WO2009096478A1 - 白色セラミックス - Google Patents
白色セラミックス Download PDFInfo
- Publication number
- WO2009096478A1 WO2009096478A1 PCT/JP2009/051485 JP2009051485W WO2009096478A1 WO 2009096478 A1 WO2009096478 A1 WO 2009096478A1 JP 2009051485 W JP2009051485 W JP 2009051485W WO 2009096478 A1 WO2009096478 A1 WO 2009096478A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- white ceramic
- white
- less
- decorative part
- ceramic
- Prior art date
Links
Images
Classifications
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
- C04B35/4885—Composites with aluminium oxide
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
- G04B37/225—Non-metallic cases
-
- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/604—Pressing at temperatures other than sintering temperatures
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
-
- 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
- C04B2235/9653—Translucent or transparent ceramics other than alumina
-
- 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 exhibiting a clean white color and decorative parts made of the white ceramics.
- ceramics exhibiting white color include alumina, magnesia, zirconia, etc.
- zirconia has high fracture toughness and high durability against impact when dropped. In particular, it is frequently used as a decorative part.
- Patent Document 1 the present applicants also use zirconia partially stabilized by one or more stabilizers among Y 2 O 3 , MgO, CaO, and CeO 2 as a main component.
- a timepiece dial made of white zirconia ceramics containing alumina and having a brightness (L *) of 88 or more in the L * a * b * color system has been proposed. JP 2000-75053 A
- the white zirconia ceramic described in Patent Document 1 has light transparency and high transparency, and is used for a solar cell driving type timepiece having a built-in power source for converting light energy such as solar cell into electric energy.
- a dial when white zirconia ceramics with such light transmission and high transparency are used as a case for constituting various operation keys and casings of mobile phones, white zirconia ceramics The interior of the mobile phone can be seen through the various operation keys and the case constituting the casing, and the color tone becomes dark, which may give an impression of impairing the luxury.
- the present invention provides high-quality, aesthetic satisfaction, mental comfort, etc. to owners who seek decorative value by presenting a clean white color that hardly transmits light even if the thickness of the ceramic is reduced.
- Another object of the present invention is to provide a white ceramic having excellent mechanical properties and a decorative part made of the white ceramic.
- the white ceramic of the present invention is composed of zirconia ceramics containing a stabilizer and a colorant.
- the main component of the colorant is aluminum oxide (Al 2 O 3 ), and the surface is in the CIE1976L * a * b * color space.
- the lightness index L * and the chromaticness index a * and b * are 83 to 87, -1.5 to 1.5, and -2.0 to 3.0, respectively.
- the white ceramic of the present invention is composed of zirconia ceramics containing a stabilizer and a colorant, the main component of the colorant is aluminum oxide (Al 2 O 3 ), and the surface has CIE1976L * a * b * color.
- Lightness index L * in space is 83 to 87 and chromaticness index a * and b * is -1.5 to 1.5 and -2.0 to 3.0 Even so, it is possible to give the owner a sense of luxury, aesthetic satisfaction, and mental comfort by visually presenting a clean white without impairing the decorative value through the interior of the decorative part.
- the white ceramic of the present invention is composed of zirconia ceramics containing a stabilizer and a colorant.
- the main component of the colorant is aluminum oxide (Al 2 O 3 ), and the brightness of the surface in the CIE1976L * a * b * color space. It is important that the index L * is 83 to 87 and the chromaticness indices a * and b * are ⁇ 1.5 to 1.5 and ⁇ 2.0 to 3.0, respectively.
- the white ceramic of the present invention is obtained by adding a stabilizer and a colorant mainly composed of aluminum oxide (Al 2 O 3 ) exhibiting a relatively low white color to a zirconia ceramic originally exhibiting a highly transparent white color.
- a stabilizer and a colorant mainly composed of aluminum oxide (Al 2 O 3 ) exhibiting a relatively low white color to a zirconia ceramic originally exhibiting a highly transparent white color.
- the lightness index L * is an index indicating the lightness and darkness of the color tone.
- the value of the lightness index L * is 83 or more and 87 or less, and if it is within this range, a white color that is not found in conventional ceramics having a moderate brightness can be obtained, and the sense of quality increases. And higher aesthetic satisfaction.
- the value of the lightness index L * is less than 83, the transparency increases, and when used as a decorative part, the inside can be seen through, so the brightness decreases and the color tone becomes dark, so it is difficult to obtain aesthetic satisfaction.
- the lightness index L * exceeds 87, the color tone is excessively reflected and the color tone becomes too bright, and the high-class feeling is impaired.
- the chromaticness index a * is an index indicating the degree of color tone from red to green.
- the value of the chromaticness index a * is large in the positive direction, the color tone becomes red.
- the absolute value is small, the color tone is vivid.
- the value of the chromaticness index a * is large in the negative direction, the color tone becomes green.
- the value of the chromaticness index a * is ⁇ 1.5 or more and 1.5 or less, and if it is within this range, a white color with vividness can be obtained.
- the value of chromaticness index a * is less than -1.5, the color tone is green.
- the value of chromaticness index a * is greater than 1.5, the color tone is red and close to pink. Is not preferred because it is difficult to say and the sense of quality is impaired.
- the chromaticness index b * is an index indicating the degree of yellow to blue color tone.
- the chromaticness index b * is large in the positive direction, the color tone becomes yellow, and when the absolute value is small, the color tone is vivid.
- the value of the chromaticness index b * is large in the negative direction, the color tone becomes blue.
- the value of the chromaticness index b * is -2.0 or more and 3.0 or less, and within this range, a white having a color tone with suppressed vividness can be obtained as in the index a *.
- the value of the lightness index L * and the value of the chromaticness index a * and b * in the CIE 1976 L * a * b * color space on the surface can be obtained by measuring in accordance with JIS Z 8722-2000.
- a color difference meter (former Minolta CR-221) is used, the reference light source is D65, the illumination light receiving method is condition a ((45-n) [45-0]), and the measurement diameter is 3 mm. Can be set and measured. If a sufficient measurement diameter cannot be ensured, an arbitrary place may be polished and then set to the above-described conditions for measurement.
- the white ceramic of the present invention preferably has a visible light transmittance of 20% or less at a thickness of 1.0 mm.
- the white ceramic of the present invention is used as a decorative part, if the visible light transmittance at a thickness of 1.0 mm is 20% or less, the inside can be seen through the white ceramic used as the decorative part. And there is no loss of decorative value due to dark colors. In addition, 80% of the light hitting the surface is reflected, which makes it possible to create a clean white with moderate brightness, giving the owner a sense of luxury, aesthetic satisfaction and Can give mental comfort.
- the thickness is 1.0 mm here, it goes without saying that the light transmittance of the white ceramic of the present invention having a thickness exceeding 1.0 mm is less than 20% if the light transmittance is 1.0% or less at 1.0 mm. Yes.
- the white ceramic of the present invention preferably has a light transmittance of 15% or less for visible light having a wavelength of 580 nm or more and 740 nm or less at a thickness of 1.0 mm. Visible light with a wavelength between 580 nm and 740 nm is a color that is perceived by human vision as yellow, orange, and red according to the wavelength, and illuminates numbers and letters on the various operation keys of white mobile terminals. Often used for the color of LED light-emitting diodes in backlights. If the white ceramic of the present invention is used for various operation keys of this portable terminal, the light transmittance in the above range is 15% or less, so that the inside is not seen through and used as a backlight. Since it is difficult to transmit the light of yellow, orange, and red LED light-emitting diodes, it is possible to clearly illuminate the numbers and letters only from the portions processed into the numbers and letters.
- the light transmittance of visible light having a wavelength of 1.0 mm to a thickness of 580 nm or more and 740 nm or less 15% or less, it is obtained by containing 3.0% by mass or more of aluminum oxide which is a main component of the colorant. be able to.
- a sample processed to a thickness of 1.0 mm is used as a measurement sample, a spectrocolorimeter (such as Konica Minolta Co., Ltd.
- CM-3700d CM-3700d
- the reference light source is D65
- the wavelength range is 360 to Measurement can be performed in accordance with JIS Z 8722-2000 using a mask (LAV) with 740 nm, viewing angle 10 °, measurement diameter ⁇ 25.4 mm, and illumination diameter ⁇ 28 mm.
- LAV mask
- the content of the stabilizer is preferably 1 mol% or more and less than 3 mol% with respect to the zirconia ceramic. If it is within this range, the reason is not clear, but it contains 3 mol% or more of a stabilizer to stabilize the crystal structure and is mechanical compared to conventional zirconia ceramics that emphasizes the improvement of thermal characteristics. Characteristics can be improved. If this mechanical property is a three-point bending strength, it can be set to 1000 MPa or more in the measurement according to JIS R1601-1995. In addition, the value of fracture toughness that affects the occurrence of chipping and cracking in the impact of the decorative part when dropped can be improved to a value of 5 MPa ⁇ m or more.
- the amount of stabilizer added has a considerable influence on the color tone of white ceramics.
- Zirconia ceramics to which 3 mol% or more of a stabilizer is added tend to have a low brightness index L * and a dark color.
- the addition amount is less than 1 mol%, a large amount of monoclinic crystals are generated in the zirconia ceramics, and the mechanical and thermal characteristics of the white ceramics may be deteriorated.
- the white ceramic of this invention is a compound in which a stabilizer contains yttrium (Y).
- Y yttrium
- MgO, CaO and CeO 2 can be used as a stabilizer, but the crystal structure of zirconia ceramics is maintained at room temperature to be stable cubic or tetragonal, and mechanical properties are improved.
- examples of the yttrium (Y) compound that can stabilize the crystal structure of zirconia ceramics and improve the mechanical properties include yttrium oxide (Y 2 O 3 ), yttrium nitrate hexahydrate (Y (NO 3 )). 3 , 6H 2 O), yttrium chloride hexahydrate (YCl 3 ⁇ 6H 2 O), yttrium acetate trihydrate (Y (CH 3 COO) 3 ⁇ 3H 2 O), and the like.
- YAlO 3 (YAP), Y 3 Al 5 O 12 (YAG), Y 4 Al 5 O 9 (YAM), which are compounds of yttrium (Y) and aluminum (Al) can be used.
- the content of the colorant is preferably 0.3% by mass or more and 5.0% by mass or less. If it is within this range, the amount of light reflection that gives the surface of the decorative part a moderate brightness will be the amount of light reflected, and the owner should give the owner a sense of luxury, aesthetic satisfaction and mental comfort with a clean white color. it can.
- the content of the colorant is less than 0.3% by mass, the value of the lightness index L * of the white ceramics becomes low and the color tone may become dark.
- the content of the colorant exceeds 5.0% by mass, the value of the lightness index L * becomes too large, resulting in a color tone that reflects light excessively. Since it may be damaged, it is not preferable.
- the white ceramic of this invention contains iron (Fe) as a subcomponent of a coloring agent.
- Iron (Fe) tends to form a compound with aluminum oxide (Al 2 O 3 ), which is the main component of the colorant, and the reason is not clear, but it is thought that the formation of this compound can reduce the transparency. . Therefore, even if the white ceramic of the present invention is processed as a decorative part to reduce the thickness, the inside is not seen through the decorative part, and the color tone is less likely to impair the sense of quality.
- the white ceramic of the present invention preferably has an apparent density of 5.9 g / cm 3 or more and 6.1 g / cm 3 or less.
- the apparent density is 5.9 g / cm 3 or more and 6.1 g / cm 3 or less.
- An apparent density value in this range can be obtained by firing at a sintering temperature in the range of 1350 ° C. or higher and 1550 ° C. or lower.
- the apparent density may be obtained according to JIS R 1634-1998.
- the maximum diameter of open pores on the surface is preferably 10 ⁇ m or less. If the maximum diameter of the open pores on the surface of the white ceramic is 10 ⁇ m or less, the shadows of the open pores are not visually recognized as uneven color, and decorative values such as luxury, cleanliness and aesthetic satisfaction are obtained. Can be increased.
- the maximum diameter of the open pores can be measured using a metal microscope. Specifically, first, the surface of the white ceramic is photographed at a magnification of 100 using a metal microscope. Then, the photograph taken is imaged with a CCD camera, and the open pores within 9 ⁇ 10 ⁇ 2 mm 2 in this image are observed, and the outer diameter of the largest open pore is determined from the image. With this as one time, the other observation sites are observed a total of 10 times, and the outer diameter of the largest open pore obtained from the observation results of 10 times is defined as the maximum diameter of the open pore here.
- the occupied area ratio of open pores on the surface is preferably 1% or less. If the area ratio of the open pores on the surface of the white ceramic is 1% or less, even if the small open pores are finely dispersed, the shadow of the open pores is not reflected on the entire surface, so the surface tone is moderate. A white ceramic having brightness can be obtained. More preferably, the occupied area ratio of open pores on the surface is 0.8% or less.
- the occupation area ratio of the open pore in the surface of white ceramics it can measure using a metal microscope similarly to the maximum diameter of an open pore. Specifically, first, the surface of the white ceramic is photographed at a magnification of 100 times using a metal microscope. Then, the photograph taken is imaged with a CCD camera, and the open pores within 9 ⁇ 10 ⁇ 2 mm 2 in this image are observed, the total area of the open pores is calculated, and the total area is 9 ⁇ 10 ⁇ By dividing by 2 mm 2 , the area occupied by the open pores in the observed part is obtained. This is done once, and the other observation sites are observed 10 times in total, and the average value is calculated from the occupied area ratio of the open pores at each time to obtain the occupied area ratio of the open pores.
- the white ceramic of the present invention preferably has an average crystal grain size of aluminum oxide, which is the main component of the colorant, of 0.5 ⁇ m or more and 2.0 ⁇ m or less. If the average crystal grain size of aluminum oxide is 0.5 ⁇ m or more and 2.0 ⁇ m or less, the colorant is uniformly dispersed, so that the white coloring effect can be enhanced.
- the average crystal grain size of aluminum oxide is less than 0.5 ⁇ m, the crystal grain size is so small that it is difficult to lower the transparency of the white ceramics, and there is a risk that the color tone of the white ceramics cannot be given a high-class feeling.
- an average crystal grain size exceeding 2.0 ⁇ m is preferable in terms of reducing the transparency of white ceramics to a high-grade color tone, but a subtle color difference between zirconia ceramics crystals and aluminum oxide crystals. Is not preferred because it may be reflected on the surface of the white ceramic.
- the average particle diameter of aluminum oxide, which is the main component of the colorant is larger than the average particle diameter of zirconium oxide, which is the main component as a raw material.
- the average crystal grain size ratio of the zirconia ceramic crystal to the aluminum oxide crystal is 0.05 to 0.5. Is preferred. If the average crystal grain size ratio between the zirconia ceramic crystal and the aluminum oxide crystal is 0.05 or more and 0.5 or less, the aggregation of the crystal particles is suppressed when the raw materials are mixed and pulverized, and the zirconia ceramics are formed in the compact and sintered body. The crystals are less likely to be unevenly distributed, and the color tone difference between the zirconia ceramic crystal and the aluminum oxide crystal can be suppressed.
- the average crystal grain size ratio between the zirconia ceramic crystal and the aluminum oxide crystal is less than 0.05, the particles aggregate when the raw materials are mixed and pulverized, resulting in uneven distribution of the zirconia ceramic crystal, and the aluminum oxide as a colorant It becomes difficult to uniformly disperse the zirconia ceramics, and it becomes difficult to reduce the transparency of the zirconia ceramics, and when the thickness is reduced by processing as a decorative part, the interior can be seen through the decorative part. , There is a risk of deteriorating the luxury.
- the average crystal grain size ratio between the zirconia ceramic crystal and the aluminum oxide crystal exceeds 0.5, the transparency of the white ceramic can be reduced, but the boundary between the zirconia ceramic crystal and the aluminum oxide crystal. Is likely to be visually confirmed, and the color difference between the two may be reflected on the surface of the white ceramic, which is not preferable.
- the white ceramic of the present invention is suitably used as a decorative part.
- Examples of the decorative part for a watch made of the white ceramic of the present invention include a watch case and a watch band piece.
- FIG. 1A and 1B show an example of a watch case that is a decorative part for a watch according to the present invention.
- FIG. 1A is a perspective view of the watch case as viewed from the front side
- FIG. 1B is a watch case of FIG. It is the perspective view which looked at the case from the back side.
- FIG. 2 is a perspective view showing another example of a watch case which is a decorative part for watch of the present invention.
- FIG. 3 is a schematic view showing an example of the configuration of a watch band which is a decorative part for watch of the present invention.
- symbol is attached
- a watch case 10A shown in FIG. 1 includes a recess 11 for housing a movement (drive mechanism) (not shown) and a foot 12 for fixing a watch band (not shown) for mounting the watch on an arm.
- the concave portion 11 includes a thin bottom portion 13 and a thick body portion 14.
- a watch case 10B shown in FIG. 2 is formed in a body portion 14 for fixing a hole 15 for receiving a movement (drive mechanism) (not shown) and a watch band (not shown) for mounting the watch on the arm. Foot 12 is provided.
- the band piece constituting the watch band 50 shown in FIG. 3 has a middle piece 20 having a through hole 21 into which the pin 40 is inserted and a pin hole 31 into which both ends of the pin 40 are inserted.
- the pin 40 is inserted into the through hole 21 of the middle piece 20, and both ends of the inserted pin 40 are inserted into the pin holes 31 of the outer piece 30, thereby And the outer piece 30 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 10A and 10B and the watch band 50 are made of the white ceramics of the present invention. You can get enough satisfaction and you can get mental comfort through vision.
- the surface Vickers hardness (Hv) is one of the factors affecting the long-term reliability, and the Vickers hardness (Hv) is preferably 8 GPa or more. If the Vickers hardness (Hv) is within this range, the surface of the decorative part is less likely to be damaged, so even if it comes into contact with a hard material such as dust made of glass or metal, the surface of the decorative part can be easily damaged. Is less likely to occur.
- the Vickers hardness (Hv) of the surface of this decorative part can be measured according to JIS R 1610-2003.
- the fracture toughness affects the wear resistance of the surface of the decorative part, and the higher the value, the better.
- the fracture toughness of the white ceramic of the present invention is preferably 4 MPa ⁇ m 1/2 or more. This fracture toughness can be measured in accordance with an indenter press-in method (IF method) defined in JIS R 1607-1995.
- the lighter one is preferred, so the apparent density is 6 g / cm 3 or less (excluding 0 g / cm 3 ). This apparent density is measured in accordance with JIS R 1634-1998.
- the white ceramic of the present invention has a tensile strength of 196 N or more.
- a cemented carbide pin (not shown) longer than the length of the through hole 21 into the through holes 21a and 21b of the middle piece 20
- the pin is pulled in the direction of separating, The strength when 20 is broken can be read with a load cell.
- a ferromagnetic metal having a mass magnetization of 162 G ⁇ cm 3 / g or more is considered in consideration of an adverse effect on a movement (drive mechanism) not shown.
- the content of cobalt (Co) is preferably 0.1% by mass or less in total with respect to 100% by mass of white ceramics.
- the content of such a ferromagnetic metal can be measured by ICP (Inductivity Coupled Plasma) emission analysis.
- FIG. 4 is a perspective view showing an example of a mobile phone using the decorative part for a mobile terminal of the present invention
- FIG. 5 shows a state in which the casing of the mobile phone in the example shown in FIG. 4 is opened. It is a perspective view shown.
- the decorative part for portable terminal of the present invention is preferably made of the white ceramic of the present invention, and specific examples thereof include various operation keys and cases shown in FIGS.
- the cellular phone 60 in the example shown in FIG. 4 includes a mode key 61a for changing to a radio mode that is a radio listening mode, a music mode that is a music listening mode, and a manner key 61b for setting the cellular phone 60 to a manner mode.
- the first casing 62 includes a touch key 63 for detecting contact with a finger or the like, and input is performed by this contact, a camera 64 for imaging a subject, a light 65, a touch sensor 63, and the like.
- the second casing 67 is provided with a slide switch 66 for setting whether to enable or disable the input.
- the second casing 67 includes a front case 69a and a rear case 69b, and a liquid crystal display unit 70 is provided in the front case 69a.
- the first casing 62 also has a front case 71a and a rear case 71b, and various operation keys are provided on the front case 71a.
- the operation keys include a numeric keypad 72a for inputting a telephone number, a cursor movement key 72b for moving a cursor for various function menus, a call key 72c for starting a call by pressing when receiving a call, turning on / off the power, and pressing after a call.
- the owner is provided with a sense of luxury, aesthetic satisfaction and mental comfort over a long period of time, and is satisfied by owning the mobile phone 60 exhibiting such a color tone. A feeling can be made.
- the white ceramic of the present invention has good compatibility with other color tones, it can be used in combination with members of various color tones, which can meet the diversification of consumer preferences.
- the portable terminal in which the decoration component for portable terminals of this invention is used is not limited to the mobile telephone 60, A portable information terminal (PDA) ), A portable terminal such as a portable car navigation system or an audio player, and various portable terminals are applicable as long as the parts are required to have decorativeness.
- PDA portable information terminal
- a portable terminal such as a portable car navigation system or an audio player
- various portable terminals are applicable as long as the parts are required to have decorativeness.
- FIG. 6 is a schematic diagram showing an example of the configuration of a soap case which is a decorative part for daily goods of the present invention.
- a soap case 80 shown in FIG. 6 includes a main body 83 and a lid 82, and a discharge hole 85 for cutting off water adhering to the surface of the soap 81 is formed on the mounting surface 84 of the soap 81 of the main body 83.
- the soap 81 is placed on the mounting surface 84 of the main body 83 and stored by fitting the lid 82 to the main body 83.
- the lid 82 is removed from the main body 83. Remove the soap 81 and use it. And by placing the used soap 81 on the mounting surface 84 of the main body 83, the water adhering to the surface of the soap 81 can be cut off by the discharge hole 85, and the soap 81 is prevented from melting. It is something that can be done.
- One or both of the lid 82 and the main body 83, which are the soap case 80, are made of the white ceramic of the present invention. Can give satisfaction and mental comfort.
- FIG. 7 is a perspective view showing an example of a coffee cup set which is a decorative part for daily goods of the present invention.
- the coffee cup set 90 shown in FIG. 7 includes a coffee cup 91, a saucer 92, and a spoon 93. Since the coffee cup 91, the saucer 92, and the spoon 93 are made of the white ceramic of the present invention, they are owned by many customers. Can give a sense of luxury, aesthetic satisfaction, and mental comfort through visual sense when used and when used.
- the white ceramic of the present invention is compatible with other color tones
- at least one of the coffee cup 91, the saucer 92 or the spoon 93 is made of the white ceramic of the present invention, and the other types are used in combination with different color tones. You can also.
- the decorative part for daily goods of the present invention can be suitably used not only for the soap case 80 and the coffee cup set 90 but also for decorative parts for daily goods such as a brush, razor pattern, earpick and scissors.
- the use of the decorative parts for daily necessities of the present invention that presents a white color on the amenity goods marked with various logos, etc. provides a sense of luxury and aesthetic satisfaction with a strong extraordinary feeling. Can give feeling and mental comfort.
- FIG. 8 is a perspective view showing an example of a vehicle body to which a vehicle article decorative part of the present invention is attached.
- the vehicle body 100 shown in FIG. 8 is provided with an emblem 101 which is a decorative part for vehicle articles.
- the emblem 101 is made of the white ceramic of the present invention, so that the owner can visually feel high-class feeling, aesthetic satisfaction and Since it can provide mental comfort, the decorative value of the vehicle body 100 can be increased.
- the emblem 101 attached to the front of the vehicle body 100 is shown.
- the emblem 101 such as a manufacturer name or a vehicle model name is used as a decorative part for a vehicle article of the present invention made of the white ceramic of the present invention behind the vehicle body 100.
- the decorative value of the vehicle body 100 can also be increased by attaching it.
- FIG. 9 is a front view showing an example of a corner pole using the vehicle article decorative part of the present invention.
- the corner pole 102 shown in FIG. 9 is attached to mark the left front of the vehicle body (in the case of a right-hand drive vehicle) that is difficult to see from the driver's seat when the vehicle is taken in and out of the parking lot.
- a lighting unit 105 including a unit 103, a pole unit 104, and an LED is provided.
- the decorative parts for vehicle articles of the present invention include not only the emblem 101 and the corner pole 102 but also a part of the wheel cap, a part of the hood ornament provided on the hood of the vehicle body, and small items and accessories attached to the interior of the vehicle, or these. Even if it is used as a part, it is preferable because the decorative value is improved.
- FIG. 10 is a front view showing an example of a golf club using the decorative component for sports equipment of the present invention.
- a golf club 110 shown in FIG. 10 includes a shaft 111, a grip 112 at one end of the shaft 111, and a head 113 at the other end of the shaft 111.
- the head 113 has a face surface 113F that is a portion for capturing a golf ball and a sole surface 113S that is a portion that contacts the ground, and an accessory 114 embedded in the face surface 113F is made of the white ceramic of the present invention.
- the decorative value can be increased.
- the accessory 114 which is a decorative part for sports equipment of the present invention made of the white ceramic of the present invention, is embedded in the sole surface 113S and the grip 112 as well as the face surface 113F.
- FIG. 11 is a bottom view showing an example of spike shoes using the decorative component for sports equipment of the present invention.
- a spike shoe 120 shown in FIG. 11 is used, for example, for soccer or rugby, and a plurality of studs 122 formed in a protruding shape for fixing a shaft foot when kicking a ball are attached to a shoe sole 121.
- the stud 122 is made of the white ceramic of the present invention as a decorative part for sports equipment of the present invention, so that the decorative value is improved, and the stud 122 is more resistant to abrasion than a conventionally used aluminum alloy stud. Since the wearability is excellent, the replacement frequency of the stud 122 can be reduced, so that the cost of replacement can be reduced. Note that the surface of the stud 122 may be covered with a transparent resin in order to prevent the stud 122 from being chipped that may occur during the competition.
- FIG. 12 is a perspective view showing an example of a guitar using the musical instrument decorative part of the present invention.
- the main configuration of the guitar 130 shown in FIG. 12 includes a main body 131 and a neck 132 extending forward from the main body 131.
- a nut 133 is disposed at the tip of the neck 132, and a tuning beg 135 capable of adjusting the tension of the string 134 is provided for each string 134 in front of the nut 133.
- a clamp mechanism 136 for holding the string 134 so as not to move with respect to the nut 133 is disposed near the nut 133.
- a tremolo device 137 for giving an impressive sound effect by simultaneously increasing or decreasing the tension of the string 134 is attached to the main body 131.
- the tremolo device 137 includes a base plate 138 attached to the main body 131, a bridge saddle 139 that is held by the base plate 138 and holds the string 134 in a tunable manner, and a tremolo bar 140 that operates the tremolo device.
- the decorative value of the guitar 130 is improved by forming the base plate 138, the bridge saddle 139, the tremolo bar 140, etc. of the guitar 130 with the white ceramics of the present invention as the decorative parts for musical instruments of the present invention. You can feel the satisfaction of owning 130 and attract many spectators.
- FIG. 13 is a schematic view showing an example of an artificial dental crown using the decorative part for accessory of the present invention.
- FIG. 13 shows an artificial dental crown 141 attached to an abutment (apatment) 144 fixed to an artificial tooth root (implant) 143 embedded in the jawbone 142 inside the gingiva 145.
- this artificial dental crown 141 With the white ceramics of the present invention as a decorative part for jewelry of the present invention, it becomes beautiful white teeth and can give a healthy and refreshing impression, so the owner is highly satisfied Can be given.
- the artificial tooth root 143 embedded in the jawbone 142 is formed in a screw shape, and at least one of chitin, collagen, and derivatives thereof having a high ability to induce the formation of new bone is formed in the screw-shaped portion.
- a hard bonding layer made of a biodegradable substrate containing seeds may be formed.
- a soft bonding layer made of the crosslinked biodegradable base material may be formed on the base of the abutment 144 so as to contact the gingiva 145 located on the upper side of the jawbone 142.
- the decorative part for jewelry of the present invention made of the white ceramic of the present invention is made of zirconia ceramics, it is easy to adapt to the living body. Taking advantage of this advantage, not only the artificial crown 141 but also the artificial tooth root 143 and the abutment It is also suitable for use in 144.
- FIG. 14 is a front view showing an example of an earphone unit using the decorative component for accessory of the present invention.
- the earphone unit 150 shown in FIG. 14 is inserted through a speaker 151 that is inserted into the listener's ear shell to generate sound waves, a case 152 that incorporates the speaker 151, and a cord derivation unit 153 that contacts the case 152. And a cord 154 for supplying an electric signal to the speaker 151.
- the decorative value is enhanced, and many owners can feel high-quality, aesthetic satisfaction and spirit through the visual senses. It can be set as a decorative part for jewelry that can be given peace of mind.
- FIG. 15 is a perspective view showing an example of eyeglasses using the decorative part for accessory of the present invention.
- the eyeglass 160 shown in FIG. 15 includes a pair of lenses 161a and 161b for correcting vision and protecting eyes from ultraviolet rays, a bridge 162 connecting the pair of lenses 161a and 161b, and the lenses 161a and 161b.
- the armor 163a, 163b connected to 161b, the temples 164a, 164b connected to the armor 163a, 163b so as to be able to rotate via a hinge, and the lenses 161a, 161b via nose pad connecting members, respectively.
- a nose pad 165 to be attached.
- the decorative value is increased, It can be used as a decorative part for jewelry that gives the owners a sense of quality, aesthetic satisfaction and mental comfort.
- the additive amount of yttrium oxide as a stabilizer is 1 mol% or more and less than 3 mol%, and 100 wt% of zirconium oxide produced by the coprecipitation method is used as a colorant.
- Aluminum oxide in a range of mass% to 5.0 mass% is added and mixed, and water as a solvent is further added to the mixed raw material, and mixed and pulverized by a vibration mill or a ball mill.
- the average particle diameter of zirconium oxide as a raw material is 0.05 ⁇ m or more and 0.5 ⁇ m or less, and the average particle diameter of aluminum oxide is 0.5 ⁇ m or more and 2.0 ⁇ m or less.
- white ceramic balls made of zirconia, alumina, or zirconia and alumina as the balls used for mixing and grinding.
- white ceramic balls include zirconium oxide (ZrO 2 ) 91 to 99 mol% with a purity of 99.5% or more, yttrium oxide (Y 2 O 3 ), hafnium oxide (HfO 2 ), cerium oxide (CeO 2 ), and oxide.
- a composition comprising 1 to 9 mol% of at least one stabilizer selected from magnesium (MgO) and calcium oxide (CaO), and aluminum oxide (Al 2 O 3 ) having a purity of 99.5% or more are further added to this composition. It is preferable to use a composition containing 1 to 40% by mass or consisting only of aluminum oxide having a purity of 99.5% or more.
- the white ceramic balls used for the average particle diameter of this raw material powder and mixed pulverization have a lightness index L * in the CIE1976 L * a * b * color space of the surface of the white ceramic of the present invention of 83 to 87, and a chromaticness index. This is an important factor for a * and b * to be ⁇ 1.5 to 1.5 and ⁇ 2.0 to 3.0, respectively.
- a predetermined amount of various binders as a binder is added to the mixed and pulverized raw material, and dried by spray drying to form granules. And, using this granule, a desired shape of a disk, flat plate, torus, etc. by a desired molding method, for example, a dry pressure molding method, a cold isostatic pressing method, an extrusion molding method, an injection molding method, etc. To form.
- the obtained molded body is degreased as necessary, and then fired at a temperature of 1350 ° C. or higher and 1550 ° C. or lower in an air atmosphere to obtain a sintered body.
- the apparent density of the white ceramic of the present invention is affected by the sintering temperature, and the apparent density increases as the sintering temperature is increased.
- the apparent density is 5.9 g / cm 3 or more and 6.1 g / cm 3 or less, and it has excellent mechanical properties and is The number of open pores on the surface is reduced, and degranulation from the end face of the open pores can be suppressed.
- the obtained sintered body is barrel polished to obtain the white ceramic of the present invention in which the surface of the sintered body becomes a beautiful white decorative surface.
- the shape of the white ceramic product is complex, it is molded into a block shape or a shape close to the product shape in advance by a dry pressure molding method, cold isostatic pressing method, extrusion molding method, injection molding method, etc. Then, after firing and grinding so as to obtain a product shape, barrel polishing may be performed. Alternatively, a product shape may be formed from the beginning by an injection molding method, and barrel polishing may be performed after firing.
- a small diamond paste having an average particle size of 1 ⁇ m or less may be supplied to a tin lapping machine for lapping.
- a centrifugal barrel polishing machine is used, and media and green carborundum (GC) are charged into the centrifugal barrel polishing machine, and may be performed wet for about 24 hours.
- GC green carborundum
- the molding pressure affects the area ratio of the open pores on the surface, the maximum diameter of the open pores, and the Vickers hardness (Hv).
- the molding pressure is 49 MPa or more and 196 MPa or less.
- the molding pressure is set to 49 MPa or more because if the molding pressure is less than 49 MPa, the occupied area ratio of open pores on the surface of the white ceramic exceeds 1% or the Vickers hardness (Hv) becomes less than 8 GPa. is there.
- the reason why the molding pressure is 196 MPa or less is that if it exceeds 196 MPa, the life of the molding die is shortened.
- the life of the mold can be extended, the occupied area ratio of open pores on the surface of the white ceramic can be reduced to 1% or less, and the Vickers hardness (Hv) is 8 GPa. This can be done.
- the molding pressure is 96 MPa or more, the maximum diameter of open pores on the surface can be made 10 ⁇ m or less, which is more preferable.
- the white ceramic of the present invention obtained as described above has a clean and beautiful color tone and has a highly evaluated white color, and can provide a high-class feeling and aesthetic satisfaction, and as a result, mental comfort can be obtained through vision.
- decorative parts for watches such as watch cases and watchpieces
- decorative parts for portable terminals such as various operation keys and cases to be operated, soap cases, coffee cup sets, knives , Fork, toothbrush, razor handle, earpick, scissors
- decorative parts for daily necessities such as stamps and business cards, emblems of manufacturers and car models
- decorative parts for vehicle parts such as corner poles, golf club accessories and spike shoes
- Decorative parts for sports equipment such as studs
- decorative parts for musical instruments such as guitar base plates, artificial tooth crowns and earphone units It can be suitably used for jewelry decorative component for a bridge or the like of the case and glasses.
- the white ceramic of the present invention can be suitably used for a watch-type mobile phone or the like in which a watch and a mobile phone are combined and have both functions. .
- zirconium oxide having an average particle size of 0.1 ⁇ m produced by a coprecipitation method to which 2 mol% of yttrium oxide as a stabilizer was added was prepared. Then, with respect to 100 parts by mass of the zirconium oxide, aluminum oxide having a purity of 99% or more and an average particle diameter of 1 ⁇ m is added and mixed at a ratio of 3 parts by mass, and water is added to the mixed raw material as a solvent. A fixed amount was added to form a slurry. Next, this slurry was put into a ball mill using zirconia balls having a purity of 99.5% or more and mixed and ground.
- a predetermined amount of paraffin wax was further added as a binder, and then spray-dried with a spray dryer to obtain granules. Then, the granules are formed into a disk-shaped molded body by a dry pressure molding method using a pressure press molding machine, and the molded body is fired at a maximum temperature of 1450 ° C., and the outer diameter is 30 mm and the thickness is increased.
- a white ceramic of the present invention having a disk shape of 5 mm was obtained.
- the same amount as that of the white ceramics of the present invention is obtained except that two kinds of zirconium oxides having an addition amount of yttrium oxide of 2 mol% and 3 mol% are added and no aluminum oxide is added. It was produced in the process.
- the thing with the addition amount of 2 mol% of the yttrium oxide powder was made into the comparative example 1, and the thing with the addition amount of 3 mol% of the yttrium oxide powder was made into the comparative example 2.
- the lightness index L *, chromaticness in the CIE1976L * a * b * color space of each surface The indices a * and b * were measured according to JIS Z 8722-2000.
- a color difference meter (former Minolta CR-221) is used, the reference light source is D65, the illumination light receiving method is condition a ((45-n) [45-0]), and the measurement diameter is The measurement was set at 3 mm.
- Table 1 The results are shown in Table 1.
- the value of the brightness index L * was low in the conventional white ceramics of Comparative Examples 1 and 2 in which 2 mol% and 3 mol% of aluminum oxide were not added. Moreover, there was little reflection of light and it was a thing more transparent than the white ceramics of this invention.
- the value of the lightness index L * is in the range of 83 to 87, more light is reflected than Comparative Examples 1 and 2, and the transparency can be lowered.
- the chromaticness indices a * and b * are also 0.1 and 0.7, respectively, which are within the scope of the present invention, ⁇ 1.5 to 1.5 and ⁇ 2.0 to 3.0, so that a sense of quality and cleanliness through visual sense. It was a white ceramic that gave aesthetic satisfaction and mental comfort.
- white ceramics of the present invention with different amounts of addition of yttrium oxide as a stabilizer and aluminum oxide as a colorant were prepared, and the lightness index L * and chromati in the CIE1976L * a * b * color space on the surface.
- the Knes index a * b * and the three-point bending strength were measured, and an investigation was made as to whether the color tone gives a high-class feeling to monitors including foreigners.
- the amount of yttrium oxide, which is a stabilizer, is varied in the range of 0.9 to 3.0 mol%, and the zirconium oxide having an average particle size of 0.1 ⁇ m produced by the coprecipitation method has a purity of An aluminum oxide having an average particle diameter of 1 ⁇ m or more with 99% or more was prepared.
- Example 2 aluminum oxide was added in an amount shown in Table 2 and mixed with 100% by mass of zirconium oxide. After that, the same process as in Example 1 was performed, and sample No. 1 which is a white ceramic of the present invention having a disk shape with an outer diameter of 30 mm and a thickness of 5 mm is used. 1-16 were obtained.
- Sample No. Test pieces having a shape conforming to JIS R1601-1995 were prepared separately from 1 to 16, and the three-point bending strength was measured.
- Sample No. 1 to 16 were all good with a monitor evaluation of 80% or more.
- Sample No. in which the addition amount of the stabilizer is 1 mol% or more and less than 3 mol% is used.
- 2 to 6 and sample no. Nos. 8 to 16 were found to have excellent mechanical properties with a three-point bending strength exceeding 1000 MPa.
- 2 to 6 and 9 to 15 were even better with a monitor evaluation of 85% or more.
- the sample No. in which the addition amount of the stabilizer is 2 mol% and the addition amount of the colorant is 1.0 mass% or more and 4.0 mass% or less. 11-14 were able to give a high-class feeling to over 90% of monitors.
- sample no After processing samples 1 to 16 to a thickness of 1.0 mm, using a spectrocolorimeter (Konica Minolta Co., Ltd. CM-3700d), the reference light source is D65, the wavelength range is 360 to 740 nm, and the viewing angle is 10
- the light transmittance was measured according to JIS Z 8722-2000 using a mask (LAV) having a measurement diameter of ⁇ 25.4 mm and an illumination diameter of ⁇ 28 mm.
- LAV mask
- the white ceramic of the present invention to which iron (Fe) is added as a subcomponent of the colorant is prepared, and the lightness index L *, chromaticness index a * and b * in the CIE 1976 L * a * b * color space on the surface Measurement and light transmittance were measured.
- Example 2 For sample preparation, the sample No. of Example 2 was used. Iron (Fe) was added to the same composition as 13 as an auxiliary component of the colorant in an amount of 25, 50, 100 ppm in terms of Fe 2 O 3 , and then the same process as in Example 1 was performed. Sample No. 1 which is a disk-shaped white ceramic of the present invention having a thickness of 5 mm. 17-19 were obtained. And sample no. The lightness index L *, chromaticness index a * and b * in the CIE1976 L * a * b * color space on the surfaces 17 to 19 were measured according to JIS Z 8722-2000. The apparatus and measurement conditions used were the same as in Example 1.
- the sample was processed to a thickness of 1.0 mm in the same manner as in Example 3, and measured according to JIS Z 8722-2000.
- the light transmittance for visible light having a wavelength of 740 nm was measured. Numbered in ascending order. The results are shown in Table 3.
- samples with different firing temperatures in the range of 1340 to 1560 ° C. were prepared, and the apparent density was measured.
- the sample No. of Example 2 was used.
- a raw material having the same composition as 13 was used. This was produced up to a molded body in the same process as in Example 1, and fired at the firing temperatures shown in Table 4, respectively.
- Sample No. which is a disk-shaped white ceramic of the present invention having an outer diameter of 30 mm and a thickness of 5 mm. . 20-26 were obtained.
- This apparent density was measured in accordance with JIS R 1634-1998. The results are shown in Table 4.
- Sample No. No. 20 had an apparent density of 5.9 g / cm 3 or less because the firing temperature was 1340 ° C. and sintering was insufficient.
- Sample No. For 26 the apparent density decreased because the firing temperature was as high as 1560 ° C and crystal grain growth occurred.
- sample No. 1 fired at a sintering temperature in the range of 1350 ° C. to 1550 ° C. 21 to 25 are in the range of 5.9 g / cm 3 or more and 6.1 g / cm 3 or less, which is a preferable apparent density, and have high decorative value and can suppress the grain detachment and improve the mechanical characteristics. It turned out to be a suitable white ceramic.
- samples with different molding pressures were prepared by a dry pressure molding method using a pressure press, and the maximum diameter of open pores on the surface and the occupied area ratio of the open pores were measured.
- sample preparation the sample No. A raw material having the same composition as 13 was used. Using this, it was produced in the same process as in Example 1 except for the molding pressure shown in Table 5.
- Sample No. 1 was a disc-shaped white ceramic of the present invention having an outer diameter of 30 mm and a thickness of 5 mm. 27-33 were obtained.
- the surface of the white ceramic of the present invention was photographed at a magnification of 100 using a metal microscope. Next, this photograph was imaged with a CCD camera, and the open pores within 9 ⁇ 10 ⁇ 2 mm 2 in this image were observed, and the outer diameter of the largest open pore was determined from the image. Then, once this was done, the other observation sites were observed a total of 10 times, and the outer diameter of the largest open pore was determined as the maximum diameter of the open pore based on the 10 observation results.
- the surface of the white ceramic of the present invention was photographed at a magnification of 100 using a metal microscope in the same manner as the maximum diameter of the open pores.
- this photographed image is imaged with a CCD camera, and the open pores within 9 ⁇ 10 ⁇ 2 mm 2 in this image are observed, the total area of the open pores is calculated, and this total area is 9 ⁇
- the area occupied by the open pores in the portion observed by dividing by 10 ⁇ 2 mm 2 was determined.
- another observation site was observed 10 times with this as one time, and the average value was calculated from the occupied area ratio of the open pores at each time to obtain the occupied area ratio of the open pores.
- Table 5 The results are shown in Table 5.
- the mold has no wear, the maximum diameter of the open pores is 10 ⁇ m or less, the occupied area ratio of the open pores is 1% or less, and the shadow of the pores is not visually recognized as uneven color.
- the surface color tone has a moderate brightness, and it can be a white ceramic with high decorative value such as luxury, cleanliness and aesthetic satisfaction. I understood.
- the white ceramics of the present invention exhibits a highly clean white with a high evaluation as a beautiful color tone, has a high-class feeling, and can obtain aesthetic satisfaction, and as a result, obtain mental comfort through vision.
- the decorative parts for watches the decorative parts for mobile terminals, the decorative parts for daily goods, the decorative parts for vehicle equipment, the decorative parts for sports equipment, and the musical instruments shown in FIGS.
- the decorative parts and decorative parts for jewelry it was possible to obtain a sense of luxury, aesthetic satisfaction, and spiritual comfort through the sense of clean whiteness in all cases.
- the wall thickness is reduced, the interior does not show through, and the color tone is dark and does not impair the decorative value. It was confirmed that it was suitably used.
- FIG. 1 shows an example of a watch case that is a decorative part for a watch according to the present invention
- (a) is a perspective view of the watch case seen from the front side
- (b) is a perspective view of the watch case of (a) seen from the back side.
- FIG. It is a perspective view which shows another example of the case for timepieces which is the decorative component for timepieces of this invention.
- 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 invention.
- It is a perspective view which shows an example of the mobile telephone using the decoration component for portable terminals of this invention.
- FIG. 1 It is a schematic diagram which shows an example of a structure of the soap case which is a decorative part for household goods of this invention. It is a perspective view which shows an example of the coffee cup set which is a decorative component for daily goods of this invention. It is a perspective view which shows an example of the vehicle body which attached the decorative component for vehicle articles of this invention. It is a front view which shows an example of the corner pole using the decorative component for vehicle articles of this invention. It is a front view which shows an example of the golf club using the decorative component for sporting goods of this invention. It is a bottom view which shows an example of the spike shoes using the decorative component for sporting goods of this invention. It is a perspective view which shows an example of the guitar using the decorative component for musical instruments of this invention.
- FIG. 1 It is a schematic diagram which shows an example of the artificial dental crown using the decorative component for accessory of the present invention. It is a front view which shows an example of the earphone unit using the decorative component for accessory of the present invention. It is a perspective view which shows an example of spectacles using the decorative component for jewelry of the present invention.
- 10A, 10B watch case 20: center piece 30: outer piece 40: pin 50: watch band 60: mobile phone 70: liquid crystal display unit 80: soap case 90: coffee cup 100: car body 110: golf club 120: shoes 130: Guitar 141: Artificial dental crown 150: Earphone unit 160: Glasses
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
20:中駒
30:外駒
40:ピン
50:時計用バンド
60:携帯電話機
70:液晶表示ユニット
80:石鹸ケース
90:コーヒーカップ
100:車体
110:ゴルフクラブ
120:シューズ
130:ギター
141:人工歯冠
150:イヤホンユニット
160:めがね
Claims (17)
- 安定化剤および着色剤を含むジルコニアセラミックスからなり、前記着色剤の主成分が酸化アルミニウム(Al2O3)であって、表面のCIE1976L*a*b*色空間における明度指数L*が83以上87以下であり、クロマティクネス指数a*およびb*がそれぞれ-1.5以上1.5以下および-2.0以上3.0以下であることを特徴とする白色セラミックス。
- 1.0mmの厚みにおける可視光線の光透過率が20%以下であることを特徴とする請求項1に記載の白色セラミックス。
- 1.0mmの厚みにおける波長が580nm以上740nm以下の可視光線の光透過率が15%以下であることを特徴とする請求項1に記載の白色セラミックス。
- 前記安定化剤の含有量が前記ジルコニアセラミックスに対して1mol%以上3mol%未満であることを特徴とする請求項1に記載の白色セラミックス。
- 前記安定化剤がイットリウム(Y)を含む化合物であることを特徴とする請求項1に記載の白色セラミックス。
- 前記着色剤の含有量が0.3質量%以上5.0質量%以下であることを特徴とする請求項1に記載の白色セラミックス。
- 前記着色剤の副成分として鉄(Fe)を含むことを特徴とする請求項1に記載の白色セラミックス。
- 見掛け密度が5.9g/cm3以上6.1g/cm3以下であることを特徴とする請求項1に記載の白色セラミックス。
- 表面における開気孔の最大径が10μm以下であることを特徴とする請求項1に記載の白色セラミックス。
- 表面における開気孔の占有面積率が1%以下であることを特徴とする請求項1に記載の白色セラミックス。
- 請求項1に記載の白色セラミックスからなることを特徴とする時計用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とする携帯端末機用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とする生活用品用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とする車両用品用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とするスポーツ用品用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とする楽器用装飾部品。
- 請求項1に記載の白色セラミックスからなることを特徴とする装身具用装飾部品。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020107018388A KR101138264B1 (ko) | 2008-01-29 | 2009-01-29 | 백색 세라믹스 |
EP09705329.2A EP2243756B1 (en) | 2008-01-29 | 2009-01-29 | White ceramic |
JP2009551572A JP5197634B2 (ja) | 2008-01-29 | 2009-01-29 | 白色セラミックス |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008017101 | 2008-01-29 | ||
JP2008-017101 | 2008-01-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009096478A1 true WO2009096478A1 (ja) | 2009-08-06 |
Family
ID=40912822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/051485 WO2009096478A1 (ja) | 2008-01-29 | 2009-01-29 | 白色セラミックス |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2243756B1 (ja) |
JP (1) | JP5197634B2 (ja) |
KR (1) | KR101138264B1 (ja) |
WO (1) | WO2009096478A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011111624A1 (ja) * | 2010-03-09 | 2011-09-15 | 東ソー株式会社 | 赤色透光性ジルコニア焼結体、その製造方法、その焼結体からなる部材、及びその部材を用いる宝飾品及び外装部品 |
JP2015089863A (ja) * | 2013-11-06 | 2015-05-11 | 東ソー株式会社 | 複合プレート及びその製造方法 |
JP2015163558A (ja) * | 2014-02-28 | 2015-09-10 | 香川県 | 可視光遮蔽性白色系セラミックス、その製造方法および白色系セラミックス可視光遮蔽体 |
JP2015231934A (ja) * | 2013-12-19 | 2015-12-24 | 東ソー株式会社 | 白色ジルコニア焼結体及びその製造方法並びにその用途 |
JP2016088842A (ja) * | 2014-10-29 | 2016-05-23 | 京セラ株式会社 | 通信機器外装部品およびこれを備えてなる通信機器 |
JP2017075086A (ja) * | 2015-09-03 | 2017-04-20 | 東ソー株式会社 | 赤色ジルコニア焼結体及びその製造方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012108433A1 (ja) * | 2011-02-07 | 2012-08-16 | 京セラ株式会社 | 装飾品用部材およびこれを備える装飾品 |
CH707475A1 (fr) * | 2013-01-17 | 2014-07-31 | Tih Sa Tech Et Innovation Horlogère | Procédé de fabrication d'un objet d'une forme choisie en matière céramique ou réfractaire. |
US9750322B2 (en) | 2015-03-08 | 2017-09-05 | Apple Inc. | Co-molded ceramic and polymer structure |
US10703680B2 (en) | 2015-05-25 | 2020-07-07 | Apple Inc. | Fiber-reinforced ceramic matrix composite for electronic devices |
US11104616B2 (en) | 2015-09-30 | 2021-08-31 | Apple Inc. | Ceramic having a residual compressive stress for use in electronic devices |
US11604514B2 (en) | 2016-04-14 | 2023-03-14 | Apple Inc. | Substrate having a visually imperceptible texture for providing variable coefficients of friction between objects |
US10264690B2 (en) * | 2016-09-01 | 2019-04-16 | Apple Inc. | Ceramic sintering for uniform color for a housing of an electronic device |
US11088718B2 (en) | 2016-09-06 | 2021-08-10 | Apple Inc. | Multi-colored ceramic housings for an electronic device |
US10420226B2 (en) | 2016-09-21 | 2019-09-17 | Apple Inc. | Yttria-sensitized zirconia |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005170719A (ja) * | 2003-12-10 | 2005-06-30 | Nippon Denko Kk | 明度および白色度が高い酸化ジルコニウム粉末、その焼結体及びその製造方法 |
JP2005306664A (ja) * | 2004-04-21 | 2005-11-04 | Nitsukatoo:Kk | 中空体形状ジルコニア質焼結体及びその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0551255A (ja) * | 1991-08-23 | 1993-03-02 | Toshiba Corp | 装飾用セラミツクス部品 |
JP3631621B2 (ja) * | 1998-08-31 | 2005-03-23 | 京セラ株式会社 | 時計用文字盤 |
WO2007108416A1 (ja) * | 2006-03-20 | 2007-09-27 | Kyocera Corporation | 着色ジルコニア質焼結体及びその製造方法並びに装飾部材 |
-
2009
- 2009-01-29 WO PCT/JP2009/051485 patent/WO2009096478A1/ja active Application Filing
- 2009-01-29 KR KR1020107018388A patent/KR101138264B1/ko not_active IP Right Cessation
- 2009-01-29 JP JP2009551572A patent/JP5197634B2/ja active Active
- 2009-01-29 EP EP09705329.2A patent/EP2243756B1/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005170719A (ja) * | 2003-12-10 | 2005-06-30 | Nippon Denko Kk | 明度および白色度が高い酸化ジルコニウム粉末、その焼結体及びその製造方法 |
JP2005306664A (ja) * | 2004-04-21 | 2005-11-04 | Nitsukatoo:Kk | 中空体形状ジルコニア質焼結体及びその製造方法 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011111624A1 (ja) * | 2010-03-09 | 2011-09-15 | 東ソー株式会社 | 赤色透光性ジルコニア焼結体、その製造方法、その焼結体からなる部材、及びその部材を用いる宝飾品及び外装部品 |
CN102791653A (zh) * | 2010-03-09 | 2012-11-21 | 东曹株式会社 | 红色透光性氧化锆烧结体、其制造方法、由该烧结体形成的构件、及使用该构件的珠宝首饰及外部部件 |
US9249057B2 (en) | 2010-03-09 | 2016-02-02 | Tosoh Corporation | Red light transmitting zirconia sintered body, method for producing the same, member comprising the sintered body, and jewelry goods and exterior component using the member |
JP2015089863A (ja) * | 2013-11-06 | 2015-05-11 | 東ソー株式会社 | 複合プレート及びその製造方法 |
JP2015231934A (ja) * | 2013-12-19 | 2015-12-24 | 東ソー株式会社 | 白色ジルコニア焼結体及びその製造方法並びにその用途 |
JP2015163558A (ja) * | 2014-02-28 | 2015-09-10 | 香川県 | 可視光遮蔽性白色系セラミックス、その製造方法および白色系セラミックス可視光遮蔽体 |
JP2016088842A (ja) * | 2014-10-29 | 2016-05-23 | 京セラ株式会社 | 通信機器外装部品およびこれを備えてなる通信機器 |
JP2017075086A (ja) * | 2015-09-03 | 2017-04-20 | 東ソー株式会社 | 赤色ジルコニア焼結体及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20100120158A (ko) | 2010-11-12 |
KR101138264B1 (ko) | 2012-04-25 |
EP2243756A4 (en) | 2012-01-11 |
JP5197634B2 (ja) | 2013-05-15 |
EP2243756A1 (en) | 2010-10-27 |
JPWO2009096478A1 (ja) | 2011-05-26 |
EP2243756B1 (en) | 2015-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5197634B2 (ja) | 白色セラミックス | |
JP5329529B2 (ja) | 装飾部品用セラミックス | |
JP5511661B2 (ja) | ピンク色〜紫色系セラミックスおよび装飾部品 | |
JP5566292B2 (ja) | 濃青色系セラミックスおよび装飾部品 | |
JP5361866B2 (ja) | 装飾部品用セラミックスおよびこれを用いた装飾部品 | |
JP5094875B2 (ja) | 装飾部品用セラミックスおよびこれを用いた装飾部品 | |
WO2010123104A1 (ja) | 装飾部品用セラミックスおよびこれを用いた装飾部品 | |
JP5328784B2 (ja) | 装飾部品用セラミックスおよびこれを用いた装飾部品 | |
JPWO2010050493A1 (ja) | 装飾部品用セラミックスおよび装飾部品 | |
JP2011047033A (ja) | 装飾部品用セラミックスおよびこれを用いた装飾部品 | |
WO2010087092A1 (ja) | 装飾部品用セラミックスおよび装飾部品 | |
JP2011093725A (ja) | 装飾部品用セラミックスおよび装飾部品 | |
JP5590896B2 (ja) | 金色セラミック焼結体およびこれを用いた装飾部材 | |
JP5235548B2 (ja) | 装飾部品用セラミックスおよび装飾部品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09705329 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009551572 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107018388 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009705329 Country of ref document: EP |