WO2009147676A1 - Procede d’impression sur le cote interieur d’un verre stratifie et stratifies de verre ainsi formes - Google Patents

Procede d’impression sur le cote interieur d’un verre stratifie et stratifies de verre ainsi formes Download PDF

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Publication number
WO2009147676A1
WO2009147676A1 PCT/IL2009/000559 IL2009000559W WO2009147676A1 WO 2009147676 A1 WO2009147676 A1 WO 2009147676A1 IL 2009000559 W IL2009000559 W IL 2009000559W WO 2009147676 A1 WO2009147676 A1 WO 2009147676A1
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WO
WIPO (PCT)
Prior art keywords
glass
pattern
less
firing
sheets
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Ceased
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PCT/IL2009/000559
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English (en)
Inventor
Matti Ben-Moshe
Ilan Hidana
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DIP Tech Ltd
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DIP Tech Ltd
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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
    • 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
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • B32B17/10348—Specific parts of the laminated safety glass or glazing being colored or tinted comprising an obscuration band
    • 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
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.

Definitions

  • This invention relates to a printing process for laminated glass.
  • the laminated glass typically includes two or more layers of glass with polymeric laminate deployed between the layers.
  • Common polymeric laminates include, but are not limited to, polyvinyl butyral (PVB).
  • PVB polyvinyl butyral
  • a typical laminate including two sheets of glass there are four "sides".
  • a nomenclature which relates to the side facing the outside of the vehicle as Side 1 (Sl) and to the side facing the inside of the vehicle as Side 4 (S4) is typically employed.
  • Side 1 Side 1
  • S4 Side 4
  • side 2 (S2) indicates the opposite face of the Sl sheet
  • S3 indicates the opposite face of the S 4 sheet.
  • JP62072548A describes preparation of a glass laminate with desired characteristics by baking a coated film on a glass sheet, superposing another glass sheet, bending the assembly, interposing a plastic laminating intermediate film and then integrally bonding the sheets by compression.
  • the application describes a paint printed on the specified part of one face of a first glass sheet and baked to form a coated film. The face having the coated film is positioned at the upper part, a second glass sheet is superposed thereon and the assembly is placed on a bender.
  • the assembly is introduced into a heating furnace, heated to the softening temperature of the two glass sheets and simultaneously bent by an own- weight bending method.
  • the assembly is then annealed, a plastic laminating intermediate film (e.g., a polyvinyl butyral film) is interposed between the bonding faces during bending and preliminary compression bonding is carried out.
  • the sheets are integrally bonded by compression in an autoclave to obtain the desired glass laminate.
  • US 5,443,669 describes production of a glass laminate wherein two panes are subjected to deformation with single or double curvature, a screen-printed pattern on at least one of the panes is dried by heating below 300 degrees centigrade to evaporate the printing oil before the panes are stacked for deformation and simultaneously baking on the dry enamel pattern. The panes are then separated, a plastic sheet interposed and the resulting stack is bonded to form the laminate.
  • the glass frits include from about 0.1 percent by weight to about 15 percent by weight Nb 2 O 5 , less than about 3 percent by weight alkali metal oxides, less than about 3 percent by weight ZnO, less than about 1 percent by weight B 2 O 3 , and precursors from which Bi 2 SiO 5 can be crystallized upon firing, the precursors including Bi 2 O 3 and SiO 2 .
  • Glass frits according to this patent preferably further include up to about 25 percent by weight of coloring oxides, such as CeO 2 , Co 3 O 4 , In 2 O 3 , SnO, Cr 2 O 3 , CuO, Fe 2 O 3 , MnO 2 , MoO 3 , NiO, and V 2 O 5 .
  • coloring oxides such as CeO 2 , Co 3 O 4 , In 2 O 3 , SnO, Cr 2 O 3 , CuO, Fe 2 O 3 , MnO 2 , MoO 3 , NiO, and V 2 O 5 .
  • US 2006/154799 describes a ceramic ink including a glass frit, a pigment, an organic vehicle and an oxidizing agent.
  • the oxidizing agent comprises a bismuth salt of nitric acid.
  • the inks provide good quality, non-stick coatings and are particularly suitable for use in the production of laminated automotive glass.
  • a method of coating or decorating a substrate includes the step of applying the ceramic ink to the substrate.
  • WO 2007/036942 describes ink-jet ink compositions for printing on a ceramic substrate comprising: (a) a liquid vehicle; (b) sub-micron particles of binding composition having a melting point below 6000C; and (c) sub-micron particles causing an etch-like effect.
  • the sub-micron particles causing an etch-like effect are selected from metal oxide particles, high melting point frit particles, and a combination thereof and have a melting point of at least 500C above the melting point of the sub-micron particles of binding composition.
  • WO 2005/0129360 describes ink for printing on ceramic surfaces such as glass, which contains glass frits for silica nanoparticles and optionally a pigment, and is suitable for ink jet printing.
  • US/2006/191625 describes a method of decorating laminated glass in which a pigment package composition comprising a cross-linkable thermoset resin, a crosslinker capable of crosslinking the thermoset resin, and a pigment is applied to a glass substrate.
  • the crosslinker and thermoset resin are cured at a relatively low temperature (ca. 400 degree Fahrenheit).
  • a relatively low temperature ca. 400 degree Fahrenheit
  • use of an organic based pigment composition allows use of thinner glass sheets than with traditional ceramic enamel pigment compositions.
  • WO 2005/018941 describes digital ink-jet glass printers for printing flat glass boards with glass based ink.
  • the printers include a horizontal support for a glass board, at least one digital ink-jet printing head moveable from above the area of the glass board by means of a respective moving mechanism.
  • the printing head is capable of moving above the glass board and injecting glass based ink according to positioning and injecting commands received from a computer or controller.
  • the printer also includes an ink supply system in liquid communication with the printing head. A method for printing flat glass boards with glass based ink is also described.
  • US 7,232,213 describes a decorative glass laminate including a rigid interlayer bearing a printed image that has been ink-jetted onto at least one of the interlayer surfaces, and a process for preparing same.
  • GB993943 and GBl 138619 describe production of glass laminates suitable for use as automobile and aircraft windshields respectively. - A -
  • US 3853693 describes a method for quenching glass laminates.
  • a printed pattern on an inner surface of a glass laminate is characterized by a low surface roughness.
  • the low surface roughness is Ra of less than 0.8 ⁇ m and/or Rz values of less than 3.5 ⁇ m.
  • pre-firing contributes to a reduction in surface roughness and/or burns off organic polymeric binder.
  • a pre-firing temperature below 550 degrees centigrade, optionally in the range of 350 to 450 degrees centigrade is employed.
  • the pre-firing temperature is selected to be less than the strain point of a relative glass type.
  • the strain point of soda lime glass is 514 degrees so that pre-firing below this temperature can reduce or eliminate stress on individual sheets prior to laminate construction.
  • some exemplary embodiments of the invention employ formulations including small diameter glass frit particles to contribute to lower surface roughness post firing.
  • Ra and Rz refer to the parameters used to measure surface roughness.
  • Ra measures the average roughness by comparing all the peaks and valleys to the mean value which is the average of all values measured in an entire cross section.
  • Rz is the mean roughness depth. It averages the height of the five highest peaks and the depth of the five lowest valleys over the measuring length, using an unfiltered profile.
  • surface roughness may be measured using an inductance sensor.
  • the sensor typically scans the surface by a driving mechanism.
  • the surface roughness causes displacement of the probe which results in change of inductive signal of the induction coils which is proportional to the surface roughness.
  • an ink used to form a printed pattern on an inner surface (e.g. S2 and/or S3) of a glass laminate is characterized by particles of binding composition having mean particle diameter of less than 2 micron.
  • the binding composition includes one or more types of glass frit.
  • an ink used to form a printed pattern on an inner surface of a glass laminate is characterized by inorganic pigment particles having mean particle diameter of less than 2 micron.
  • particle sizes of the binding composition and/or pigment contribute to surface roughness.
  • mean particle diameter refers to d (50).
  • d (50) relates to the diameter of 50% by volume of the particles.
  • d (50) 2 micrometer, indicates that 50% by volume of the particles have a diameter less than 2 micrometer.
  • the diameter values of the particles as used herein refer to d (50) as measured by volume using dynamic light scattering or laser diffraction.
  • particle size is determined utilizing Malvern's Zetasizer dynamic light scattering.
  • binding composition refers to a composition which comprises at least one type of glass frit which upon firing sinters and fuses to the glass sheet becoming an integral part thereof.
  • firing is at a temperature of 580° C, 600 0 C, 630° C or intermediate or greater temperatures.
  • an increase in firing temperature contributes to a reduction in surface roughness.
  • the binding composition consists essentially of glass frit.
  • the glass frit includes one or more of lead based glass frit, Bi 2 O 3 based glass frit, zinc oxide based glass frit, Bi 2 O 3 and zinc oxide based glass frit, and mixtures thereof.
  • the glass frits may be "crystallizing", “non-crystallizing” or “partly crystallizing” at the firing conditions.
  • An aspect of some exemplary embodiments of the invention relates to preparation of an S2 or S3 glass laminate with efficient fusion of the ink to the inner side of one glass sheet without sticking to the adjacent surface of an opposing second sheet.
  • glass frit particle size of less than 2 micron contributes to efficient and/or uniform firing and/or fusion of the glass enamel to one side of the inner glass surface without sticking to the adjacent surface of the opposing sheet.
  • a production process for S2 or S3 printed glass laminates includes: (a) printing, via a non-screen printing process, a pattern on a first glass sheet using an ink composition including particles of glass frit, inorganic pigment particles and organic polymeric binder; (b) pre-f ⁇ ring the pattern at a temperature of 350 to 450 degrees centigrade; (c) laying a second glass sheet on top of the pre-fired pattern on the first glass sheet to produce a stack; (d) firing the stack at a temperature of at least 575 degrees centigrade; and (e) inserting a plastic spacer between the first and second sheets to produce a glass laminate.
  • the pre-f ⁇ ring reduces a surface roughness of the pattern to Ra of less than 0.8 ⁇ m.
  • the pre-f ⁇ ring reduces a surface roughness of the pattern to Rz of less than 3.5 ⁇ m.
  • the firing is at a temperature of at least 580 degrees C.
  • the firing is at a temperature of at least 600 degrees C.
  • the process includes bending the stack to produce a desired curvature.
  • the glass frit particles have mean particle diameter of less than 2 micron.
  • the glass frit particles have mean particle diameter of less than 0.6 micron.
  • the inorganic pigment particles have mean particle diameter of less than 2.0 micron.
  • the inorganic pigment particles have mean particle diameter of less than 0.6 micron.
  • the printing is performed by an ink-jet printer.
  • the first and second glass sheets comprise a substantially straight portion upon which the patter is printed.
  • substantially straight portion includes substantially the whole glass sheet.
  • a glass laminate includes: (a) at least two sheets of glass arranged in a stack; (b) a plastic spacer deployed between each pair of sheets in the stack; and (c) a printed pattern on at least one of the sheets on a side facing a spacer; the pattern characterized by a low surface roughness.
  • the surface roughness is Ra of less than 0.8 ⁇ m.
  • the surface roughness is Rz of less than 3.5 ⁇ m.
  • all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although suitable methods and materials are described below, methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. In case of conflict, the patent specification, including definitions, will control. All materials, methods, and examples are illustrative only and are not intended to be limiting.
  • method refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of architecture and/or computer science.
  • Fig. 1 is simplified flow diagram illustrating exemplary methods according to various exemplary embodiments of the invention.
  • Figs. 2A and 2B are schematic depictions of a glass laminate according to an exemplary embodiment of the invention in exploded and assembled transverse views respectively.
  • Embodiments of the invention relate to processes for non-screen printing on an inner side (e.g. S2 or S3) of a glass laminate as well as to glass laminates produced thereby.
  • an inner side e.g. S2 or S3
  • S3 inner side
  • the discussion hereinbelow is primarily related to a glass laminate including two glass sheets and a single intervening spacer, it is stressed that the described processes are applicable also to more complex laminates (e.g. three glass sheets and two spacers or four glass sheets and three spacers).
  • some embodiments of the invention can be used to reduce optical imperfections in windshields (e.g. of automobiles, boats or aircraft).
  • Fig. 1 is a simplified flow diagram depicting a production process 100 for S2 or S3 printed glass laminates according to some exemplary embodiments of the invention.
  • Depicted exemplary method 100 includes printing 110, via a non-screen printing process, a pattern on a first glass sheet using an ink composition comprising particles of glass frit, inorganic pigment particles and organic polymeric binder.
  • the glass sheet is substantially flat at least in the portion upon which the pattern is printed.
  • the flat portion of the glass sheet is flat, or straight, only with respect to a direction of motion of a print head.
  • printing 100 is ink-jet printing.
  • the ink includes a liquid vehicle selected from an aqueous vehicle, an organic solvent, and a mixture thereof.
  • addition of a liquid vehicle has a desired influence on viscosity.
  • the ink composition includes one or more additives such as, but not limited to wetting agents, dispersing agents, defoamers, rheology control agents, anti-corrosive agents, evaporation control agents, and mixtures thereof.
  • additives such as, but not limited to wetting agents, dispersing agents, defoamers, rheology control agents, anti-corrosive agents, evaporation control agents, and mixtures thereof.
  • printed pattern is then pre-fired 120 at a temperature of 350 to 450 degrees centigrade.
  • pre-firing burns off the organic polymeric binder.
  • the temperature for pre-firing is selected in consideration of a strain point of the first glass sheet.
  • the first glass sheet is cooled.
  • the pre-firing contributes to a reduction in surface roughness of the pattern.
  • pre-firing reduces a surface roughness of the pattern to Ra of less than 0.8 ⁇ m and/or to Rz of less than 3.5 ⁇ m.
  • a second glass sheet is then laid 130 on top of the pre-fired pattern on the first glass sheet to produce a stack which is then fired 140 at a temperature of at least 575 degrees centigrade.
  • the relatively high firing temperature optionally serves to sinter and/or fuse the pattern to the first glass sheet and/or to further reduce surface roughness of the pattern.
  • firing is at a temperature of at least 580 degrees C, optionally, at least 600 degrees C.
  • the fired pattern becomes an integral part of the glass sheet upon which it was printed.
  • the stack can optionally be cooled and/or the first and second sheets can be separated.
  • production of the laminate is completed by inserting 150 a plastic spacer between the first and second glass sheets.
  • the plastic spacer contains polyvinylbutyral.
  • the sheets can be bent 160 to produce a desired curvature as depicted.
  • method 100 produces curved laminates, for example to be used as windshields or curved windows in buildings.
  • bending 160 is performed during firing 140 as indicated by the double headed arrow.
  • bending 160 is performed as a separate operation.
  • this separate operation includes heating of all, or part of, the stack.
  • Figs. 2A and 2B are schematic depictions of an exemplary glass laminate resulting from practice of method 100 of Fig. 1 in transverse cross section.
  • Fig. 2 A is an exploded view 202
  • Fig 2B is an assembled view 204.
  • an exemplary glass laminate according to embodiments of the invention includes at least two sheets 210 and 240 of glass arranged in a stack (as depicted in Fig. 2B) with a plastic spacer 230 deployed between each pair of sheets sheet in the stack and a printed pattern 220 on at least one of the sheets (210 in the depicted embodiment on a side 212 facing space 230.
  • pattern 220 is characterized by a low surface roughness such as Ra of less than 0.8 ⁇ m and/or Rz of less than 3.5 ⁇ m.
  • pattern 220 is depicted on surface 212 of sheet 210 it could also be applied to surface 238 of second sheet 240.
  • Surfaces 208 and 212 of sheet 210 correspond to Sl and S2 according to conventional nomenclature.
  • method 100 employs an ink composition with glass frit particles characterized by a mean particle diameter of less than 2 micron, optionally less than 0.6 micron. In some exemplary embodiments of the invention, method 100 employs an ink composition with inorganic pigment particles characterized by a mean particle diameter of less than 2.0 micron, optionally less than 0.6 micron.
  • Exemplary Organic solvents
  • the organic solvent includes one or more of PM (propylene glycol mono methyl ether), DPM (dipropylene glycol mono methyl ether), TPM (tripropylene glycol mono methyl ether), PnB (propylene glycol mono n-butyl ether), DPnB
  • TPnB tripropylene glycol mono n-butyl ether
  • PnP propylene glycol mono propyl ether
  • DPnP dipropylene glycol mono propyl ether
  • PMA propylene glycol mono methyl ether acetate
  • Dowanol DB Diethylene glycol mono butyl ether
  • Propylene Glycol diacetate Butyl Glycol Ether
  • the ink used to print the pattern on the first glass sheet is liquid at jetting temperature.
  • the jetting temperature is typically close to room temperature but might be lower or higher depending upon conditions such as weather, ventilation and proximity to a hot substrate.
  • jetting temperature may be 10 0 C, 15 0 C, 20 0 C, 25 0 C, 30 0 C, 35 0 C, 40 0 C, 45 0 C, 50 0 C, 55 0 C, 60 0 C, 65 0 C 5 or 70 0 C or intermediate temperatures.
  • the liquid ink has a viscosity of 100 cP, 50 cP, or 25 cP or lesser or intermediate values at the relevant jetting temperature.
  • Indicated viscosity of inks is measured by a Brookf ⁇ eld DV-II + viscometer, with small sample adapter, while using spindle S 18, at 80 rpm.
  • Exemplary polymeric binders
  • the organic polymeric binder includes one or more of acrylic resins, carboxylated acrylic resins, polyvynilpyrrolidone, polyvinylbutyral, condensate of urea and aldehydes, polyvinyl resins and cellulose acetate butyrate.
  • acrylic resins carboxylated acrylic resins
  • polyvynilpyrrolidone polyvynilpyrrolidone
  • polyvinylbutyral polyvinylbutyral
  • condensate of urea and aldehydes polyvinyl resins
  • cellulose acetate butyrate cellulose acetate butyrate
  • the glass frit can selected from lead based glass frit, Bi 2 O 3 based glass frit, zinc oxide based glass frit, Bi 2 O 3 and zinc oxide based glass frit, and mixtures thereof. Glass frits can be characterized as non-crystallizing, partially crystallizing, or crystallizing.
  • the concentration of crystals in the glass frit determines the crystallinity of the frit.
  • the crystallinity of a glass frit may be controlled through the manufacturing process and by addition of nucleating or crystallization-promoting agents. (Such as zircon, alumina or other glass ceramic fillers) to the glass-forming raw material batch, melting the batch, and quenching or fast cooling the melt into a fritted form. This heat treatment in the presence of the crystallization promoting agents causes the glass frit to be converted into a fine-grain crystals randomly oriented and dispersed throughout the frit with the crystals comprising a portion of the frit.
  • the crystallinity of the frit results in physical properties differing considerably from those of a non-crystallizing frit. Crystallizing glass frits have a lower tendency to flow during firing and thus lesser tendency to migrate into the glass substrate relative to non-crystallizing frits. Partly crystallizing provides intermediate flow properties.
  • Lead based glass frit systems (which may partially crystallize upon firing, as described for example in US 4882301 fully incorporated herein by reference). These glass frits usually include 40 to 70 wt% lead oxide (PbO); (2) lead-free glass frit systems that include large amounts of B12O3, with small amount or without zinc oxide (as described for example in US 5203902, US 5578533, US 6105394 each of which is fully incorporated herein by reference). These glass frits typically include 10 to 50 wt % of SiO2, 50 to 75 wt % OfBi 2 O 3 , 0 to 15 wt % of B 2 O 3 and 0 to 5 wt% of zinc oxide. This type of glass frit is also referred to as Bi 2 O 3 based glass frit.
  • the binding composition is a
  • Bismuth (Bi)-containing glass frit selected, for example, from groups (2), (3), or (4) described above.
  • Glass frit is meant that the glass frit is composed of networks of at least Si and Bi interrupted by oxygen atoms (for example - O-Si-O-Bi-0- , or other combinations containing different percentages of Si and Bi ).
  • the binding composition is a Bi-containing glass frit composed of
  • SiO 2 , Bi 2 O 3 , and B 2 O 3 which are covalently linked, i.e. forming network of Si, Bi, B interrupted by oxygen atom (for example -0-Si-O-Bi-O-B-O-).
  • Use of Bi-containing glass frits containing different percentages of Si 5 Bi, and B is within the scope of the invention.
  • the weight/weight (w/w) of SiO 2 in the glass frit is 10-70%.
  • the w/w of the Bi 2 O 3 in the glass frit is 10-60%.
  • the w/w of the B 2 O 3 in the glass frit is 3-50%.
  • the constituents of the glass frit can form a network of one or more of Pb, Si, Bi, B 5 Zn (depending on the frit composition) which are interrupted by oxygen atom.
  • crystallizing glass frit or partially crystallizing glass frit with low melting temperatures are employed in printing 110 of exemplary method 100.
  • glass frits of the binding composition of inks employed in printing 110 of exemplary method 100 have a melting point below 600 0 C, optionally below 580 0 C.
  • the inorganic pigment includes one or more of chromium oxide, copper oxide, titanium oxide, Cu- Cr 2 O 3 oxides; titanium dioxide, iron oxide, Nickel antimony titanium yellow rutile and Cobalt aluminium blue spinel.
  • the plastic spacer is polyvinylbutyral (PVB).
  • the spacer is provided as a sheet.
  • PVB polyvinylbutyral
  • Commercially available PVB suitable for use in the context of exemplary embodiments of the invention include, but are not limited to, Butacite® PVB Interlayer, (DuPont Inc. USA), TROSIFOL VG (Kuraray Co. Ltd., Japan) and Saflex® (Solutia Inc., USA).
  • Exemplary additional processing include, but are not limited to, Butacite® PVB Interlayer, (DuPont Inc. USA), TROSIFOL VG (Kuraray Co. Ltd., Japan) and Saflex® (Solutia Inc., USA).
  • method 100 includes bonding the plastic spacer to the glass sheets.
  • bonding includes heating the stack to form the laminate.
  • Printing on S2 or S3 has the potential to provide several advantages. From an aesthetic point of view S2 or S3 printing enables concealment of conductive contacts on a windshield and reduces optical defects common in windshields printed on side 4. Alternatively or additionally printing on S2 or S3 has the potential to eliminate undesired chemical reactions with IR [infra red] coatings commonly deposited on Sl or S4.
  • Exemplary technical problem S2 or S3 printing is complicated by a tendency of printed patterns to stick, transfer to, or abrade a facing surface of an opposing glass sheet.
  • Organic polymeric binders have traditionally contributed to "stickiness". It is expected that during the life of this patent many types of glass, plastic spacers, and uses for glass laminates will be developed and the scope of the invention is intended to include all such new technologies a priori.
  • features used to describe a method can be used to characterize an apparatus and features used to describe an apparatus can be used to characterize a method.
  • the ink also includes copper chromite black pigment milled to a similar size.
  • a wet layer thickness of 40 ⁇ m was ink-jet printed on the glass to produce a flat printed glass.
  • the resultant flat printed glass was pre-fired using an IR (Infra Red) kiln at a temperature of 42O 0 C for 5 minutes.
  • a second imprinted glass sheet was placed on top of the flat printed glass to produce a glass stack which was fired at 63O 0 C and bent using HTBS ProETM tempering and bending system (Tamglass, Finland).
  • the second unprinted glass sheet was lifted after cooling to room temperature. There was no evidence of sticking, transfer of the digitally printed black edge to the second unprinted glass or any visible defect.
  • a PVB sheet was laid in-between the separated glass sheets and heated to bond together into a glass laminate at a temperature of HO 0 C.
  • This example illustrates that printing with an ink containing glass frit with a final particle size of less than 1 micron contributes to an improvement in an S2 printed glass laminate.
  • EXAMPLE 2 Printing with ink containing frit with larger particle size
  • a standard screen printing black enamel comprising the same bismuth silicate glass frit J5405F (Johnson Matthey, Maastricht, NL) with particles size 15 ⁇ m and same copper chromite black pigment with particle size of more than 2 ⁇ m was used for screen printing a similar black strip edge coating on a glass sheet. The same procedures were used as in example 1.
  • This example confirms that the particle size of less than 1 micron contributes to an improvement in an S2 printed glass laminate as suggested by example 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L’invention concerne un procédé de production de stratifiés de verre imprimés S2 ou S3, consistant : à imprimer un motif sur une première feuille de verre au moyen d’une composition d’encre contenant des particules de fritte de verre, des particules de pigment inorganique et un liant polymère organique ; à précuire ce motif à une température comprise entre 350 et 450 degrés Celsius ; à déposer une deuxième feuille de verre sur le motif précuit sur la première feuille de verre pour former un empilement ; à cuire l’empilement à une température d’au moins 575 degrés Celsius ; et à insérer une pièce d’espacement plastique entre la première et la deuxième feuille pour produire un stratifié de verre.
PCT/IL2009/000559 2008-06-05 2009-06-04 Procede d’impression sur le cote interieur d’un verre stratifie et stratifies de verre ainsi formes Ceased WO2009147676A1 (fr)

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US61/129,111 2008-06-05

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011114335A1 (fr) * 2010-03-17 2011-09-22 Hanita Coatings R.C.A. Ltd Substrat polymère comportant une couche de verre stratifié
WO2013130332A3 (fr) * 2012-02-29 2013-11-28 Wki Holding Company, Inc. Procédé et système pour impression à jet d'encre d'images sur des surfaces à contours complexes d'articles en céramique et en verre tels que de la vaisselle
EP2711346A1 (fr) 2012-09-25 2014-03-26 Falco Technologies BVBA Panneau multicouche et procédé de fabrication d'un panneau multicouche
WO2015003736A1 (fr) * 2013-07-08 2015-01-15 Fenzi Spa Encre céramique pour impression par jet d'encre
CN111716688A (zh) * 2020-06-29 2020-09-29 东莞市铂华光电材料有限公司 一种盖板热弯防护成型工艺
CN113677521A (zh) * 2019-03-29 2021-11-19 Agp美洲股份公司 具有优异美观性和亮度的照明层压件
EP3665131B1 (fr) 2017-08-09 2023-05-03 Fenzi AGT Netherlands B.V. Mélange de particules
DE102021134016A1 (de) 2021-12-21 2023-06-22 Webasto SE Verfahren zum Herstellen einer Verbundglasscheibe

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786784A (en) * 1987-02-17 1988-11-22 Libbey-Owens-Ford Co. Method for producing an electrically heated window assembly and resulting article
US5605591A (en) * 1993-03-26 1997-02-25 Saint-Gobain Vitrage International Process for the preparation of a laminated enamelled glazing and enamel composition used
US20040086652A1 (en) * 1998-11-06 2004-05-06 Etienne Degand Glazing panels
WO2005052071A1 (fr) * 2003-11-25 2005-06-09 Johnson Matthey Public Limited Company Composition d'encre d'impression numerique
US20070199349A1 (en) * 2003-10-03 2007-08-30 Glaverbel Compound Glass Bowing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786784A (en) * 1987-02-17 1988-11-22 Libbey-Owens-Ford Co. Method for producing an electrically heated window assembly and resulting article
US5605591A (en) * 1993-03-26 1997-02-25 Saint-Gobain Vitrage International Process for the preparation of a laminated enamelled glazing and enamel composition used
US20040086652A1 (en) * 1998-11-06 2004-05-06 Etienne Degand Glazing panels
US20070199349A1 (en) * 2003-10-03 2007-08-30 Glaverbel Compound Glass Bowing
WO2005052071A1 (fr) * 2003-11-25 2005-06-09 Johnson Matthey Public Limited Company Composition d'encre d'impression numerique

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011114335A1 (fr) * 2010-03-17 2011-09-22 Hanita Coatings R.C.A. Ltd Substrat polymère comportant une couche de verre stratifié
WO2013130332A3 (fr) * 2012-02-29 2013-11-28 Wki Holding Company, Inc. Procédé et système pour impression à jet d'encre d'images sur des surfaces à contours complexes d'articles en céramique et en verre tels que de la vaisselle
US9758684B2 (en) 2012-02-29 2017-09-12 Wki Holding Company, Inc. Method and system for ink jet printing images to complex contoured surfaces of ceramic and glass items such as dishware
EP2711346A1 (fr) 2012-09-25 2014-03-26 Falco Technologies BVBA Panneau multicouche et procédé de fabrication d'un panneau multicouche
WO2015003736A1 (fr) * 2013-07-08 2015-01-15 Fenzi Spa Encre céramique pour impression par jet d'encre
EP3665131B1 (fr) 2017-08-09 2023-05-03 Fenzi AGT Netherlands B.V. Mélange de particules
CN113677521A (zh) * 2019-03-29 2021-11-19 Agp美洲股份公司 具有优异美观性和亮度的照明层压件
CN111716688A (zh) * 2020-06-29 2020-09-29 东莞市铂华光电材料有限公司 一种盖板热弯防护成型工艺
CN111716688B (zh) * 2020-06-29 2021-04-06 东莞市铂华光电材料有限公司 一种盖板热弯防护成型工艺
DE102021134016A1 (de) 2021-12-21 2023-06-22 Webasto SE Verfahren zum Herstellen einer Verbundglasscheibe
WO2023117806A1 (fr) * 2021-12-21 2023-06-29 Webasto SE Procédé de production d'une vitre en verre feuilleté
DE102021134016B4 (de) 2021-12-21 2024-06-13 Webasto SE Verfahren zum Herstellen einer Verbundglasscheibe

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