WO2016001055A1 - Procédé de traitement de la surface de substrats en verre mince - Google Patents

Procédé de traitement de la surface de substrats en verre mince Download PDF

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Publication number
WO2016001055A1
WO2016001055A1 PCT/EP2015/064367 EP2015064367W WO2016001055A1 WO 2016001055 A1 WO2016001055 A1 WO 2016001055A1 EP 2015064367 W EP2015064367 W EP 2015064367W WO 2016001055 A1 WO2016001055 A1 WO 2016001055A1
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WO
WIPO (PCT)
Prior art keywords
glass
glass substrate
thin
less
weight
Prior art date
Application number
PCT/EP2015/064367
Other languages
German (de)
English (en)
Inventor
Carsten RENZ
Marten Walther
Thomas Wiegel
Original Assignee
Schott Ag
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 Schott Ag filed Critical Schott Ag
Priority to TW104121099A priority Critical patent/TW201605754A/zh
Publication of WO2016001055A1 publication Critical patent/WO2016001055A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float 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
    • 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
    • B32B17/061—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 metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0085—Drying; Dehydroxylation
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/75—Hydrophilic and oleophilic coatings
    • 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
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/365—Coating different sides of a glass substrate

Definitions

  • the present invention relates to a method of treating the surface of thin glass substrates and the thin glass substrates obtainable by the method.
  • Adsorption layers, impurities and the like which determine the chemical and physical properties of the surface accordingly.
  • Coatings on the glass generally show lower adhesion because the moisture bound to the surface is in the form of one or more
  • a homogeneous coating can be produced with high reproducibility.
  • a surface usually has localized densifications or such chemical modifications that the coating is in certain areas is bound better than in other areas, resulting in an inhomogeneous coating.
  • a surface treatment is used.
  • Known methods to achieve this are, for example, acid baths, wax coatings, flaming and plasma and Koronavor opposition.
  • Another known method of removing adsorbed water from the glass surface is, for example, heating the glass in vacuum to a temperature of about 250 ° C, or alternatively heating in air to one
  • GB 816 479 describes a method and a device for
  • Glass disc is described, wherein the activation is achieved by abrasion by means of a closed belt on which abrasive grains are located and the glass plate is pressed by means of a robot against the disc.
  • the surface is therefore mechanically regenerated by abrasion.
  • DD 236 516 A1 discloses a method for generating
  • the surface under normal ambient pressure is first treated with a flame jet whose temperature is in a range between 800 and 1500 ° C, which sprays the metal oxide or metal oxide mixture serving for modification or the metal or metal alloy underlying the oxide in the case of a strongly oxygen-enriched fuel gas composition and on the substrate whose temperature is in a range between 300 and 800 ° C, injected, and in a subsequent flame radiation with reducing
  • Gas composition is a regulation of transparency and conductivity.
  • EP 1 148 036 B1 relates to a method for modifying a
  • the surface is modified with at least one oxidizing flame, the surface thus produced is modified in a second step with at least one silicating flame and subsequently applied at least one printing ink on the surface.
  • the application of the polymer layer always takes place in WO 2000 / 66507A1 from the liquid phase.
  • the processes described in the prior art in which a glass sheet is applied to a thin glass by lamination are described as disadvantageous in WO 2000 / 66507A1, in particular with regard to the optical properties.
  • the surface treatment described in WO 2000 / 66507A1 is limited to UV irradiation in an ozone atmosphere.
  • the required glass transition temperature is provided in an annealing module.
  • EP 1 148 036A1 describes a method for modifying a surface of a compact substrate, which may also be glass. Here is the
  • DE 10 2009 051 397 A1 describes a method for pretreating a glass surface of a photovoltaic module.
  • the surface of the glass writing of the photovoltaic module according to DE 10 2009 051 397 A1 is cleaned by flame treatment and the wettability of the glass writing is increased.
  • the flame of the ignited glass mixture has a temperature between 700 ° C and 1000 ° C.
  • DE 10 2009 051 397A1 does not disclose the use of a thin or ultrathin glass substrate.
  • the silicate glass substrate comprises a float glass substrate having a thickness of 3 mm.
  • a coating is applied to the surface of the float glass substrate.
  • a disadvantage of the approaches of the prior art is that the described method can not be readily used for thin or ultra-thin glass. Since the glass is already very thin, mechanical
  • Abrasion method not suitable because they stress the surface too much and easily lead to breakage of the glass.
  • thin glasses deform very quickly at too high temperatures, become wavy, for example, resulting in undesirable bending or warping of the thin glass. If too high temperatures are used, the glass may also melt, causing the surface of the glass to contract; this is comparable to the shrinkage of a plastic film.
  • Thin or ultra-thin glass is in this respect even more sensitive than thicker glass, so that the Removal of undesirable surface layers is extremely difficult to carry out. But even thin or ultra-thin glass has a wide range of applications, especially where chemical and physical properties, such as transparency, chemical and thermal resistance and low weight, are of great importance. These are, for example, a variety of electronic applications, such as sensors.
  • the present invention is therefore based on the object to overcome the disadvantages of the prior art and to provide a method for the treatment of the surface of glass, which can be used in particular for thin or ultra-thin glass.
  • the method should be inexpensive to carry out in a simple manner and the adsorbed layer
  • the object underlying the invention is achieved by a method for treating the surface of a thin or ultrathin glass substrate, comprising the steps of: - treating the surface of the glass substrate by flaming with
  • Temperature T in the glass substrate during flaming is: T ⁇ Tg, where Tg represents the glass transition temperature of the glass, and
  • the method according to the invention thus makes it possible, even with thin or ultrathin glass, to reliably remove the gel layer of adsorbed water by the flame treatment, and to achieve a homogeneous one
  • the inventive method is under an open system
  • the method of the present invention could be coupled directly to glass production. However, this is usually not necessary, since immediately after the glass production virtually no gel layers adsorbed out
  • a thin glass substrate may be treated which has been stored for a certain period of time so that the aged surface of the thin glass is again activated and clean as immediately after the glass surface is formed and has the desired chemical and physical properties, i. behaves like a freshly made glass surface.
  • organic impurities should also be removed.
  • Glass substrates understood as having a thickness in the range ⁇ 2 mm, preferably ⁇ 1, 2 mm, more preferably ⁇ 1, 0 mm, more preferably ⁇ 500 ⁇ , in particular ⁇ 400 ⁇ , very particularly preferably ⁇ 300 ⁇ .
  • Ultrathin glasses are, for example, glasses with thicknesses in the range of ⁇ 300 ⁇ , in particular ⁇ 200 ⁇ , more preferably ⁇ 100 ⁇ , most preferably ⁇ 50 ⁇ .
  • the surface of the thin or ultrathin glass substrate is first exposed to at least one oxidizing flame.
  • An oxidizing flame in the present invention means any ignited gas, gas / air mixture, aerosol or spray which contains excess oxygen and / or can have an oxidizing effect.
  • the strongly oxidizing atmosphere in the flame jet area which is caused by a
  • Oxygen excess of the fuel gases reduces the bound moisture in the form of water molecules and preferably leads to their virtually complete removal, whereby the desired advantageous
  • the customary fuel gases can be used to produce the flame, with propane, butane, luminescent gas and / or natural gas being particularly preferred.
  • propane, butane, luminescent gas and / or natural gas being particularly preferred.
  • Oxygen excess is present, for example, the ratio of fuel gas: air or fuel gas: oxygen in the range of 1:10 to 1:30, preferably in the range of 1:15 to 1:30, more preferably in the range of 1:20 to 1: 30th
  • a silicon-containing substance can be introduced into the oxidizing flame and applied to the surface with flame-pyrolytic decomposition of the silicon-containing substance.
  • a silane as the silicon-containing substance.
  • a preferred silicon-containing compound is, for example
  • Tetramethoxysilane Due to the flame pyrolysis of the silicon-containing compound, the production of an SiO x coating on the surface of the
  • Thin glass surface during flame treatment with at least one oxidizing flame is achieved for a thin or even ultra-thin glass, in particular, when the speed at which the glass substrate is moved past the flame, or the speed at which the flame on
  • the process speed is selected such that the temperature T in the glass substrate by the flame treatment is such that: T ⁇ Tg, particularly preferably T ⁇ Tg, where Tg the
  • Glass transition temperature of the glass represents.
  • the speed with which the oxidizing flame and / or the glass substrate are passed to one another ie the speed at which the flame treatment is carried out, is controlled in such a way that the temperature T in the glass is sufficiently remote from the glass transition temperature Tg of the respective glass substrate.
  • the surface treatment is achieved that it has a highly hydrophilic character and a good wettability of the surface with water.
  • the contact angle after the Beflannn Vietnamese is less than 10 °, preferably less than 8 °, in particular less than 5 °, more preferably less than 3 °. This makes it possible to apply a film by laminating on the thin glass. In this case, a particularly good adhesion of the film is achieved on the thin glass.
  • Lamination is preferably carried out in a period after the flame treatment in which the contact angle has not risen above 10 °, preferably not above 8 °, in particular not above 5 °, more preferably not above 3 °.
  • this period of time is like experiments according to Table 5 show less than 2 hours, preferably less than one hour, in particular less than 20 minutes, preferably less than 5 minutes.
  • the time depends on the environmental conditions, especially the
  • the determination of the contact angle takes place in the case of a lying drop with the aid of a goniometer.
  • the contact angle is recorded from the lying drop with a camera.
  • the flame also removes impurities, in particular organic impurities, from the surface.
  • a measure of how much organic contaminants have been removed from the surface by flame treatment is the contact angle.
  • Tg is based on the upper cooling temperature. Therefore, the preferred
  • Cooling temperature T k ühi annealing temperature
  • the temperature T can be easily measured on the surface of the glass substrate.
  • the temperature T at the glass surface is usually in the range of 300 to 650 ° C during the flame treatment.
  • Glass transition temperature Tg is preferably present when both temperatures differ by about 10 to 50 ° C, more preferably about 50 to 100 ° C, more preferably about 100 to 200 ° C, most preferably about 200 to 350 ° C. If the distance to the glass transition temperature Tg is not met, the energy input into the glass may be too high and the
  • Thin glass can deform and bend.
  • the distance of the temperature T in the glass substrate to the upper cooling temperature T k ühi of the glass substrate is set to T ⁇ T k ühi, both temperatures being preferably about 10 to 50 ° C, more preferably about 50 to 100 ° C, even more preferably about 100 to 200 ° C, most preferably about 200 to 350 ° C differ.
  • Tg T k ühi it is expedient to T ⁇ T k ühi so that the energy input is not too high in the glass and the thin glass does not deform, bend or even break.
  • the glass substrates are passed at a corresponding process speed to a fixed burner system having at least one oxidizing flame.
  • the distance of the surface of the glass substrate of thin or ultra-thin glass from the at least one oxidizing flame may be adjusted accordingly by those skilled in the art. This depends, among other things, on the type of fuel gas selected, the set ratio to the oxygen and the resulting flame length, the glass composition and other parameters. As a rule of thumb, a distance in the range of about 80 to 200 mm, but more preferably in the range of about 80 to 150 mm can be set as advantageous. A standard flame length of the flame is usually in the range of 100 to 200 mm.
  • the glass can also be additionally cooled during the flame treatment, so that the temperature within the glass can be kept as low as possible. This leads to
  • the thin or ultra-thin glasses are not particularly limited. Particular preference is given to using soda-lime glasses, borosilicate glasses, aluminosilicate glasses, lithium-aluminum silicate glasses and glass-ceramic.
  • lithium-aluminum silicate glasses which are the following:
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 1 wt .-%, and refining agents such as As 2 0 3 , Sb 2 0 3 , Sn0 2 , S0 3 , Cl, F, Ce0 2 , in contents of 0 - 2% by weight.
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 1 wt .-%
  • refining agents such as As 2 0 3 , Sb 2 0 3 , Sn
  • soda-lime silicate glasses which are the following:
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 5 wt .-% and for "black glass" of 0 - 15 wt .-%, and refining agents such as As 2 0 3 , Sb 2 0 3 , Sn0 2 , S0 3 , Cl, F, Ce0 2 , in contents of 0-2% by weight.
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 5 wt .-% and for "black glass" of 0
  • borosilicate glasses which have the following glass composition or consist thereof (in% by weight):
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 ,
  • alkali aluminosilicate glasses which are the following
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 ,
  • refining agents such as As 2 O 3 , Sb 2 O 3 , SnO 2 , S0 3 , Cl, F, CeO 2 , in contents of 0-2% by weight.
  • alkali-free aluminosilicate glasses which have the following glass composition or consist of (in% by weight):
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 5 wt .-% and for "black glass" of 0 - 15 wt .-%, and refining agents such as As 2 0 3 , Sb 2 0 3 , Sn0 2 , S0 3 , Cl, F, Ce0 2 , in contents of 0-2% by weight.
  • low-alkali aluminosilicate glasses which have the following glass composition or consist thereof (in% by weight):
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 5 wt .-% and for "black glass" of 0 - 15 wt .-%, and refining agents such as As 2 0 3 , Sb 2 0 3 , Sn0 2 , S0 3 , Cl, F, Ce0 2 , in contents of 0-2% by weight.
  • coloring oxides such as Nd 2 0 3 , Fe 2 0 3 , CoO, NiO, V 2 0 5 , Nd 2 0 3 , Mn0 2 , Ti0 2 , CuO, Ce0 2 , Cr 2 0 3 , rare earth oxides in contents of 0 - 5 wt .-% and for "black glass" of 0
  • flame treatment In addition to the removal of the adsorbed water molecules, flame treatment also leads to an activation of the glass surface, which is reflected in a highly hydrophilic character of the surface. This hydrophilic character results in a particularly good wettability of the surface with water, which is distributed homogeneously on the surface.
  • a measure of the wettability of the surface is the so-called contact angle.
  • the contact angle is the angle that a drop of liquid forms on the surface of a solid to that surface.
  • the size of the contact angle depends on the interactions between the contact surfaces of the
  • the contact angle therefore provides information about certain properties of the surface of the glass.
  • the surface In the case of water, the surface is called hydrophilic at low contact angles, hydrophobic at 90 °, and superhydrophobic at even larger angles.
  • Glass surface leads to a change in the contact angle, it becomes a marked decrease in the contact angle when using water, which corresponds to the highly hydrophilic nature of the surface.
  • Flaming is performed, more preferably within 60 + 5 min, most preferably within 30 + 5 min followed.
  • Process step is performed several times in succession.
  • silicon-containing compound is added, several silicon-containing layers can be applied to the glass surface in several treatments.
  • the oxidizing flame for pretreatment, the molecular chains on the surface of the glass substrate are broken by heat and oxygen components contained in the flame are bound to these fractures.
  • the flame heat sets the process in motion, whereby the oxidation of the surface is the air-gas or oxygen-gas mixture, which provides an excess of oxygen during combustion.
  • polar units are formed, which are now available for a particularly good connection, which can be used, for example, in the form of a subsequent lamination.
  • the lamination is not particularly limited according to the invention.
  • a film of polymer material or metal is preferably applied to the glass surface by means of an adhesive.
  • the polymer material is preferably selected from the group consisting of silicone polymer, a sol-gel polymer, polycarbonate (PC), polyethersulfone, polyacrylate, polyimide (PI), an inorganic silica / polymer hybrid, a cycloolefin copolymer, a silicone resin, polyethylene,
  • PMMA Polymethyl methacrylate
  • ethylene-vinyl acetate copolymer Polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer,
  • PET Polyethylene terephthalate
  • polybutylene terephthalate polyamide
  • polyacetal polyphenylene oxide
  • polyphenylene sulfide polyurethane or mixtures thereof.
  • the metal of the metal foil may be selected from one or more metals, alloys also being possible; Examples include iron, aluminum, copper, steel, brass and the like.
  • the laminate film preferably has a thickness which is preferably ⁇ 500 ⁇ m, more preferably ⁇ 100 ⁇ m, more preferably less than 50 ⁇ m and most preferably less than 25 ⁇ m.
  • the ratio of the thickness of the laminate film to the thickness of the glass is preferably 200% or less, more preferably 100% or less, and in FIG more preferably 50% or less and even more preferably 20% or less, and in very specific cases 10% or less.
  • the polymer material or metal of the film may be formed to have a very high water vapor transmission rate (WVTR) over conventional polymer materials.
  • WVTR water vapor transmission rate
  • the film of the laminate may provide some functions that glass does not have, such as adhesive properties, color filter function, or polarization function.
  • the film can also be removed after lamination, the film is therefore only temporarily applied as a protective film on the glass surface of the thin glass substrate. After removing the film, the thin glass can be further processed, for example, coated.
  • an additional low bond layer may be provided between the glass and the film. The low-bond layer has a weak bond between it and the film or the glass substrate, which causes the film or the glass substrate to be easily peeled off.
  • both sides of the thin glass substrate are pre-treated with flame treatment and each laminated with foil to form a foil-glass-foil triple structure that performs well, especially in thermal terms.
  • the lamination process involves directly laminating a glass substrate with a polymer or metal foil, with or without adhesive.
  • Another method of laminating a polymer film comprises applying a liquid to the glass substrate to first form a polymer precursor, which is then cured by UV light or a thermal process.
  • the polymer precursor may be, for example, by dip coating, inkjet coating, Casting, screen printing, painting or spraying are applied to the thin glass.
  • the adhesive method includes direct lamination, pressing and heating, static electrical bonding, laser sealing or bonding with adhesives such as silicone, resin, superglue, epoxy adhesive, UV-curing adhesive,
  • thermoplastic material hot melt adhesive
  • OCR hot melt adhesive
  • OCA hot melt adhesive
  • PSA latex and the like.
  • the laminate produced according to the invention has an adjustable transmission of 0 to 90%.
  • the laminates produced have many uses, and may be e.g. be applied to the surfaces of other objects. Possible applications include electronic devices such as touch sensors, tablets, laptops, televisions, thin film batteries, displays, solar cells, cell phones, cameras, gaming machines, mirrors, windows, aircraft windows, furniture, and home appliance applications.
  • electronic devices such as touch sensors, tablets, laptops, televisions, thin film batteries, displays, solar cells, cell phones, cameras, gaming machines, mirrors, windows, aircraft windows, furniture, and home appliance applications.
  • the inventive method is also suitable for a continuous
  • the inventive method is suitable for thin or ultra-thin glass to reliably and in the removal of adsorbed water layers
  • the energy input during the flame treatment can be lowered by maintaining the temperature T in the glass substrate during flaming that T ⁇ Tg, where Tg represents the glass transition temperature of the glass.
  • Tg represents the glass transition temperature of the glass.
  • the temperature T in the glass substrate is preferred
  • the glass transition temperature Tg by about 10 to 50 ° C, more preferably about 50 to 100 ° C, even more preferably about 100 to 200 ° C, most preferably about 200 to 350 ° C.
  • the upper cooling temperature T k ühi can be taken instead of the glass transition temperature Tg.
  • Oxygen mixture can be adjusted. Another way the
  • the process speed with which the glass substrate surface is passed by the flameproofing device and / or with which the flameproofing device is guided past the glass substrate surface to adjust accordingly is particularly preferably> 10 m / min.
  • a silicon-containing substance can be introduced into the oxidizing flame and onto the surface
  • ultra-thin glass substrates to lower the contact angle of about 45 ° to 50 ° to about 5 °. If the laminating according to the invention takes place within about 80 minutes, a laminate film with particularly good adhesion to the
  • the first process step of the flame treatment can also be carried out several times in succession. If a silicon-containing organic compound having the following properties:
  • a laminate film of polymer material or metal can be laminated in any desired manner.
  • the glass substrate can be given further advantageous properties and functions.
  • the film can also be removed later, so that it is applied only temporarily.
  • the method according to the invention makes it possible to provide a reproducible homogeneous surface which has extraordinary adhesion properties, so that the application of a film by the subsequent lamination leads to a particularly good bond to the glass surface. This improves the durability of the applied film and overall improves the quality.
  • the invention also relates to the glass product obtainable by the process according to the invention.
  • the invention also relates to a thin glass substrate used as
  • Figure 1 is a schematic view of a Beflammungsvoroplasty with a
  • Figure 2 shows the contact angle in °, plotted against the storage time in
  • FIG. 1 shows the first step of the method according to the invention
  • Flaming device 10 is not shown lines with
  • Fuel gas / air or fuel gas / oxygen and optionally supplied a silicon-containing compound includes, for example, propane, butane, luminescent gas and / or natural gas.
  • the fuel gases, the air or the oxygen and optionally the silicon-containing compound are applied to the surface of the thin glass substrate 20 via a nozzle 15 in the form of a combustion mixture 18.
  • the fuel gas / air or oxygen mixture has a proportion of excess oxygen, so that it acts oxidizing.
  • the thin glass substrate 20 is passed in the direction of the arrow under the flameproofing device.
  • the flameproofing device 10 can also be movable and guided above and / or below the glass substrate 20.
  • the surface of the thin glass substrate 20 may be moved under the flaming device 10 at a speed of 10 m / min to about 15 m / min.
  • a preferred silicon-containing compound is, for example, tetramethoxysilane. The flame pyrolysis of the silicon-containing compound causes the formation of an SiO x coating on the surface of the glass substrate 20
  • the speed with which the glass substrate is moved is selected so that the temperature of the glass substrate T becomes smaller than that
  • Glass transition temperature Tg is preferably about 50 to 100 ° C, more preferably about 100 to 200 ° C,
  • the glass substrate 20 is laminated with a corresponding foil, preferably selected from polymer material or metal (not shown). This further process step is preferably completed within 80 + 5 min of the first process step
  • FIG. 2 is explained in the examples.
  • the glass substrates had the following dimensions:
  • Thickness 70 ⁇
  • the flaming step was carried out with the following parameters: Gas type: Propane
  • the contact angle of the glass substrates was determined.
  • the contact angle measurement was carried out by determining the contact angle with different liquids.
  • deionized water, toluene and ethanol were used.
  • the measure of the contact angle is a measure of how many organic contaminants have been removed from the surface.
  • samples of any size can be measured, but the sample must be at least large enough for a drop to be applied without conflicting with the sample edge.
  • the sample surface is cleaned with ethanol. Then the sample is positioned, the measuring liquid is dropped and the contact angle is measured.
  • the contact angle measurement was performed by optical measurement through a video system with image evaluation by taking an angle on a target photograph
  • the contact angle determination was carried out on a lying drop using a goniometer. Depending on the surface procurement (cleanliness, uniformity of the surface), the contact angle can be determined with an error tolerance of the measurement results of ⁇ 5 °.
  • the contact angle can be kept virtually constant in a surprising manner. After 90 min. the properties are significantly worse, the contact angle has increased dramatically. The special ones Properties of the glass surface disappear quickly, even if the thin glass surface was covered with paper.
  • Sample 1 and Sample 2 were stored in air, Sample 3 was covered with paper. Three glass substrates were taken per sample. It was measured twice on about 5 drops and the results were then averaged. The sample size was: 125 x 125 mm, the thickness was: 70 ⁇ . The drop size was 5 ⁇ . The measuring tolerance was about ⁇ 5 °.
  • FIG. Figure 2 shows the contact angle in [°], which is plotted against the storage time in hours. Regardless of the intermediate storage shows that the contact angle steadily increases over time. For each of the three samples studied, linear compensation curves were plotted, showing the steady increase in
  • the contact angle determines as appropriate the surface of the thin glass for a coating, in particular the application by lamination.
  • a particularly good adhesion of the film at a contact angle of the surface is less than 10 °, in particular less than 8 °, preferably less than 5 °, more preferably less than 3 ° is possible.
  • the surface was adequately cleaned by flame treatment, and adsorbed water molecules and / or organic contaminants were removed.

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

Abstract

L'invention concerne un procédé de traitement de la surface de substrats en verre mince ou ultramince, comprenant les étapes consistant à : ‑ traiter la surface du substrat en verre par flammage avec au moins une flamme oxydante, le substrat en verre et/ou la ou les flammes oxydantes étant déplacés le long l'un de l'autre à une vitesse telle que la température (T) dans le substrat en verre satisfait la relation T < Tg, où Tg représente la température de transition vitreuse du verre, et, après le traitement de la surface, l'angle de contact est inférieur à 10°, de préférence inférieur à 8° et notamment inférieur à 5°, de préférence inférieur à 3°, ‑ stratifier une feuille sur la surface du substrat en verre. Le procédé selon l'invention permet, sur du verre mince ou ultramince, d'éliminer les couches d'eau adsorbées de manière fiable et reproductible sans provoquer de déformation ni de gauchissement du verre.
PCT/EP2015/064367 2014-07-01 2015-06-25 Procédé de traitement de la surface de substrats en verre mince WO2016001055A1 (fr)

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DE102014009767.6A DE102014009767A1 (de) 2014-07-01 2014-07-01 Verfahren zum behandeln der oberfläche von dünnglas- oder dünnglaskeramiksubstraten
DE102014009767.6 2014-07-01

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CN114867803A (zh) * 2019-12-20 2022-08-05 Sabic环球技术有限责任公司 制备接合结构的方法，接合结构和所述接合结构用于制备汽车零件的用途
CN115353292A (zh) * 2022-09-14 2022-11-18 晶研一材料科技(宜兴)有限公司 一种高精度的微晶玻璃加工用镀膜装置及其镀膜方法
CN115784636A (zh) * 2022-11-10 2023-03-14 福耀玻璃工业集团股份有限公司 一种弯曲玻璃板及表面处理方法

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TWI709544B (zh) * 2016-10-12 2020-11-11 美商康寧公司 玻璃基板及處理玻璃基板的方法
KR102579100B1 (ko) * 2018-10-10 2023-09-14 쇼오트 글라스 테크놀로지스 (쑤저우) 코퍼레이션 리미티드. 초박형 유리 세라믹 물품 및 초박형 유리 세라믹 물품의 제조 방법

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EP1048628A1 (fr) * 1999-04-30 2000-11-02 Schott Glas Substrat de folie en verre revêtu avec une couche polymerisée
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CN115353292A (zh) * 2022-09-14 2022-11-18 晶研一材料科技(宜兴)有限公司 一种高精度的微晶玻璃加工用镀膜装置及其镀膜方法
CN115353292B (zh) * 2022-09-14 2023-12-05 虎石新材料(宜兴)有限公司 一种高精度的微晶玻璃加工用镀膜装置及其镀膜方法
CN115784636A (zh) * 2022-11-10 2023-03-14 福耀玻璃工业集团股份有限公司 一种弯曲玻璃板及表面处理方法

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