WO2014030738A1 - Substrat de verre pour un cache de verre pour un dispositif électronique, cache de verre pour un dispositif électronique et procédé de fabrication du substrat de verre pour un cache de verre pour un dispositif électronique - Google Patents

Substrat de verre pour un cache de verre pour un dispositif électronique, cache de verre pour un dispositif électronique et procédé de fabrication du substrat de verre pour un cache de verre pour un dispositif électronique Download PDF

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Publication number
WO2014030738A1
WO2014030738A1 PCT/JP2013/072547 JP2013072547W WO2014030738A1 WO 2014030738 A1 WO2014030738 A1 WO 2014030738A1 JP 2013072547 W JP2013072547 W JP 2013072547W WO 2014030738 A1 WO2014030738 A1 WO 2014030738A1
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WIPO (PCT)
Prior art keywords
glass substrate
glass
compressive stress
cover glass
chemical strengthening
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PCT/JP2013/072547
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English (en)
Japanese (ja)
Inventor
高野　徹朗
Original Assignee
Hoya株式会社
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Publication date
Application filed by Hoya株式会社 filed Critical Hoya株式会社
Priority to JP2014531682A priority Critical patent/JP6025156B2/ja
Priority to CN201380033281.4A priority patent/CN104379533B/zh
Publication of WO2014030738A1 publication Critical patent/WO2014030738A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133331—Cover glasses

Definitions

  • the present invention relates to a portable device cover that serves as a cover for a display screen of a portable device such as a mobile phone, a portable game machine, a PDA (Personal Digital Assistant), a digital still camera, a video camera, or a slate PC (Personal Computer).
  • a portable device such as a mobile phone, a portable game machine, a PDA (Personal Digital Assistant), a digital still camera, a video camera, or a slate PC (Personal Computer).
  • This invention relates to a method for producing a glass substrate.
  • an acrylic resin plate having excellent transparency and light weight has been generally used for its display screen.
  • the cover glass is made of a glass material that has high strength and is superior to conventional acrylic resin plates in terms of surface smoothness, protection (weather resistance, antifouling properties), appearance and luxury. It has come to be.
  • touch-panel electronic devices have become dominant.
  • an electronic device is operated mainly by pressing a predetermined part (for example, an icon displayed on the screen) of the display screen. Therefore, improvement of the strength of the display screen is required.
  • efforts have been made to reduce the thickness of electronic devices from the viewpoint of weight reduction and design. For this purpose, there is a demand for a cover glass having sufficient strength even if it is thin, lightweight, and has a large screen (large area).
  • the cover glass is subjected to a chemical strengthening treatment for improving its strength.
  • This chemical strengthening treatment is performed by immersing the glass substrate in a chemical strengthening treatment liquid obtained by heating and melting the chemical strengthening salt.
  • a chemical strengthening treatment liquid obtained by heating and melting the chemical strengthening salt.
  • Patent Document 1 discloses a tempered glass article having a central tension lower than a limit value at which the glass exhibits brittleness beyond that, and includes central tension CT, compressive stress, stress layer depth, glass plate thickness, and the like.
  • the chemical strengthening conditions which do not show brittleness in relation to the above are disclosed.
  • an object of the present invention is to provide a glass substrate for an electronic device cover glass that has improved the strength of the end face having the top, the cover glass for an electronic device provided with this glass substrate, and the glass substrate for an electronic device cover glass. It is to provide a manufacturing method.
  • the present inventors have intensively studied the relationship between the end face shape of the glass substrate and chemical strengthening, and as a result, have completed the present invention based on the obtained knowledge. That is, the present invention has the following configuration.
  • a glass substrate used for a cover glass for electronic equipment wherein the glass substrate contains, as main components, SiO 2 50 to 70 wt%, Al 2 O 3 5 to 20 wt%, Na 2 O 6 to 20 wt%, K 2 O 0-10 wt%, MgO 0-10 wt%, CaO 0-10 wt% glass composition, wherein the glass substrate comprises a pair of main surfaces and end faces adjacent to the pair of main surfaces And the end surface has a shape having a top portion in a cross-sectional view, and the glass substrate has a compressive stress layer formed on the surface by chemical strengthening by ion exchange, and has a maximum compressive stress on the main surface.
  • the value is 600 MPa or more, the depth of the compressive stress layer is 60 ⁇ m or less, the apex angle of the apex is ⁇ [degrees], the maximum compressive stress value of the main surface is CS [MPa], and the compressive stress layer of the main surface If the depth of d is [ ⁇ m], 600 MPa ⁇ ⁇ 3.5 ⁇ ⁇ (d / sin ( ⁇ / 2)) ⁇ d ⁇ + CS It is a glass substrate of the cover glass for electronic devices characterized by satisfy
  • (Configuration 2) The glass substrate of a cover glass for an electronic device according to Configuration 1, wherein the apex angle ⁇ of the apex is not less than 30 degrees and not more than 135 degrees.
  • (Configuration 3) The end surface of the glass substrate has a shape in which two concave surfaces that draw a substantially arc toward the inside of the substrate in a cross-sectional view intersect each other near the center in the thickness direction of the substrate, and the thickness direction at the end surface of the glass substrate.
  • the glass substrate of a cover glass for an electronic device according to Configuration 1 or 2 wherein the top portion is disposed in each of a central portion and a thickness direction main surface side of an end surface.
  • (Configuration 8) A method for producing a glass substrate used for a cover glass for electronic equipment, wherein the glass substrate contains 50 to 70% by weight of SiO 2 , 5 to 20% by weight of Al 2 O 3 and 6 to 20% of Na 2 O as main components.
  • the end surface is adjacent to the surface, and the end surface forms a glass substrate having a shape having a top portion in cross-sectional view.
  • the chemical strengthening step the apex angle of the top portion is set to ⁇ [degree], and chemical strengthening is performed.
  • (Configuration 9) The electronic device according to Configuration 8, wherein the outer shape processing step includes a step of cutting out a predetermined outer shape from a sheet glass by machining and a step of processing an end surface shape of the cut glass substrate by wet etching. It is a manufacturing method of the glass substrate of a cover glass.
  • the strength of the end face having the top is improved due to the brittleness of the end face having the top, such as the strength of the end face having the top and the reduction of the compressive stress due to the chemical strengthening of the conventional structure or deeper than expected.
  • the glass substrate of the cover glass for electronic devices which can reduce generation
  • (A), (b), (c) is sectional drawing which shows the end surface shape example of the glass substrate in connection with this invention.
  • (A)-(c) is a reference drawing for demonstrating the definition of the apex angle heel of the end face top part in this invention, respectively. It is a figure which shows the relationship between an apex angle and the compressive-stress layer depth in a top part. It is a figure which shows the relationship between chemical strengthening conditions, a compressive-stress layer depth, and a maximum compressive-stress value.
  • the cover glass for electronic equipment according to the present invention is incorporated as a cover glass for mobile equipment, for example, on a display screen of a mobile phone.
  • the cover glass for an electronic device in the present invention is a cover for a display screen of a mobile device such as a mobile phone, a portable game machine, a PDA (Personal Digital Assistant), a digital still camera, a video camera, or a slate PC (Personal Computer).
  • the cover glass for mobile devices is required to be strong because it is necessary to protect the display screen from being damaged by an external impact.
  • a cellular phone is operated by pressing a predetermined part (for example, an icon displayed on the screen) of the display screen. Is required to have a cover glass having sufficient strength even if it is thin, lightweight, and has a large screen (large area).
  • the cover glass for an electronic device according to the present invention is manufactured by a process as described below.
  • a cover glass for a mobile device such as a mobile phone
  • a glass material large plate glass formed into a sheet shape is cut into a predetermined size by etching (small piece) to produce a glass substrate for cover glass.
  • a sheet-like glass material (sheet glass) having a thickness of, for example, about 0.5 mm manufactured by a downdraw method or a float method is cut into small pieces of a predetermined size by etching.
  • the size of the small piece may be determined in consideration of the size of the product cover glass plus the margin necessary for the outer peripheral shape processing.
  • the thickness of the glass substrate for cover glass is preferably in the range of, for example, about 0.1 mm to 1.5 mm, more preferably from the viewpoint of responding to the recent market needs for thinner and lighter portable devices.
  • the range is about 0.3 mm to 0.7 mm.
  • the glass constituting the glass substrate for cover glass is preferably a glass composition that can be chemically strengthened by ion exchange, for example, amorphous aluminosilicate glass.
  • a glass substrate made of such an aluminosilicate glass is excellent in strength after chemical strengthening.
  • an aluminosilicate glass for example, SiO 2 is 50 to 70 wt%, Al 2 O 3 is 5 to 20 wt%, Na 2 O is 6 to 20 wt%, and K 2 O is 0 to 10 wt%.
  • An aluminosilicate glass containing 0 to 10% by weight of MgO and 0 to 10% by weight of CaO as main components can be used.
  • etching method When the above plate glass is cut into small pieces, if an etching method is applied, it is possible to cut out a desired shape, particularly a complicated outer shape, and the outer shape processing and perforation processing can be performed simultaneously with the formation of the outer periphery of the glass substrate. It can be carried out. That is, a resist (photosensitive organic material) is applied to the surface of the plate glass, and predetermined exposure and development are performed to form a resist pattern having a cutting line pattern (a pattern in which no resist exists on the cutting line). Form.
  • a resist photosensitive organic material
  • the glass material on which such a resist pattern is formed is cut into small pieces of a predetermined size by wet etching using an etching solution that can dissolve the glass material (for example, an acidic solution containing hydrofluoric acid as a main component).
  • an etching solution that can dissolve the glass material for example, an acidic solution containing hydrofluoric acid as a main component.
  • the remaining resist pattern is peeled off and washed.
  • FIGS. 1A and 1B are cross-sectional views showing examples of the shape of the end face of a glass substrate obtained by etching a plate glass and cutting the outer shape into, for example, a rectangular shape.
  • a glass substrate 1 shown in FIG. 1 has a pair of opposing main surfaces 11 and 12 and an end face 13 adjacent to the pair of main surfaces 11 and 12.
  • the etching is performed from both the main surfaces 11 and 12 facing the glass substrate, respectively. Therefore, the top portion 16 is formed on the end surface 13 by etching that proceeds from the main surface 11 side and etching that proceeds from the main surface 12 side.
  • the etching proceeds so as to draw a substantially circular arc from the main surface 11 side and the main surface 12 side toward the inside of the glass substrate in a cross-sectional view
  • Two concave surfaces that draw a substantially circular arc toward the center of the substrate have an end surface shape that intersects near the center in the thickness direction of the substrate (see FIG. 1A).
  • the top portion 16 is formed at the center in the thickness direction of the substrate, and the top portions 14 and 15 are formed at the edge portions between the end surface 13 and the main surfaces 11 and 12. That is, the end surfaces of the obtained glass substrate 1 have the top portions 14, 15, and 16 disposed at the center portion in the thickness direction at the end surface and the main surface side in the thickness direction at the end surface.
  • FIG. 1B shows an example in which the top shape is improved by grinding or chamfering the top portions 14 and 15 on the main surfaces 11 and 12 side after the etching.
  • the above describes the case where the plate glass is shredded by an etching method.
  • the present invention is not limited to this.
  • a large-sized plate glass is cut (cut into small pieces) to a predetermined size by machine (cutter) processing.
  • the glass substrate 1 for cover glass can also be produced by polishing the surface with a grindstone or the like.
  • a large number (for example, about several tens) of sheet glass having a thickness of, for example, about 0.5 mm manufactured by the downdraw method or the float method is laminated (laminated), and, for example, a predetermined size is obtained using a glass cutter. Cut into small pieces. As described above, if the laminated state is cut at a time, the laminated pieces can be shaped at the same time in the next shape processing step, which is advantageous in production. Then, after performing necessary shape processing by machining, processing by wet etching is mainly performed to remove a damaged layer such as micro cracks on the processed surface.
  • apexes 14 and 15 are formed at the edge portions of the end surface 13 and both the main surfaces 11 and 12. That is, the end surface of the glass substrate 1 obtained by external processing using both machining and wet etching is curved at the center in the thickness direction at the end surface, and the top portion 14 on the main surface side in the thickness direction at the end surface. , 15 are arranged.
  • the apex angle ⁇ of the apex formed on the end surface 13 of the glass substrate 1 cut out from the plate glass by etching or machining is defined as follows in the present invention. This will be described with reference to FIG.
  • the top 16 formed at the center in the thickness direction of the glass substrate 1 is drawn at the apex (the most protruding point) and a circle with a radius of 10 ⁇ m from the apex (drawn with a broken line in FIG. 2).
  • the angle formed by two imaginary lines L1 and L2 that respectively connect the contact point between the contour of the glass substrate 1 and the contour line of the glass substrate 1 is defined as an apex angle ⁇ (see FIG. 2A).
  • apex angle ⁇ (see FIG. 2B).
  • one virtual line (for example, virtual line L2) is located on main surface 12.
  • the apex angle of the apex 14 is defined similarly.
  • the apex 15 on the end surface in the thickness direction main surface side when the vertex (the most protruding point) and a circle with a radius of 10 ⁇ m are drawn from the vertex (the circle drawn with a broken line in FIG. 2).
  • An apex angle ⁇ is an angle formed by two virtual lines L1 and L2 that connect the contact points of the glass substrate 1 and the contour line of the glass substrate 1 (see FIG. 2C).
  • the apex angle of the apex 14 is defined similarly.
  • a chemical strengthening treatment is performed on the glass substrate that has been cut into pieces by etching or machining to improve the strength.
  • a method of chemical strengthening treatment for example, a low temperature ion exchange method in which ion exchange is performed in a temperature range not exceeding the temperature of the glass transition point, for example, a temperature of 300 to 600 degrees Celsius is preferable.
  • the chemical strengthening treatment is a process in which a molten chemical strengthening salt is brought into contact with a glass substrate, whereby an alkali metal element having a relatively large atomic radius in the chemical strengthening salt and a relatively small atomic radius in the glass substrate. This is a treatment in which an alkali metal element is ion-exchanged, an alkali metal element having a large ion radius is permeated into the surface layer of the glass substrate, and compressive stress is generated on the surface of the glass substrate.
  • alkali metal nitrates such as potassium nitrate and sodium nitrate can be preferably used.
  • a chemically strengthened glass substrate is improved in strength and excellent in impact resistance, and thus is suitable for a cover glass used for a portable device that requires impact and pressure and requires high strength.
  • a rectangular glass substrate is immersed in a chemical strengthening treatment liquid obtained by heating and melting a chemically strengthened salt, thereby chemically strengthening the glass substrate; and And a cooling step of taking out the glass substrate from the chemical strengthening treatment liquid and lowering the temperature of the glass substrate.
  • the inventor has intensively studied the relationship between the end face shape of the glass substrate, in particular, the end face shape having a top as shown in FIG. 1 and chemical strengthening.
  • the compressive stress layer generated at the top of the end surface by chemical strengthening proceeds with ion exchange from the two directions on both sides of the top, so the compressive stress layer generated on the region surface other than the top on the end surface and the main surface It is presumed that the depth (thickness) becomes deep, and it is considered that the compressive stress value at the top portion is smaller than the compressive stress value at the main surface.
  • the top surface of the end surface is measured in the direction of the bisector of the apex angle ⁇ .
  • the depth d ′ of the compressive stress layer at the top can be theoretically calculated when d / sin ( ⁇ / 2).
  • FIG. 3 shows the result of the relationship with the% ratio. As shown in FIG. 3, it has been found that the depth of the compressive stress layer at the top of the end face becomes deeper as the apex angle is less than 90 degrees, that is, an acute angle.
  • FIG. 4 is a figure which shows the relationship between chemical strengthening conditions, the compressive-stress layer depth of a main surface, and the maximum compressive-stress value.
  • the fracture strength and scratch resistance of the chemically strengthened glass substrate correlate with the maximum compressive stress value of the substrate surface, and it is considered that the larger the compressive stress value, the stronger the impact from the outside.
  • FIG. 4 shows the compressive stress layer depth and maximum when chemical heating conditions are changed within the range of 440 ° C. to 500 ° C. and the processing time (immersion time) within the range of 2 to 9 hours. The relationship with the compressive stress value is shown. According to FIG.
  • the maximum compressive stress value of the compressive stress layer measured in the direction perpendicular to the end face (region surface other than the top) or the main surface decreases as the depth increases. That is, if the chemical strengthening is made too deep with respect to the glass substrate, the maximum compressive stress value is lowered.
  • the top (especially when the apex angle is an acute angle) is likely to concentrate stress when it hits, and it is desirable to have higher strength.
  • ion exchange more than expected proceeds as described above, and a compressive stress layer deeper than the compressive stress layer generated on the main surface or the like is formed by the chemical strengthening conditions, and as a result, more than expected. Only low compressive stress can be obtained. For this reason, it is considered that the top portion is more likely to generate cracks and scratches due to external impacts, and the cracks and cracks starting from the cracks are more likely to occur.
  • the present inventor has examined the conditions for obtaining a sufficient strength against an impact at the top of the end face. Some overlap with what has already been described, but the depth of the compressive stress layer measured in the direction perpendicular to the end face (area surface other than the top) or the main surface is d [ ⁇ m] (actual value), and the top at the top.
  • the theoretical value of the depth of the compressive stress layer measured in the direction of the bisector of the angle is d ′ [ ⁇ m]
  • the apex angle of the apex is ⁇ [degrees]
  • the maximum compressive stress value is CS [MPa] (actual value)
  • the theoretical value of the maximum compressive stress value at the top is CS ′ [MPa].
  • d ′ d / sin ( ⁇ / 2).
  • A is the ratio of the change amount of the compressive stress value to the change amount of the depth of the compressive stress layer, and a value within the range of ⁇ 10 MPa / ⁇ m to ⁇ 0.5 MPa / ⁇ m can be selected.
  • A is larger than ⁇ 0.5 MPa / ⁇ m, the amount of change (decrease) in the compressive stress value relative to the amount of change in the depth of the compressive stress layer is small.
  • the glass substrate has a large amount of change (decrease) in the compressive stress value relative to the amount of change in the depth of the compressive stress layer. Not suitable as a cover glass.
  • the theoretical value CS ′ of the compressive stress value of the top is preferably 600 MPa or more. Confirmed by the person.
  • CS ′ ⁇ 600 MPa the compressive stress layer depth d, apex angle ⁇ , and the maximum compressive stress value CS on the surface are obtained by the following relational expression, and the results are shown in FIG.
  • the value of A that is, the ratio of the amount of change in the compressive stress value to the amount of change in the depth of the compressive stress layer, is that the glass composition is SiO 2 : 60.2 wt%, Al 2 O 3 : 13.2 wt%.
  • this strengthening condition using a molten salt of potassium nitrate 100%, at the heating temperature of the chemical strengthening treatment liquid of Tg (glass transition temperature of the glass) -150 ° C. which is a general chemical strengthening temperature range,
  • Tg glass transition temperature of the glass
  • the ratio of the change amount of the compressive stress value to the change amount of the depth of the compressive stress layer can be obtained from the measured value under the strengthening condition where d is 20 ⁇ m and 40 ⁇ m, for example, and the ratio can be used as A.
  • A is set to ⁇ 3.5 MPa / ⁇ m from the result of FIG.
  • a chemically strengthenable aluminosilicate glass applied to the present invention SiO 2 is 50 to 70 wt%, Al 2 O 3 is 5 to 20 wt%, Na 2 O is 6 to 20 wt%,
  • SiO 2 is 50 to 70 wt%
  • Al 2 O 3 is 5 to 20 wt%
  • Na 2 O is 6 to 20 wt%
  • the amount of change in the depth of the compressive stress layer It was confirmed that the amount of change in the compressive stress value was substantially equivalent to the experimental result shown in FIG. Therefore, within this composition range, the theoretical value CS ′ of the compressive stress value at the top can be obtained by using ⁇ 3.5 MPa / ⁇ m as the value of A.
  • the apex angle ⁇ is usually 30 degrees or more and 135 degrees or less.
  • the apex angle is 135 degrees or less, the reduction in compressive stress due to the chemical strengthening at a depth greater than expected is significant, and the present invention is preferably applied, and more preferably in the range of 30 degrees to 120 degrees. is there.
  • the apex angle is less than 30 degrees, the structure is easily chipped regardless of the presence or absence of chemical strengthening, and therefore chamfering or the like is necessary in advance.
  • the apex angle exceeds 135 degrees, as shown in FIG. 5, the difference between CS and CS ′ is extremely small, so that the compressive stress is reduced due to the chemical strengthening beyond the expected depth. Hateful.
  • CS ′ for example, in order to satisfy CS ′ ⁇ 600 MPa, for example, ⁇ is 30 degrees and d exceeds 60 ⁇ m, and since CS ⁇ 1400 MPa is difficult to realize, d is 60 ⁇ m or less, CS Is suitably 600 MPa or more.
  • the glass substrate used for the cover glass for electronic equipment according to the present invention has a pair of main surfaces and end faces adjacent to the pair of main surfaces, and the end faces have a top portion in a cross-sectional view.
  • the glass substrate has a compressive stress layer formed on the surface by chemical strengthening by ion exchange, the maximum compressive stress value of the main surface is 600 MPa or more, and the depth of the compressive stress layer is 60 ⁇ m.
  • the maximum compressive stress value of the main surface is CS [MPa]
  • the depth of the compressive stress layer of the main surface is d [ ⁇ m], 600 MPa ⁇ A ⁇ ⁇ (d / sin ( ⁇ / 2)) ⁇ d ⁇ + CS
  • A is the ratio of the change amount of the compressive stress value to the change amount of the depth of the compressive stress layer, and is a value in the range of ⁇ 10 MPa / ⁇ m to ⁇ 0.5 MPa / ⁇ m. It is characterized by satisfying.
  • the above-described chemical strengthening conditions are preferably adjusted as appropriate.
  • SiO 2 is 50 to 70 wt%
  • Al 2 O 3 is 5 to 20 wt%
  • Na 2 O is 6 to 20 wt%
  • K 2 O is 0 to 10 wt%
  • MgO is 0 to 10 wt%.
  • the relational expression relating to compressive stress is as follows. 600 MPa ⁇ ⁇ 3.5 ⁇ ⁇ (d / sin ( ⁇ / 2)) ⁇ d ⁇ + CS
  • the strength of the end surface having the top portion is improved, for example, the maximum compressive stress value at the top portion is 600 MPa or more, and the depth of the conventional structure or more than expected. Occurrence of chipping, cracking, etc. due to brittleness of the end face having the apex, such as a reduction in compressive stress due to the chemical strengthening, can be reduced.
  • FIG. 1 described above when the shape has the apexes 14, 15, 16 on the end surface 13 of the glass substrate 1, it is particularly desirable to further improve the strength of the apex where the apex angle is an acute angle. From this point of view, it is preferable to appropriately adjust the aforementioned chemical strengthening conditions.
  • a cover glass for an electronic device is produced using the glass substrate that has been subjected to the chemical strengthening treatment described above.
  • the glass substrate itself may be used as a cover glass for electronic equipment.
  • the decorative layer includes an anti-reflection coating, an anti-glare coating, a half mirror coating, a layer having an optical function such as a polarizing film, and a layer having an electrical function such as a transparent conductive film typified by an ITO (Indium Tin Oxide) film. And a layer having a function of improving aesthetics such as a printing layer.
  • various devices such as a touch panel, can also be formed in a cover glass by laminating
  • means for forming these decorative layers include film forming methods such as vapor deposition and sputtering, and printing methods such as screen printing.
  • the display screen is directly touched and operated, so that dirt such as fingerprints tends to adhere to the cover glass that protects the display screen. Therefore, it is desirable to prevent or suppress the dirt such as fingerprints from adhering to the cover glass, or to easily wipe off even if dirt such as fingerprints adheres. Therefore, it is preferable that the surface of the cover glass is subjected to an antifouling coating process using, for example, a fluorine resin material.
  • the final cover glass for electronic devices is produced by forming arbitrarily the above-mentioned decorating layer and antifouling coating layer with respect to the chemically strengthened glass substrate.
  • the cover glass for an electronic device including the glass substrate, and the method for manufacturing the glass substrate the strength of the end face having the top portion can be particularly improved. It is possible to reduce the occurrence of chipping or cracking of the glass substrate or the cover glass for electronic equipment of the product due to a reduction in compressive stress caused by chemical strengthening at a depth higher than expected.
  • a predetermined shape (rectangular shape) and size (100 mm ⁇ 50 mm) are etched from a 0.5 mm thick plate glass made of an aluminosilicate gate glass manufactured by a downdraw method or a float method.
  • a glass substrate for cover glass having an improved apex shape was prepared by grinding or chamfering the apex on the main surface side by grinding.
  • aluminosilicate glass SiO 2: 60.2 wt%, Al 2 O 3: 13.2 wt%, Na 2 O: 13.9 wt%, K 2 O: 3.3 wt%, MgO: 2
  • a glass for chemical strengthening containing 0.2 wt%, CaO: 3.2 wt%, and ZrO: 4.0 wt% was used. After the produced glass substrate was scribed with a glass cutter, the cut surface was observed with a microscope. As a result, it was a shape having a top portion similar to that shown in FIG.
  • the glass substrate was chemically strengthened.
  • a chemical strengthening treatment liquid in which potassium nitrate and sodium nitrate were mixed (see Table 1 for the mixing ratio) was prepared.
  • the chemical strengthening treatment solution was heated to a predetermined temperature, and the glass substrate was immersed for a predetermined time to perform chemical strengthening.
  • the heating temperature of the chemical strengthening treatment liquid was changed within the range of 440 ° C. to 500 ° C. and the treatment time (immersion time) within the range of 2 to 9 hours (see Table 1). 4 and Comparative Examples 1 to 3.
  • the external shape of the glass substrate was formed by machining, the end surface of the glass substrate was etched, chemical strengthening was carried out, and it was set as Example 5 and Comparative Example 4 shown in Table 1.
  • the cut surface was observed with a microscope. As a result, it was a shape having the same top as in FIG.
  • the glass substrate is taken out from the chemical strengthening treatment solution, and after cooling, the glass substrate is removed from each of neutral detergent, pure water, IPA, and IPA (steam drying) in order to remove deposits on the glass substrate. It was immersed in a washing tank sequentially, ultrasonically washed, and dried.
  • glass substrates for cover glasses of Examples 1 to 5 and Comparative Examples 1 to 4 were produced.
  • the apex angle ⁇ of the top surface of each glass substrate is formed on the top 16 formed near the center in the thickness direction of the end surface or on the main surface side in the thickness direction in accordance with the definition described with reference to FIG.
  • the apex angle of the apex 15 (or 14) was determined.
  • the compressive stress value CS and the compressive stress layer depth (thickness) d of the main surface of each glass substrate were measured using a surface stress measuring apparatus by a web guide method.
  • the pin 2 is inclined 45 degrees from the horizontal, and the upper side (15 cm) is directed toward the pin.
  • the glass substrate 1 was dropped vertically, and the presence or absence of cracks in the glass substrate or chipping at the top of the main surface rather than the center of the end face was evaluated.
  • the edge hitting location of the glass substrate in the edge drop test is shown in Table 1 as “1 (b) -16” in the case of the top 16 in FIG. 1 (b), and the top 15 (or 14) in FIG. 1 (b). In this case, the case of “1 (b) -15” and the case of the top 15 (or 14) of FIG. In Table 1, those without cracks and chips were marked with “ ⁇ ”. The above results are summarized in Table 1 below.
  • the cover glass for an electronic device may be a cover glass for a touch sensor or a cover glass for a track pad.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne un substrat de verre pour un cache de verre pour un dispositif électronique, dans lequel la résistance d'une face d'extrémité ayant un sommet est améliorée. Ce substrat de verre a une paire de faces d'extrémité avoisinant une surface principale, et les faces d'extrémité façonnées en ayant un sommet tel qu'observé en section transversale et ont une couche de contrainte de compression en raison du renforcement chimique, la contrainte de compression maximale étant de 600 MPa ou plus, et la profondeur de la couche de contrainte de compression étant de 60 µm ou moins. L'angle au sommet θ (degrés) du sommet, la contrainte de compression maximale (CS) [MPa] de la surface et la profondeur (d) [µm] de la couche de contrainte de compression satisfont la relation 600 MPa ≤ -3,5 × {(d/sin(θ/2)) - d} + CS.
PCT/JP2013/072547 2012-08-23 2013-08-23 Substrat de verre pour un cache de verre pour un dispositif électronique, cache de verre pour un dispositif électronique et procédé de fabrication du substrat de verre pour un cache de verre pour un dispositif électronique WO2014030738A1 (fr)

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JP2014531682A JP6025156B2 (ja) 2012-08-23 2013-08-23 電子機器用カバーガラスのガラス基板及び電子機器用カバーガラス、並びに電子機器用カバーガラスのガラス基板の製造方法
CN201380033281.4A CN104379533B (zh) 2012-08-23 2013-08-23 电子设备用玻璃盖片的玻璃基板和电子设备用玻璃盖片、以及电子设备用玻璃盖片的玻璃基板的制造方法

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US9302937B2 (en) 2010-05-14 2016-04-05 Corning Incorporated Damage-resistant glass articles and method
WO2016057590A1 (fr) * 2014-10-07 2016-04-14 Corning Incorporated Article en verre à profil de contraintes déterminé et son procédé de production
WO2016170931A1 (fr) * 2015-04-23 2016-10-27 日本電気硝子株式会社 Verre renforcé
US9522836B2 (en) 2011-07-25 2016-12-20 Corning Incorporated Laminated and ion-exchanged strengthened glass laminates
WO2017065286A1 (fr) * 2015-10-16 2017-04-20 旭硝子株式会社 Stratifié verre-résine
WO2017082199A1 (fr) * 2015-11-12 2017-05-18 旭硝子株式会社 Plaque avec couche d'impression, dispositif d'affichage utilisant celle-ci, et verre avec couche fonctionnelle pour dispositifs d'affichage embarqués
US9868664B2 (en) 2012-02-29 2018-01-16 Corning Incorporated Low CTE, ion-exchangeable glass compositions and glass articles comprising the same
WO2018097096A1 (fr) * 2016-11-22 2018-05-31 日本電気硝子株式会社 Plaque de verre renforcée et procédé de production de plaque de verre renforcée
JP2019137575A (ja) * 2018-02-08 2019-08-22 日本電気硝子株式会社 カバー部材及びその製造方法
US11167528B2 (en) 2015-10-14 2021-11-09 Corning Incorporated Laminated glass article with determined stress profile and method for forming the same

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JP7151551B2 (ja) * 2019-02-28 2022-10-12 Ａｇｃ株式会社 カバーガラスの製造方法、カバーガラスおよび表示装置
CN114096490B (zh) * 2019-06-27 2023-12-19 Ａｇｃ株式会社 强化玻璃板及其制造方法

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JP2012148955A (ja) * 2010-09-30 2012-08-09 Avanstrate Inc カバーガラスの製造方法及びカバーガラス
JP2012148957A (ja) * 2010-12-27 2012-08-09 Hoya Corp 携帯型電子機器用カバーガラスのガラス基板、携帯型電子機器用画像表示装置、携帯型電子機器、および携帯型電子機器用カバーガラスのガラス基板の製造方法
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10843439B2 (en) 2010-05-14 2020-11-24 Corning Incorporated Damage-resistant glass articles and method
US9302937B2 (en) 2010-05-14 2016-04-05 Corning Incorporated Damage-resistant glass articles and method
US10196295B2 (en) 2011-07-25 2019-02-05 Corning Incorporated Laminated and ion-exchanged strengthened glass laminates
US9522836B2 (en) 2011-07-25 2016-12-20 Corning Incorporated Laminated and ion-exchanged strengthened glass laminates
US11059736B2 (en) 2011-07-25 2021-07-13 Corning Incorporated Laminated and ion-exchanged strengthened glass laminates
US11780758B2 (en) 2011-07-25 2023-10-10 Corning Incorporated Laminated and ion-exchanged strengthened glass laminates
US9868664B2 (en) 2012-02-29 2018-01-16 Corning Incorporated Low CTE, ion-exchangeable glass compositions and glass articles comprising the same
US11123959B2 (en) 2014-10-07 2021-09-21 Corning Incorporated Glass article with determined stress profile and method of producing the same
WO2016057590A1 (fr) * 2014-10-07 2016-04-14 Corning Incorporated Article en verre à profil de contraintes déterminé et son procédé de production
CN107531563A (zh) * 2015-04-23 2018-01-02 日本电气硝子株式会社 强化玻璃
JPWO2016170931A1 (ja) * 2015-04-23 2018-02-15 日本電気硝子株式会社 強化ガラス
KR20170139031A (ko) * 2015-04-23 2017-12-18 니폰 덴키 가라스 가부시키가이샤 강화유리
US11236015B2 (en) 2015-04-23 2022-02-01 Nippon Electric Glass Co., Ltd. Tempered glass
KR102289447B1 (ko) * 2015-04-23 2021-08-11 니폰 덴키 가라스 가부시키가이샤 강화유리
WO2016170931A1 (fr) * 2015-04-23 2016-10-27 日本電気硝子株式会社 Verre renforcé
US11167528B2 (en) 2015-10-14 2021-11-09 Corning Incorporated Laminated glass article with determined stress profile and method for forming the same
WO2017065286A1 (fr) * 2015-10-16 2017-04-20 旭硝子株式会社 Stratifié verre-résine
JPWO2017065286A1 (ja) * 2015-10-16 2018-09-06 Ａｇｃ株式会社 ガラス樹脂積層体
WO2017082199A1 (fr) * 2015-11-12 2017-05-18 旭硝子株式会社 Plaque avec couche d'impression, dispositif d'affichage utilisant celle-ci, et verre avec couche fonctionnelle pour dispositifs d'affichage embarqués
JPWO2017082199A1 (ja) * 2015-11-12 2018-08-30 Ａｇｃ株式会社 印刷層付き板及びこれを用いた表示装置、並びに機能層付き車載表示装置用ガラス
WO2018097096A1 (fr) * 2016-11-22 2018-05-31 日本電気硝子株式会社 Plaque de verre renforcée et procédé de production de plaque de verre renforcée
JP2019137575A (ja) * 2018-02-08 2019-08-22 日本電気硝子株式会社 カバー部材及びその製造方法

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JPWO2014030738A1 (ja) 2016-08-08
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CN104379533B (zh) 2016-11-16
JP6025156B2 (ja) 2016-11-16

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