at least one of cobalt and nickel exceeds 35%, a molybdenum-rich phase precipitates in the binder phase, resulting in a partially non-uniform structure. It can be seen that it became difficult to process the entire surface uniformly, and that the degranulation and chipping increased. On the other hand, sample No. which is an example of the first embodiment is used. For 35 to 39, 41 to 44, and 46 to 49, the content ratio of molybdenum to cobalt is 35% or less, so that in addition to small color unevenness, the firing temperature is lowered and crystal grain growth occurs. It can be seen that degranulation and chipping are less likely to occur during processing. From this, if the ratio of molybdenum to cobalt is 35% or less, it is possible to form a beautiful silver-colored decorative surface that can provide a higher-class feeling, aesthetic satisfaction, and mental comfort, and less uneven color. It can be seen that degranulation and chipping during mechanical processing were suppressed and the mechanical strength was maintained.
　第２の実施形態についての実施例
　（実施例３）
　まず、炭化チタン粉末（純度99％，平均粒径22.3μｍ），コバルト粉末（純度99％以上，平均粒径1.3μｍ），クロム粉末（純度99％，平均粒径55μｍ），ニオブ粉末（純度99.5％，平均粒径33μｍ）を焼結体での比率（含有量）が表１に示す比率になるように秤量し、粉砕・混合して調合原料とした。 Example of the second embodiment (Example 3)
First, titanium carbide powder (purity 99%, average particle size 22.3μm), cobalt powder (purity 99% or more, average particle size 1.3μm), chromium powder (purity 99%, average particle size 55μm), niobium powder (purity 99.5) %, Average particle size 33 μm) was weighed so that the ratio (content) in the sintered body would be the ratio shown in Table 1, and pulverized and mixed to prepare a blended raw material.
　次に、得られた各調合原料にイソプロパノール溶液を加えて、振動ミルを用いて72～96時間粉砕・混合した後、バインダとしてパラフィンワックスを調合原料に対し３質量部添加して、噴霧乾燥法により乾燥させて顆粒とした。そして、得られた顆粒を98ＭＰａの圧力で加圧成形して、成形体を作製した。次に、この成形体を真空雰囲気中にて400℃で脱脂した後、1300～1600℃で２時間保持して焼成して、直径が10ｍｍで高さが10ｍｍの円柱状の焼結体を得た。 Next, an isopropanol solution is added to each of the prepared raw materials, pulverized and mixed for 72 to 96 hours using a vibration mill, and then 3 parts by weight of paraffin wax as a binder is added to the prepared raw materials. Were dried into granules. And the obtained granule was pressure-molded with the pressure of 98 Mpa, and the molded object was produced. Next, this molded body was degreased at 400 ° C. in a vacuum atmosphere and then fired by holding at 1300-1600 ° C. for 2 hours to obtain a cylindrical sintered body having a diameter of 10 mm and a height of 10 mm. It was.
　そして、錫製のラップ盤に平均粒径が１μｍのダイヤモンド砥粒を供給して焼結体の端面をラップ加工した。引き続き、回転バレル研磨機を用いて、水と主成分がアルミナのメディアとグリーンカーボランダム（ＧＣ）とを入れて、70時間バレル研磨を行ない端面および外周面を鏡面に仕上げ、第２の実施形態の装飾部品用セラミックスである試料No．53～56，59～62および65～68の試料と、比較例として、51，52，57，58，63，64および69の炭化チタン質焼結体からなる装飾部品用セラミックスを得た。 Then, diamond abrasive grains having an average particle diameter of 1 μm were supplied to a tin lapping machine to lapping the end face of the sintered body. Subsequently, using a rotating barrel polishing machine, water, a medium whose main component is alumina, and green carborundum (GC) are added, barrel polishing is performed for 70 hours, and the end surface and the outer peripheral surface are finished to be mirror surfaces. Second Embodiment Sample No., which is a ceramic for decorative parts. Samples 53 to 56, 59 to 62, and 65 to 68, and ceramics for decorative parts made of titanium carbide sintered bodies 51, 52, 57, 58, 63, 64, and 69 were obtained as comparative examples.
　その後、各試料を構成するチタン，コバルト，クロムおよびニオブの含有量はＩＣＰ発光分光分析装置を用いて測定した。また、チタンは炭化物として換算した。 Thereafter, the contents of titanium, cobalt, chromium and niobium constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide.
　そして、20歳代～50歳代の各年代について男女５名ずつ計40名のモニターに、試料を黒色の台に並べて色むらを感じるかのアンケート調査を実施し、色むらを感じる人数が３名以下の場合は◎とし、色むらを感じる人数が４～10名の場合は○として、使用可能で合格と判定し、色むらを感じる人数が11名以上の場合は×として、使用不可能で不合格とした。 Then, a questionnaire survey was conducted on 40 monitors, 5 men and women for each age group in their 20s and 50s, to see if they felt color irregularities by arranging samples on a black table, and 3 people felt color irregularities. ◎ if the number of people is less than one name, ◯ if the number of people who feel uneven color is 4-10 people, can be used and judged as acceptable, and × if the number of people who feel uneven color is more than 11 people, cannot be used It was rejected.
　また、チッピングについては、各試料10個のラップ加工が終了した時点で表裏の端部に長さが0.5ｍｍ以上のチッピングが試料１個につき計２個以下である場合は◎とし、計２個以上４個以下の場合は○として、それぞれ使用可能であり合格と判定し、計５個以上である場合は×として、使用不可能であり不合格とした。 As for chipping, when lapping of 10 samples is finished, if there are 2 or less chippings with a length of 0.5mm or more on the front and back edges, 2 is a total. When the number was 4 or less, it was judged as “good” as “good” and judged as acceptable.
　また、耐傷性については、図１に示す時計用ケースに図３に示す時計用バンドを組み付けたものを製作して、20歳代～50歳代の各年代について男女５名ずつ計40名のモニターが300時間（約30日間）身に付けた後、時計用ケースおよび時計用バンドを目から30～40ｃｍ離した位置に置き、蛍光灯で照らして５人以下のモニターが目視で傷を見つけた場合は◎とし、６人以上10人以下のモニターが目視で傷を見つけた場合は○として、それぞれ使用可能であり合格と判定し、11人以上のモニターが目視で傷を見つけた場合は×として、使用不可能であり不合格とした。結果を表３に示す。 In addition, regarding scratch resistance, a watch case shown in FIG. 1 assembled with the watch band shown in FIG. 3 was manufactured, and a total of 40 men and women of each age group in their 20s to 50s. After the monitor has been worn for 300 hours (about 30 days), place the watch case and watch band at a position 30 to 40 cm away from the eyes. ◎ if there are 6 or more and 10 or less monitors visually found scratches, ○ if each is acceptable and judged to be acceptable, and 11 or more monitors find scratches visually As x, it was unusable and rejected. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３に示す通り、比較例である試料Ｎｏ．51，52，57，58，63，64および69は、色むら，チッピングおよび耐傷性について各評価が×のものもあり、高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができなかった。それに比べて、第２の実施形態の範囲内の試料である試料Ｎｏ．３～６，９～12，15～18は、色むら，チッピングおよび耐傷性について○または◎となり、高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができた。 As shown in Table 3, sample No. which is a comparative example. 51, 52, 57, 58, 63, 64, and 69 are rated as x for uneven color, chipping, and scratch resistance, and have beautiful silver color that gives a sense of luxury, aesthetic satisfaction, and mental comfort. A decorative surface could not be formed. Compared to that, sample No. which is a sample within the range of the second embodiment. 3 to 6, 9 to 12, 15 to 18 are ○ or ◎ in terms of color unevenness, chipping and scratch resistance, and form a beautiful silver decorative surface that gives a sense of luxury, aesthetic satisfaction and mental comfort. I was able to.
　まず、コバルトについて、比較例である試料Ｎｏ．51，52は、コバルトの含有量が５質量％未満と少なく、焼結時には炭化チタン結晶粒子の表面を均一に濡らすことが困難なため、緻密化が進まず、加工時に炭化チタンの結晶粒子が脱粒して鏡面が荒れた状態となったために、色むらが大きくなったことが分かる。また、炭化チタンの結晶粒子が脱粒しやすいため、試料の角部は脆くなりチッピングが発生しやすくなったために、試料の平面部でも脱粒痕が筋状に残って、耐傷性が低下したことが分かる。また、試料Ｎｏ．７はコバルトの含有量が25質量％を超えていることから、セラミックスの表面で結合相の占める割合が大きくなって耐傷性が低下したため、鏡面が荒れた状態となり、色むらが大きくなったことが分かる。 First, for cobalt, sample No. 51 and 52 have a cobalt content of less than 5% by mass, and it is difficult to uniformly wet the surface of the titanium carbide crystal particles during sintering. Therefore, densification does not proceed, and the titanium carbide crystal particles are not processed during processing. It can be seen that the color unevenness has increased because the mirror surface has become rough due to shedding. In addition, because the crystal grains of titanium carbide are easy to shed, the corners of the sample became brittle and chipping was likely to occur. I understand. Sample No. No. 7 has a cobalt content exceeding 25% by mass, so the proportion of the binder phase on the ceramic surface increased and scratch resistance decreased, resulting in a rough mirror surface and increased color unevenness. I understand.
　これに対して、第２の実施形態の実施例である試料Ｎｏ．３～６は、コバルトの含有量が５～25質量％の範囲であることから、炭化チタンが脱粒しにくく、試料の角部の強度が保たれてチッピングが生じにくいため、試料の平面部では脱粒痕が残らず、耐傷性に優れたセラミックスになったことが分かる。従って、炭化チタンの脱粒や傷跡などの機械的な因子により、色むらが悪化したりすることを抑制できたことが分かる。 On the other hand, sample No. which is an example of the second embodiment is used. In Nos. 3 to 6, since the cobalt content is in the range of 5 to 25% by mass, titanium carbide is less likely to be crushed, the strength of the corners of the sample is maintained, and chipping is less likely to occur. It can be seen that there was no degranulation trace and the ceramic was excellent in scratch resistance. Therefore, it can be seen that the color unevenness can be prevented from worsening due to mechanical factors such as grain separation and scarring of titanium carbide.
　次に、クロムについて、比較例である試料Ｎｏ．58は、クロムの含有量が１質量％未満と少ないことから、セラミックスの表面に酸化クロムの被膜を十分に形成できず耐食性が低下し、そのために試料の表面が研削液や洗浄液などと反応したり乾燥時に水垢が付着しやすくなったりして、色むらが大きくなったと考えられる。また、試料Ｎｏ．63は、クロムの含有量が10質量％を超えているため、結合相が硬くなり過ぎて炭化チタンの結晶粒子が脱粒しやすくなり、鏡面が荒れた状態となって色むらが大きく、さらに試料の角部は脆くなりチッピングが発生しやすく、試料の平面部でも脱粒痕が筋状に残って耐傷性が低下したことが分かる。 Next, with respect to chromium, sample No. as a comparative example. 58 has a low chromium content of less than 1% by mass, so that a sufficient chromium oxide film cannot be formed on the ceramic surface, resulting in a decrease in corrosion resistance, and the surface of the sample reacts with grinding or cleaning liquid. It is thought that the color unevenness became large due to the adhesion of water scale during drying. Sample No. No. 63 has a chromium content of over 10% by mass, so that the binder phase becomes too hard and the titanium carbide crystal particles are easily grained, the mirror surface is rough, and the color unevenness is large. It can be seen that the corner portion of the sample becomes brittle and chipping is likely to occur, and the degranulation trace remains in a streak shape even in the flat portion of the sample, and the scratch resistance is lowered.
　これに対して、第２の実施形態の試料である試料Ｎｏ．59～62は、クロムの含有量が１～10質量％の範囲であることから、セラミックスの表面に酸化クロムの被膜が形成されて色調が安定したことが分かる。また、結合相が適度な硬さに保たれるため、炭化チタンの脱粒が抑制されて、チッピングや耐傷性は良好な評価となったことが分かる。 On the other hand, sample No. which is the sample of the second embodiment. In Nos. 59 to 62, the chromium content is in the range of 1 to 10% by mass, so that it can be seen that a chromium oxide film is formed on the ceramic surface and the color tone is stabilized. Moreover, since the binder phase is kept at an appropriate hardness, it can be seen that titanium carbide degranulation is suppressed, and that chipping and scratch resistance are evaluated well.
　次に、ニオブについて、比較例である試料Ｎｏ．64は、ニオブの含有量が２質量％未満と少なく、結合相の表面の化学的安定性が低下して変色しやすくなり、セラミックスの色調がばらついて色むらが大きくなったと考えられる。また、試料Ｎｏ．19は、ニオブの含有量が10質量％を超えているため、結合相の液相温度が高くなり、焼結性が低下して炭化チタンの結晶粒が脱粒しやすくなったことから、セラミックスの表面が荒れた状態となり、色むらが発生したことが分かる。 Next, for niobium, sample No. as a comparative example. In No. 64, the niobium content is less than 2% by mass, the chemical stability of the surface of the binder phase is lowered and the color is liable to be discolored, and the color tone of the ceramic varies and the color unevenness increases. Sample No. 19 has a niobium content of more than 10% by mass, which increases the liquidus temperature of the binder phase, lowers the sinterability, and makes it easy for the grains of titanium carbide to fall. It can be seen that the surface becomes rough and uneven color occurs.
　これに対して、第２の実施形態の試料である試料Ｎｏ．65～68は、ニオブの含有量が２～10質量％の範囲であるため、ニオブが主に結合相のコバルトに固溶することにより、結合相はセラミックスの表面で安定した状態に維持され、色調も安定して色むらが発生しなかった。また、コバルトと炭化チタンとの結合力が高く保たれると考えられ、炭化チタンの脱粒が抑制されて、チッピングや耐傷性は良好な評価となったことが分かる。 On the other hand, sample No. which is the sample of the second embodiment. In 65 to 68, since the niobium content is in the range of 2 to 10% by mass, niobium is mainly dissolved in cobalt as the binder phase, so that the binder phase is maintained in a stable state on the ceramic surface. The color tone was stable and no color unevenness occurred. Moreover, it is thought that the bonding force between cobalt and titanium carbide is kept high, and it is understood that the titanium carbide is prevented from degranulating and the chipping and scratch resistance are evaluated well.
　（実施例４）
　モリブデンのコバルトに対する割合を変化させることによる特性の変化を確認する試験を行なった。 Example 4
A test was conducted to confirm the change in characteristics by changing the ratio of molybdenum to cobalt.
　まず、炭化チタン粉末（純度99％，平均粒径22.3μｍ），コバルト粉末（純度99％以上，平均粒径1.3μｍ），クロム粉末（純度99％，平均粒径55μｍ），ニオブ粉末（純度99.5％，平均粒径33μｍ）およびモリブデン粉末（純度99％以上，平均粒径3.3μｍ）を焼結体での比率（含有量）が表２に示す比率になるように秤量し、粉砕・混合して調合原料とした。 First, titanium carbide powder (purity 99%, average particle size 22.3μm), cobalt powder (purity 99% or more, average particle size 1.3μm), chromium powder (purity 99%, average particle size 55μm), niobium powder (purity 99.5) %, Average particle size 33 μm) and molybdenum powder (purity 99% or more, average particle size 3.3 μm) are weighed, pulverized and mixed so that the ratio (content) in the sintered body is the ratio shown in Table 2. And used as a blended raw material.
　次に、実施例３と同様の製造方法にて試料Ｎｏ．70～75の炭化チタン質焼結体からなる装飾部品用セラミックスを得た。 Next, the sample No. 1 was manufactured by the same manufacturing method as in Example 3. Ceramics for decorative parts made of 70 to 75 titanium carbide sintered bodies were obtained.
　その後、実施例３と同様に各試料を構成するチタン，コバルト，クロムおよびモリブデンの含有量はＩＣＰ発光分光分析装置を用いて測定した。また、チタンは炭化物として換算した。 Thereafter, as in Example 3, the contents of titanium, cobalt, chromium and molybdenum constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide.
　その後、実施例１と同様に、色むら，チッピングおよび耐傷性のテストを行なった。結果を表４に示す。 Thereafter, in the same manner as in Example 1, tests for uneven color, chipping and scratch resistance were performed. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示す通り、第２の実施形態の実施例のうちで試料Ｎｏ．75においては、モリブデンのコバルトに対する割合が35％を超えているため、結合相にモリブデンリッチな相が析出して組織が部分的に不均一な状態となり、セラミックスを全体的に均一に加工することが難しくなって、脱粒やチッピングが増加したことが分かる。これに対して、第２の実施形態の実施例である試料Ｎｏ．70～74においては、モリブデンのコバルトに対する含有量の割合が35％以下であることから、色むらが小さいことに加えて、焼成温度が下がって結晶粒の粒成長を抑制し、加工時には脱粒やチッピングが生じにくくなったことが分かる。このことから、モリブデンのコバルトに対する割合が35％以下であれば、より高級感，美的満足感および精神的安らぎを得られるような美しい銀色の装飾面を形成することができるとともに、色むらも少なく、機械的加工時の脱粒やチッピングが抑制され、機械的強度が保たれたことが分かる。 As shown in Table 4, among the examples of the second embodiment, the sample No. In 75, since the ratio of molybdenum to cobalt exceeds 35%, a molybdenum-rich phase precipitates in the binder phase, resulting in a partially non-uniform structure, and the ceramic is processed uniformly throughout. It can be seen that threshing and chipping increased. On the other hand, sample No. which is an example of the second embodiment. In 70 to 74, since the content ratio of molybdenum to cobalt is 35% or less, in addition to small color unevenness, the firing temperature is lowered to suppress grain growth of the crystal grains. It can be seen that chipping is less likely to occur. From this, if the ratio of molybdenum to cobalt is 35% or less, it is possible to form a beautiful silver-colored decorative surface that can provide a higher-class feeling, aesthetic satisfaction, and mental comfort, and less uneven color. It can be seen that degranulation and chipping during mechanical processing were suppressed and the mechanical strength was maintained.
　（実施例５）
　ジルコニアを含有することによる特性の変化を確認する試験を行なった。 (Example 5)
A test was conducted to confirm the change in characteristics due to the inclusion of zirconia.
　まず、炭化チタン粉末（純度99％，平均粒径22.3μｍ），ジルコニア粉末（純度99％以上，平均粒径1.5μｍ），コバルト粉末（純度99％以上，平均粒径1.3μｍ），クロム粉末（純度99％，平均粒径55μｍ），ニオブ粉末（純度99.5％，平均粒径33μｍ）およびモリブデン粉末（純度99％以上，平均粒径3.3μｍ）を焼結体での比率（含有量）が表３に示す比率になるように秤量し、粉砕・混合して調合原料とした。 First, titanium carbide powder (purity 99%, average particle size 22.3μm), zirconia powder (purity 99% or more, average particle size 1.5μm), cobalt powder (purity 99% or more, average particle size 1.3μm), chromium powder ( Purity 99%, average particle size 55μm), niobium powder (purity 99.5%, average particle size 33μm) and molybdenum powder (purity 99% or more, average particle size 3.3μm) ratio (content) in the sintered body 3 was weighed so as to have the ratio shown in FIG.
　次に、実施例３と同様の製造方法にて試料Ｎｏ．76～88の炭化チタン質焼結体からなる装飾部品用セラミックスを得た。 Next, the sample No. 1 was manufactured by the same manufacturing method as in Example 3. Ceramics for decorative parts made of 76 to 88 sintered titanium carbide were obtained.
　その後、実施例１と同様に各試料を構成するチタン，ジルコニウム，コバルト，クロム，ニオブおよびモリブデンの含有量はＩＣＰ発光分光分析装置を用いて測定した。また、チタンは炭化物として換算し、ジルコニウムはジルコニア（酸化ジルコニウム）として換算した。 Thereafter, as in Example 1, the contents of titanium, zirconium, cobalt, chromium, niobium and molybdenum constituting each sample were measured using an ICP emission spectroscopic analyzer. Titanium was converted as carbide, and zirconium was converted as zirconia (zirconium oxide).
　その後、実施例３と同様に、色むら，チッピングおよび耐傷性のテストとを行なった。 Thereafter, in the same manner as in Example 3, color unevenness, chipping, and scratch resistance tests were performed.
　そして、新たに耐磨耗性の評価も行なった。耐磨耗性の評価については、図２に示す例の耐磨耗性評価装置を用いて、試料Ｎｏ．76～88の円柱状の装飾部品用セラミックスを所定位置（図２において、装飾部品用セラミックス11の位置）に治具で固定した後、水0.001ｍ３に対して半磁器土（粘土の中に磁器土を配合した粘土）を10ｇ投入し混合して水槽14中に泥水を準備した。そして、おもり15の質量を500ｇに、糸12が円柱状の装飾部品用セラミックスの外周側を摺動する速度を60ｍ／分に、糸12の走行距離を3000ｍとなるように設定し、泥水が付着したナイロン製（東レ製　銀鱗Σ３号）の糸12を、円柱状の装飾部品用セラミックスの外周側で摺動させた。その後、表面形状測定顕微鏡（キーエンス製　測定部ＶＦ－7510／コントローラＶＦ－7500）を用いて、糸12を摺動させることによって円柱状の装飾部品用セラミックスが磨耗して生じた傷の最も深い部分を測定し、各試料６個の平均値を磨耗深さとして算出した。そして、磨耗深さが10μｍ以下の場合は磨耗痕が目立たないため○として使用可能で合格と判定し、磨耗深さが10μｍを超える場合は磨耗痕が目立つため×として使用不可能で不合格とした。結果を表５に示す。 Then, the abrasion resistance was newly evaluated. For the evaluation of wear resistance, sample No. 1 was used using the wear resistance evaluation apparatus shown in FIG. (2, positions of the ceramics for decorative component 11) 76 predetermined position a cylindrical ceramics for decorative component of ~ 88 was fixed by a jig, the semi-porcelain earth in water 0.001 m 3 (in clay 10 g of clay mixed with porcelain earth) was added and mixed to prepare muddy water in the water tank 14. The mass of the weight 15 is set to 500 g, the speed at which the thread 12 slides on the outer peripheral side of the cylindrical ceramic for decorative parts is set to 60 m / min, and the traveling distance of the thread 12 is set to 3000 m. The adhered nylon thread 12 (Toray made silver scale Σ3) was slid on the outer peripheral side of the cylindrical ceramic for decorative parts. Then, using the surface shape measuring microscope (Keyence measuring unit VF-7510 / controller VF-7500), the deepest part of the flaw caused by the wear of the cylindrical ceramics for decorative parts by sliding the thread 12 Was measured, and the average value of 6 samples was calculated as the wear depth. And if the wear depth is less than 10μm, the wear mark is inconspicuous, so it can be used as ○, and it is judged as acceptable, and if the wear depth exceeds 10μm, the wear mark is conspicuous and cannot be used as x. did. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５に示す通り、第２の実施形態の実施例のうちで試料Ｎｏ．76，77および84においては、ジルコニアの含有量が９質量％未満と少ないことから、セラミックスの表面にジルコニアの粒子が十分に存在せず、釣糸が摺動したときに炭化チタンや結合相の酸化や磨耗を抑える効果が低下し、そのために磨耗量が増加したと考えられる。また、第２の実施形態の実施例のうちで試料Ｎｏ．82においては、ジルコニアの含有量が30質量％を超えているため、焼結時のジルコニアの相変態に伴う体積膨張や体積収縮の変化量のセラミックス全体の体積に対する比率が大きくなり、焼結後のセラミックスにクラックが残留して、チッピング、耐傷性、耐磨耗性が低下したと考えられる。また、第２の実施形態の実施例のうちで試料Ｎｏ．83および88においては、ジルコニアの含有量が30質量％を超え、ジルコニア，コバルト，クロム，ニオブおよびモリブデンの合計が50質量％以上であるため、チッピング，耐傷性および耐磨耗性がさらに低下して色むらが目立つようになったことが分かる。 As shown in Table 5, among the examples of the second embodiment, the sample No. In 76, 77 and 84, since the content of zirconia is as low as less than 9% by mass, there are not enough zirconia particles on the surface of the ceramic, and oxidation of titanium carbide and the binder phase occurs when the fishing line slides. It is thought that the effect of suppressing wear and wear decreased, and the amount of wear increased. Further, among the examples of the second embodiment, the sample No. In 82, since the content of zirconia exceeds 30% by mass, the ratio of the volume expansion / contraction change due to the phase transformation of zirconia during sintering to the total volume of the ceramic becomes large. It is considered that cracks remained in the ceramics and chipping, scratch resistance, and wear resistance were lowered. Further, among the examples of the second embodiment, the sample No. In 83 and 88, since the content of zirconia exceeds 30% by mass and the total of zirconia, cobalt, chromium, niobium and molybdenum is 50% by mass or more, chipping, scratch resistance and wear resistance are further reduced. It can be seen that uneven color has become noticeable.
　また、表３には記載していないが、特許文献４に記載されたジルコニアを含有しない組成でセラミックスを作製し、同じ方法で耐摩耗性の評価を行なったところ、第２の実施形態の実施例のうちでジルコニアの一番少ない試料Ｎｏ．76よりも磨耗量が増加しており、第２の実施形態品の方が耐磨耗性について改善されていることが分かった。 Although not described in Table 3, ceramics were prepared with a composition not containing zirconia described in Patent Document 4, and the wear resistance was evaluated by the same method. As a result, the second embodiment was carried out. Sample No. with the fewest zirconia among the examples. The amount of wear increased from 76, and it was found that the product of the second embodiment had improved wear resistance.
　これに対して、第２の実施形態の実施例である試料Ｎｏ．78～81および85～87は、ジルコニアの含有量が９～30質量％の範囲であることから、釣糸が摺動したときに炭化チタンや結合相が磨耗しても、ジルコニアの結晶粒子が表面に突起状に残り、これが釣糸と接触することから炭化チタンや結合相の酸化は進行が遅くなり、磨耗が抑制されたことが分かる。 On the other hand, sample No. which is an example of the second embodiment is used. Since 78 to 81 and 85 to 87 have a zirconia content in the range of 9 to 30% by mass, the zirconia crystal particles remain on the surface even if the titanium carbide or the binder phase wears when the fishing line slides. Since this remains in the shape of a protrusion and comes into contact with the fishing line, it can be seen that the oxidation of titanium carbide and the binder phase slows down and wear is suppressed.
　（実施例６）
　また、第１，第２の実施形態を用いた装飾部品用セラミックスを用いて、釣糸案内用装飾部品である釣糸用ガイドリングおよびこの釣糸用ガイドリングを備えた釣糸用ガイドおよび時計用装飾部品である時計用ケースや時計バンド駒を作製したところ、耐磨耗性に優れ高い硬度を有していることから表面に傷が付きにくく、銀色の色調を長期にわたり維持することができるので、これらの装飾部品を用いれば、高級感，美的満足感および精神的安らぎを長期間与え続ける魅力的な商品を構成することができることが分かった。 (Example 6)
Further, using the decorative part ceramics according to the first and second embodiments, a fishing line guide ring that is a fishing line guide decorative part, and a fishing line guide and a watch decorative part provided with the fishing line guide ring. When a watch case or watch band piece was made, it has excellent wear resistance and high hardness, so the surface is not easily scratched and the silver color can be maintained for a long time. It has been found that if decorative parts are used, it is possible to construct an attractive product that continues to give luxury, aesthetic satisfaction and mental comfort for a long time.
　以上説明したような第１，第２の実施形態を用いた装飾部品用セラミックスを用いて、釣糸案内用装飾部品および時計用装飾部品として用いれば、美しい色調として評価の高い銀色を呈し、高級感があって、美的満足感を得ることができ、その結果、視覚を通じて精神的安らぎを得ることができて好適である。 If the ceramics for decorative parts using the first and second embodiments as described above are used as decorative parts for fishing line guides and decorative parts for watches, they exhibit a highly evaluated silver color as a beautiful color tone, and have a high-class feeling. Therefore, aesthetic satisfaction can be obtained, and as a result, mental comfort can be obtained through vision.
　１：釣糸用ガイドリング
　10：耐磨耗性評価装置
　20：時計用ケース
　21：凹部
　22：足部
　23：底部
　24：胴部
　30：中駒
　31：貫通孔
　32：ピン穴
　33：外駒
　40：ピン
　50：時計用バンド 1: Guide ring for fishing line 10: Wear resistance evaluation device 20: Watch case 21: Recess 22: Foot 23: Bottom 24: Body 30: Middle piece 31: Through hole 32: Pin hole 33: Outer piece 40 : Pin 50: Watch band

Claims (5)

  1. 　炭化チタン質焼結体からなる装飾部品用セラミックスであって、ジルコニアが９質量％以上３０質量％以下、コバルトおよびニッケルの少なくとも１種が５質量％以上２５質量％以下、クロムが１質量％以上１０質量％以下、ジルコニア、コバルト、ニッケルおよびクロムの合計が５０質量％未満の含有量で含まれており、クロムがコバルトまたはニッケルと固溶していることを特徴とする装飾部品用セラミックス。 A ceramic for decorative parts comprising a titanium carbide sintered body, wherein zirconia is 9% by mass to 30% by mass, at least one of cobalt and nickel is 5% by mass to 25% by mass, and chromium is 1% by mass or more. A ceramic for decorative parts, comprising 10% by mass or less and a total amount of zirconia, cobalt, nickel and chromium of less than 50% by mass, wherein chromium is solid-solved with cobalt or nickel.
  2. 　炭化チタン質焼結体からなる装飾部品用セラミックスであって、コバルトを５質量％以上２５質量％以下、クロムを１質量％以上１０質量％以下、ニオブを２質量％以上１０質量％以下の含有量で含み、クロムおよびニオブがコバルトと固溶していることを特徴とする装飾部品用セラミックス。 A ceramic for decorative parts made of a titanium carbide sintered body, containing cobalt in an amount of 5% by mass to 25% by mass, chromium in an amount of 1% by mass to 10% by mass, and niobium in an amount of 2% by mass to 10% by mass. A ceramic for decorative parts, characterized in that chromium and niobium are in solid solution with cobalt.
  3. 　モリブデンをコバルトに対して３５質量％以下の含有量で含むことを特徴とする請求項１または２に記載の装飾部品用セラミックス。 The ceramic for decorative parts according to claim 1 or 2, comprising molybdenum in a content of 35% by mass or less based on cobalt.
  4. 　ジルコニアを９質量％以上３０質量％以下の含有量で含み、ジルコニア、コバルト、クロム、ニオブおよびモリブデンの合計が５０質量％未満であることを特徴とする請求項１または２に記載の装飾部品用セラミックス。 The decorative component according to claim 1 or 2, wherein zirconia is contained in a content of 9% by mass or more and 30% by mass or less, and a total of zirconia, cobalt, chromium, niobium and molybdenum is less than 50% by mass. Ceramics.
  5. 　請求項１～５のいずれかに記載の装飾部品用セラミックスからなることを特徴とする釣糸案内用装飾部品。 A decorative part for fishing line guide, comprising the ceramic for decorative parts according to any one of claims 1 to 5.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103370948A (en) * 2011-02-07 2013-10-23 京瓷株式会社 Accessory member and accessory comprising same
CN108366549A (en) * 2016-01-27 2018-08-03 古洛布莱株式会社 Fishline guiding element with high hardness surface layer and the fishing rod for having the fishline guiding element

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204149A (en) * 1982-05-21 1983-11-28 Toshiba Tungaloy Co Ltd Sintered alloy for decoration
JPH04271739A (en) * 1991-02-28 1992-09-28 Kyocera Corp Part for fishing rod
JPH05287432A (en) * 1992-04-13 1993-11-02 Mitsubishi Materials Corp Sintered hard alloy for decoration
JP2002105577A (en) * 2000-09-28 2002-04-10 Kyocera Corp Decorative member and its production method
WO2005093110A1 (en) * 2004-03-29 2005-10-06 Kyocera Corporation Ceramic sintered product and method for production thereof, and decorative member using the ceramic sintered product
JP2007284779A (en) * 2005-09-27 2007-11-01 Kyocera Corp Ceramics for decorative component and decorative component for watch using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58204149A (en) * 1982-05-21 1983-11-28 Toshiba Tungaloy Co Ltd Sintered alloy for decoration
JPH04271739A (en) * 1991-02-28 1992-09-28 Kyocera Corp Part for fishing rod
JPH05287432A (en) * 1992-04-13 1993-11-02 Mitsubishi Materials Corp Sintered hard alloy for decoration
JP2002105577A (en) * 2000-09-28 2002-04-10 Kyocera Corp Decorative member and its production method
WO2005093110A1 (en) * 2004-03-29 2005-10-06 Kyocera Corporation Ceramic sintered product and method for production thereof, and decorative member using the ceramic sintered product
JP2007284779A (en) * 2005-09-27 2007-11-01 Kyocera Corp Ceramics for decorative component and decorative component for watch using the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103370948A (en) * 2011-02-07 2013-10-23 京瓷株式会社 Accessory member and accessory comprising same
CN103370948B (en) * 2011-02-07 2016-02-17 京瓷株式会社 Ornament component and possess the ornament of this ornament component
CN108366549A (en) * 2016-01-27 2018-08-03 古洛布莱株式会社 Fishline guiding element with high hardness surface layer and the fishing rod for having the fishline guiding element
EP3409111A4 (en) * 2016-01-27 2019-10-30 Globeride, Inc. Fishing line guide having high hardness surface layer and fishing rod provided with such fishing line guide
US11076585B2 (en) 2016-01-27 2021-08-03 Globeride, Inc. Fishing line guide having high-hardness surface layer and fishing rod provided with said fishing line guide

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