WO2019069628A1 - 自動車用合せガラス、及びその製造方法 - Google Patents

自動車用合せガラス、及びその製造方法 Download PDF

Info

Publication number
WO2019069628A1
WO2019069628A1 PCT/JP2018/033386 JP2018033386W WO2019069628A1 WO 2019069628 A1 WO2019069628 A1 WO 2019069628A1 JP 2018033386 W JP2018033386 W JP 2018033386W WO 2019069628 A1 WO2019069628 A1 WO 2019069628A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass plate
glass
mass
thickness
plate
Prior art date
Application number
PCT/JP2018/033386
Other languages
English (en)
French (fr)
Inventor
洋貴 中村
直樹 三田村
拓真 内藤
Original Assignee
セントラル硝子株式会社
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
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Priority to EP18865189.7A priority Critical patent/EP3670466A4/en
Priority to US16/651,937 priority patent/US20200282706A1/en
Priority to CN202210651467.7A priority patent/CN115179618A/zh
Priority to CN201880064908.5A priority patent/CN111183124B/zh
Priority to JP2019546592A priority patent/JP7174262B2/ja
Publication of WO2019069628A1 publication Critical patent/WO2019069628A1/ja

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
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10889—Making laminated safety glass or glazing; Apparatus therefor shaping the sheets, e.g. by using a mould
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10779—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyester
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/001—Double glazing for vehicles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/025—Re-forming glass sheets by bending by gravity
    • C03B23/0252—Re-forming glass sheets by bending by gravity by gravity only, e.g. sagging
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
    • C03B23/0307—Press-bending involving applying local or additional heating, cooling or insulating means
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present invention relates to laminated glass for automobiles and a method of manufacturing the same.
  • laminated glass for automobiles which is used for window glass of automobiles, is laminated glass having different thicknesses, and the thickness of the glass sheet disposed on the outdoor side is 1.45 mm to 1
  • a structure has been proposed in which the thickness of the glass plate disposed on the indoor side is 1.0 mm to 1.4 mm and the thickness of the glass plate disposed on the indoor side is smaller (for example, Patent Document 1).
  • the laminated glass for automobiles has a curved structure
  • the two glass sheets need to be formed in the same curved shape. Therefore, the two glass plates are heated in the vicinity of the softening point temperature of each glass plate in an overlapping state, and are bent and formed (see, for example, Patent Documents 2 and 3). In the said method, shaping
  • Patent Document 2 is a forming furnace for bending and forming two stacked glass sheets, under which the glass sheet (upper side glass sheet) disposed on the upper side is more easily heated (ie, the upper side) In order to equalize the curved shapes of the two glass plates in the case where the glass plates arranged in the above are more easily bent), the lower glass plates are more likely to be softened more quickly Disclose that. And as a structural example, making infrared absorptivity of the glass plate arrange
  • Patent document 3 makes it a subject that a thin glass plate deforms more easily than a thick glass plate at the time of bending by heating, and a glass plate having a viscosity of a thin glass plate is thin under a temperature atmosphere for bending the glass plate.
  • the glass composition of each glass plate is adjusted so as to have a viscosity lower than that of
  • the glass plate disposed indoors thin in order not to reduce the rigidity of the glass plate disposed outside the vehicle.
  • a thin glass plate is more easily deformed than a thick glass plate at the time of bending by heating, it becomes difficult to form two sheet glasses into the same curved shape.
  • An object of the present invention is to provide a laminated glass structure which is easy to form a glass plate disposed on an inner side and an outer side of a vehicle into the same curved shape when using a thin glass plate.
  • the laminated glass for automobiles of the present invention is A thermoplastic interlayer, and a curved first glass plate disposed on the outdoor side and disposed opposite to each other via the thermoplastic interlayer, and a curved second glass plate disposed on the indoor side.
  • the difference between the annealing temperatures of the first and second glass plates is within ⁇ 5 ° C.
  • the difference of the softening point temperatures is within ⁇ 5 ° C.
  • the FeO content in the glass composition of the first glass plate is 0.1% by mass to 0.5% by mass
  • the FeO content in the glass composition of the second glass plate is 0% by mass to 0.05% %
  • the thickness of the first glass plate is 1.1 times to 1.4 times the thickness of the second glass plate.
  • the flat plate-like first glass plate and the flat plate-like second glass plate are stacked, they are heated to the vicinity of the softening point and curved and formed into a desired shape by the self weight bending method or press forming method Forming a glass sheet, and Laminating the curved first glass plate and the second glass plate via a thermoplastic interlayer; And a laminating step of thermocompression bonding the thermoplastic interlayer, the first glass plate, and the second glass plate, Between the first glass plate and the second glass plate, the first glass plate and the second glass plate have an annealing temperature difference within ⁇ 5 ° C., and a softening point temperature difference within ⁇ 5 ° C.
  • the difference between The FeO content in the glass composition of the first glass plate is 0.1% by mass to 0.5% by mass,
  • the FeO content in the glass composition of the second glass plate is 0% by mass to 0.05% by mass,
  • the thickness of the second glass plate is 0.5 mm to 1.8 mm,
  • the thickness of the first glass plate is 1.1 times to 1.4 times the thickness of the second glass plate.
  • the bending of the glass sheet is governed by the viscosity of the glass sheet, so when the first glass sheet and the second glass sheet have the same or similar glass composition, under static temperature conditions, The bending behavior of the two glass plates is expected to be equal regardless of the thickness of the glass plate.
  • the first and second glass plates are heated under the given time from room temperature to bending temperature, and the dynamic conditions are such that the factor of the bending behavior of the glass plate is more It becomes complicated.
  • the FeO content in the glass composition of the first glass plate is 0.1% by mass to 0.5% by mass
  • the FeO content in the glass composition of the second glass plate is 0% by mass to 0.05 Since the first glass plate has a thickness of 1.1% to 1.4 times the thickness of the second glass plate, and the thickness of the first glass plate is two or more at the time of bending of the glass plate. Was successful in making the glass plate of the same curved shape.
  • the annealing temperature and the softening point temperature can be obtained according to JIS R 3103-2 (2001) and JIS R 3103-1 (2001), respectively.
  • the laminated glass for an automobile according to the present invention has a structure in which even when a thin glass plate is used, it is easy to form the glass plates disposed on the vehicle inner side and the vehicle outer side into the same curved shape. ADVANTAGE OF THE INVENTION According to this invention, it becomes easy to provide the laminated glass for motor vehicles which contributes to weight reduction.
  • FIG. 1 schematically illustrates the cross section of the laminated glass for automobiles of the present invention.
  • the automotive laminated glass 1 includes a thermoplastic intermediate film 3 and a curved first glass plate 21 and a curved second glass plate 22 disposed to face each other via the thermoplastic intermediate film.
  • first glass plate 21 and the second glass plate 22 those obtained by processing the flat first glass plate 21 and the second glass plate 22 into a curved shape are used.
  • materials of the first glass plate 21 and the second glass plate 22 both of them are known glasses such as aluminosilicate glass and borosilicate glass in addition to soda lime silicate glass as defined in ISO 16293-1
  • the composition can be used.
  • the first glass plate 21 and the second glass plate 22 may be obtained by a float process.
  • the annealing point temperature between the first glass plate 21 and the second glass plate 22 is the difference, and the difference between the softening point temperatures is within ⁇ 5 ° C. and ⁇ 5 ° C., respectively.
  • the annealing temperature is 500 ° C. to 600 ° C.
  • the softening point temperature is 700 ° C. to 800 ° C. .
  • the glass composition which comprises both glass plates which has such a thermophysical property can apply a thing substantially the same or similar, and the annealing point temperature of the 1st glass plate 21 and the 2nd glass plate 22
  • the glass composition is selected such that the difference in the softening point temperature is within ⁇ 5 ° C. and ⁇ 5 ° C., respectively.
  • the temperature difference between the respective physical properties is preferably within ⁇ 4 ° C., preferably ⁇ 3 ° C., in order to ensure that the glass compositions constituting both glass plates are substantially the same or similar.
  • the inside may be, more preferably, within ⁇ 2 ° C., and still more preferably, within ⁇ 1 ° C.
  • each component is mass%, SiO 2; 60% ⁇ 80% , preferably from 64% to 77%, more preferably 67% ⁇ 74% Al 2 O 3; 0% ⁇ 20%, preferably from 0% to 12%, more preferably from 0% to 6% Na 2 O: 10% to 20%, preferably 10% to 18%, more preferably 10% to 15% K 2 O: 0% to 8%, preferably 0% to 5%, more preferably 0% to 3% MgO: 0% to 15%, preferably 0% to 12%, more preferably 0% to 6% CaO: 0% to 15%, preferably 3% to 13%, more preferably 5% to 10% Iron oxide (Fe 2 O 3 equivalent); 0.2% to 2%, preferably 0.2% to 1.8%, More preferably 0.2% to 1.6% FeO: 0.1% to 0.50%, preferably 0.1% to 0.45% More preferably, 0.1% to 0.40% And those containing The component amount of the iron oxide is the component amount in terms of Fe 2
  • each component is mass%, SiO 2; 60% ⁇ 80% , preferably from 64% to 77%, more preferably 67% ⁇ 74% Al 2 O 3; 0% ⁇ 20%, preferably from 0% to 12%, more preferably from 0% to 6% Na 2 O: 10% to 20%, preferably 10% to 18%, more preferably 10% to 15% K 2 O: 0% to 8%, preferably 0% to 5%, more preferably 0% to 3% MgO: 0% to 15%, preferably 0% to 12%, more preferably 0% to 6% CaO: 0% to 15%, preferably 3% to 13%, more preferably 5% to 10% Iron oxide (Fe 2 O 3 equivalent); 0% to 0.15%, preferably 0% to 0.13%, More preferably, 0% to 0.11%
  • FeO include those containing 0% to 0.05%, preferably 0% to 0.04%, and more preferably 0% to 0.03%.
  • the component amount of the iron oxide is the component amount in terms of Fe 2 O 3 and therefore includes the overlap with the component amount of FeO.
  • barium oxide, zirconium oxide, sulfur oxide or the like may be contained as an optional component to the extent that the effect of the present invention is impaired, for example, up to 1.0 mass%.
  • FIG. 2 is a figure which shows typically the principal part of the apparatus for verifying the bending behavior of the glass plate at the time of heating.
  • FIG. 3 is a figure which shows typically the measuring method of the amount of bending of the glass plate sample bent by dead weight through heating.
  • the environment in which the jigs 4 arranged at an interval of 34 mm are placed is 470 ° C. Place the glass plate sample 2s on the jig 4 as shown in FIG. 2, and heat the environment at a heating rate of 6 ° C./min to 630 ° C., 640 ° C., or 650 ° C. Holding at 630 ° C., 640 ° C., or 650 ° C. for 1 minute, the glass plate sample 2sb bent by its own weight is removed from the environment. -As the amount of bending of the glass plate sample 2sb, the distance shown by the arrow in FIG. 3, that is, the amount of bending was measured based on the flat glass plate sample 2s.
  • the glass plate B With respect to the glass plate B, a thickness which gives the same amount of deflection as the glass plate A having a thickness of 1 mm was determined. As a result, when the maximum temperatures reached 630 ° C., 640 ° C., and 650 ° C., the amount of deflection of the glass plate A was 0.2 mm, 0.35 mm, and 0.5 mm, respectively. And the thickness of the glass plate which became the same deflection amount with the glass plate B is 0.7 mm-0.9 mm, 0.8 mm, respectively, in the case of maximum reach
  • the FeO content in the glass composition of the first glass plate is 0.1% by mass to 0.5% by mass
  • the FeO content in the glass composition of the second glass plate is 0% by mass to 0.05% by mass
  • the thickness of the first glass plate 21 is the thickness of the second glass plate 22. If it is 1 to 1.4 times, it is possible to easily form the glass plates disposed on the vehicle interior and the vehicle exterior into the same curved shape.
  • the above thickness ratio may be further 1.1 times to 1.3 times from the viewpoint of easy formation into the same curved shape.
  • the amount of FeO in the glass composition is affected not only by the amount of iron oxide (in terms of Fe 2 O 3 ), but also by the amount of oxidizing agent and reducing agent in the glass raw material, and the redox conditions of the atmosphere in the glass melting furnace .
  • components that affect the redox conditions include cerium oxide, titanium oxide, manganese oxide, chromium oxide, cobalt oxide, nickel oxide, selenium and the like, and for the purpose of adjusting the amount of FeO, these components are used as the first glass plate
  • the glass composition of or the glass composition of the second glass plate may contain, for example, 0% by mass to 3% by mass.
  • the thickness of the glass plates 21 and 22 is 0.7 mm to 2 mm, preferably 0.7 mm to 1.7 mm in the case of the glass plate 21 from the viewpoint of easy formation into the same curved shape. , And more preferably 0.7 to 1.4 mm. And in the case of the said glass plate 22, 0.5 mm-1.6 mm, Preferably 0.5 mm-1.4 mm, More preferably, 0.5-1.1 mm, Still more preferably, 0.5 mm-0.9 mm It may be
  • the thermoplastic interlayer 3 is formed by combining the first glass plate 21 and the second glass plate 22 by heating, and is made of polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), acrylic resin (PMMA) Urethane resin, polyethylene terephthalate (PET), cycloolefin polymer (COP), etc. can be used.
  • the intermediate layer may be made of a plurality of resins.
  • the laminated glass 1 for an automobile it is desirable to heat near the softening point of both glass plates in a state where the flat first glass plate 21 and the flat second glass plate 22 are stacked.
  • the method comprises a bonding step of thermocompression bonding the first glass plate 21, the thermoplastic intermediate film 3, and the second glass plate 22.
  • FIG. 4 is a view schematically illustrating a step of bending the planar first and second glass plates 21 and 22 in the method of manufacturing the laminated glass 1 for an automobile according to the present invention.
  • the step of forming the glass plate As shown in FIG. 4, a state in which the planar first glass plate 21 and the planar second glass plate 22 are stacked such that the main surfaces of both glass plates face each other. Then, each lath plate is heated to near the softening point, and is curved into a predetermined shape.
  • the vicinity of the softening point refers to a range from a temperature higher by 50 ° C. than the softening point temperature to a temperature lower by 150 ° C. from the softening point temperature.
  • the stacked glass plates 21 and 22 are placed on a ring mold and passed through a heating furnace, and the glass plates 21 and 22 are heated and softened, and bent and formed into a predetermined shape by gravity.
  • a self weight bending method of cooling is used. Furthermore, a press forming method in which the glass plates 21 and 22 are preformed by a self-weight bending method, and then the glass plates 21 and 22 are sandwiched between a ring mold and a press mold and heated and pressurized to form and cool. May be used. Among these forming methods, it is preferable to adopt a self-weight bending method.
  • the first glass plate 21 and the second glass plate 22 are heated at a heating rate of 3 to 100 ° C./minute from a temperature range of 200 to 400 ° C. to near the softening point.
  • the sheet After being conveyed in the preheating zone for heating and preheating, the sheet may be conveyed to the self-weight bending forming zone of the glass sheet, and may be curved and cooled to a desired shape in the forming zone.
  • the glass plates 21, 22 may be transported using transport rolls.
  • first glass plate 21 and the second glass plate be overlapped via a release agent.
  • this mold release agent ceramic powder etc. which are not melted at the time of heating near the softening point of a glass plate are used suitably.
  • the thermoplastic interlayer 3 the concave main surface of the first glass plate 21 and the convex main surface of the second glass plate 22 are disposed to face each other, and the laminate before forming the laminated glass is formed.
  • the laminated body is held at 100 to 150 ° C. for 15 to 60 minutes while being pressure-bonded by thermocompression bonding, for example, 1.0 to 1.5 MPa, whereby a laminated glass 1 for an automobile as shown in FIG. 1 is obtained.
  • the thermocompression bonding can be performed, for example, in an autoclave.
  • the space between the plastic middle layer 3 and each of the glass plates 21 and 22 is degassed. Is preferable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Ceramic Engineering (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Glass Compositions (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

【課題】本発明は、薄い厚さのガラス板を用いた場合における、車内側、車外側に配置されるガラス板を同一の湾曲形状に成形しやすい、合せガラス構造を提供することを課題とする。 【解決手段】自動車用合せガラスであって、 熱可塑性中間膜層、及び前記熱可塑性中間膜層を介して対向して配置された、室外側に配置される湾曲した第一ガラス板と、室内側に配置される湾曲した第二ガラス板とを備え、前記第一ガラス板と前記第二ガラス板とは、徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内の差であり、 前記第一ガラス板のガラス組成中のＦｅＯ含有量が０．１質量％～０．５質量％であり、前記第二ガラス板のガラス組成中のＦｅＯ含有量が０質量％～０．０５質量％であり、 前記第二ガラス板の厚さが０．５ｍｍ～１．８ｍｍであり、 前記第一ガラス板の厚さは、前記第二ガラス板の厚さの、１．１倍～１．４倍である、こと。

Description

自動車用合せガラス、及びその製造方法
　本発明は、自動車用合せガラス、及びその製造方法に関する。
　自動車では、年々、ガソリン燃料や、電気などのエネルギー効率向上が要求されてきており、それに使用される部材の軽量化が求められてきている。この背景のもと、自動車の窓ガラスに使用される、自動車用合せガラスでは、各ガラス板の厚みが異なる合せガラスであって、室外側に配置されるガラス板の厚みを１．４５ｍｍ～１．８ｍｍ、室内側に配置されるガラス板の厚みを１．０ｍｍ～１．４ｍｍとし、室内側に配置されるガラス板の方の厚みを薄いものとする、構造が提案されている（例えば、特許文献１参照）。
　自動車用合せガラスは、湾曲した構造を有しているため、２枚の板ガラスは、同一の湾曲形状に成形されている必要がある。そのため、２枚のガラス板は、重ねられた状態で、各ガラス板の軟化点温度近傍に加熱されて、曲げ成形される（例えば、特許文献２、３参照）。当該方法では、２枚のガラス板の同一の湾曲形状への成形が技術的課題となる。特許文献２は、積層された２枚のガラス板を曲げ成形するための成形炉にて、上側に配置されたガラス板（室内側のガラス板）の方が加熱されやすい条件下（すなわち、上側に配置されたガラス板の方が曲がりやすい）での、２枚のガラス板の湾曲形状を同等とするために、下側に配置されるガラス板の方が早く軟化されやすい構成のものとすることを開示している。そして、その構成例として、下側に配置されるガラス板の赤外吸収性を高いものとすることが開示されている。特許文献３は、加熱による曲げ成形時には、薄いガラス板は、厚いガラス板よりも変形しやすいことを課題とし、ガラス板を曲げ成形する温度雰囲気下で、厚いガラス板の粘度が、薄いガラス板の粘度よりも低い粘度となるように各ガラス板のガラス組成を調整している。
特表２０１３－５２５２３５号公報 特開平３－２０５３２１号公報 ＷＯ２０１４／０５４４６８号
　自動車用合せガラスの軽量化のためには、車外側に配置されるガラス板の剛性を下げないために、室内側に配置されるガラス板を薄いものとすることが好ましい。しかし、前途したように、加熱による曲げ成形時に、薄いガラス板は、厚いガラス板よりも変形しやすいので、２枚の板ガラスを、同一の湾曲形状に成形することが難しいものとなる。
　本発明は、薄い厚さのガラス板を用いた場合における、車内側、車外側に配置されるガラス板を同一の湾曲形状に成形しやすい、合せガラス構造を提供することを課題とする。
　本発明の自動車用合せガラスは、
熱可塑性中間膜、及び前記熱可塑性中間膜を介して対向して配置された、室外側に配置される湾曲した第一ガラス板と、室内側に配置される湾曲した第二ガラス板とを備え、前記第一ガラス板と前記第二ガラス板とは、徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内の差であり、
前記第一ガラス板のガラス組成中のＦｅＯ含有量が０．１質量％～０．５質量％であり、前記第二ガラス板のガラス組成中のＦｅＯ含有量が０質量％～０．０５質量％であり、
前記第一ガラス板の厚さは、前記第二ガラス板の厚さの、１．１倍～１．４倍である、ことを特徴とするものである。
　また、本発明の自動車用合せガラスの製造方法は、
平板状の第一ガラス板と、平板状の第二ガラス板とを重ねた状態で、軟化点近傍まで加熱して自重曲げ成形法、又はプレス成形法によって、所望の形状に湾曲成形して冷却する、ガラス板の成形工程と、
曲化した前記第一ガラス板と前記第二ガラス板とを、熱可塑性中間膜を介して積層する、積層工程と、
前記熱可塑性中間膜と、第一ガラス板と、第二ガラス板とを熱圧着する、合せ化工程とを備え、
前記第一ガラス板と前記第二ガラス板は、前記第一ガラス板と前記第二ガラス板とは、徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内の差であり、
前記第一ガラス板のガラス組成中のＦｅＯ含有量０．１質量％～０．５質量％であり、
前記第二ガラス板のガラス組成中のＦｅＯ含有量０質量％～０．０５質量％であり、
前記第二ガラス板の厚さが０．５ｍｍ～１．８ｍｍであり、
前記第一ガラス板の厚さは、前記第二ガラス板の厚さの、１．１倍～１．４倍である、ことを特徴とするものである。
　ガラス板の曲げ成形は、ガラス板の粘度に支配されるので、第一ガラス板と、第二ガラス板とが、同じガラス組成や、近似したガラス組成からなる場合、静的な温度条件では、２枚のガラス板の曲げ挙動はガラス板の厚さによらず同等になると見込まれる。しかしながら、工業的な生産条件においては、第一、第二ガラス板は、室温から曲げ成形温度まで所定時間で、加熱される、動的な条件となるので、ガラス板の曲げ挙動の要因はより複雑となる。
　厚いガラス板の粘度が、薄いガラス板の粘度よりも低い粘度となるように各ガラス板のガラス組成を調整することは一つの解決手段のように思われる。しかしながら、その場合、各ガラス板が、異なる徐冷点温度、異なる軟化点温度を持つため、ガラス板の曲げ挙動の要因をより複雑なものとするおそれがある。本発明の合せガラス、及び合せガラスの製造方法においては、まず、第一、第二ガラス板の徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内として、この懸念が無いものとした。
　その上で、前記第一ガラス板のガラス組成中のＦｅＯ含有量を０．１質量％～０．５質量％、前記第二ガラス板のガラス組成中のＦｅＯ含有量０質量％～０．０５質量％とし、さらには、前記第一ガラス板の厚さを、前記第二ガラス板の厚さの、１．１倍～１．４倍としているので、ガラス板の曲げ成形時において、２枚のガラス板を同等の湾曲形状とすることに奏功した。
　尚、前記徐冷点温度、前記軟化点温度は、それぞれ、ＪＩＳ　Ｒ　３１０３－２（２００１年）、ＪＩＳ　Ｒ　３１０３－１（２００１年）に従って得るこができる。
　本発明の自動車用合せガラスは、薄い厚さのガラス板を用いた場合でも、車内側、車外側に配置されるガラス板を同一の湾曲形状に成形しやすい構造である。本発明によれば、軽量化に資する自動車用の合せガラスを提供しやすくなる。
本発明の自動車用合せガラス（断面）を概略的に説明する図である。 加熱時のガラス板の曲げ挙動を検証するための装置の要部を模式的に示す図である。 加熱を経て自重により曲げられたガラス板試料の曲げ量の計測方法を模式的に示す図である。 本発明の自動車用合せガラスの製造方法における、平面状の第一・第二ガラス板を湾曲化する工程を模式的に説明する図である。
　本発明の自動車用合せガラス１を図面で説明する。図１は、本発明の自動車用合せガラスの断面を概略的に説明するものである。自動車用合せガラス１は、熱可塑性中間膜３、及び前記熱可塑性中間膜を介して対向して配置された、湾曲した第一ガラス板２１と湾曲した第二ガラス板２２とを備える。前記第一ガラス板２１、前記第二ガラス板２２としては、平板の第一ガラス板２１、第二ガラス板２２が湾曲形状に加工されたものが使用される。第一ガラス板２１、第二ガラス板２２の材質としては、双方とも、ＩＳＯ１６２９３－１で規定されているようなソーダ石灰珪酸塩ガラスの他、アルミノシリケートガラスやホウケイ酸塩ガラス等の公知のガラス組成のものを使用することができる。また、第一ガラス板２１、第二ガラス板２２は、フロートプロセスによって得られたものとしてもよい。
　第一ガラス板２１と、第二ガラス板２２との徐冷点温度は差、軟化点温度の差は、それぞれ、±５℃内、±５℃内とされる。例えば、両ガラス板が、ＩＳＯ１６２９３－１で規定されているようなソーダ石灰珪酸塩ガラスからなる場合、徐冷点温度は、５００℃～６００℃、軟化点温度は、７００℃～８００℃となる。
　このような熱物性を有する、両ガラス板を構成するガラス組成は、実質的には同じか、類似したものを適用でき、第一ガラス板２１と、第二ガラス板２２との徐冷点温度は差、軟化点温度の差が、それぞれ、±５℃内、±５℃内となるようにガラス組成が選択される。両ガラス板を構成するガラス組成は、実質的には同じか、類似したものを適用することをより確実なものとするために、各物性の温度差は、±４℃内、好ましく±３℃内、より好ましくは±２℃内、さらに好ましくは±１℃内としてもよい。
　第一ガラス板２１を構成する、ガラス組成例として、各成分を質量％で、
ＳｉＯ２；６０％～８０％、好ましくは６４％～７７％、より好ましくは６７％～７４％Ａｌ２Ｏ３；０％～２０％、好ましくは０％～１２％、より好ましくは０％～６％
Ｎａ２Ｏ　；１０％～２０％、好ましくは１０％～１８％、より好ましくは１０％～１５％
Ｋ２Ｏ　；０％～８％、好ましくは０％～５％、より好ましくは０％～３％
ＭｇＯ　；０％～１５％、好ましくは０％～１２％、より好ましくは０％～６％
ＣａＯ　；０％～１５％、好ましくは３％～１３％、より好ましくは５％～１０％
鉄酸化物（Ｆｅ２Ｏ３換算）；０．２％～２％、好ましくは０．２％～１．８％、
より好ましくは０．２％～１．６％
ＦｅＯ　；０．１％～０．５０％、好ましくは０．１％～０．４５％、
より好ましくは０．１％～０．４０％
を含有するものが挙げられる。前記鉄酸化物の成分量は、Ｆｅ２Ｏ３換算での成分量なので、ＦｅＯの成分量との重複を包含する。また、これら成分以外にも、酸化バリウム、酸化ジルコニウム、酸化硫黄等を任意成分として本発明の趣旨を損なわい程度に、例えば、１．０質量％まで含んでもよい。
　第二ガラス板２２を構成する、ガラス組成例として、各成分を質量％で、
ＳｉＯ２；６０％～８０％、好ましくは６４％～７７％、より好ましくは６７％～７４％Ａｌ２Ｏ３；０％～２０％、好ましくは０％～１２％、より好ましくは０％～６％
Ｎａ２Ｏ　；１０％～２０％、好ましくは１０％～１８％、より好ましくは１０％～１５％
Ｋ２Ｏ　；０％～８％、好ましくは０％～５％、より好ましくは０％～３％
ＭｇＯ　；０％～１５％、好ましくは０％～１２％、より好ましくは０％～６％
ＣａＯ　；０％～１５％、好ましくは３％～１３％、より好ましくは５％～１０％
鉄酸化物（Ｆｅ２Ｏ３換算）；０％～０．１５％、好ましくは０％～０．１３％、
より好ましくは０％～０．１１％
　ＦｅＯ　；０％～０．０５％、好ましくは０％～０．０４％、より好ましくは０％～０．０３％を含有するものが挙げられる。前記鉄酸化物の成分量は、Ｆｅ２Ｏ３換算での成分量なので、ＦｅＯの成分量との重複を包含する。また、これら成分以外にも、酸化バリウム、酸化ジルコニウム、酸化硫黄等を任意成分として本発明の趣旨を損なわい程度に、例えば、１．０質量％まで含んでもよい。
　以上に挙げられた成分の中でも、ＦｅＯの含有量は、平板の第一、第二ガラス板２１、２２の加熱時の湾曲形状の形成に影響を与える。以下に各種平板のガラス板を加熱したときのガラス板の曲げ挙動を検証した結果を示す。図２は、加熱時のガラス板の曲げ挙動を検証するための装置の要部を模式的に示す図である。図３は、加熱を経て自重により曲げられたガラス板試料の曲げ量の計測方法を模式的に示す図である。
　検証用のガラス板として、
ＳｉＯ２（７１質量％）－Ａｌ２Ｏ３（２質量％）－Ｎａ２Ｏ（１３質量％）－Ｋ２Ｏ（１．４質量％）－ＭｇＯ（３．６質量％）－ＣａＯ（８．５質量％）－鉄酸化物（Ｆｅ２Ｏ３換算で、０．５質量％；ＦｅＯは０．１２質量％）のガラス組成から構成されるガラス板Ａ（徐冷点温度５５１℃、軟化点温度７３４℃）、
ＳｉＯ２（７２質量％）－Ａｌ２Ｏ３（２質量％）－Ｎａ２Ｏ（１３質量％）－Ｋ２Ｏ（１．３質量％）－ＭｇＯ（３．７質量％）－ＣａＯ（８．４質量％）－鉄酸化物（Ｆｅ２Ｏ３換算で、０．１質量％；ＦｅＯは０．０２質量％）のガラス組成から構成されるガラス板Ｂ（徐冷点温度５５１℃、軟化点温度７３３℃）、
につき、平板のガラス板試料２ｓ（６０ｍｍ×４５ｍｍサイズ）を準備した。そして、以下の手順に各種ガラス板試料２ｓの曲げ挙動が測定された。
　　・３４ｍｍの間隔で配置された治具４がおかれた環境を４７０℃とする。
　　・前記治具４上に前記ガラス板試料２ｓを図２のように配置し、６３０℃、６４０℃、又は６５０℃まで６℃／分の加熱速度で前記環境を加熱する。
　　・６３０℃、６４０℃、又は６５０℃で１分保持し、自重により曲げられたガラス板試料２ｓｂを前記環境から取り出す。
　　・ガラス板試料２ｓｂの曲げ量として、平板のガラス板試料２ｓを基準とし、図３内の矢印で示される距離、すなわち撓み量を計測した。
　ガラス板Ｂに対して、１ｍｍの厚さのガラス板Ａと同じ撓み量となる厚さを求めた。結果、最高到達温度が、６３０℃、６４０℃、６５０℃の場合で、ガラス板Ａの撓み量は、それぞれ、０．２ｍｍ、０．３５ｍｍ、０．５ｍｍとなった。そして、ガラス板Ｂで、同じ撓み量となったガラス板の厚さは、最高到達温度が、６３０℃、６４０℃、６５０℃の場合で、それぞれ、０．７ｍｍ～０．９ｍｍ、０．８ｍｍ～０．９ｍｍ、０．８ｍｍ～０．９ｍｍであった。
　このことから、ガラス中のＦｅＯ量のガラス板の曲げ挙動に影響することがわかる。すなわち、前記第一ガラス板のガラス組成中のＦｅＯ含有量を０．１質量％～０．５質量％
、前記第二ガラス板のガラス組成中のＦｅＯ含有量を０質量％～０．０５質量％とし、前記第一ガラス板２１の厚さを、前記第二ガラス板２２の厚さの、１．１倍～１．４倍とすれば、車内側、車外側に配置されるガラス板を同一の湾曲形状に成形しやすいものとできる。前述の厚さの比率は、同一の湾曲形状に成形しやすいものとするとの観点から、さらには、１．１倍～１．３倍としてもよい。
　ガラス組成中のＦｅＯ量は、鉄酸化物（Ｆｅ２Ｏ３換算）の量だけでなく、ガラス原料中の酸化剤、還元剤の量、ガラス溶融炉内雰囲気の酸化還元条件にも影響される。前記酸化還元条件に影響する成分として、酸化セリウム、酸化チタン、酸化マンガン、酸化クロム、酸化コバルト、酸化ニッケル、セレン等があり、ＦｅＯ量を調整する目的で、これら成分を、前記第一ガラス板のガラス組成、又は前記第二ガラス板のガラス組成が、例えば０質量％～３質量％含んでいてもよい。
　前記ガラス板２１、２２の厚さについては、同一の湾曲形状に成形しやすいものとするとの観点から、前記ガラス板２１の場合は、０．７ｍｍ～２ｍｍ、好ましくは０．７ｍｍ～１．７ｍｍ、より好ましくは０．７～１．４ｍｍとしてもよい。そして、前記ガラス板２２の場合は、０．５ｍｍ～１．６ｍｍ、好ましくは、０．５ｍｍ～１．４ｍｍ、より好ましくは０．５～１．１ｍｍ、さらに好ましくは０．５ｍｍ～０．９ｍｍとしてもよい。
　前記熱可塑性中間膜３は加熱することで、第一ガラス板２１と、第二ガラス板２２とを合せ化するもので、ポリビニルブチラール（ＰＶＢ）、エチレン酢酸ビニル（ＥＶＡ）、アクリル樹脂（ＰＭＭＡ）、ウレタン樹脂、ポリエチレンテレフタレート（ＰＥＴ）、シクロオレフィンポリマー（ＣＯＰ）等を使用することができる。なお、中間層は複数の樹脂で構成されていても良い。
　前記自動車用合せガラス１の好適な製造方法は、平板状の第一ガラス板２１と、平板状の第二ガラス板２２とを重ねた状態で、両ガラス板の軟化点近傍まで加熱して所望の形状に湾曲する、ガラス板の成形工程と、
湾曲化した前記第一ガラス板２１と前記第二ガラス板２２とを、熱可塑性中間膜３を介して積層する、積層工程と、
前記第一ガラス板２１と、前記熱可塑性中間膜３と、前記第二ガラス板２２とを熱圧着する、合せ化工程とを備える、というものである。
　前記ガラス板の成形工程を、図４を用いて説明する。図４は本発明の自動車用合せガラス１の製造方法における、平面状の第一・第二ガラス板２１、２２を湾曲化する工程を模式的に説明する図である。
　ガラス板の成形工程において、図４に示すように、平面状の第一ガラス板２１と、平面状の第二ガラス板２２とが、両ガラス板の主面が面するように重ねられた状態で、各ラス板を、軟化点近傍まで加熱し、所定の形状に湾曲化する。ここで、軟化点近傍とは、軟化点温度から５０℃高い温度～軟化点温度から１５０℃低い温度の範囲のことを言う。
この工程では、例えば、重ねられたガラス板２１、２２をリング型上に載置して加熱炉に通し、ガラス板２１、２２を加熱して軟化させ、重力によって所定の形状に曲げ成形して冷却する自重曲げ成形法が用いられる。さらには、自重曲げ成形法によってガラス板２１、２２を予備成形し、次いでリング型とプレス型との間にガラス板２１、２２を挟んで加熱、及び加圧して成形して冷却するプレス成形法が用いられても良い。これら成形法の中では、自重曲げ成形法を採用することが好ましい。
　前記成形工程において、前記第一ガラス板２１と、前記第二ガラス板２２とは、両ガラス板を、２００～４００℃の温度領域から、軟化点近傍まで、３～１００℃／分の加熱速度で、加熱する、予熱する予熱ゾーン内を搬送されて後、ガラス板の自重曲げ成形ゾーン
に搬送され、前記成形ゾーンで所望の形状に湾曲成形して冷却する、方法としてもよい。この方法では、ガラス板２１、２２は、搬送ロールを用いて搬送されてもよい。
　第一ガラス板２１と、第二ガラス板とは、離型剤を介して重ねられることが好ましい。この離型剤としては、ガラス板の軟化点付近の加熱時に溶融することのないセラミックス粉末などが好適に用いられる。この湾曲化成形後の冷却工程の後、重ねられた、第一ガラス板２１と第二ガラス板２２とは、一旦分離される。
　合せ化工程では、熱可塑性中間膜３と、第一ガラス板２１の凹面側主面と、第二ガラス板２２の凸面側主面とを対向して配置し、合せガラス形成前の積層体を形成する。そして、該積層体を熱圧着、例えば、１．０～１．５ＭＰａで加圧しながら、１００～１５０℃で１５～６０分保持することで、図１に示すような自動車用合せガラス１が得られる。熱圧着は、例えば、オートクレーブ内で行うことができる。また、熱可塑性中間膜３と、第一ガラス板２１と、第二ガラス板２２とを熱圧着を行う前に、可塑性中間層３と、各ガラス板２１、２２との間を脱気しておくことが好ましい。
１　　　自動車用合せガラス
２１　　第一ガラス板
２２　　第二ガラス板
２ｓ　　ガラス板試料
２ｓｂ　曲げ加工されたガラス板試料
３　　　熱可塑性中間膜
４　　　ガラス板試料の曲げ成形の検証のための治具

Claims (5)

  1. 自動車用合せガラスであって、
    熱可塑性中間膜層、及び前記熱可塑性中間膜層を介して対向して配置された、室外側に配置される湾曲した第一ガラス板と、室内側に配置される湾曲した第二ガラス板とを備え、前記第一ガラス板と前記第二ガラス板とは、徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内の差であり、
    前記第一ガラス板のガラス組成中のＦｅＯ含有量が０．１質量％～０．５質量％であり、前記第二ガラス板のガラス組成中のＦｅＯ含有量が０質量％～０．０５質量％であり、
    前記第二ガラス板の厚さが０．５ｍｍ～１．８ｍｍであり、
    前記第一ガラス板の厚さは、前記第二ガラス板の厚さの、１．１倍～１．４倍である、
    自動車用合せガラス。
  2. 前記第一ガラス板の厚さが０．７ｍｍ～２ｍｍであることを特徴とする請求項１に記載の自動車用合せガラス。
  3. 第二ガラス板の厚さが０．５～０．９ｍｍである、請求項１又は２に記載の自動車用合せガラス。
  4. 自動車用合せガラスの製造方法であって、
    平板状の第一ガラス板と、平板状の第二ガラス板とを重ねた状態で、軟化点近傍まで加熱して自重曲げ成形法、又はプレス成形法によって、所望の形状に湾曲成形して冷却する、ガラス板の成形工程と、
    重ねた状態で湾曲化した第一ガラス板と第二ガラス板とを一旦分離する工程と、
    湾曲化した前記第一ガラス板と前記第二ガラス板とを、熱可塑性中間膜層を介して積層する、積層工程と、
    前記熱可塑性中間膜層と、第一ガラス板と、第二ガラス板とを熱圧着する、合せ化工程とを備え、
    前記第一ガラス板と前記第二ガラス板は、前記第一ガラス板と前記第二ガラス板とは、徐冷点温度の差が±５℃内で、軟化点温度の差が±５℃内の差であり、
    前記第一ガラス板のガラス組成中のＦｅＯ含有量０．１質量％～０．５質量％であり、
    前記第二ガラス板のガラス組成中のＦｅＯ含有量０質量％～０．０５質量％であり、
    前記第二ガラス板の厚さが０．５ｍｍ～１．８ｍｍであり、
    前記第一ガラス板の厚さは、前記第二ガラス板の厚さの、１．１倍～１．４倍である、
    自動車用合せガラスの製造方法。
  5. 前記成形工程において、前記第一ガラス板と、前記第二ガラス板とは、ガラス板を予熱する予熱ゾーン内を搬送されて後、ガラス板の曲げ成形ゾーンに送られ、前記成形ゾーンで所望の形状に湾曲する、請求項４に記載の自動車合せガラスの製造方法。
PCT/JP2018/033386 2017-10-06 2018-09-10 自動車用合せガラス、及びその製造方法 WO2019069628A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18865189.7A EP3670466A4 (en) 2017-10-06 2018-09-10 LAMINATED GLASS FOR AUTOMOTIVE AND METHOD FOR MANUFACTURING IT
US16/651,937 US20200282706A1 (en) 2017-10-06 2018-09-10 Laminated Glass for Automobile, and Method for Manufacturing Same
CN202210651467.7A CN115179618A (zh) 2017-10-06 2018-09-10 汽车用夹层玻璃及其制造方法
CN201880064908.5A CN111183124B (zh) 2017-10-06 2018-09-10 汽车用夹层玻璃及其制造方法
JP2019546592A JP7174262B2 (ja) 2017-10-06 2018-09-10 自動車用合せガラス、及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-195577 2017-10-06
JP2017195577 2017-10-06

Publications (1)

Publication Number Publication Date
WO2019069628A1 true WO2019069628A1 (ja) 2019-04-11

Family

ID=65994222

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/033386 WO2019069628A1 (ja) 2017-10-06 2018-09-10 自動車用合せガラス、及びその製造方法

Country Status (5)

Country Link
US (1) US20200282706A1 (ja)
EP (1) EP3670466A4 (ja)
JP (1) JP7174262B2 (ja)
CN (2) CN111183124B (ja)
WO (1) WO2019069628A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020046668A1 (en) * 2018-08-30 2020-03-05 Corning Incorporated Glass compositions for use in co-formed laminates

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113771433B (zh) * 2021-09-30 2022-08-19 福耀玻璃工业集团股份有限公司 车用夹层玻璃

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03205321A (ja) 1989-08-24 1991-09-06 Asahi Glass Co Ltd 曲げ合せガラス及び合せガラス用素板ガラスの曲げ加工方法
US6538192B1 (en) * 1999-04-13 2003-03-25 Glaverbel, S.A. Glazing for the roof of a motor vehicle
JP2004155632A (ja) * 2002-11-08 2004-06-03 Nippon Sheet Glass Co Ltd 熱遮蔽膜、それを用いた熱遮蔽ガラス板、および熱遮蔽合わせガラス板
WO2005063643A1 (ja) * 2003-12-26 2005-07-14 Nippon Sheet Glass Company, Limited 近赤外線吸収グリーンガラス組成物、およびこれを用いた合わせガラス
JP2008516878A (ja) * 2004-10-18 2008-05-22 ピルキントン グループ リミテッド 日照調整ガラス
JP2009526731A (ja) * 2006-02-14 2009-07-23 ピルキントン オートモーティヴ リミテッド 板ガラス
JP2013525235A (ja) 2009-04-20 2013-06-20 サン−ゴバン グラス フランス 透明積層ガラスおよびその使用法
WO2014054468A1 (ja) 2012-10-02 2014-04-10 旭硝子株式会社 合わせガラスの製造方法
JP2017518950A (ja) * 2014-05-20 2017-07-13 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． 高及び低酸化鉄含量を有するリチウム含有ガラス、その作製方法並びにそれを用いた製品

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6797658B2 (en) * 2001-02-09 2004-09-28 Ppg Industries Ohio, Inc. Methods of adjusting temperatures of glass characteristics and glass articles produced thereby
EP1550376A1 (en) * 2003-12-29 2005-07-06 SOLVAY (Société Anonyme) Process for the disinfection and/or preservation of harvested plant material
GB0710808D0 (en) * 2007-06-06 2007-07-18 Pilkington Automotive Ltd Tinted laminated vehicle glazing
JP5929903B2 (ja) * 2011-04-01 2016-06-08 旭硝子株式会社 合わせガラス、およびその製造方法
US9658437B2 (en) * 2012-02-24 2017-05-23 Ppg Industries Ohio, Inc. Lithium containing glass with high oxidized iron content and having specified base, colorant, and oxidizer
JP5647380B1 (ja) * 2013-02-18 2014-12-24 日本板硝子株式会社 合わせガラス、及びこれが取り付けられた取付構造体
FR3012072B1 (fr) * 2013-10-23 2021-01-01 Saint Gobain Verre feuillete mince pour pare-brise
FR3045596B1 (fr) * 2015-12-17 2018-01-19 Saint-Gobain Glass France Verre mince colore renforce chimiquement

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03205321A (ja) 1989-08-24 1991-09-06 Asahi Glass Co Ltd 曲げ合せガラス及び合せガラス用素板ガラスの曲げ加工方法
US6538192B1 (en) * 1999-04-13 2003-03-25 Glaverbel, S.A. Glazing for the roof of a motor vehicle
JP2004155632A (ja) * 2002-11-08 2004-06-03 Nippon Sheet Glass Co Ltd 熱遮蔽膜、それを用いた熱遮蔽ガラス板、および熱遮蔽合わせガラス板
WO2005063643A1 (ja) * 2003-12-26 2005-07-14 Nippon Sheet Glass Company, Limited 近赤外線吸収グリーンガラス組成物、およびこれを用いた合わせガラス
JP2008516878A (ja) * 2004-10-18 2008-05-22 ピルキントン グループ リミテッド 日照調整ガラス
JP2009526731A (ja) * 2006-02-14 2009-07-23 ピルキントン オートモーティヴ リミテッド 板ガラス
JP2013525235A (ja) 2009-04-20 2013-06-20 サン−ゴバン グラス フランス 透明積層ガラスおよびその使用法
WO2014054468A1 (ja) 2012-10-02 2014-04-10 旭硝子株式会社 合わせガラスの製造方法
JP2017518950A (ja) * 2014-05-20 2017-07-13 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． 高及び低酸化鉄含量を有するリチウム含有ガラス、その作製方法並びにそれを用いた製品

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3670466A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020046668A1 (en) * 2018-08-30 2020-03-05 Corning Incorporated Glass compositions for use in co-formed laminates

Also Published As

Publication number Publication date
EP3670466A4 (en) 2020-10-21
US20200282706A1 (en) 2020-09-10
CN111183124A (zh) 2020-05-19
EP3670466A1 (en) 2020-06-24
JP7174262B2 (ja) 2022-11-17
CN111183124B (zh) 2022-06-10
CN115179618A (zh) 2022-10-14
JPWO2019069628A1 (ja) 2020-09-17

Similar Documents

Publication Publication Date Title
JP7090134B2 (ja) 積層ガラス
CN111761893B (zh) 冷成形的层压制品
EP3251839A1 (en) Chemically-strengthened glass laminates
CN109803825B (zh) 弯曲夹层玻璃及弯曲夹层玻璃的制造方法
JPWO2012176813A1 (ja) 合わせガラスの製造方法、および合わせガラス
TW201302457A (zh) 輕量之混成式玻璃層疊物
WO2018131281A1 (ja) 自動車用合せガラス、及びその製造方法
WO2018131280A1 (ja) 自動車用合せガラス、及びその製造方法
JP7174262B2 (ja) 自動車用合せガラス、及びその製造方法
CN112424137B (zh) 汽车的前挡风玻璃用夹层玻璃及其制造方法
US20200325056A1 (en) System and process for forming curved glass laminate article utilizing glass viscosity differential for improved shape matching
WO2018122767A1 (en) Method and apparatus for bending thin glass
CN110300737B (zh) 夹层玻璃及其制造方法
US20210221103A1 (en) Process
WO2019008496A1 (en) METHOD FOR THIN GLASS BENDING AND STRATIFICATION WITH RECOVERY PLATE
WO2019008470A1 (en) METHOD OF THIN GLASS STRATIFICATION WITH PRESSURE PLATE
WO2019008495A1 (en) THIN GLASS BONDING AND STRATIFICATION METHOD WITH PRESSURE PLATE

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: 18865189

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019546592

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018865189

Country of ref document: EP

Effective date: 20200320

NENP Non-entry into the national phase

Ref country code: DE