WO2015026169A1 - Method for preparing high hardness material having logo, text, or pattern - Google Patents

Method for preparing high hardness material having logo, text, or pattern Download PDF

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Publication number
WO2015026169A1
WO2015026169A1 PCT/KR2014/007753 KR2014007753W WO2015026169A1 WO 2015026169 A1 WO2015026169 A1 WO 2015026169A1 KR 2014007753 W KR2014007753 W KR 2014007753W WO 2015026169 A1 WO2015026169 A1 WO 2015026169A1
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WIPO (PCT)
Prior art keywords
high hardness
logo
hardness material
letters
patterns
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PCT/KR2014/007753
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French (fr)
Korean (ko)
Inventor
이재형
우명훈
이문희
Original Assignee
영남대학교 산학협력단
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Publication of WO2015026169A1 publication Critical patent/WO2015026169A1/en

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    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/18—Working by laser beam, e.g. welding, cutting or boring using absorbing layers on the workpiece, e.g. for marking or protecting purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/361—Removing material for deburring or mechanical trimming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
    • B24B7/20—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground
    • B24B7/22—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor characterised by a special design with respect to properties of the material of non-metallic articles to be ground for grinding inorganic material, e.g. stone, ceramics, porcelain
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
    • B23K2103/52—Ceramics

Definitions

  • the present invention relates to a method of manufacturing a high hardness material for forming a logo, letters or patterns of various colors having an excellent aesthetic on the surface of the high hardness material that can be used in the case of a portable device.
  • plastic such as polycarbonate and ABS resin, or metal such as stainless steel or aluminum alloy.
  • plastic has the advantage of making the case by relatively inexpensive and simple manufacturing method, but it is not luxurious and metal has high manufacturing cost but relatively good aesthetic, but it is limited in color, and in general, its hardness is not high. It has a fundamental problem of scratching easily on the surface.
  • chemically tempered glass using ion exchange commonly used as a transparent display front panel, is used as a rear panel, but is relatively harder than plastic or metal, but still vulnerable to scratching.
  • zirconia which is ceramics.
  • Zirconia ceramics require stabilizers, with the addition of 3 mol% yttrium oxide (Y 2 O 3 ) being most widely used.
  • Y 2 O 3 yttrium oxide
  • tetragonal zirconia is obtained. Since tetragonal zirconia exhibits well-known phase transformation ignition behavior and cracks do not grow well, it has high strength and toughness and is widely used as a structural material.
  • zirconia ceramics have a high hardness, scratch resistance is very high.
  • zirconia ceramics can implement various colors with the material itself by adding an inorganic pigment, the surface is polished beautiful luster.
  • Zirconia ceramics with such excellent aesthetics and mechanical properties are used in jewelry materials and ornaments such as watch cases.
  • Transparent chemical tempered glass which is also used as the outer case material of portable devices, can be replaced with monocrystalline artificial sapphire, which has a high hardness and hardly scratches.
  • Such artificial sapphire is widely used as a transparent window of a watch.
  • harder transparent polycrystalline ceramics have been developed, such as more economical aluminum oxynitride, which have many characteristics similar to artificial sapphire.
  • the surface of the pigment is decal transfer, screen printing, or spray coating, which is well known in various types of household ceramics. There may be a conventional method of coating and firing on.
  • an image formed through this method has a relatively poor aesthetics and a high resolution, and it is embossed, so it is relatively weak to scratches, and in some cases, can easily fall off the surface of the base.
  • US Pat. No. 5,298,717 discloses a method of engraving negative images with a high energy laser instead of environmentally friendly sandblasting or chemical etching to form identification numbers, barcodes or vignettes on glass or ceramic surfaces.
  • U.S. Patent 5,543,269 discloses a method of engraving an image on ceramics, in particular zirconia ceramics using a laser
  • U.S. Patent 5,804,342 discloses a method of engraving a barcode that can be erased on zirconia ceramics.
  • These methods irradiate the surface of the milky zirconia ceramics with a laser to reduce the irradiated surface and turn it into a dark color close to black to make a high resolution image.
  • the surface is oxidized by heat treatment, the image is erased to the original milk liquor. Go back.
  • This laser marking method is widely used to form high resolution logos, letters, patterns, etc. on the surface of various materials, but it does not give a desired color or glossiness, resulting in poor aesthetics.
  • U.S. Patent Nos. 4,769,310, 4,861,620, 6,238,847, 6,313,436, 6,413,619, 6,852,948 and 6,855,910 attach inorganic pigment marking materials to the laser on the ceramics and irradiate only the desired portions of the laser.
  • Various methods have been disclosed for making colored markings on ceramic surfaces by bonding them with color. However, this method controls the surface roughness of the colored coating layer, which is exposed to the color coated layer on the ceramics and is particularly susceptible to scratches due to insufficient interface bonding with the ceramics, or the glass is not sufficiently plasticized. The surface gloss is not uniform and the aesthetics are inferior.
  • Japanese Laid-Open Patent Publication No. 2003-137677 uses a laser marker to engrav a negative angle of 0.5 to 30 ⁇ m on a first baked ceramic surface for the purpose of putting barcodes of heat resistance, chemical resistance and abrasion resistance on the ceramic surface. After the density is increased by the main firing, the glass is filled with glass or ceramics and heat-treated, and the surface is processed so that the glass remains only in the intaglio portion.
  • this method can only be used for relatively small or narrow letters or patterns on a relatively light colored background material, and for thick logos or large logos or letters or patterns, the thickness of the engraved glass is greatly thinned after the surface finish. The color may not be sufficient or the color of the ceramics in the background may appear.
  • the present inventors researched to form a logo, letters or patterns having an excellent aesthetic on the surface of high-strength and high-hardness material that can be used in a portable device, the surface polishing is well enough Letters, logos or patterns on hardened materials are engraved deeply into the engraving using a laser marking machine, and the glass frit containing inorganic pigments of various colors that do not form cracks is filled into the engraving, and heat treated and then again
  • the hardened material and the glassy letters, logos or patterns have the surface polished at the same time, so that the scratches are not easily generated, the cracks do not occur in the glassy material, and the logos and letters of various vivid colors with excellent aesthetics Or it can be found that a pattern can be formed to complete the present invention.
  • an object of the present invention is a logo of various and vivid colors having excellent aesthetics without scratches or cracks on the surface of zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics having high strength and hardness that can be used in a mobile device case. To provide a way to form letters or patterns at high resolution.
  • the present invention comprises the steps of polishing the surface of any one of the high hardness material selected from zirconia ceramics, single crystal artificial sapphire or transparent polycrystalline ceramics; Engraving the intaglio portion on the surface of the polished high hardness material to a depth of more than 30 ⁇ m and less than 100 ⁇ m in the intaglio using a laser; Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material; Heat-treating the hardened material filled with the glass frit to make the glass frit vitreous and bonding to the hardened material; And surface-grinding the heat-treated high-hardness material again, such that the calcined glassy surface remains polished only in the intaglio portion, and the heat-treated glassy surface is lower than the surface of the surrounding high-hardness material.
  • a high hardness material manufacturing method having a pattern is
  • the zirconia high hardness material may have a color itself by adding an inorganic pigment.
  • the polishing prior to engraving the intaglio causes the surface roughness Ra of the hardened material to be 10 nm to 100 nm, and when the surface roughness is greater than 100 nm, the final surface polishing, which removes the extra vitreous around the intaglio, becomes excessively long, so that the thickness of the glass is further increased.
  • the surface of the thinned or hardened material loses its aesthetics, and if the surface roughness is less than 10 nm, it is uneconomical because it does not greatly help the aesthetics and requires high precision polishing.
  • the intaglio portion filled with the glass frit is more preferably 35 ⁇ m to 60 ⁇ m, and the thermal expansion coefficient of the glassy material may be 4 ⁇ 10 ⁇ 6 / ° C. to 9.5 ⁇ 10 ⁇ 6 / ° C. at 300 ° C., and the heat treatment may be performed. It may be performed at 400 °C to 1000 °C.
  • the present invention comprises the steps of polishing the surface of any one of the high hardness material selected from zirconia ceramics, single crystal artificial sapphire or transparent polycrystalline ceramics so that the surface roughness Ra is 100nm or less; Engraving the intaglio portion on the surface of the polished high hardness material at a depth of 35 ⁇ m to 60 ⁇ m in the intaglio using a laser; Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material; Heat-treating the hardened material filled with the glass frit at 400 ° C. to 1000 ° C.
  • Glass surfaces containing inorganic pigment particles filled in the intaglio area have a lower surface hardness than zirconia ceramics, monocrystalline artificial sapphire, or transparent polycrystalline ceramics.
  • the dishing effect is lower than the surface of the material, and this naturally occurring dishing effect reduces the chance of scratching or falling off the glassy surface in the indentation, or with extreme handling.
  • this dishing effect greatly reduces the thickness of the final glass, resulting in a much thinner glass than the original depth of the indentation.
  • the thickness of the glassy after the final polishing may be 20 to 30 ⁇ m smaller than the depth of the original engraved portion.
  • the thickness of the intaglio or intaglio glass is not sufficient, the glassy color is not properly expressed.
  • the high hardness material serving as the base member has a dark color, the color of the glassy logo is difficult to be expressed as intended.
  • the depth of the intaglio portion filled with the glass frit should be at least deeper than 30 ⁇ m in order to take into account the thinning thickness after the final surface polishing and to express sufficient color, but the indentation is excessively inscribed to unnecessarily increase the cost or zirconia It is preferable to make it 100 micrometers or less so that the intensity
  • the glass filled in the intaglio should be thick enough. If the thickness of the intaglio glass becomes thick, cracking or crazing easily occurs. When cooled to room temperature after heat treatment, the high hardness material and the glass material shrink, and the shrinkage rate is also different because the coefficients of thermal expansion of the two materials are different. Therefore, if the shrinkage rate of the glass material is a little too large, the tensile stress is generated in the glass direction during the cooling process. Cracking may occur.
  • a further problem is that these tensile stresses degrade the glassy strength so that cracking can easily occur during subsequent use even if there is no cracking at first. This is especially acute when the glass is thicker.
  • the shrinkage ratio of the glass is smaller than that of the hardened material, the hardened material is further contracted upon cooling, and the compressive stress acts toward the surface of the glass so that the glassy may not be cracked and may be strengthened.
  • glass having a relatively low thermal expansion coefficient has a small content of components such as Na 2 O or K 2 O, and thus requires a thermal expansion coefficient that is not excessively low because the heat treatment temperature is relatively high.
  • Zirconia added with 3 mol% Y 2 O 3 has a thermal expansion coefficient of about 10 x 10 -6 / °C at 300 ° C, so glassy has a coefficient of thermal expansion smaller than this, thus 4 x 10 -6 / ° C.
  • An organic or inorganic binder may be added to fill the glass frit with the engraved portion, and filling the glass frit with the engraved portion may use a transfer sheet of the glass frit.
  • the filling of the glass frit may be performed by screen printing, inkjet printing, or spray coating.
  • the glass frit may be a glass frit that requires various heat treatment temperatures depending on the component, but a glass material that is heat-treated at a relatively high temperature to a high hardness of the glass material is preferable, and the glass frit may also be used with zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics. The temperature at which sufficient conjugation reactions occur is preferred. On the other hand, in order to heat-treat at a temperature that is not excessively high so as not to bleed, it is preferable to use a glass frit heat-treated at 400 °C to 1000 °C.
  • the high hardness material may be any one selected from zirconia ceramics having a relative density of 99% or more, monocrystalline artificial sapphire, or transparent polycrystalline ceramics.
  • zirconia ceramics having a relative density of 99% or more, monocrystalline artificial sapphire, or transparent polycrystalline ceramics.
  • the presence of a large number of relatively large pores, especially in hard materials, causes the glass that flows around the intaglio to penetrate into the pores and grain boundaries, requiring more surface polishing to completely remove the extra vitreous traces. Make it even thinner.
  • the zirconia ceramics may be a zirconia-alumina composite containing 5 to 80% by volume of alumina.
  • the present invention also provides an external material for a portable device and a portable ornament, which is manufactured according to the above production method and includes a high hardness material having a logo, letters or patterns.
  • Hard materials having a pattern such as a logo having various and vivid colors manufactured according to the present invention may be used as an external material of a mobile device such as a mobile phone, an MP3 player, a tablet PC or a watch, or an external material of a mobile ornament such as a key ring. Can be.
  • high-strength and hardness zirconia ceramics, single crystal sapphire or transparent polycrystalline ceramics can be formed at high resolution in a variety of vivid color letters, logos or patterns with good aesthetics without scratching. Therefore, these high strength and hard materials can be widely used as external materials for portable devices and ornaments.
  • FIG. 1 is a cross-sectional view of zirconia ceramics having an logo (inlaid logo) produced by the manufacturing method of an embodiment of the present invention
  • FIG. 2 is a cross-sectional view of zirconia ceramics engraved with a laser engraved in one embodiment of the present invention
  • FIG. 3 is a cross-sectional view of the zirconia ceramics placed on the transfer paper after engraving the engraved portion with a laser in an embodiment of the present invention
  • FIG. 4 is a zirconia ceramic panel having an logo (inlaid logo) produced by the manufacturing method of an embodiment of the present invention.
  • the surface of a zirconia ceramic panel containing 3 mol% Y 2 O 3 having a relative density of 99.3% having blue color by adding 4% by weight of a cobalt-based blue pigment having a thickness of 0.5 mm has an average surface roughness Ra of 42 nm. Polishing; Engraving the logo (110) and letters on the polished surface in an intaglio of an average depth of 50 ⁇ m; Attaching a glass frit transfer paper containing an inorganic pigment to the intaglio portion and having a color and having a thermal expansion coefficient of 7.2 ⁇ 10 ⁇ 6 / ° C. at 300 ° C .; Heat-treating the zirconia ceramics at 775 ° C.
  • the heat-treated zirconia ceramics are again surface-polished to leave calcined glassy material having a color only in the logo and the text portion, wherein the average surface roughness Ra of the surface-polished glassy glass is 56 nm and has colored glassy letters, logos and patterns. So that the surface of is not higher than the surrounding zirconia ceramics surface.
  • FIG. 1 is a cross-sectional view of a logo of a zirconia ceramics 100 having an inlaid logo 110 as it relates to an embodiment using zirconia ceramics as a high hardness material.
  • the surface of a zirconia ceramic panel containing 3 mol% Y 2 O 3 having a relative density of 99.3% having blue color by adding 4% by weight of a cobalt-based blue pigment having a thickness of 0.5 mm has an average surface roughness Ra of 42 nm. Polishing; Engraving the logo (110) and letters on the polished surface in an intaglio of an average depth of 50 ⁇ m; Attaching a glass frit transfer paper containing an inorganic pigment to the intaglio portion and having a color and having a thermal expansion coefficient of 7.2 ⁇ 10 ⁇ 6 / ° C. at 300 ° C .; Heat-treating the zirconia ceramics at 775 ° C.
  • the heat-treated zirconia ceramics are again surface-polished to leave calcined glassy material having a color only in the logo and the text portion, wherein the average surface roughness Ra of the surface-polished glassy glass is 56 nm and has colored glassy letters, logos and patterns. So that the surface of is not higher than the surrounding zirconia ceramics surface.
  • the zirconia ceramics are zirconia containing about 3 mol% yttrium oxide (Y 2 O 3 ) of about 5% by weight of aluminium (Er), aluminum, manganese, cobalt, chromium, nickel, iron, vanadium, and the like. Oxide or salt compounds or combinations of these elemental compounds can be added to give a variety of desired colors such as pink, white, black, purple, ivory, green, blue, yellow, brown and the like.
  • zirconia reinforced alumina, zirconia-alumina complex (alumina volume ratio of 5% to 80%), in which alumina contains 20% by volume or more of zirconia containing pure zirconia or 3 mol% of yttrium oxide (Y 2 O 3 ).
  • Fig. 1 is a high strength, high toughness and high hardness zirconia-based ceramics in which a large amount of zirconia is present and exhibits phase transformation ignition behavior.
  • the zirconia ceramics have a high relative density of 99% or more, so that the pores are small so that the glassy material does not spread to the outside of the intaglio, and surface polishing is sufficiently performed before the intaglio is carved, so that the surface roughness Ra is 100 nm or less.
  • zirconia ceramics have a relative density of less than 99%, as is common with ceramics, the pores around the intaglio must be filled with glass to make the final surface excessive, or the resolution of logos, letters or patterns may be degraded and the aesthetics may be lowered.
  • Full surface grinding of the hard material, the base member, before engraving the intaglio reduces the final surface polishing step to maximize the flatness of the zirconia ceramics, leaving only the glass of the intaglio and minimizes the incidence of the intaglio glass being thinned by excessive surface polishing. can do.
  • the engraved pieces may be formed by sandblasting or chemical etching, but the use of a laser is more environmentally friendly and more preferable in terms of quality control and mass production.
  • FIG. 2 relates to an embodiment using zirconia ceramic as a hard material, and is a cross-sectional view of zirconia ceramics 200 engraved with a 10 mm wide logo 210 with a laser marker.
  • the depth of the intaglio should be deep enough to exceed 30 ⁇ m so that the intended color is expressed even when the filled glass is significantly thinner than before polishing after the final surface polishing, especially for quality control and indispensably excessive surface polishing to 35 ⁇ m to It is preferable that it is 60 micrometers. If a large number of small logos or small letters or patterns exist apart from each other, depending on the flatness of the zirconia ceramics, the depth of the intaglio must be deep enough to allow long surface polishing. You can certainly remove the trace.
  • the zirconia ceramics in the logo portion may decrease gradually as the depth of the intaglio is relatively thin, the zirconia ceramics high hardness material of 0.5 mm or less thick, so the depth of the intaglio is less than 1/5 of the thickness of the surrounding zirconia ceramics. Is preferred.
  • the logo, letters, or patterns formed in this way are guaranteed to have sufficient glass thickness, so that the resolution is very high and the color is well expressed, so that delicate and various colors are clearly realized and have a high aesthetic.
  • FIG 3 is a sectional view of a zirconia ceramic 300 attached with a glass frit transfer paper 310 slightly larger than the intaglio portion of FIG.
  • the thickness of the transfer paper glass frit layer to be attached is sufficiently thicker than the depth of the intaglio so that the glassy layer is sufficiently higher than the surrounding zirconia ceramics surface even after heat treatment. After heat treatment and sufficient final surface polishing, only a laser-engraved polished glass of sufficient thickness remains on the engraved portion of the laser, resulting in high resolution, desired color and high aesthetics.
  • the glass frit filled in the engraved portion may use various methods such as screen printing, inkjet printing, and spray coating, in addition to using a transfer paper.
  • the glass frit may be heat-treated at various temperatures of 200 ° C. to 1300 ° C., depending on the components, but has a relatively high hardness and has a high hardness and is 400 ° C. or higher, so that zirconia can be easily bonded to the zirconia ceramics. It is preferable to use a glass frit that is heat treated at a temperature of 1000 ° C. or lower so that an excessive reaction with the ceramic occurs to spoil the zirconia or also the color of the glass frit does not bleed into the ceramic when heat treated.
  • the coefficient of thermal expansion of glass must be smaller than that of zirconia ceramics, and when cooled to room temperature after heat treatment, the compressive stress acts on the surface of glass to prevent cracking and strengthen.
  • FIG. 4 is a front view of a zirconia ceramic panel 400 having a logo 410 and letters 420 manufactured according to one embodiment using zirconia ceramic as a high hardness material.
  • the resolution of the logo or text is very high, and after the final surface polishing, the logo and text are glossy and can realize various desired colors vividly.
  • the engraved part is deepened to about 50 ⁇ m for the purpose of expressing the desired color and to remove extra vitreous from the logo and text, there is no crack or debris on the engraved part and there is a small possibility of cracking during use. Due to the dishing effect, the surface height of the glass is 12 ⁇ m lower than the surrounding zirconia ceramics, and the thickness of the final surface polished engraved logo glass is 24 ⁇ m on average, and this glass thickness vividly implements the desired color.
  • the surface is smooth and the surface is smooth and the height of the glass in the recess is lower than that of the surrounding zirconia ceramics due to the dishing effect during the surface polishing, so that scratches are less likely to occur during use.
  • the surface of the hard material such as zirconia ceramics in which the logo, letters or patterns are formed is not limited to the plane.
  • the zirconia ceramics are hardly scratched, and the method of forming letters, logos or patterns of various vivid colors with excellent aesthetics at high resolution is equally applicable to monocrystalline artificial sapphire or transparent polycrystalline ceramics.

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Abstract

The present invention relates to a method for preparing a high hardness material having a logo, text, or a pattern. The method comprises: engraving a pattern, text, or logo deeply enough into a polished surface of a high hardness material such as zirconia ceramics, single-crystal sapphire, or transparent poly-crystal ceramics; filling the intaglio section with glass frit which is a vitreous material having a lower coefficient of thermal expansion than the high hardness material; and polishing the high hardness material again after heat treatment. Therefore, a vitreous material with a high gloss can be strongly bonded to a high hardness material without being cracked and is less likely to be scratched due to the surface thereof being lower in height than the surrounding high-hardness material, which makes it possible to form high-resolution text, logos, or patterns with various vivid colors having an excellent sense of beauty, thereby widely using the high hardness material as an external material of portable devices or ornaments.

Description

로고, 글자 또는 문양을 갖는 고경도 재료 제조방법How to make hard materials with logos, letters or patterns
본 발명은 휴대용 기기의 케이스 등에 사용할 수 있는 고경도 재료의 표면에 우수한 미감을 갖는 다양한 색상의 로고, 글자 또는 문양을 형성하는 고경도 재료 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a high hardness material for forming a logo, letters or patterns of various colors having an excellent aesthetic on the surface of the high hardness material that can be used in the case of a portable device.
휴대폰, PDA, MP3 플레이어, 노트북 컴퓨터 등과 같은 휴대용 전자기기의 외부 케이스는 대부분 폴리카보네이트, ABS 수지와 같은 플라스틱이나 스테인레스 스틸, 알루미늄 합금 등의 금속으로 만들어진다. 이들 중 플라스틱은 비교적 저렴하고 간단한 제조방법으로 케이스를 제조할 수 있는 이점이 있으나 고급스럽지 않고 금속은 제조 비용은 높으나 상대적으로 미감이 좋은 반면에 색상이 제한적이며, 공통적으로는 경도가 높지 않아서 사용 중 표면에 스크래치가 쉽게 생기는 근원적인 문제를 가지고 있다. The outer cases of portable electronic devices such as mobile phones, PDAs, MP3 players and notebook computers are mostly made of plastic such as polycarbonate and ABS resin, or metal such as stainless steel or aluminum alloy. Among these, plastic has the advantage of making the case by relatively inexpensive and simple manufacturing method, but it is not luxurious and metal has high manufacturing cost but relatively good aesthetic, but it is limited in color, and in general, its hardness is not high. It has a fundamental problem of scratching easily on the surface.
이외에 투명 디스플레이 전면 패널로 흔히 사용되는 이온 교환을 이용한 화학적 강화유리가 후면 패널로서 사용되기도 하나, 플라스틱이나 금속에 비해서는 상대적으로 경도가 높지만 여전히 스크래치에 취약하다. In addition, chemically tempered glass using ion exchange, commonly used as a transparent display front panel, is used as a rear panel, but is relatively harder than plastic or metal, but still vulnerable to scratching.
스크래치의 단점을 보완할 수 있는 재료로서 세라믹스인 지르코니아를 들 수 있다. 지르코니아 세라믹스는 안정화제를 필요로 하는데 3 몰%의 산화이트리움(Y2O3)의 첨가가 가장 널리 사용된다. 안정화제를 소량 첨가함으로써 정방정상의 지르코니아가 얻어지고, 이러한 정방정상의 지르코니아는 잘 알려진 상변태 인화 거동을 보여서 균열이 잘 자라지 못하기 때문에 높은 강도와 인성을 지니며 구조재료로서 널리 사용된다. A material that can compensate for the drawbacks of scratches is zirconia, which is ceramics. Zirconia ceramics require stabilizers, with the addition of 3 mol% yttrium oxide (Y 2 O 3 ) being most widely used. By adding a small amount of stabilizer, tetragonal zirconia is obtained. Since tetragonal zirconia exhibits well-known phase transformation ignition behavior and cracks do not grow well, it has high strength and toughness and is widely used as a structural material.
이러한 지르코니아 세라믹스는 높은 경도를 가지기 때문에 스크래치에 대한 저항성이 매우 크다. 이와 더불어, 지르코니아 세라믹스는 무기물 안료를 첨가하여 그 재료 자체로 다양한 색상을 구현할 수 있으며, 표면 연마를 행하면 광택이 미려하게 된다. 이와 같이 우수한 미감과 기계적 특성을 갖는 지르코니아 세라믹스는 보석류의 재료나 시계 케이스와 같은 장식품에 사용되고 있다. Since zirconia ceramics have a high hardness, scratch resistance is very high. In addition, zirconia ceramics can implement various colors with the material itself by adding an inorganic pigment, the surface is polished beautiful luster. Zirconia ceramics with such excellent aesthetics and mechanical properties are used in jewelry materials and ornaments such as watch cases.
휴대용 기기의 외부 케이스 재료로도 사용되는 투명한 화학적 강화유리는 높은 경도를 가져서 스크래치가 좀처럼 생기지 않는 단결정 인조 사파이어로 대체될 수 있으며, 이러한 인조 사파이어는 시계의 투명창으로 널리 사용되고 있다. 최근에는 인조 사파이어와 많은 특성이 유사한 보다 경제적인 산질화알루미늄과 같은 고경도 투명 다결정 세라믹스가 개발되었다.Transparent chemical tempered glass, which is also used as the outer case material of portable devices, can be replaced with monocrystalline artificial sapphire, which has a high hardness and hardly scratches. Such artificial sapphire is widely used as a transparent window of a watch. Recently, harder transparent polycrystalline ceramics have been developed, such as more economical aluminum oxynitride, which have many characteristics similar to artificial sapphire.
그러나, 이렇게 경도가 높은 지르코니아 세라믹스, 투명 다결정 세라믹스나 단결정 사파이어와 같은 무기물 재료의 표면에는 스크래치에 강하고 미감이 높은, 색상을 가지는 로고, 글자 및 문양을 형성하기가 어렵다. However, it is difficult to form colored logos, letters and patterns on the surface of inorganic materials such as zirconia ceramics, transparent polycrystalline ceramics or single crystal sapphire with such hardness.
예를 들어, 지르코니아 세라믹스 또는 단결정 사파이어에 로고, 글자, 문양 등을 형성하는 방법으로는, 각종 생활용 도자기 제조에서 잘 알려진, 데칼 전사(decal transfer), 스크린 프린팅, 또는 스프레이 코팅을 이용하여 안료를 표면에 코팅하여 소성하는 전통적인 방법이 있을 수 있다. For example, as a method of forming logos, letters, patterns, etc. on zirconia ceramics or single crystal sapphire, the surface of the pigment is decal transfer, screen printing, or spray coating, which is well known in various types of household ceramics. There may be a conventional method of coating and firing on.
그러나, 이러한 방법을 통해 형성된 이미지는 그 미감이 상대적으로 떨어지고 해상도가 높지 못하며, 양각으로 튀어 나와 있어서 스크래치에 비교적 약하고 경우에 따라서는 바탕의 표면에서 쉽게 떨어져 나올 수 있다. However, an image formed through this method has a relatively poor aesthetics and a high resolution, and it is embossed, so it is relatively weak to scratches, and in some cases, can easily fall off the surface of the base.
미국 특허 제5,298,717호는 유리나 세라믹스 표면에 식별번호, 바코드 또는 장식 무늬를 형성하기 위해, 환경비친화적인 샌드블라스팅이나 화학적 에칭법 대신 고에너지 레이저로 음각의 이미지를 새기는 방법을 개시하고 있다. 그리고, 미국 특허 제5,543,269호는 레이저를 사용하여 세라믹스 특히 지르코니아 세라믹스에 이미지를 새기는 방법을 개시하고 있으며, 또한 미국 특허 제5,804,342호는 지르코니아 세라믹스에 지울 수 있는 바코드를 새기는 방법을 개시하고 있다.US Pat. No. 5,298,717 discloses a method of engraving negative images with a high energy laser instead of environmentally friendly sandblasting or chemical etching to form identification numbers, barcodes or vignettes on glass or ceramic surfaces. U.S. Patent 5,543,269 discloses a method of engraving an image on ceramics, in particular zirconia ceramics using a laser, and U.S. Patent 5,804,342 discloses a method of engraving a barcode that can be erased on zirconia ceramics.
이들 방법은 우유빛의 지르코니아 세라믹스 표면에 레이저를 조사하여 조사된 표면이 환원되며 흑색에 가까운 어두운 색깔이 되어 해상도가 높은 이미지를 만들고 있으며, 표면을 열처리 등으로 산화시키면 이미지가 지워져서 원래의 우유빚으로 돌아간다. 이러한 레이저 마킹법은 다양한 재료의 표면에 해상도가 높은 로고, 글자, 문양 등을 형성하는데 널리 사용되고 있으나, 원하는 색상이나 광택을 내지 못해서 미감이 떨어진다. These methods irradiate the surface of the milky zirconia ceramics with a laser to reduce the irradiated surface and turn it into a dark color close to black to make a high resolution image. When the surface is oxidized by heat treatment, the image is erased to the original milk liquor. Go back. This laser marking method is widely used to form high resolution logos, letters, patterns, etc. on the surface of various materials, but it does not give a desired color or glossiness, resulting in poor aesthetics.
미국 특허 제4,769,310호, 제4,861,620호, 제6,238,847호, 제6,313,436호, 제6,413,619호, 제6,852,948호, 제6,855,910호는 레이저에 감응하는 무기물 안료 마킹 재료를 세라믹스 위에 부착하고 레이저를 원하는 부분만 조사해서 색상을 가지고 접합되게 하여 세라믹스 표면에 색상을 가지는 마킹을 하는 다양한 방법을 개시하고 있다. 그러나 이러한 방법은 색상을 코팅한 층이 세라믹스 위에 노출되며 특히 세라믹스와의 경계면 접합이 충분하지 않아서 쉽게 떨어져 나오거나 유리질이 충분히 소성이 되지 않아서 스크래치에 취약하고 또한 색상을 가지는 코팅 층의 표면 조도를 제어하지 못해 표면 광택이 균일하지 않으며 미감이 떨어진다.U.S. Patent Nos. 4,769,310, 4,861,620, 6,238,847, 6,313,436, 6,413,619, 6,852,948 and 6,855,910 attach inorganic pigment marking materials to the laser on the ceramics and irradiate only the desired portions of the laser. Various methods have been disclosed for making colored markings on ceramic surfaces by bonding them with color. However, this method controls the surface roughness of the colored coating layer, which is exposed to the color coated layer on the ceramics and is particularly susceptible to scratches due to insufficient interface bonding with the ceramics, or the glass is not sufficiently plasticized. The surface gloss is not uniform and the aesthetics are inferior.
일본 공개특허 특개2003-137677호는 세라믹 표면에 주로 내열성, 내화학성, 내마모의 바코드를 넣기 위한 목적으로, 1차 소성된 세라믹 표면에 레이저마킹기를 이용해서 0.5~30μm 깊이의 음각을 새기고, 이를 본 소성으로 밀도를 높인 후, 이에 유리나 세라믹스가 함유된 유리를 채우고 열처리를 한 후 표면가공을 하여 음각부에만 유리가 남도록 하는 것을 개시하고 있다. 그러나 이 방법은 음각의 깊이가 너무 얕으면, 바코드가 희미해지고 박리의 위험성이 있어서, 5μm 이상의 깊이가 바람직하며, 반대로 30μm를 초과하면 음각의 유리에 균열이 발생하기 때문에, 안정성을 위해 20μm 이하의 깊이가 보다 바람직하다고 개시하고 있다. 따라서 이 방법은 비교적 밝은 색상의 바탕 재료 위에 비교적 작거나 폭이 좁은 글자나 문양에만 이용이 가능하며, 바탕 재료가 진한 색상이거나 큰 로고나 글자 또는 문양에서는 표면가공 후에 음각부 유리의 두께가 크게 얇아져서 색상이 충분히 구현이 되지 않거나 바탕의 세라믹스 색깔이 나타날 수 있다.Japanese Laid-Open Patent Publication No. 2003-137677 uses a laser marker to engrav a negative angle of 0.5 to 30 μm on a first baked ceramic surface for the purpose of putting barcodes of heat resistance, chemical resistance and abrasion resistance on the ceramic surface. After the density is increased by the main firing, the glass is filled with glass or ceramics and heat-treated, and the surface is processed so that the glass remains only in the intaglio portion. However, in this method, if the depth of the intaglio is too shallow, the barcode is blurred and there is a risk of peeling, and a depth of 5 μm or more is preferable, whereas if the depth of the intaglio is more than 30 μm, cracks occur in the glass of the intaglio. It is disclosed that depth is more preferable. Therefore, this method can only be used for relatively small or narrow letters or patterns on a relatively light colored background material, and for thick logos or large logos or letters or patterns, the thickness of the engraved glass is greatly thinned after the surface finish. The color may not be sufficient or the color of the ceramics in the background may appear.
상기 종래기술의 문제점을 해결하기 위하여, 본 발명자는 휴대용 기기에 사용할 수 있는 고강도와 고경도 재료의 표면에 우수한 미감을 갖는 로고, 글자 또는 문양을 형성하기 위하여 연구 노력한 결과, 표면 연마가 충분히 잘 된 고경도 재료에 글자, 로고 또는 문양을 레이저 마킹기를 이용하여 음각으로 충분히 깊게 새기며, 균열이 생기지 않는 다양한 색상의 무기 안료가 함유되어 있는 유리 프릿(glass frit)을 음각부에 채우고 이를 열처리 한 후 다시 표면 연마를 수행함으로써, 고경도 재료와 유리질의 글자, 로고 또는 문양이 동시에 연마된 표면을 가져서 스크래치가 잘 생기지 않으며, 유리질에 균열이 발생하지 않으며, 우수한 미감을 갖는 다양하고 선명한 색상의 로고, 글자 또는 문양을 형성할 수 있음을 밝혀내어 본 발명을 완성하였다.In order to solve the problems of the prior art, the present inventors researched to form a logo, letters or patterns having an excellent aesthetic on the surface of high-strength and high-hardness material that can be used in a portable device, the surface polishing is well enough Letters, logos or patterns on hardened materials are engraved deeply into the engraving using a laser marking machine, and the glass frit containing inorganic pigments of various colors that do not form cracks is filled into the engraving, and heat treated and then again By performing the surface polishing, the hardened material and the glassy letters, logos or patterns have the surface polished at the same time, so that the scratches are not easily generated, the cracks do not occur in the glassy material, and the logos and letters of various vivid colors with excellent aesthetics Or it can be found that a pattern can be formed to complete the present invention.
따라서, 본 발명의 목적은 휴대기기 케이스에 사용할 수 있는 높은 강도와 경도를 가지는 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스의 표면에 스크래치나 균열이 잘 생기지 않으며 우수한 미감을 갖는 다양하고 선명한 색상의 로고, 글자 또는 문양을 높은 해상도로 형성할 수 있는 방법을 제공하는 데에 있다.Accordingly, an object of the present invention is a logo of various and vivid colors having excellent aesthetics without scratches or cracks on the surface of zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics having high strength and hardness that can be used in a mobile device case. To provide a way to form letters or patterns at high resolution.
상기 목적을 달성하기 위하여, 본 발명은 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스에서 선택된 어느 하나의 고경도 재료의 표면을 연마하는 단계; 상기 연마된 고경도 재료의 표면에 로고, 글자 또는 문양을 레이저를 사용하여 음각으로 30μm 초과 100μm 이하의 깊이로 음각부를 새기는 단계; 상기 음각부에 열팽창계수가 고경도 재료보다 낮은 무기물 안료가 함유된 유리 프릿을 주위의 고경도 재료의 표면보다 높게 채우는 단계; 상기 유리 프릿이 채워진 고경도 재료를 열처리하여 유리 프릿을 유리질로 만들고 고경도 재료에 접합시키는 단계; 및 상기 열처리된 고경도 재료를 재차 표면 연마하여, 음각부에만 표면 연마된 소성된 유리질이 남아 있으며, 열처리된 유리질 표면이 주위의 고경도 재료의 표면보다 낮게 되도록 하는 단계를 포함하는, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of polishing the surface of any one of the high hardness material selected from zirconia ceramics, single crystal artificial sapphire or transparent polycrystalline ceramics; Engraving the intaglio portion on the surface of the polished high hardness material to a depth of more than 30 μm and less than 100 μm in the intaglio using a laser; Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material; Heat-treating the hardened material filled with the glass frit to make the glass frit vitreous and bonding to the hardened material; And surface-grinding the heat-treated high-hardness material again, such that the calcined glassy surface remains polished only in the intaglio portion, and the heat-treated glassy surface is lower than the surface of the surrounding high-hardness material. Or a high hardness material manufacturing method having a pattern is provided.
상기 지르코니아 고경도 재료는 무기물 안료가 첨가되어 자체적으로 색상을 가질 수 있다.The zirconia high hardness material may have a color itself by adding an inorganic pigment.
음각부를 새기기 전의 상기 연마는 고경도 재료의 표면 조도 Ra가 10nm 내지 100nm이 되도록 하며, 상기 표면 조도가 100nm보다 크면 음각부 주위 여분의 유리질을 없애는 최종 표면연마가 과도하게 길어져서 유리질의 두께가 더 얇아지거나 고경도 재료의 표면이 미감을 잃으며, 상기 표면 조도가 10nm보다 작으면 미감에도 크게 도움이 되지 않고 고정밀 연마를 해야 하므로 비경제적이다.The polishing prior to engraving the intaglio causes the surface roughness Ra of the hardened material to be 10 nm to 100 nm, and when the surface roughness is greater than 100 nm, the final surface polishing, which removes the extra vitreous around the intaglio, becomes excessively long, so that the thickness of the glass is further increased. The surface of the thinned or hardened material loses its aesthetics, and if the surface roughness is less than 10 nm, it is uneconomical because it does not greatly help the aesthetics and requires high precision polishing.
상기 유리 프릿으로 채워지는 음각부의 깊이는 더 바람직하게는 35μm 내지 60μm이며, 상기 유리질의 열팽창계수가 300℃에서 4 X 10-6/℃ 내지 9.5 X 10-6/℃일 수 있으며, 상기 열처리는 400℃ 내지 1000℃에서 수행할 수 있다.The intaglio portion filled with the glass frit is more preferably 35 μm to 60 μm, and the thermal expansion coefficient of the glassy material may be 4 × 10 −6 / ° C. to 9.5 × 10 −6 / ° C. at 300 ° C., and the heat treatment may be performed. It may be performed at 400 ℃ to 1000 ℃.
또한, 본 발명은 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스에서 선택된 어느 하나의 고경도 재료의 표면을 표면 조도 Ra가 100nm 이하가 되도록 연마하는 단계; 상기 연마된 고경도 재료의 표면에 로고, 글자 또는 문양을 레이저를 사용하여 음각으로 35μm 내지 60μm의 깊이로 음각부를 새기는 단계; 상기 음각부에 열팽창계수가 고경도 재료보다 낮은 무기물 안료가 함유된 유리 프릿을 주위의 고경도 재료의 표면보다 높게 채우는 단계; 상기 유리 프릿이 채워진 고경도 재료를 400℃ 내지 1000℃에서 열처리하여 유리 프릿을 유리질로 만들고 고경도 재료에 접합시키는 단계; 및 상기 열처리된 고경도 재료를 재차 표면 연마하여, 음각부에만 표면 연마된 소성된 유리질이 남아 있는 단계를 포함하는, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법을 제공한다.In addition, the present invention comprises the steps of polishing the surface of any one of the high hardness material selected from zirconia ceramics, single crystal artificial sapphire or transparent polycrystalline ceramics so that the surface roughness Ra is 100nm or less; Engraving the intaglio portion on the surface of the polished high hardness material at a depth of 35 μm to 60 μm in the intaglio using a laser; Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material; Heat-treating the hardened material filled with the glass frit at 400 ° C. to 1000 ° C. to make the glass frit vitreous and bonding to the hardened material; And surface-grinding the heat-treated high-hardness material again, so that the calcined glass material surface-polished only in the intaglio portion, provides a method of manufacturing a high-hardness material having a logo, letters, or patterns.
음각부에 채워진 무기물 안료 입자들이 함유된 유리질은 열처리 후 최종 표면연마를 하면, 고경도 재료인 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스보다 유리질의 경도가 일반적으로 크게 낮으므로 유리질의 표면이 주위 고경도 재료의 표면보다 낮아지며(dishing effect), 이렇게 자연스럽게 생기는 디싱 효과(dishing effect)는 음각부 안의 유리질 표면에 사용 중 스크래치가 생기거나, 극단적인 취급으로도 균열이 가거나 떨어져 나올 확률을 적게 해 준다. 그러나 이러한 디싱 효과(dishing effect)는 최종 유리질의 두께를 크게 줄이게 되어 원래 음각부 깊이에 비해 훨씬 얇은 두께의 유리질을 초래한다. 이 뿐만 아니라, 고경도 재료의 표면으로 흘렀던 여분의 유리질 흔적을 완전히 지우려면 표면 연마를 충분히 해야 하며, 특히 로고, 글자나 문양이 하나의 고경도 재료의 표면에 여러 개가 서로 떨어져서 존재할 때는 표면의 평탄도가 완벽하지 않기 때문에 표면 연마를 과도할 정도로 많이 해야 모든 음각부 주위의 여분의 유리질이 완전히 제거된다. 이러한 이유로 최종 연마 후에 유리질의 두께는 원래 음각부의 깊이보다 20 내지 30μm가 작아질 수 있다. 그러나 음각부 또는 음각부 유리질의 두께가 충분하지 않으면 유리질 색상이 제대로 발현되지 않으며, 특히 바탕 부재인 고경도 재료가 짙은 색상을 가지면 유리질 로고의 색상이 의도했던 대로 발현되기 어렵다.Glass surfaces containing inorganic pigment particles filled in the intaglio area have a lower surface hardness than zirconia ceramics, monocrystalline artificial sapphire, or transparent polycrystalline ceramics. The dishing effect is lower than the surface of the material, and this naturally occurring dishing effect reduces the chance of scratching or falling off the glassy surface in the indentation, or with extreme handling. However, this dishing effect greatly reduces the thickness of the final glass, resulting in a much thinner glass than the original depth of the indentation. In addition, it is necessary to sufficiently polish the surface to completely remove the extra vitreous traces flowing to the surface of the hard material, especially when several logos, letters or patterns are separated from each other on the surface of one hard material. Since the degree is not perfect, excessive surface polishing should be done to completely remove excess glass around all indentations. For this reason, the thickness of the glassy after the final polishing may be 20 to 30 μm smaller than the depth of the original engraved portion. However, if the thickness of the intaglio or intaglio glass is not sufficient, the glassy color is not properly expressed. In particular, if the high hardness material serving as the base member has a dark color, the color of the glassy logo is difficult to be expressed as intended.
따라서 본 발명에서는 유리 프릿으로 채워지는 음각부의 깊이는 최종 표면 연마 후의 얇아지는 두께를 고려하고 충분한 색상을 발현하기 위해 적어도 30μm보다 깊어야 하며, 그러나 음각부를 과도로 깊게 새겨서 비용을 불필요하게 높이거나 지르코니아 세라믹스, 단결정 사파이어 또는 투명 다결정 세라믹스의 강도에는 크게 영향을 미치지 않도록 100μm 이하로 하는 것이 바람직하다. 특히 주위의 고경도 재료 두께가 0.5mm 이하로 얇을 경우에는 강도의 저하를 최소화하기 위해 고경도 재료 두께의 1/5 이하인 것이 바람직하다. Therefore, in the present invention, the depth of the intaglio portion filled with the glass frit should be at least deeper than 30 μm in order to take into account the thinning thickness after the final surface polishing and to express sufficient color, but the indentation is excessively inscribed to unnecessarily increase the cost or zirconia It is preferable to make it 100 micrometers or less so that the intensity | strength of ceramics, single crystal sapphire, or transparent polycrystal ceramics may not be largely influenced. In particular, when the surrounding high hardness material thickness is 0.5 mm or less, it is preferable that it is 1/5 or less of the high hardness material thickness in order to minimize the fall of strength.
이와 같이 음각부에 채워지는 상기 유리질은 충분히 두꺼워야 하는데, 음각부 유리질의 두께가 두꺼워지면 균열이나 잔금(crazing)이 쉽게 생긴다. 열처리 후 상온으로 냉각되면 바탕 부재인 고경도 재료와 유리질이 수축하는데 두 재질의 열팽창계수가 다르므로 수축률 역시 서로 다르고, 따라서 유리질의 수축율이 조금이라도 크면, 유리질에 표면 방향으로 인장응력이 생겨서 냉각 중 균열이 발생할 수 있다. As such, the glass filled in the intaglio should be thick enough. If the thickness of the intaglio glass becomes thick, cracking or crazing easily occurs. When cooled to room temperature after heat treatment, the high hardness material and the glass material shrink, and the shrinkage rate is also different because the coefficients of thermal expansion of the two materials are different. Therefore, if the shrinkage rate of the glass material is a little too large, the tensile stress is generated in the glass direction during the cooling process. Cracking may occur.
또한 보다 큰 문제는, 이러한 인장응력이 유리질의 강도를 저하시켜서 처음에는 균열이 없더라도 이후 사용 중에 균열이 쉽게 발생할 수 있다는 것이다. 이는 특히 유리질의 두께가 두꺼워지면 더욱 심각해진다. 그러나 이와 반대로 유리질의 수축율이 고경도 재료보다 작으면, 냉각 시 고경도 재료가 더 수축하며 유리질의 표면 방향으로 압축응력이 작용하게 되어 유리질이 균열이 생기지 않을 뿐만 아니라 오히려 강화될 수 있다. 일반적으로 열팽창계수가 비교적 작은 유리는 Na2O나 K2O와 같은 성분의 함유량이 작기 때문에 열처리 온도가 상대적으로 높아지므로 과도하게 낮지 않은 열팽창계수가 필요하다. A further problem is that these tensile stresses degrade the glassy strength so that cracking can easily occur during subsequent use even if there is no cracking at first. This is especially acute when the glass is thicker. On the contrary, if the shrinkage ratio of the glass is smaller than that of the hardened material, the hardened material is further contracted upon cooling, and the compressive stress acts toward the surface of the glass so that the glassy may not be cracked and may be strengthened. In general, glass having a relatively low thermal expansion coefficient has a small content of components such as Na 2 O or K 2 O, and thus requires a thermal expansion coefficient that is not excessively low because the heat treatment temperature is relatively high.
가장 일반적인 지르코니아 세라믹스인 3 몰% Y2O3가 첨가된 지르코니아는 300℃에서 열팽창계수가 약 10 x 10-6/℃이므로 유리질은 이보다 작은 열팽창계수를 가져야 하며, 따라서 4 x 10-6/℃ 내지 9.5 x 10-6/℃의 열팽창계수를 가지는 유리질을 사용하는 것이 바람직하다. 이는 유리질의 균열을 방지하는데 결정적이며 또한 적당한 압축응력의 작용으로 더욱 강해진다. Zirconia added with 3 mol% Y 2 O 3 , the most common zirconia ceramics, has a thermal expansion coefficient of about 10 x 10 -6 / ℃ at 300 ° C, so glassy has a coefficient of thermal expansion smaller than this, thus 4 x 10 -6 / ° C. Preference is given to using glassware having a coefficient of thermal expansion of from 9.5 x 10 -6 / 占 폚. This is crucial for preventing glassy cracking and also becomes stronger under the action of moderate compressive stress.
상기 유리 프릿을 음각부에 채우는 공정을 위해 유기 또는 무기 바인더가 첨가될 수 있으며, 상기 유리 프릿을 음각부에 채우는 단계는 유리 프릿의 전사지를 이용할 수 있다. 그리고, 상기 유리 프릿을 음각부에 채우는 단계는 스크린 프린팅, 잉크젯 프린팅 또는 스프레이 코팅을 통해 수행할 수 있다.An organic or inorganic binder may be added to fill the glass frit with the engraved portion, and filling the glass frit with the engraved portion may use a transfer sheet of the glass frit. The filling of the glass frit may be performed by screen printing, inkjet printing, or spray coating.
상기 유리 프릿은 성분에 따라 다양한 열처리 온도를 요하는 유리 프릿을 사용할 수 있으나, 유리질 자체의 경도가 되도록 높게 비교적 높은 온도에서 열처리되는 유리질이 바람직하며 또한 지르코니아 세라믹, 단결정 인조 사파이어 또는 투명 다결정 세라믹스와의 충분한 접합 반응이 일어나는 온도가 바람직하다. 반면에 색상이 번지지 않도록 과도하게 높지 않은 온도에서 열처리하기 위해서, 400℃ 내지 1000℃에서 열처리 되는 유리 프릿을 사용하는 것이 바람직하다.The glass frit may be a glass frit that requires various heat treatment temperatures depending on the component, but a glass material that is heat-treated at a relatively high temperature to a high hardness of the glass material is preferable, and the glass frit may also be used with zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics. The temperature at which sufficient conjugation reactions occur is preferred. On the other hand, in order to heat-treat at a temperature that is not excessively high so as not to bleed, it is preferable to use a glass frit heat-treated at 400 ℃ to 1000 ℃.
상기 고경도 재료는 상대밀도 99% 이상의 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스에서 선택된 어느 하나일 수 있다. 고경도 재료에 특히 상대적으로 큰 기공이 많이 존재하면 음각부 주위에 흐른 유리질이 기공 및 입계로 침투하여 여분의 유리질 흔적을 완전히 제거하기 위해 더욱 과도한 표면 연마가 요구되며, 결과적으로 음각부의 유리질 두께를 더욱 얇게 만든다. The high hardness material may be any one selected from zirconia ceramics having a relative density of 99% or more, monocrystalline artificial sapphire, or transparent polycrystalline ceramics. The presence of a large number of relatively large pores, especially in hard materials, causes the glass that flows around the intaglio to penetrate into the pores and grain boundaries, requiring more surface polishing to completely remove the extra vitreous traces. Make it even thinner.
또한, 상기 지르코니아 세라믹스는 알루미나가 5 내지 80 부피%로 포함된 지르코니아-알루미나 복합체일 수 있다.In addition, the zirconia ceramics may be a zirconia-alumina composite containing 5 to 80% by volume of alumina.
또한, 본 발명은 상기 제조방법에 따라 제조되며, 로고, 글자 또는 문양을 갖는 고경도 재료를 포함하는, 휴대 기기와 휴대 장식품의 외부 재료를 제공한다.The present invention also provides an external material for a portable device and a portable ornament, which is manufactured according to the above production method and includes a high hardness material having a logo, letters or patterns.
본 발명에 따라 제조된 다양하고 선명한 색상을 지니는 로고 등의 문양을 가지는 고경도 재료는 휴대폰, MP3 플레이어, 태블릿 PC 또는 시계와 같은 휴대 기기의 외부 재료나 열쇠고리와 같은 휴대 장식품의 외부 재료로써 사용될 수 있다. Hard materials having a pattern such as a logo having various and vivid colors manufactured according to the present invention may be used as an external material of a mobile device such as a mobile phone, an MP3 player, a tablet PC or a watch, or an external material of a mobile ornament such as a key ring. Can be.
본 발명에 따르면, 높은 강도와 경도를 가지는 지르코니아 세라믹스, 단결정 사파이어의 또는 투명 다결정 세라믹스 표면에 스크래치가 잘 생기지 않으며 우수한 미감을 갖는 다양하고 선명한 색상의 글자, 로고 또는 문양을 높은 해상도로 형성할 수 있기 때문에 이러한 고강도 고경도 재료들을 휴대용 기기나 장식품의 외부 재료로 널리 활용할 수 있다.According to the present invention, high-strength and hardness zirconia ceramics, single crystal sapphire or transparent polycrystalline ceramics can be formed at high resolution in a variety of vivid color letters, logos or patterns with good aesthetics without scratching. Therefore, these high strength and hard materials can be widely used as external materials for portable devices and ornaments.
도 1은 본 발명의 일실시예의 제조방법에 의해 제조된 로고(inlaid logo)를 갖는 지르코니아 세라믹스의 단면도이고,1 is a cross-sectional view of zirconia ceramics having an logo (inlaid logo) produced by the manufacturing method of an embodiment of the present invention,
도 2는 본 발명의 일실시예에서 레이저로 음각부를 새긴 지르코니아 세라믹스의 단면도이고,2 is a cross-sectional view of zirconia ceramics engraved with a laser engraved in one embodiment of the present invention,
도 3은 본 발명의 일실시예에서 레이저로 음각부를 새긴 후 전사지를 올려 놓은 지르코니아 세라믹스의 단면도이고,3 is a cross-sectional view of the zirconia ceramics placed on the transfer paper after engraving the engraved portion with a laser in an embodiment of the present invention,
도 4는 본 발명의 일실시예의 제조방법에 의해 제조된 로고(inlaid logo)를 갖는 지르코니아 세라믹 패널이다.4 is a zirconia ceramic panel having an logo (inlaid logo) produced by the manufacturing method of an embodiment of the present invention.
상기 실시예는 0.5mm 두께의 4 중량%의 코발트계의 청색안료가 첨가되어 청색을 띄는 상대밀도 99.3%인 3 몰% Y2O3를 함유하는 지르코니아 세라믹 패널의 표면을 평균 표면조도 Ra 42nm로 연마하는 단계; 상기 연마된 표면에 레이저 마킹기로 로고(110)와 글자를 평균 50μm 깊이의 음각으로 새기는 단계; 상기 음각부에 무기 안료를 함유하여 색상을 가지고 열팽창계수가 300℃에서 7.2 X 10-6/℃인 유리질이 되는 유리 프릿 전사지를 부착하는 단계; 상기 지르코니아 세라믹스를 775℃에서 30분간 열처리하는 단계; 상기 열처리된 지르코니아 세라믹스를 다시 표면 연마하여, 로고와 글자 부분에만 색상을 가지는 소성된 유리질이 남아 있으며, 이때 표면 연마된 로고 유리질의 평균 표면조도 Ra는 56nm이고, 색상을 가지는 유리질 글자, 로고 및 문양의 표면이 주위의 지르코니아 세라믹스 표면보다 높지 않도록 하는 단계를 포함한다.In the above embodiment, the surface of a zirconia ceramic panel containing 3 mol% Y 2 O 3 having a relative density of 99.3% having blue color by adding 4% by weight of a cobalt-based blue pigment having a thickness of 0.5 mm has an average surface roughness Ra of 42 nm. Polishing; Engraving the logo (110) and letters on the polished surface in an intaglio of an average depth of 50 μm; Attaching a glass frit transfer paper containing an inorganic pigment to the intaglio portion and having a color and having a thermal expansion coefficient of 7.2 × 10 −6 / ° C. at 300 ° C .; Heat-treating the zirconia ceramics at 775 ° C. for 30 minutes; The heat-treated zirconia ceramics are again surface-polished to leave calcined glassy material having a color only in the logo and the text portion, wherein the average surface roughness Ra of the surface-polished glassy glass is 56 nm and has colored glassy letters, logos and patterns. So that the surface of is not higher than the surrounding zirconia ceramics surface.
이하에서는 첨부된 도면을 근거로 하여 본 발명을 보다 상세하게 설명한다. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
도 1은 고경도 재료로서 지르코니아 세라믹을 이용한 일실시예에 관한 것으로, 로고(inlaid logo)(110)를 갖는 지르코니아 세라믹스(100)의 로고 부분 단면도이다. 1 is a cross-sectional view of a logo of a zirconia ceramics 100 having an inlaid logo 110 as it relates to an embodiment using zirconia ceramics as a high hardness material.
상기 실시예는 0.5mm 두께의 4 중량%의 코발트계의 청색안료가 첨가되어 청색을 띄는 상대밀도 99.3%인 3 몰% Y2O3를 함유하는 지르코니아 세라믹 패널의 표면을 평균 표면조도 Ra 42nm로 연마하는 단계; 상기 연마된 표면에 레이저 마킹기로 로고(110)와 글자를 평균 50μm 깊이의 음각으로 새기는 단계; 상기 음각부에 무기 안료를 함유하여 색상을 가지고 열팽창계수가 300℃에서 7.2 X 10-6/℃인 유리질이 되는 유리 프릿 전사지를 부착하는 단계; 상기 지르코니아 세라믹스를 775℃에서 30분간 열처리하는 단계; 상기 열처리된 지르코니아 세라믹스를 다시 표면 연마하여, 로고와 글자 부분에만 색상을 가지는 소성된 유리질이 남아 있으며, 이때 표면 연마된 로고 유리질의 평균 표면조도 Ra는 56nm이고, 색상을 가지는 유리질 글자, 로고 및 문양의 표면이 주위의 지르코니아 세라믹스 표면보다 높지 않도록 하는 단계를 포함한다.In the above embodiment, the surface of a zirconia ceramic panel containing 3 mol% Y 2 O 3 having a relative density of 99.3% having blue color by adding 4% by weight of a cobalt-based blue pigment having a thickness of 0.5 mm has an average surface roughness Ra of 42 nm. Polishing; Engraving the logo (110) and letters on the polished surface in an intaglio of an average depth of 50 μm; Attaching a glass frit transfer paper containing an inorganic pigment to the intaglio portion and having a color and having a thermal expansion coefficient of 7.2 × 10 −6 / ° C. at 300 ° C .; Heat-treating the zirconia ceramics at 775 ° C. for 30 minutes; The heat-treated zirconia ceramics are again surface-polished to leave calcined glassy material having a color only in the logo and the text portion, wherein the average surface roughness Ra of the surface-polished glassy glass is 56 nm and has colored glassy letters, logos and patterns. So that the surface of is not higher than the surrounding zirconia ceramics surface.
상기 지르코니아 세라믹스는 3 몰% 내외의 산화이트리움(Y2O3)을 포함하고 있는 지르코니아에 5 중량% 내외의 어비움(Er), 알루미늄, 망간, 코발트, 크롬, 니켈, 철, 바나듐 등의 산화물 또는 염 화합물이나 이들 원소 화합물의 조합을 첨가하여 핑크색, 백색, 흑색, 자주색, 아이보리, 녹색, 청색, 노란색, 갈색 등의 다양한 원하는 색상을 띄게 할 수 있다. 또한, 알루미나에 순수한 지르코니아 또는 3 몰% 내외의 산화이트리움(Y2O3)이 함유된 지르코니아가 20 부피% 이상 첨가된 지르코니아 강화 알루미나 즉 지르코니아-알루미나 복합체(알루미나 부피비가 5% 내지 80%)도 지르코니아가 다량 존재하여 상변태 인화 거동을 보이는 고강도, 고인성 및 고경도의 지르코니아계 세라믹스이며, 따라서 본 발명에 적용할 수 있다.The zirconia ceramics are zirconia containing about 3 mol% yttrium oxide (Y 2 O 3 ) of about 5% by weight of aluminium (Er), aluminum, manganese, cobalt, chromium, nickel, iron, vanadium, and the like. Oxide or salt compounds or combinations of these elemental compounds can be added to give a variety of desired colors such as pink, white, black, purple, ivory, green, blue, yellow, brown and the like. In addition, zirconia reinforced alumina, zirconia-alumina complex (alumina volume ratio of 5% to 80%), in which alumina contains 20% by volume or more of zirconia containing pure zirconia or 3 mol% of yttrium oxide (Y 2 O 3 ). Fig. 1 is a high strength, high toughness and high hardness zirconia-based ceramics in which a large amount of zirconia is present and exhibits phase transformation ignition behavior.
상기 지르코니아 세라믹스는 상대밀도가 99% 이상으로 높아서 기공이 적음으로써 유리질이 음각부 외로 퍼지지 않는 것이 바람직하며, 음각부를 새기기 전에 표면연마가 충분히 행해져서 표면조도 Ra가 100 nm 이하가 되는 것이 바람직하다. 특히 지르코니아 세라믹스가 일반적인 세라믹스처럼 상대밀도가 99% 미만이면, 음각부 주위의 기공에도 유리가 채워져서 최종 표면 연마를 과도하게 해주어야 하거나, 로고, 글자나 문양의 해상도가 떨어지게 되고 미감이 낮아질 수 있으며, 음각부를 새기기 전에 바탕 부재인 고경도 재료를 충분히 표면 연마하는 것은 지르코니아 세라믹스의 평탄도를 최대한 높여서 음각부의 유리질만 남기도록 하는 최종 표면 연마 단계를 단축시키고 음각부 유리질이 과도한 표면 연마로 얇아지는 것을 최소화할 수 있다. The zirconia ceramics have a high relative density of 99% or more, so that the pores are small so that the glassy material does not spread to the outside of the intaglio, and surface polishing is sufficiently performed before the intaglio is carved, so that the surface roughness Ra is 100 nm or less. In particular, if zirconia ceramics have a relative density of less than 99%, as is common with ceramics, the pores around the intaglio must be filled with glass to make the final surface excessive, or the resolution of logos, letters or patterns may be degraded and the aesthetics may be lowered. Full surface grinding of the hard material, the base member, before engraving the intaglio, reduces the final surface polishing step to maximize the flatness of the zirconia ceramics, leaving only the glass of the intaglio and minimizes the incidence of the intaglio glass being thinned by excessive surface polishing. can do.
상기 음각부 조각은 샌드블라스팅법이나 화학적 에칭으로도 형성 가능하나, 레이저의 사용이 환경 친화적이고 품질관리 및 양산 측면에서 보다 바람직하다.The engraved pieces may be formed by sandblasting or chemical etching, but the use of a laser is more environmentally friendly and more preferable in terms of quality control and mass production.
도 2는 고경도 재료로서 지르코니아 세라믹을 이용한 일실시예에 관한 것으로, 레이저 마킹기로 폭 10 mm의 음각 로고(210)를 새긴 지르코니아 세라믹스(200)의 단면도이다. 음각의 깊이는 채워진 유리질이 최종 표면 연마 후 두께가 연마 전보다 현저히 얇아졌을 때도 의도했던 색상이 발현되도록 30μm를 초과하여 충분히 깊어야 하며, 특히 품질관리를 위해 그리고 불가결하게 과도한 표면 연마를 고려하여 35μm 내지 60μm인 것이 바람직하다. 크기가 작은 로고나 선폭이 작은 글자 또는 문양도 다수가 서로 떨어져서 존재하면, 지르코니아 세라믹스의 평탄도에 따라, 음각부의 깊이가 충분히 깊어서 표면 연마를 오래해 줄 수 있어야 모든 음각부 주위의 여분의 유리질과 이의 흔적을 확실히 제거할 수 있다. 그러나, 0.5mm 이하 두께의 비교적 얇은 지르코니아 세라믹스 고경도 재료는 음각의 깊이가 깊어질수록 로고 부분의 지르코니아 세라믹스의 강도가 점점 감소할 수 있으므로, 음각의 깊이는 주위의 지르코니아 세라믹스 두께의 1/5 이하가 바람직하다. 이렇게 형성된 로고, 글자 또는 문양은 충분한 유리질 두께가 보장되어, 해상도가 매우 높고 색상의 발현이 좋아서 섬세하고 다양한 색상이 선명하게 구현되며 높은 미감을 갖는다.FIG. 2 relates to an embodiment using zirconia ceramic as a hard material, and is a cross-sectional view of zirconia ceramics 200 engraved with a 10 mm wide logo 210 with a laser marker. The depth of the intaglio should be deep enough to exceed 30μm so that the intended color is expressed even when the filled glass is significantly thinner than before polishing after the final surface polishing, especially for quality control and indispensably excessive surface polishing to 35μm to It is preferable that it is 60 micrometers. If a large number of small logos or small letters or patterns exist apart from each other, depending on the flatness of the zirconia ceramics, the depth of the intaglio must be deep enough to allow long surface polishing. You can certainly remove the trace. However, since the strength of the zirconia ceramics in the logo portion may decrease gradually as the depth of the intaglio is relatively thin, the zirconia ceramics high hardness material of 0.5 mm or less thick, so the depth of the intaglio is less than 1/5 of the thickness of the surrounding zirconia ceramics. Is preferred. The logo, letters, or patterns formed in this way are guaranteed to have sufficient glass thickness, so that the resolution is very high and the color is well expressed, so that delicate and various colors are clearly realized and have a high aesthetic.
도 3은 고경도 재료로서 지르코니아 세라믹을 이용한 일실시예에 관한 것으로, 도 2의 음각부보다 약간 큰 유리 프릿 전사지(310)를 부착한 지르코니아 세라믹스(300)의 단면도이다. 부착되는 전사지 유리 프릿 층의 두께는 음각부의 깊이보다 충분히 두꺼워서 열처리 후에도 유리질 층이 주위의 지르코니아 세라믹스 표면보다 충분히 높은 것이 바람직하다. 열처리를 거치고 충분한 최종 표면 연마를 하면 레이저로 새겨진 음각부에만 표면 연마된 광택이 나는 충분한 두께의 유리질이 남아 높은 해상도와 원하는 색상 그리고 높은 미감을 갖게 된다. 상기 음각부에 채워지는 유리 프릿은 전사지를 사용하는 방법 외에도 스크린 프린팅, 잉크젯 프린팅, 스프레이 코팅 등의 다양한 방법을 사용할 수 있다.3 is a sectional view of a zirconia ceramic 300 attached with a glass frit transfer paper 310 slightly larger than the intaglio portion of FIG. The thickness of the transfer paper glass frit layer to be attached is sufficiently thicker than the depth of the intaglio so that the glassy layer is sufficiently higher than the surrounding zirconia ceramics surface even after heat treatment. After heat treatment and sufficient final surface polishing, only a laser-engraved polished glass of sufficient thickness remains on the engraved portion of the laser, resulting in high resolution, desired color and high aesthetics. The glass frit filled in the engraved portion may use various methods such as screen printing, inkjet printing, and spray coating, in addition to using a transfer paper.
상기 유리 프릿은 성분에 따라 200℃ 내지 1300℃의 다양한 온도에서 열처리를 행할 수 있는 것들이 있으나, 비교적 높은 경도를 지니고 지르코니아 세라믹스와 반응이 충분히 일어나 접합이 잘 되게 하기 위해 400℃ 이상, 한편으로는 지르코니아 세라믹스와 과잉 반응이 일어나서 지르코니아를 상하게 하거나 또한 열처리할 때 유리 프릿의 색상이 세라믹스로 번지지 않도록 1000℃ 이하의 온도에서 열처리되는 유리 프릿을 사용하는 것이 바람직하다. The glass frit may be heat-treated at various temperatures of 200 ° C. to 1300 ° C., depending on the components, but has a relatively high hardness and has a high hardness and is 400 ° C. or higher, so that zirconia can be easily bonded to the zirconia ceramics. It is preferable to use a glass frit that is heat treated at a temperature of 1000 ° C. or lower so that an excessive reaction with the ceramic occurs to spoil the zirconia or also the color of the glass frit does not bleed into the ceramic when heat treated.
또한, 유리질의 열팽창계수는 지르코니아 세라믹스의 열팽창계수보다 필히 작아야 하며, 열처리 후 상온으로 냉각되면 유리질에 표면 방향으로 압축응력이 작용하여 균열이 생기지 않으며 오히려 강화된다.In addition, the coefficient of thermal expansion of glass must be smaller than that of zirconia ceramics, and when cooled to room temperature after heat treatment, the compressive stress acts on the surface of glass to prevent cracking and strengthen.
도 4는 고경도 재료로서 지르코니아 세라믹을 이용한 일실시예에 따라 제조된 로고(410)와 글자(420)를 갖는 지르코니아 세라믹 패널(400)의 정면도이다. 로고나 글자의 해상도가 매우 높으며, 최종 표면 연마를 거쳐서 로고와 글자가 광택이 나고 다양한 원하는 색상을 선명하게 구현할 수 있어서 우수한 미감을 갖는다. 의도하는 색상의 발현을 위해서 또한 여분의 유리질을 로고와 글자에서 확실히 제거하기 위해 음각부를 약 50μm으로 깊게 팠는데도 불구하고 음각부의 유리질에 균열이나 잔금이 생기지 않으며 사용 중에도 균열이 생길 확률이 작다. 디싱 효과(dishing effect)에 의해 유리질의 표면 높이는 주위의 지르코니아 세라믹스보다 12μm 낮으며, 최종 표면 연마된 음각부 로고 유리질의 두께는 평균 24μm이었고, 이러한 유리질 두께는 원하는 색상을 선명하게 구현한다. 4 is a front view of a zirconia ceramic panel 400 having a logo 410 and letters 420 manufactured according to one embodiment using zirconia ceramic as a high hardness material. The resolution of the logo or text is very high, and after the final surface polishing, the logo and text are glossy and can realize various desired colors vividly. Despite the fact that the engraved part is deepened to about 50μm for the purpose of expressing the desired color and to remove extra vitreous from the logo and text, there is no crack or debris on the engraved part and there is a small possibility of cracking during use. Due to the dishing effect, the surface height of the glass is 12 μm lower than the surrounding zirconia ceramics, and the thickness of the final surface polished engraved logo glass is 24 μm on average, and this glass thickness vividly implements the desired color.
또한, 표면연마가 되어 표면이 매끄럽고 표면연마 중 디싱 효과(dishing effect)에 의해 음각부 안의 유리질의 높이가 주위의 지르코니아 세라믹스보다 낮아져서, 사용 중 스크래치가 생길 확률이 적다.In addition, the surface is smooth and the surface is smooth and the height of the glass in the recess is lower than that of the surrounding zirconia ceramics due to the dishing effect during the surface polishing, so that scratches are less likely to occur during use.
상기 로고, 글자 또는 문양이 형성되는 지르코니아 세라믹스와 같은 고경도 재료의 표면은 평면에 국한되지 않는다. The surface of the hard material such as zirconia ceramics in which the logo, letters or patterns are formed is not limited to the plane.
상기 지르코니아 세라믹스에 스크래치가 잘 생기지 않으며 우수한 미감을 갖는 다양하고 선명한 색상의 글자, 로고 또는 문양을 높은 해상도로 형성하는 방법은 단결정 인조 사파이어나 투명 다결정 세라믹스에도 똑같이 적용된다.The zirconia ceramics are hardly scratched, and the method of forming letters, logos or patterns of various vivid colors with excellent aesthetics at high resolution is equally applicable to monocrystalline artificial sapphire or transparent polycrystalline ceramics.
이상과 같이, 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술 사상과 아래에 기재될 특허 청구범위의 균등 범위 내에서 다양한 수정 및 변형이 가능함은 물론이다.As mentioned above, although this invention was demonstrated by the limited embodiment and drawing, this invention is not limited by this, The person of ordinary skill in the art to which this invention belongs, Of course, various modifications and variations are possible within the scope of equivalent claims.

Claims (11)

  1. 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스에서 선택된 어느 하나의 고경도 재료의 표면을 연마하는 단계;Polishing the surface of any one of the high hardness materials selected from zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics;
    상기 연마된 고경도 재료의 표면에 로고, 글자 또는 문양을 레이저를 사용하여 음각으로 30μm 초과 100μm 이하의 깊이로 음각부를 새기는 단계;Engraving the intaglio portion on the surface of the polished high hardness material to a depth of more than 30 μm and less than 100 μm in the intaglio using a laser;
    상기 음각부에 열팽창계수가 고경도 재료보다 낮은 무기물 안료가 함유된 유리 프릿을 주위의 고경도 재료의 표면보다 높게 채우는 단계;Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material;
    상기 유리 프릿이 채워진 고경도 재료를 열처리하여 유리 프릿을 유리질로 만들고 고경도 재료에 접합시키는 단계; 및Heat-treating the hardened material filled with the glass frit to make the glass frit vitreous and bonding to the hardened material; And
    상기 열처리된 고경도 재료를 재차 표면 연마하여, 음각부에만 표면 연마된 소성된 유리질이 남아 있으며, 열처리된 유리질 표면이 주위의 고경도 재료의 표면보다 낮게 되도록 하는 단계를 포함하는,Surface-grinding the heat-treated high hardness material again, such that only the engraved surface remains calcined glassy, and wherein the heat-treated glassy surface is lower than the surface of the surrounding high hardness material,
    로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.Process for producing hard materials with logos, letters or patterns.
  2. 청구항 1에 있어서, The method according to claim 1,
    음각부를 새기기 전의 상기 연마는 표면 조도 Ra가 10nm 내지 100nm이 되도록 하는, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The method of producing a hard material having a logo, letters or patterns, wherein the polishing before engraving the engraved portion causes the surface roughness Ra to be 10 nm to 100 nm.
  3. 청구항 1에 있어서, The method according to claim 1,
    상기 유리 프릿으로 채워지는 음각부의 깊이는 35μm 내지 60μm이며, 주위의 고경도 재료 두께의 1/5 이하인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The depth of the intaglio portion filled with the glass frit is 35μm to 60μm, the method of producing a hard material having a logo, letters or patterns that is 1/5 or less of the surrounding high hardness material thickness.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 지르코니아 세라믹스 고경도 재료에서는 유리질의 열팽창계수가 300℃에서 4 X 10-6/℃ 내지 9.5 X 10-6/℃인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.In the zirconia ceramics high hardness material, glassy thermal expansion coefficient of 4 X 10 -6 / ℃ to 9.5 X 10 -6 / ℃ at 300 ℃, a hard material having a logo, letters or patterns.
  5. 청구항 1에 있어서, The method according to claim 1,
    상기 열처리는 400℃ 내지 1000℃에서 수행하는 단계인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The heat treatment is a step of performing at 400 ℃ to 1000 ℃, a high hardness material manufacturing method having a logo, letters or patterns.
  6. 청구항 1에 있어서, The method according to claim 1,
    상기 지르코니아 세라믹스는 상대밀도 99% 이상의 지르코니아 세라믹스인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The zirconia ceramics is a zirconia ceramics having a relative density of 99% or more, a high hardness material having a logo, letters or patterns.
  7. 청구항 1에 있어서, The method according to claim 1,
    상기 지르코니아 세라믹스는 알루미나가 5 내지 80 부피%로 포함된 지르코니아-알루미나 복합체인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The zirconia ceramics is a zirconia-alumina composite containing 5 to 80% by volume of alumina, the method of producing a hard material having a logo, letters or patterns.
  8. 지르코니아 세라믹스, 단결정 인조 사파이어 또는 투명 다결정 세라믹스에서 선택된 어느 하나의 고경도 재료의 표면을 표면 조도 Ra가 10nm 내지 100nm이 되도록 연마하는 단계;Polishing the surface of any one of the high hardness materials selected from zirconia ceramics, monocrystalline artificial sapphire or transparent polycrystalline ceramics such that the surface roughness Ra is 10 nm to 100 nm;
    상기 연마된 고경도 재료의 표면에 로고, 글자 또는 문양을 레이저를 사용하여 음각으로 35μm 내지 60μm의 깊이로 음각부를 새기는 단계;Engraving the intaglio portion on the surface of the polished high hardness material at a depth of 35 μm to 60 μm in the intaglio using a laser;
    상기 음각부에 열팽창계수가 고경도 재료보다 낮은 무기물 안료가 함유된 유리 프릿을 주위의 고경도 재료의 표면보다 높게 채우는 단계;Filling the concave portion with a glass frit containing an inorganic pigment having a lower coefficient of thermal expansion than a high hardness material above a surface of a surrounding high hardness material;
    상기 유리 프릿이 채워진 고경도 재료를 400℃ 내지 1000℃에서 열처리하여 유리 프릿을 유리질로 만들고 고경도 재료에 접합시키는 단계; 및Heat-treating the hardened material filled with the glass frit at 400 ° C. to 1000 ° C. to make the glass frit vitreous and bonding to the hardened material; And
    상기 열처리된 고경도 재료를 재차 표면 연마하여, 음각부에만 표면 연마된 소성된 유리질이 남아 있는 단계를 포함하는,Surface-grinding the heat-treated high-hardness material again, so that the calcined glass material surface-polished only in the intaglio portion remains;
    로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.Process for producing hard materials with logos, letters or patterns.
  9. 청구항 8에 있어서, The method according to claim 8,
    상기 지르코니아 세라믹스는 상대밀도 99% 이상의 지르코니아 세라믹스인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The zirconia ceramics is a zirconia ceramics having a relative density of 99% or more, a high hardness material having a logo, letters or patterns.
  10. 청구항 8에 있어서, The method according to claim 8,
    상기 지르코니아 세라믹스는 알루미나가 5 내지 80 부피%로 포함된 지르코니아-알루미나 복합체인, 로고, 글자 또는 문양을 갖는 고경도 재료 제조방법.The zirconia ceramics is a zirconia-alumina composite containing 5 to 80% by volume of alumina, the method of producing a hard material having a logo, letters or patterns.
  11. 청구항 1 내지 청구항 10 중 어느 한 항에 따른 제조방법에 따라 제조되며, 로고, 글자 또는 문양을 갖는 고경도 재료를 포함하는, 휴대 기기와 휴대 장식품의 외부 재료.An external material for a mobile device and a mobile ornament, manufactured according to the method according to any one of claims 1 to 10, comprising a high hardness material having a logo, letters or patterns.
PCT/KR2014/007753 2013-08-21 2014-08-21 Method for preparing high hardness material having logo, text, or pattern WO2015026169A1 (en)

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KR20130099118A KR20150021762A (en) 2013-08-21 2013-08-21 Manufacturing method of forming inlaid logos, letters or patterns on hard materials
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10399905B2 (en) 2017-08-31 2019-09-03 Corning Incorporated Ceramic housing with texture

Families Citing this family (1)

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CN115583845B (en) * 2022-10-24 2023-05-09 广东简一(集团)陶瓷有限公司 High-hardness high-wear-resistance concave-convex ceramic tile and preparation method thereof

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JPH08268779A (en) * 1995-03-29 1996-10-15 Kyocera Corp Translucent ceramic member
JP2002201070A (en) * 2000-12-27 2002-07-16 Kyocera Corp Silicon carbide sintered compact and its manufacturing method
KR20040093434A (en) * 2003-04-28 2004-11-05 주식회사 서울세라믹스 Photoluminescent Tile and Method for Fabricating the same
KR20110130148A (en) * 2010-05-27 2011-12-05 송재경 Processing method for basalt using sand blast device
KR20130029114A (en) * 2010-08-17 2013-03-21 영남대학교 산학협력단 Method for producing a zirconia ceramic case having a logo for a portable electronic device

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Publication number Priority date Publication date Assignee Title
JPH08268779A (en) * 1995-03-29 1996-10-15 Kyocera Corp Translucent ceramic member
JP2002201070A (en) * 2000-12-27 2002-07-16 Kyocera Corp Silicon carbide sintered compact and its manufacturing method
KR20040093434A (en) * 2003-04-28 2004-11-05 주식회사 서울세라믹스 Photoluminescent Tile and Method for Fabricating the same
KR20110130148A (en) * 2010-05-27 2011-12-05 송재경 Processing method for basalt using sand blast device
KR20130029114A (en) * 2010-08-17 2013-03-21 영남대학교 산학협력단 Method for producing a zirconia ceramic case having a logo for a portable electronic device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10399905B2 (en) 2017-08-31 2019-09-03 Corning Incorporated Ceramic housing with texture

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