[go: up one dir, main page]

WO2018131863A1 - Verre à couche et verre feuilleté comprenant ce dernier - Google Patents

Verre à couche et verre feuilleté comprenant ce dernier Download PDF

Info

Publication number
WO2018131863A1
WO2018131863A1 PCT/KR2018/000390 KR2018000390W WO2018131863A1 WO 2018131863 A1 WO2018131863 A1 WO 2018131863A1 KR 2018000390 W KR2018000390 W KR 2018000390W WO 2018131863 A1 WO2018131863 A1 WO 2018131863A1
Authority
WO
WIPO (PCT)
Prior art keywords
dielectric layer
conductive metal
glass
functional conductive
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/000390
Other languages
English (en)
Korean (ko)
Inventor
윤윤희
강현민
오영훈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KCC Corp
Original Assignee
KCC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170003749A external-priority patent/KR101797426B1/ko
Application filed by KCC Corp filed Critical KCC Corp
Publication of WO2018131863A1 publication Critical patent/WO2018131863A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
    • H05B3/86—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields the heating conductors being embedded in the transparent or reflecting material

Definitions

  • the present invention relates to a coated glass and a laminated glass comprising the same.
  • Transparent heating coating technology for glass has been used to solve the accident problem caused by the difficulty of securing visibility due to the frost of the outer and outer shaft glass due to the indoor and outdoor temperature difference, such as winter.
  • transparent heat-coated glass when transparent heat-coated glass is applied to a window pane of an automobile, laminated glass in which the transparent heat-coated glass is bonded to another glass substrate by a polymer film in order to reduce scattering of glass fragments due to external impact. Since it is provided as may cause a decrease in the visible light transmittance accordingly.
  • the transparent heating coated glass applied to the window glass of the car uses a lower voltage than the transparent heating coating technology applied to the building swimming pool and the transparent freezer door, so it has low surface resistance due to high conductivity and high transmittance for ensuring visibility. Should have
  • the functional conductive metal layer such as the silver layer
  • the decrease in the visible light transmittance can be minimized, so that the coating having low resistance and high visible light transmittance suitable for practical use in various applications such as building or automotive window glass Development of glass or laminated glass is required.
  • the present invention can minimize the deterioration of the visible light transmittance while the overall thickness of the functional conductive metal layer such as the silver layer is secured to a certain level, thereby providing a low resistance and high visible light transmittance suitable for practical use in various applications such as building window panes and automotive window panes.
  • Eggplant provides a coated glass and laminated glass comprising the same.
  • the present invention provides a first glass substrate, a first dielectric layer sequentially formed on the first glass substrate, a first functional conductive metal layer, a second dielectric layer, a second functional conductive metal layer, a third dielectric layer, a third functional conductive metal layer, and a first 4 comprising a dielectric layer, wherein the physical thickness ratio of the first functional conductive metal layer to the total thickness of the first, second and third functional conductive metal layers is 25 to 30%, wherein the first, second and third functional conductive metal layers The physical thickness ratio of the second and third functional conductive metal layers to the total physical thickness of is 35 to 37.5%, respectively, and the total physical thickness of the first, second and third functional conductive metal layers is 34 to 40 nm.
  • the optical thickness ratio of the fourth dielectric layer to the optical thickness of the first dielectric layer is 0.9 to 1.2, and the optical thickness ratio of the third dielectric layer to the optical thickness of the second dielectric layer is 1.0 to 1.2.
  • Phosphorus and coated glass can be provided.
  • the coated glass may be heat treatable.
  • the coating glass may have a visible light transmittance of 70% or more (A light).
  • the coated glass may have a surface resistance of 1.0 ⁇ / sq or less.
  • the coated glass may further include a barrier layer on at least one of upper and lower layers of the first, second and third functional conductive metal layers.
  • the barrier layer may be at least one of Ni, Cr, Ni-Cr alloy and NiCrNx (where x is 0.1 to 10).
  • At least one of the first, second, third and fourth dielectric layers each comprises a main dielectric layer comprising a Si based nitride or a Ti based oxide and at least one sub including a Zn based oxide. It may comprise a dielectric layer.
  • the topmost protective layer comprises TiOxNy, where 0 ⁇ x ⁇ 2.5, 0 ⁇ y ⁇ 0.6, x: y is 100 mol%: 0 mol% to 75 mol%: 25 It may be mole%.
  • the first, second and third functional conductive metal layers may include those selected from Ag, Au, Cu and combinations thereof.
  • the present invention provides a step of providing a first glass substrate, a first dielectric layer, a first functional conductive metal layer, a second dielectric layer, a second functional conductive metal layer, a third dielectric layer, a third functional layer sequentially on the first glass substrate.
  • Forming a conductive metal layer and a fourth dielectric layer wherein the physical thickness ratio of the first functional conductive metal layer to the total thickness of the first, second and third functional conductive metal layers is 25 to 30%, wherein the first, The ratio of the physical thickness of the second and third functional conductive metal layers to the total physical thickness of the second and third functional conductive metal layers is 35 to 37.5%, respectively, and the total physical thickness of the first, second and third functional conductive metal layers.
  • the thickness is 34 to 40 nm
  • the optical thickness ratio of the fourth dielectric layer to the optical thickness of the first dielectric layer is 0.9 to 1.2
  • the third dielectric to the optical thickness of the second dielectric layer is 1.0 to 1.2
  • the formation of the layers provides a method of coating glass are carried out by sputter deposition.
  • a laminated glass comprising the coating glass, a polymer film laminated on the coating glass and a second glass substrate laminated on the polymer film.
  • the laminated glass may be one containing a visible light transmittance of 70% or more.
  • the laminated glass may be one containing a surface resistance of 1.0 ⁇ / sq or less.
  • the present invention can be useful as a coating glass for various applications, such as architectural glazing, automotive glazing, as the overall thickness of the functional conductive metal layer, such as a silver layer, is secured to a certain level, while the resistance is low and the degradation of visible light transmittance can be minimized. Can be used.
  • 1 is a penetration view of a coated glass according to an embodiment of the present invention.
  • FIG. 2 is a penetration view of the coated glass according to another embodiment of the present invention.
  • 3 is a penetration view of the coated glass according to another embodiment of the present invention.
  • Figure 4 is a penetrating view of the coated glass according to another embodiment of the present invention.
  • the coated glass 1 of the present invention comprises first, second and third functional conductive metal layers 5, 9 and 13 and first, second, third and fourth dielectric layers 3 and 7. , 11 and 15).
  • the coating glass 1 is sequentially formed on the first glass substrate 2, the first dielectric layer 3, the first functional conductive metal layer 5, the second dielectric layer 7, the second functional conductive metal layer 9,
  • the third dielectric layer 11, the third functional conductive metal layer 13, and the fourth dielectric layer 15 may be coated with glass.
  • the physical thickness ratio of each of the functional conductive metal layers 5, 9, and 13 has a specific ratio
  • an optical thickness ratio between each of the dielectric layers 3, 7, 11, and 15 has a specific ratio of coated glass ( May be 1).
  • Coating glass 1 according to an embodiment of the present invention may be heat treatment possible.
  • the coating glass 1 may have a visible light transmittance of 70% or more (A light) after heat treatment, and a sheet resistance of 1.0 ⁇ / sq or less.
  • the coated glass 1 according to the embodiment of the present invention may have a visible light transmittance of 70% or more, preferably 72% or more, and a sheet resistance of 1.0 ⁇ / sq or less under a D65 light standard light source of 380 to 780 nm. have.
  • the first glass substrate 2 may be a conventional glass, for example, soda-lime glass used for building or automobile.
  • a glass having a thickness of 2 to 12mm depending on the purpose of use for example, soda-lime glass having a thickness of 2.1 mm can be used, but is not limited thereto.
  • the first, second and third functional conductive metal layers 5, 9 and 13 are respectively coated between the dielectric layers and selectively transmit solar visible light and provide high conductivity relative to transmittance.
  • the first, second and third functional conductive metal layers 5, 9 and 13 may comprise a material selected from Ag, Au, Cu and combinations thereof.
  • at least one of the first, second and third functional conductive metal layers 5, 9 and 13 may comprise Ag which best matches high transmittance and good conductivity in the visible region.
  • the overall physical thickness of the first, second and third functional conductive metal layers 5, 9 and 13 may be 34 to 40 nm.
  • the physical thickness ratio of the first functional conductive metal layer 5 to the total physical thickness of the first, second and third functional conductive metal layers 5, 9, and 13 may be 25 to 30%. Further, the physical thickness ratios of the second and third functional conductive metal layers 9 and 13 to the total physical thicknesses of the first, second and third functional conductive metal layers 5, 9 and 13 may be 35 to 37.5%, respectively. Can be. In the thickness ratio range of the functional conductive metal layer, the total physical thickness of the silver layer may be secured to a certain level, and may exhibit high visible light transmittance of 70% or more while exhibiting low sheet resistance of 1.0 ⁇ / sq or less.
  • each layer of the first to third functional conductive metal layers 5, 9 and 13 may each independently range from 8 to 16 nm, for example from 9 to 14 nm.
  • the first to third functional conductive metal layers 5, 9 and 13 may not be formed normally, and thus electrical conduction performance may be insufficient. If it exceeds 16 nm, the transmittance may decrease, and the reflectance may increase, thereby reducing visibility.
  • the first to fourth dielectric layers 3, 7, 11, and 15 block oxygen or ions transferred to the first to third functional conductive metal layers 5, 9, and 13 during heat treatment such as reinforcement and bending. Play a role.
  • the optical thickness ratio of the fourth dielectric layer 15 to the optical thickness of the first dielectric layer 3 may be 0.9 to 1.2, and the optical thickness of the third dielectric layer 11 to the optical thickness of the second dielectric layer 7.
  • the ratio may be 1.0 to 1.2.
  • the optical thickness of the third dielectric layer 11 may be thicker than the optical thickness of the second dielectric layer 7. It can exhibit low surface resistance (electrical conductivity) and high visible light transmittance after heat treatment within the thickness ratio range between the dielectric layers.
  • each of the first dielectric layer 3 and the fourth dielectric layer 15 is 38 to 100 nm, specifically 59 to 96 nm, based on the wavelength of 550 nm, and their total thickness may be 76 to 200 nm.
  • a second dielectric layer 7 and a third dielectric layer 11 are positioned between the first dielectric layer 3 and the fourth dielectric layer 15.
  • the optical thickness of each of the second dielectric layer 7 and the third dielectric layer 11 may be 80 to 200 nm, specifically 148 to 192 nm based on a wavelength of 550 nm, and their total thickness may be 160 to 400 nm.
  • the term "optical thickness” is the thickness obtained by "physical thickness of the layer x refractive index of the material used in that layer".
  • the refractive index differs depending on the material used for the dielectric layer, and accordingly, the physical thickness of the dielectric layer is adjusted according to the material used for the dielectric layer to satisfy the optical thickness range.
  • the refractive index of SiNx 1.0 ⁇ x ⁇ 1.5
  • the refractive index of TiOx (0 ⁇ x ⁇ 2.5) is 2.43
  • the refractive index of ZnOx 1.5 ⁇ x ⁇ 2.0
  • At least one of the first to fourth dielectric layers 3, 7, 11 and 15 may be a main dielectric layer 3.1, 7.1, 11.1 and 15.1 and at least one sub dielectric layer 3. 2, 7.2, 7.3, respectively. , 11.2, 11.3 and 15.2).
  • at least one of the first to fourth dielectric layers 3, 7, 11, and 15 may have a sub-dielectric layer formed on at least one of the upper and lower portions of the main dielectric layer.
  • the main dielectric layer may be thicker than the sub dielectric layer.
  • the main dielectric layer and the sub dielectric layer included in the first dielectric layer 3 are described as the first main dielectric layer 3.1 and the first sub dielectric layer 3.2, respectively.
  • the main dielectric layer and the sub dielectric layer included in the second dielectric layer 7 are described as the second main dielectric layer 7.1, the second sub dielectric layer 7.2, and the third sub dielectric layer 7.3, respectively.
  • the main dielectric layer and the sub dielectric layer included in the third dielectric layer 11 are described as the third main dielectric layer 11.1, the fourth sub dielectric layer 11.2, and the fifth sub dielectric layer 11.3, respectively.
  • the main dielectric layer and the sub dielectric layer included in the fourth dielectric layer 15 are described as the fourth main dielectric layer 15.1 and the sixth sub dielectric layer 15.2, respectively.
  • the first to fourth main dielectric layers 3.1, 7.1, 11.1, and 15.1 may block Na + diffused from the lower soda lime glass during heat treatment for reinforcement and bending, and oxygen may be transferred to the functional conductive metal layer. It blocks the ions.
  • the optical thicknesses of the main dielectric layers 3.1, 7.1, 11.1, and 15.1 may range from 38 to 200 nm, eg, 59 to 192 nm, based on the 550 nm wavelength. If the optical thickness of the main dielectric layer (3.1, 7.1, 11.1 and 15.1) is less than 38nm or more than 200nm based on the 550nm wavelength, there may be a problem that the durability and chemical resistance of the coating glass or the optical properties are degraded. More specifically, the optical thicknesses of the first main dielectric layer 3.1 directly formed on the first glass substrate 2 and the fourth main dielectric layer 15. 1 formed at the end of the multilayer coating structure are each independently 38 to 100 nm.
  • the second main dielectric layer 7.1 and the third main dielectric layer 11. 1 formed in the middle of the coated glass 1 in the range of 59 to 96 nm may be independently 80 to 200 nm, for example. , 148 to 192 nm.
  • the optical thickness ratio of the fourth main dielectric layer to the optical thickness of the first main dielectric layer formed on the first glass substrate is 0.9 to 1.2, and the optical thickness ratio of the third main dielectric layer to the optical thickness of the second main dielectric layer is 1.0. To 1.2. In this case, the optical thickness of the third main dielectric layer may be thicker than the optical thickness of the second main dielectric layer.
  • the main dielectric layer (3.1, 7.1, 11.1 and 15.1) may include Si-based nitride (SiNx, 1.0 ⁇ x ⁇ 1.5) or Ti-based oxide (TiOx, 0 ⁇ x ⁇ 2.5).
  • the Si-based nitride may further include one or more elements selected from Zr, Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni.
  • the Si-based nitride may be Si-based nitride containing Al.
  • the Ti-based oxide may further include one or more elements selected from Sn, Nb, Al, Sb, Mo, Cr, and Ni.
  • Si or Ti content may be 80% by weight, for example, 80 to 99% by weight, more preferably 90 to 99% by weight, It is not limited.
  • the main dielectric layers 3.1, 7.1, 11.1, and 15.1 may use Ti-based oxides to further improve visible light transmittance.
  • the first to sixth sub dielectric layers 3.2, 7.2, 7.3, 11.2, 11.3, and 15.2 may include Zn-based oxides (SiNx, 1.5 ⁇ x ⁇ 2.0).
  • the Zn-based oxide may further include a Zn-based oxide further containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, for example, a Zn-based oxide containing Al. Can be.
  • Each sub-dielectric layer is positioned above and below the functional conductive metal layers 5, 9 and 13 to induce crystallization of the functional conductive metal layers 5, 9 and 13 well.
  • an oxygen defect is prevented from being diffused into dielectric layers positioned above and below the heat treated functional conductive metal layers 5, 9, and 13, and an optical defect such as agglomeration is performed. This can be suppressed from occurring.
  • X-Ray Diffractrometer (XRD) analysis shows that the Zn-based layer surface and the first to third functional conduction of the first to sixth sub-dielectric layers (3.2, 7.2, 7.3, 11.2, 11.3 and 15.2)
  • the peak of the Ag layer surface which is the metal layers 5, 9 and 13, appears, which means that the Zn-based layer and the Ag layer have crystallinity.
  • crystallinity may improve crystallization of the functional conductive metal layers 5, 9, and 13, thereby reducing the sheet resistance of the coated glass, thereby improving heat generation performance.
  • the first to sixth sub-dielectric layers (3.2, 7.2, 7.3, 11.2, 11.3 and 15.2) have a Zn content of 85 wt% or more, for example, in order to facilitate crystallization of the functional conductive metal layers 5, 9 and 13. , 85 to 99% by weight, more preferably 92 to 99% by weight, but is not limited thereto.
  • the physical thickness of each of the sub dielectric layers 3.2, 7.2, 7.3, 11.2, 11.3, and 15.2 may be 5 to 20 nm, preferably 5 to 15 mm, more preferably 7 to 12 mm. Can be. If the physical thickness of each of the sub-dielectric layers (3.2, 7.2, 7.3, 11.2, 11.3, and 15.2) is less than 5 mm, the crystallization of the functional conductive metal layers (5, 9, and 13) may not be performed well. There may be a problem of this lowering.
  • Figure 3 is a penetration of the coated glass according to another embodiment of the present invention
  • Figure 4 is a penetration of the coated glass according to another embodiment of the present invention.
  • the barrier layer 6 may be further included in at least one of upper and lower portions of the first, second and third functional conductive metal layers 5, 9, and 13.
  • the barrier layer 6 may include at least one of Ni, Cr, Ni-Cr alloy, and NiCrNx.
  • the barrier layer 6 may include Ni-Cr alloy. In the case of Ni-Cr alloys, it is preferable that they are alloys of 75 to 85 wt% Ni and 15 to 25 wt% Cr.
  • X may be 0.1 to 10.
  • the barrier layer 6 serves as a barrier to prevent the movement of Na + and O 2 in the air diffused from the first glass substrate 2 during heat treatment for reinforcement and bending, and the functional conductive metal layers 5, 9 and 13. ) Serves to assist the fusion of the functional conductive metal layers 5, 9 and 13 to enable stable behavior even under high heat treatment conditions. Finally, it absorbs O 2 penetrating into the functional conductive metal layers 5, 9 and 13 to help maintain electrical conduction performance.
  • the physical thickness of the barrier layer 6 may be each independently preferably in the range of 0.1 to 5 nm, more preferably 0.2 to 2.5 nm. If the thickness of the barrier layer 6 is less than 0.1 nm, there may be a problem that the cloudyness of the coated glass is increased after the heat treatment and the bending process. If the thickness of the barrier layer 6 is greater than 5 nm, the transmittance is lowered or the cloudyness of the coated glass is also increased after the heat treatment and the bending process. There may be a problem.
  • the uppermost protective layer 17 may be further included on the fourth dielectric layer 15 of the coated glass 1 of the present invention.
  • the top protective layer 17 comprises TiOxNy using a TiOx (0 ⁇ x ⁇ 2.5) ceramic material, where 0 ⁇ x ⁇ 2.5, 0 ⁇ y ⁇ 0.6, y / x ⁇ 1, for example , x: y may be 100 mol%: 0 mol% to 75 mol%: 25 mol% based on 100 mol% of the sum of x and y.
  • the uppermost protective layer 17 may reduce surface roughness, increase scratch resistance, and increase mechanical and chemical durability of the coated glass 1.
  • the physical thickness of the top protective layer 17 may be 2 to 15 nm, preferably 2 to 9 nm. If the thickness of the uppermost protective layer 17 is less than 2 nm, the durability may be lowered. If the thickness of the uppermost protective layer 17 is more than 15 nm, the transmittance may be reduced or cause blur.
  • the coating glass 1 of the present invention may include a first glass substrate, at least three transparent conductor multilayer coating film sets formed on the first glass substrate, and an additional dielectric layer formed on the transparent conductor multilayer coating film sets. Can be.
  • the coating glass 1 may include a first glass substrate 2 and a set of first to third transparent conductor multilayer coating layers 4, 1, 4, formed on the first glass substrate 2. 2 and 4,3), the fourth dielectric layer 15 and the uppermost protective layer 17 formed on the first to third transparent conductor multilayer coating film sets 4,1, 4,2 and 4,3. can do.
  • the first to third transparent conductor multilayer coating film sets 4, 1, 4, 2, and 4, 3 may include first to third functional conductive metal layers 5, 9, and 13, and first to third dielectric layers 3,. 7 and 11), respectively.
  • the first to third transparent conductor multilayer coating film sets 4, 1, 4, 2, and 4, 3 further include at least one barrier layer.
  • the first transparent conductor multilayer coating film set 4.1 includes a first dielectric layer 3, a barrier layer 6, a first functional conductive metal layer 5 and a barrier layer 6 sequentially coated.
  • the second transparent conductor multilayer coating film set (4.2) comprises a second dielectric layer (7), a barrier layer (6), a second functional conductive metal layer (9) and a barrier layer (6) sequentially coated, and
  • the third transparent conductor multilayer coating layer set 4.3 may include a third dielectric layer 11, a barrier layer 6, a third functional conductive metal layer 13, and a barrier layer 6 sequentially coated.
  • coated glass of the present invention may have any one of the following multilayer structures, but the present invention is not limited thereto.
  • the transparent conductor multilayer coating film set may independently have any one of the following multilayer structures:
  • the first, second, third and fourth dielectric layers may each include a main dielectric layer and at least one sub dielectric layer. At least one of the first to fourth dielectric layers may have a sub dielectric layer formed on at least one of an upper portion and a lower portion of the main dielectric layer.
  • the coated glass of the present invention may further include a functional layer conventionally adopted for the coated glass within the scope of achieving the object of the present invention.
  • Such a method of manufacturing the coated glass 1 of the present invention is as follows.
  • Method for producing a coated glass (1) of the present invention comprises the steps of providing a first glass substrate; Sequentially forming a first dielectric layer, a first functional conductive metal layer, a second dielectric layer, a second functional conductive metal layer, a third dielectric layer, a third functional conductive metal layer, and a fourth dielectric layer on the first glass substrate, The formation of each of the layers can be performed by sputter deposition.
  • the coated glass of the present invention may be manufactured by the following procedure. First, into a glass substrate in a vacuum chamber vacuum is 5 ⁇ 10 - may be evacuated until the 6 torr to form a vacuum of 7 to 9 ⁇ 10. After injecting argon (Ar), oxygen (O 2 ), nitrogen (N 2 ) gas into the vacuum chamber and applying a direct current or an alternating voltage between the two electrodes, a discharge occurs. As gas ions collide with a cathode provided with a metal target to be deposited on the substrate, atoms may be released from the metal target and stacked on the substrate.
  • Ar argon
  • O 2 oxygen
  • N 2 nitrogen
  • An appropriate gas may be introduced according to the type of coating film to be laminated, and the thickness of the coating film to be formed may be appropriately controlled by appropriately adjusting the deposition rate of each coating film and the time exposed to the sputtering process. At this time, there is no particular limitation on the temperature of the substrate.
  • the coated glass of the present invention can be prepared by sequentially coating the functional layers onto the first glass substrate using a tubular Magnettron sputter coater.
  • argon and nitrogen are used to coat the nitride film
  • a SiAl metal target may be used and the ratio of nitrogen in the mixed gas may be 45 to 60% by volume. If the ratio of nitrogen is too high, the deposition rate of the film is lowered. If the ratio of nitrogen is too low, the absorption coefficient may be high, and thus high transmittance may not be realized.
  • the oxide film is coated using argon and oxygen, the ratio of oxygen in the mixed gas using the ZnAl metal target is 80 to 90% by volume or the ratio of oxygen in the mixed gas is 5 to 20% by volume using the ZnAlOx ceramic target. May be suitable. If the ratio of oxygen is too high, the functional conductive metal layer (eg, Ag layer) may be oxidized during the coating process. If the ratio of oxygen is too low, it may be coated with a metal film instead of a partial oxide film
  • the coated glass prepared as described above may be heat treated.
  • the heat treatment may be performed for 10 to 20 minutes at a temperature of 650 to 750 °C. Outside the heat treatment temperature and time may reduce the surface stress of each coating film coated on the first glass substrate, which may cause a problem that the coating film may be peeled off.
  • the laminated glass of the present invention includes a polymer film laminated on the above-described coating glass and a second glass substrate laminated on the polymer film.
  • the laminated glass is based on 5.72T laminated glass (e.g., coated glass (2.1T) / polymer (e.g. PVB) film (1.52T) / second glass substrate (e.g. CLR glass) (2.1T))
  • 5.72T laminated glass e.g., coated glass (2.1T) / polymer (e.g. PVB) film (1.52T) / second glass substrate (e.g. CLR glass) (2.1T)
  • the visible light transmittance may be 70% or more, and the sheet resistance may be 1.0 ⁇ / sq or less.
  • the physical thickness ratio of the functional conductive metal layers included in the above-described coating glass and the optical thickness ratio between the dielectric layers may be controlled such that the visible light transmittance of the laminated glass is 70% or more (A light) and the sheet resistance is 1.0 ⁇ / sq or less. have.
  • the polymer film laminated on the coating glass may be used by adopting a (co) polymer film having a material and thickness that is commonly used as a bonding layer of laminated glass in the art without particular limitation.
  • a polymer film a polyvinyl butyral (PVB) film, a polyester film, an ethylene vinyl acetate (EVA) film, a polyethylene terephthalate (PET) film, or the like may be used, and in particular, a polyvinyl butyral (PVB) film may be used.
  • the thickness may be 0.1 to 2mm, for example, 1.2 to 1.7mm level, but is not limited thereto.
  • the second glass substrate laminated on the polymer film may be the same material and thickness range as the first glass substrate of the coating glass.
  • the method of manufacturing the laminated glass there is no particular limitation on the method of manufacturing the laminated glass, and the conventional laminated glass manufacturing method and equipment may be used as it is or modified appropriately.
  • the coated glass and the second glass substrate as described above are cut and chamfered and then washed.
  • the laminated glass of the present invention may be manufactured through a process of simultaneously forming a curved molding and a compressive stress by heat treatment at a temperature of 650 to 750 ° C. between the second glass substrate and the coated glass as described above through a polymer film. .
  • coating glass was prepared by forming layers having a composition and thickness shown in Table 1 below on a 2.1 mm thick glass substrate.
  • x is 1.0 to 1.5 in SiNx
  • x is 1.5 to 2.0 in ZnOx
  • x is 0 ⁇ x ⁇ 2.5
  • y is 0 ⁇ y ⁇ 0.6 in TiOxNy.
  • the physical thickness ratio of the first functional conductive metal layer to the total physical thickness of the first, second and third functional conductive metal layers is 25 to 30%, and the first and second The ratio of the physical thickness of the second and third functional conductive metal layers to the total physical thickness of the second and third functional conductive metal layers is 35 to 37.5%, respectively, and the total physical thickness of the first, second and third functional conductive metal layers.
  • the optical thickness ratio of the fourth dielectric layer to the optical thickness of the first dielectric layer is 0.9 to 1.2
  • the optical thickness ratio of the third dielectric layer to the optical thickness of the second dielectric layer is 1.0 to 1.2. It has a phosphorus coating film structure.
  • the physical thickness ratio of the first, second and third functional conductive metal layers was out of the above range, and the coated glass prepared according to Comparative Example 3 had optical properties of the dielectric layer.
  • the thickness ratio is out of the above range.
  • Example 1 Glass / SiNx (63.8) / ZnOx (7) / Ag (9.6) / NiCr (0.2) / ZnOx (7) / SiNx (151.5) / ZnOx (7) / Ag (12.4) / NiCr (0.2) / ZnOx (7 ) / SiNx (159.5) / ZnOx (7) / Ag (12.4) / NiCr (0.36) / ZnOx (7) / SiNx (68.8) / TiOxNy (3)
  • Example 2 Glass / TiOx (63.8) / ZnOx (7) / Ag (9.6) / NiCr (0.2) / ZnOx (7) / TiOx (151.5) / ZnOx (7) / Ag (12.4) / NiCr (0.2) / ZnOx (7 ) / TiOx (159.5) / ZnOx (7) / Ag (12.4) / NiCr (0.36)
  • coating glass was prepared by forming layers having the composition and thickness shown in Table 2 below on a 2.1 mm thick first glass substrate.
  • x is 1.0 to 1.5 in SiNx
  • x is 1.5 to 2.0 in ZnOx
  • x is 0 ⁇ x ⁇ 2.5
  • y is 0 ⁇ y ⁇ 0.6 in TiOxNy.
  • the coated glass prepared according to Examples 6 to 11 has a physical thickness ratio of 25 to 30% of the total thickness of the first to third functional conductive metal layers, and the first to third functional conductive metal layers.
  • the physical thickness ratio of the second and third functional conductive metal layers to the total physical thickness is 35 to 37.5%, respectively, and the optical thickness ratio of the third dielectric layer to the optical thickness of the dielectric layer formed on the first glass substrate is 0.9 to 1.2.
  • the optical thickness ratio of the second dielectric layer to the optical thickness of the first dielectric layer has a coating film structure of 1.0 to 1.2.
  • the physical thickness ratio of the functional conductive metal layers was outside the above range
  • the coated glass prepared according to Comparative Examples 7 and 8 had an optical thickness ratio between the dielectric layers within the above range. Got out.
  • Each coated glass was bonded with a 1.52 mm thick PVB film and a 2.1 mm thick second glass substrate to prepare a 5.72T laminated glass. At this time, the bonding was performed so that the coating film of the coating glass is located outside.
  • the heat treatment was performed for 15 minutes at a temperature of 700 °C.
  • Visible light transmittance was measured according to KS L 2514 with a D65 light standard light source of 380-780 nm.
  • the sheet resistance was measured by a non-contact sheet resistance meter (717B, Delcom) at room temperature.
  • the visible light transmittance was measured according to KS A 0066 with an A light standard light source of 300 to 780 nm.
  • the sheet resistance was measured by a non-contact sheet resistance meter (717B, Delcom) at room temperature.

Landscapes

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

Abstract

La présente invention porte sur un verre à couche et sur un verre feuilleté comprenant ce dernier, le verre à couche comprenant : un premier substrat de verre ; et une première couche diélectrique, une première couche métallique conductrice fonctionnelle, une deuxième couche diélectrique, une deuxième couche métallique conductrice fonctionnelle, une troisième couche diélectrique, une troisième couche métallique conductrice fonctionnelle et une quatrième couche diélectrique qui sont formées consécutivement sur le premier substrat de verre.
PCT/KR2018/000390 2017-01-10 2018-01-09 Verre à couche et verre feuilleté comprenant ce dernier Ceased WO2018131863A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0003739 2017-01-10
KR20170003739 2017-01-10
KR10-2017-0003749 2017-01-10
KR1020170003749A KR101797426B1 (ko) 2017-01-10 2017-01-10 코팅유리 및 그 제조방법

Publications (1)

Publication Number Publication Date
WO2018131863A1 true WO2018131863A1 (fr) 2018-07-19

Family

ID=62839652

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/000390 Ceased WO2018131863A1 (fr) 2017-01-10 2018-01-09 Verre à couche et verre feuilleté comprenant ce dernier

Country Status (1)

Country Link
WO (1) WO2018131863A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11401206B2 (en) * 2017-10-30 2022-08-02 Saint-Gobain Glass France Substrate provided with a stack having thermal properties
EP3898546B1 (fr) 2018-12-18 2025-01-29 Türkiye Sise Ve Cam Fabrikalari Anonim Sirketi Verre pourvu d'un revêtement à faible émissivité

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110066921A (ko) * 2008-09-30 2011-06-17 쌩-고벵 글래스 프랑스 특히 가열 글레이징을 생산하기 위해 열적 특성을 가지는 다층을 구비하는 기판을 제조하는 방법
JP2013505198A (ja) * 2009-09-25 2013-02-14 エルジー・ハウシス・リミテッド 誘電体層を含有する低放射ガラスおよびその製造方法
KR20140003460A (ko) * 2011-01-06 2014-01-09 쌩-고벵 글래스 프랑스 가열 유리 제작을 위한 열 특성을 갖는 적층체가 구비된 기판
KR20140088704A (ko) * 2013-01-03 2014-07-11 주식회사 케이씨씨 내충격성 및 내마모성이 개선된 접합유리
KR20160147387A (ko) * 2015-06-15 2016-12-23 주식회사 케이씨씨 내구성이 향상된 열처리 가능한 저방사 유리 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110066921A (ko) * 2008-09-30 2011-06-17 쌩-고벵 글래스 프랑스 특히 가열 글레이징을 생산하기 위해 열적 특성을 가지는 다층을 구비하는 기판을 제조하는 방법
JP2013505198A (ja) * 2009-09-25 2013-02-14 エルジー・ハウシス・リミテッド 誘電体層を含有する低放射ガラスおよびその製造方法
KR20140003460A (ko) * 2011-01-06 2014-01-09 쌩-고벵 글래스 프랑스 가열 유리 제작을 위한 열 특성을 갖는 적층체가 구비된 기판
KR20140088704A (ko) * 2013-01-03 2014-07-11 주식회사 케이씨씨 내충격성 및 내마모성이 개선된 접합유리
KR20160147387A (ko) * 2015-06-15 2016-12-23 주식회사 케이씨씨 내구성이 향상된 열처리 가능한 저방사 유리 및 그 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11401206B2 (en) * 2017-10-30 2022-08-02 Saint-Gobain Glass France Substrate provided with a stack having thermal properties
EP3898546B1 (fr) 2018-12-18 2025-01-29 Türkiye Sise Ve Cam Fabrikalari Anonim Sirketi Verre pourvu d'un revêtement à faible émissivité

Similar Documents

Publication Publication Date Title
US6451434B1 (en) Glass laminate, functional transparent article and method of its production
WO2013191345A1 (fr) Corps stratifié transparent à basse émissivité et matériau de construction le comprenant
WO2015030549A1 (fr) Revêtement à faible émissivité et matériau de construction pour des fenêtres et des portes comprenant celui-ci
CN102421720A (zh) 提供有包括高折射指数层的具有热性质的叠层的基材
WO2011037365A2 (fr) Verre à faible émissivité comprenant une couche diélectrique, et son procédé de production
WO2013191346A1 (fr) Stratifié transparent à basse émissivité, son procédé de fabrication et matériau de construction le comprenant
WO2019216661A1 (fr) Substrat transparent pourvu d'un revêtement multicouche et unité de vitrage isolant le comprenant
WO2013024996A2 (fr) Verre à faible émissivité traitable thermiquement et son procédé de fabrication
EA017695B1 (ru) Остекление
JP2012524707A (ja) 高い太陽熱利得係数を有する太陽光制御コーティング
WO2018048034A1 (fr) Matériau de construction fonctionnel pour fenêtres et portes
WO2015088267A1 (fr) Film de revêtement à faible émissivité, procédé de fabrication de celui-ci et matériau de construction fonctionnel pour fenêtres et portes comprenant celui-ci
KR101797426B1 (ko) 코팅유리 및 그 제조방법
WO2017047983A1 (fr) Matériau de construction fonctionnel pour fenêtres et portes
WO2011010824A2 (fr) Verre à faible émissivité et son procédé de fabrication
WO2016017999A1 (fr) Revêtement à faible émissivité et matériau de construction fonctionnel pour fenêtre/porte comprenant un revêtement à faible émissivité
WO2017126875A1 (fr) Verre à faible émissivité et procédé de production associé
WO2019112320A1 (fr) Matériau de construction fonctionnel pour fenêtres et portes
WO2014104530A1 (fr) Stratifié transparent à faible émissivité et matériau de construction le contenant
WO2019022383A2 (fr) Verre à faible émissivité
WO2019050193A1 (fr) Matériau de construction fonctionnel pour porte et fenêtre
WO2018131863A1 (fr) Verre à couche et verre feuilleté comprenant ce dernier
US7161117B2 (en) Window glass for vehicles equipped with a conductor and its production process
WO2020218880A1 (fr) Article revêtu et son procédé de fabrication
WO2020141717A1 (fr) Substrat transparent comportant un film mince multicouche et vitrage multiple le comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18738631

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18738631

Country of ref document: EP

Kind code of ref document: A1