WO2024033936A1 - Substrat de verre ayant un revêtement d'émail pouvant être traité thermiquement et son procédé de fabrication - Google Patents

Substrat de verre ayant un revêtement d'émail pouvant être traité thermiquement et son procédé de fabrication Download PDF

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Publication number
WO2024033936A1
WO2024033936A1 PCT/IN2023/050717 IN2023050717W WO2024033936A1 WO 2024033936 A1 WO2024033936 A1 WO 2024033936A1 IN 2023050717 W IN2023050717 W IN 2023050717W WO 2024033936 A1 WO2024033936 A1 WO 2024033936A1
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WO
WIPO (PCT)
Prior art keywords
glass substrate
coating
enamel
enamel coating
contact angle
Prior art date
Application number
PCT/IN2023/050717
Other languages
English (en)
Inventor
Srinivas Prasad B.S
Jagadis S
Swathi MANIVANNAN
Original Assignee
Saint-Gobain Glass France
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 Saint-Gobain Glass France filed Critical Saint-Gobain Glass France
Publication of WO2024033936A1 publication Critical patent/WO2024033936A1/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
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • 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
    • 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
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • 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
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present disclosure relates in general to a glass substrate with an enamel coating. More particularly, the present disclosure provides a heat treatable glass substrate coated with an enamel comprising a non-wetting additive. Such a coated glass substrate is hydrophobic in nature and abrasion resistant. BACKGROUND Generally, enamel coating over glass sheets are well known to those skilled in the art. Specifically, enamel coating compositions for glass can be utilized for a wide variety of applications but are of particular use in decorating glass sheets.
  • enamel coatings may be used to form borders around the edge of glass sheets which are converted into windshields, sidelites or backlites in motor vehicles. More particularly, such enamel coated glass sheets find its application in commercial and residential spaces to enhance the aesthetics in general.
  • Enamel coatings in general consist of powdered glass oxides or frits, pigments, binder and a medium.
  • the enamel coatings deposited on a glass sheet are considered to be in a ‘green state’ prior to the firing step that fuses the glass frits in the coating.
  • the green state herein refers to the state of the coating prior to high temperature firing, wherein, the glass frits and pigments are held together by a polymeric binder.
  • the mechanical strength of the coating in its green state is lower than that of the fused state.
  • a glass sheet is covered with a layer of organic paint that is then dried and/or cured in an oven, for example, at about 150°C for about 10 minutes.
  • an organic-based paint When such glass substrates are covered with an organic-based paint and are treated at high temperatures, the organic component burns and gets damaged or even completely destroyed.
  • These conventional coated sheets could therefore not generally survive at temperatures higher than 200°C without deterioration.
  • glass substrates are being cut-to-size before providing enamel coatings or ceramic designs and immediately heat treated before providing magnetron coating on the glass substrates.
  • major disadvantages associated with this process the major one being the need for the glass substrates to be cut-to-size prior to the coating of the substrates. This is because of the inability of cutting the glass substrates after heat treatment.
  • Ceramic based enamel paints when applied on glass substrates are not suitable for transportation, post-processing and subsequent coating in their dried form due to their very low green-strength and adhesion.
  • Green strength is the mechanical strength of the enamel that allows the handling of the material prior to the final processing step.
  • Commonly used water or organic diluent based ceramic enamel have very low binder content and hence show low green-strength and adhesion to the glass substrates. Therefore, immediate heat treatment becomes necessary. Transportation and further handling of the ceramic coated glass substrate before heat treatment removes/degrades the coated layer or patterns.
  • Dried ceramic enamel layers on glass substrates cannot be used for subsequent coating processes.
  • enameled glass sheets have also been developed by providing on the glass sheets a coating comprising, a first layer comprising an enamel and a second layer comprising a resin as described in publication WO2007104752.
  • Such coated glass substrates may be handled and transported before heat treatment without damaging the coating; they may be cut and ground before heat treatment without causing the coating to peel off or to be damaged at the borders of the cutting line; Also it may offer, before heat treatment, a good resistance under running water.
  • the second layer is present temporarily, to give resistance to the enameled glass sheet before heat treatment which is further removed or destroyed after heat treatment.
  • Document EP2825510A1 discloses a glass sheet having an enamel-based coating comprising a glass frit, inorganic pigments and organic compounds comprising at least one cross-linked compound, said coating exhibiting a xylene resistance. Both these patent documents rely on increased organic content to impart the green strength. The organic content is expected to completely burn out even before the enamel fusion at a temperature below 500°C.
  • the formulations disclosed in the aforesaid teachings may be susceptible to delamination in the green state when exposed to water for extended durations.
  • document WO2007135192A1 discloses enamel coatings with a static water contact angle of at least 75° to ensure good water resistance during processing.
  • the green enamel coatings having a static water contact angle above 90° are still susceptible to failure through delamination during increased exposure to water.
  • Water exposure is typically observed during edge grinding, hole drilling, beveling, etc., and also during transportation and storage when exposed to rain. Presence of water tends to soften the coating thereby making it susceptible to delamination and other defects. Higher the retention time of water on the coating, greater is the risk of defect formation.
  • the static water contact angle which is typically used to describe hydrophobicity, does not capture the complete wetting characteristics of real surfaces. Hence, it is significant to note that the dynamic contact angles including advancing and receding contact angles are essential to describe the interaction of the liquids with the solid surfaces, especially on surfaces that are rough and chemically inhomogeneous.
  • a zero receding contact angle enables a stable water film formation that allows for a high degree of water contact with the enamel coating.
  • a non-zero receding water contact angle on the coating disrupts film formation, thereby reducing the time of water contact with the coating.
  • Inventions utilizing either a single enamel coating, or a dual coat which offers protection to the enamel coating are also well established in the state of art, as above mentioned. However, these coatings suffer either from poor water resistance prior to tempering or require additional industrial steps.
  • the enamel coated glass substrate as per the disclosed invention can be stored, transported and processed prior to heat treatment, thereby reducing the defects in the final product.
  • the main object of the present invention is to provide a glass substrate with a heat treatable enamel coating, such that the coated glass substrate is hydrophobic in nature with a receding water contact angle of non-zero; and abrasion resistant.
  • Another object of the present invention is to provide a glass substrate with a heat treatable enamel coating, such that the coated glass substrate can be exposed to water over extended duration, transported and can undergo processing methods; prior to heat treatment and still avoid 100% delamination of the enamel coating.
  • Yet another object of the present invention is to provide a method for manufacturing a heat treatable glass substrate provided with an enamel coating.
  • a glass substrate with a heat treatable enamel coating is disclosed.
  • Said glass substrate with a heat treatable enamel coating comprises 0.01 to 10 wt% of non-wetting additive, extending partially on at least one surface of the glass substrate.
  • the glass substrate coated with the enamel is hydrophobic and has a non-zero receding contact angle between a water droplet and the coating.
  • a method of manufacturing a heat treatable glass substrate is disclosed.
  • Said method comprises the steps of providing a glass substrate having a first surface and a second surface; applying an enamel coating comprising 0.01 to 10 wt% of non-wetting additive to extend partially on at least one surface of the glass substrate; and drying the enamel coating so that the enamel coating is cured/dried;
  • the glass substrate thus obtained is hydrophobic and has a non-zero receding contact angle.
  • the coated glass substrate can be further processed to obtain final cut sizes; and heat-treating the processed enamel coated glass to fuse the coating to the glass.
  • FIG. 1 illustrates a glass substrate with an enamel coating, in accordance with one embodiment of the present disclosure.
  • FIG.2(a) illustrates an enamel coated glass substrate, in accordance with comparative example 1 of the present disclosure.
  • FIG. 2(b) illustrates an enamel coated glass substrate, in accordance with inventive example 1 of the present disclosure.
  • Skilled artisans appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. DETAILED DESCRIPTION As used herein, in every embodiment, it must be understood that the term ‘green strength’ refers to the state of the coating prior to high temperature firing, wherein, the glass frits and pigments are held together by a polymeric binder.
  • melt coating refers to a mixture of organic and inorganic components including non-wetting additive and diluents.
  • heat treatable enamel coating refers to the coating that can be subjected to high temperature heat treatment process resulting in glass frit fusion.
  • base enamel coating refers to a glassy, vitreous and usually opaque substance that is used in protective or decorative coating over a glass substrate. Such a base enamel coating usually is a material comprising of organic and inorganic components including pigments, binders, diluents and other additives.
  • the term ‘receding water contact angle’ refers to the contact angle of water on the surface as it dewets or ‘recedes’ from a previously wetted surface.
  • the term ‘advancing water contact angle’ refers to the contact angle of water on the surface as it wets or ‘advances’ on the previously dry surface.
  • the term ‘static water contact angle’ refers to the contact angle of water on the surface under steady state conditions.
  • non-wetting additive refers to an agent that reduces the wettability and increases the water contact angle between a water droplet and a coated surface, when such an additive is included in an enamel coating.
  • the term ‘wet conditions’ refers to a state where the surface of the enamel coating is wet.
  • the present application provides a glass substrate with a heat treatable enamel coating.
  • the glass substrate 103 having a first surface 101 and a second surface 102.
  • An enamel coating 104 comprising 0.01 to 10 wt% of a non-wetting additive extends at least partially over the first surface 101 of the glass substrate 103.
  • the enamel coating 104 provided ensures that the glass substrate 103 is hydrophobic and specifically has a non-zero receding water contact angle between a water droplet and the coating.
  • the glass substrate 103 in accordance with the present disclosure improves the reliability of the glass substrate during storage, transport and processing, thereby decreasing the percentage of defects in the final product.
  • the disclosed glass substrate 103 with an enamel coating 104 not only has an improved abrasion resistance, but the enamel coating itself is heat treatable and withstands high temperatures without causing charring.
  • the coated glass substrate 103 in accordance with the present disclosure not only ensures non-zero receding water contact angle between a water droplet and the coating 104, but also ensures to achieve a 100% reduction in the probability of delamination of the enamel coating 104 on the glass substrate 103 when exposed to water for long durations or during any processing steps, prior to heat treatment.
  • the glass substrate 103 in accordance with the present disclosure is provided with an enamel coating 104 comprising a non-wetting additive.
  • the non-wetting additive is present in the range of 0.01 to 10 wt% of the enamel coating 104.
  • the enamel coating 104 in accordance with the present disclosure which is heat treatable, is provided on at least one surface of the glass substrate 103, preferably on a first side 101 of the glass substrate 103.
  • the enamel coating 104 in an embodiment is in direct contact with the glass substrate.
  • the enamel coating 104 further comprises organic component, inorganic component, and a diluent.
  • the inorganic component further comprises of glass frits and pigments.
  • the non-wetting additive in accordance with the present disclosure is added to the afore mentioned base enamel coating.
  • the base enamel coating generally comprises initially i.e., before applying on the glass substrate, in a powder formed from inorganic pigments and a glass frit (vitreous matrix) in suspension in a medium often comprising solvent(s).
  • the enamel coating 104 provided over the glass substrate 103 comprises organic component selected from the group consisting of polyester resins, cellulose based, alkyds, acrylic, acrylamide, acrylic-styrene, vinyl-acrylic, urethane, polyurethane, polyester, urethane alkyds, amino resins, polyamide, epoxy, epoxy ester, phenolic resins, silicon resins, PVC, PVB, and water-based resins.
  • the organic component is selected from acrylic polyurethane, vinyl- acrylic polyurethane, polyester polyurethane. In a most preferred embodiment, the organic component is acrylic polyurethane.
  • the organic component is preferably present in the range of 0.5 to 20 of the total wt%.
  • the organic component in the enamel coating 104 can also advantageously comprise one or several other additives to base enamel coatings such as a dispersing agent, a flow agent, an anti-foam, an anti-UV agent, a catalyst, an adhesion promoter, a matting agent and/or structuring agent.
  • the enamel coating 104 provided over the glass substrate 103 comprises glass frit selected from a group consisting oxides of zinc, bismuth, sodium, aluminium, silicon, boron, lithium, potassium, iron, cobalt, copper, strontium, zirconium, barium, calcium, titanium, chromium or combinations thereof.
  • the glass frit is a combination of aluminium, silicon, sodium, boron, lithium, potassium, or combinations thereof.
  • the glass frit is preferably present in the range of 10 to 85 of the total wt%.
  • the enamel coating 104 provided over the glass substrate 103 comprises pigment selected from a group consisting of titanium oxide, zinc oxide, spinel, iron or metal ion doped titanium oxide, copper oxide, chromium oxide, cobalt oxide, beryllium oxide, cadmium telluride, cadmium sulphide, lithium niobate, mangnates or combinations thereof.
  • the pigment is titanium dioxide.
  • the pigment is preferably present in the range of 0 to 50 of the total wt%.
  • the enamel coating 104 comprises diluent selected from the group consisting of water, xylene, diacetone alcohol, ethanol, methanol, tetrachloroethylene, acetone, toluene, methyl acetate, ethyl acetate, hexane, benzene
  • the preferred diluent diacetone alcohol is preferably present in the range of 10 to 50 of the total wt%.
  • the enamel coating 104 provided over the glass substrate 103 comprises non-wetting additive in a range of 0.01 to 10 wt%.
  • the non-wetting additive preferably present in the range of 0.1 to 5 wt% is selected from the group consisting of methyl phenyl silicone, methoxy silicone, silanes, silicones, organometallics, polysilazane, or fluorinated compounds. In a most preferred embodiment, the non-wetting additive is methyl silicone.
  • the non-wetting additive in accordance with the present disclosure is added to the base enamel formulation to form a heat treatable enamel coating 104.
  • the enamel coating 104 in accordance with the present disclosure is heat treatable and can withstand high temperatures ranging from 450 to 750 °C. During the high temperature heat treatment, the glass frits fuse and form a continuous network while the organic binders pyrolyze without charring.
  • the glass substrate 103 provided with the enamel coating 104 prior to heat treatment, exhibits a non-zero receding water contact angle between a water droplet and the enamel coating 104.
  • a static contact angle that is synonymous with the term ‘contact angle’.
  • a static contact angle is usually associated with a lot of variability, especially on rough surfaces, due to the differences in liquid deposition protocols, evaporation rates and other measurement parameters.
  • the measurement of dynamic contact angles is followed in the field which is usually in terms of advancing contact angle and receding contact angle.
  • the advancing contact angle denotes the contact angle of a liquid on the surface as it wets or ‘advances’ on a previously dry surface and the receding contact angle denotes the contact angle of a liquid on the surface as it de-wets or ‘recedes’ from a previously wetted surface.
  • the receding contact angle in accordance the present disclosure also indicates the extent of adhesion between the liquid and the underlying surface. It is understood to a person skilled in the art that lower the receding contact angle, higher is the adhesion of water film on a surface, by forming a stable film. When the receding contact angle is zero, it indicates the presence of a thermodynamically stable liquid film that cannot be de-wetted from the surface.
  • the glass substrate 103 with the heat treatable enamel coating 104 has a finite difference between the receding water contact angle and the advancing water contact angle, due to the roughness and the chemical inhomogeneity of the surface.
  • the receding contact angle in accordance with the present disclosure is always less than the advancing contact angle due to the higher wettability of the previously ‘wet surface’ (receding contact angle) compared to the previously ‘dry surface’ (advancing contact angle).
  • the receding water contact angle is preferably greater than 10 and less than 150.
  • the receding water contact is greater than 20 and less than 150.
  • the receding water contact angle is non-zero and preferably greater than 10
  • the glass substrate is prone not just to being hydrophobic, but also de-pins or de-wets the water film completely.
  • the glass substrate 103 can thus be subjected to standard processing methods including cutting, washing, edge grinding, beveling, hole drilling, prior to heat treatment.
  • the presence of non-wetting additive in accordance with the present disclosure ensures that no water film formation occurs on the surface. This prevents the processing defects like delamination, blister formation due to water ingression, discoloration due to water uptake, etc.
  • the receding water contact angle referred herein is measured in respect of direct contact between a water droplet and the enamel coating 104.
  • the heat treatable enamel coating 104 in accordance with the present disclosure is characterized in that the receding water contact angle between the water droplet and the coating is greater than 0, preferably greater than 10, more preferably greater than 20 and less than 150.
  • the receding water contact angle measurement is indicative of, or represents the ability of a liquid film to de-wet or de-pin itself over a surface of wettability.
  • the static contact angle between a water droplet and the coating is greater than 90 degrees. In a preferred embodiment the static contact angle is greater than 95, more preferably greater than 100.
  • the advancing contact angle is greater than 105, more preferably greater than 110.
  • the enamel coating is also heat treatable.
  • the glass substrate provided with enamel coating also provides advantageous mechanical resistance properties before heat treatment. It has been not only found that, by coating glass sheets with an enamel comprising non-wetting additive possesses hydrophobic properties, but surprisingly also offers good resistance under grinding conditions and be handled and transported before heat treatment without damaging the coating, thereby avoiding complete delamination. Further particularly, the glass substrate in according to the present disclosure can undergo a heat treatment, specifically it can be temperable, i.e. it can be thermally treated with a view to being subsequently tempered.
  • the heat treatment includes a treatment at temperatures that are not lower than 500°C.
  • heat treatment can involve heating or exposing the enamel coated glass substrate to a temperature between 550°C to 750°C.
  • the enamel coating does not char.
  • the enamel coating 104 provided on the glass substrate 103 has a thickness ranging between 5 to 150 microns. In a preferred embodiment, the thickness of the enamel layer is 10 to 120 microns. In a most preferred embodiment, the thickness of the enamel layer is 20 to 100 microns.
  • the glass substrate 103 in accordance with the present disclosure can belong to various categories.
  • the glass substrate can be a soda-lime glass, a boron glass, a lead glass, a glass containing one or more additives distributed uniformly within its structure, such as for example, at least one inorganic coloring agent, an oxidizing compound, a viscosity-regulating agent and/or a melting agent.
  • the glass substrate in an embodiment is preferably a soda-lime glass.
  • the glass substrate in a further preferred embodiment can be a float glass, a drawn glass or a patterned glass. It can be a clear, extra-clear, colored in the bulk, sanded and/or frosted.
  • the enamel coating in accordance with an embodiment of the present disclosure is in direct contact with the glass substrate.
  • the glass substrate may be surface -treated, before coating, with an adhesion promoter to improve the adhesion of the coating to the glass.
  • This adhesion promoter is further selected from the group consisting of organofunctional silanes, organofunctional acids, organofunctional phosphates, and organofunctional metallates.
  • the adhesion promoter is organofunctional silane.
  • the enamel coating 104 of the present disclosure may be continuous and extend over substantially the whole surface of the glass substrate, i.e. over more than 90% of the surface of the glass substrate, preferably 100% of the surface of the glass substrate. In an alternate embodiment the enamel coating may be partially covering the surface of the glass substrate, i.e., less than 5% of the surface of the glass substrate.
  • the enamel coating 104 can also be colored. If the coated glass substrate 103 is heat treated, color does not change during heat treatment, due to the presence of non-wetting additive.
  • the enamel coating 104 provided on the glass substrate may be opaque or translucent. It may also be structured or matted.
  • the glass substrate in accordance with the present disclosure is preferably a substrate of soda-lime float glass.
  • the substrate of float glass can have a thickness varying from 2 to 12 mm. In the most preferred embodiments, according to the present disclosure the thickness of the glass substrate 103 is 4 to 6 mm.
  • the glass substrate is also provided with an additional coating.
  • the coating is provided above the enamel coating 104, extending substantially over the enamel coating.
  • the additional coating can help further increase the mechanical resistance of the final glass substrate or provide design or functional elements.
  • a glass canopy with good opaque coating as first layer and a second layer with design/company logo can be provided.
  • a PV module on top of the enameled glass canopy can be provided.
  • Different methods known per se can be suitable for providing or applying the enamel coating 104 onto the glass substrate 103. For example, it is possible to deposit the enamel coating 104 by a curtain coating process (onto a moving glass sheet), by a bar coater process, by a roller coating process, by a flow processor, by digital printing, by decal application or by a spraying process.
  • the glass substrate 103 with an enamel coating 104 according to the present disclosure advantageously offers good properties in terms of abrasion resistance of the coating, and a non-zero receding water contact angle. Different tests have been used to evaluate this abrasion resistance before heat treatment, and to evaluate the non-zero receding contact angle prior to heat treatment, which have been elaborated under the Examples.
  • the present application also discloses a method for manufacturing a heat treatable glass substrate. The method comprises the steps of providing a glass substrate 103 having a first surface 101 and a second surface 102.
  • the first surface 101 of the glass substrate 103 is provided with an enamel coating 104 comprising 0.01 to 10 wt% of non-wetting additive to extend partially over the surface of the glass substrate.
  • the enamel coating is further cured and dried.
  • the enamel coating is cured at a temperature of at least 150°C or at least 175°C and/or not exceeding 300°C, preferably not exceeding 275°C. Curing usually takes around 1 to 20 minutes, preferably 2 to 15 minutes (in a static oven); or, in an industrial oven, this may take around 5 to 10 minutes with a maximum temperature measured on the glass of around 200-250°C.
  • the method further comprises of cutting the large enamel coated glass substrate 103 into final cut sizes followed by edge grinding, beveling, hole drilling etc.
  • the enamel coated glass substrate 103 is further subjected to heat treatment at a temperature ranging between 550°C to 750°C, to fuse the enamel coating 104 into the glass substrate 103.
  • the enamel coating 104 in accordance with the present disclosure is applied by any method known in the art, for example the processes of roller coating or curtain coating, the spray process or flow process.
  • the screen printing method may also be used, especially if only portions of the glass substrate are to be coated or provided in patterns.
  • the enamel coating fuses and sinters and the organic material burns. Sintering may occur at temperatures of around 550-750°C or above.
  • the coated enamel glass substrate 103 manufactured in accordance with the present disclosure has a non-zero receding water contact angle between the water droplet and the coating. Achieving such a receding water contact angle, avoids complete delamination of coating even when exposed to water for long durations.
  • such an enamel coated glass substrate can undergo all processing steps, prior to heat treatment.
  • the enamel coated glass substrate according to the present disclosure once thermally tempered or toughened may be used in buildings, spandrels, facades, panels, kitchen splash backs, furniture (wardrobes, tabletops, workstations), claddings, lift lobbies, etc.
  • a glass substrate provided with a heat treatable enamel coating comprising 0.01 to 10 wt% of a non-wetting additive, said coating extending partially on at least one surface of the glass substrate, characterized in that the glass substrate coated with the enamel, prior to heat treatment has a non-zero receding contact angle between a water droplet and the enamel coating.
  • the glass substrate, wherein the non-wetting additive is selected from the group consisting of methyl phenyl silicone, methyl silicone, methoxy silicone, organometallics, silanes, silicones, polysilazane, or fluorinated compounds.
  • the glass substrate, wherein the non-wetting additive is methyl silicone.
  • the glass substrate, wherein the enamel coating comprises organic component, inorganic component, and diluent.
  • the glass substrate, wherein the inorganic component comprises of glass frits and pigments.
  • the glass substrate, wherein the organic component is selected from the group consisting of polyester resins, cellulose based, alkyds, acrylic, acrylamide, acrylic-styrene, vinyl-acrylic, urethane, polyurethane, polyester, urethane alkyds, amino resins, polyamide, epoxy, epoxy ester, phenolic resins, silicon resins, PVC, PVB, and water-based resins.
  • the glass substrate wherein the glass frit is selected from a group consisting oxides of zinc, bismuth, sodium, aluminium, silicon, boron, lithium, potassium, iron, cobalt, copper, strontium, zirconium, barium, calcium, titanium, chromium or combinations thereof.
  • the glass substrate, wherein the pigment is selected from a group consisting of titanium oxide, zinc oxide, spinel, iron or metal ion doped titanium oxide, copper oxide, chromium oxide, cobalt oxide, beryllium oxide, cadmium telluride, cadmium sulphide, lithium niobate, mangnates or combinations thereof.
  • the glass substrate, wherein the receding water angle is less than an advancing contact angle. In a specific embodiment, the glass substrate, wherein the receding water angle is preferably greater than 20 and less than 150. In a specific embodiment, the glass substrate, wherein the thickness of the enamel layer is between 5 to 150 microns. In a specific embodiment, the glass substrate, is heat treatable at a temperature of 550 to 750°C. In a specific embodiment, the glass substrate, withstands the standard processing methods including cutting, washing, edge grinding, beveling, hole drilling, prior to heat treatment. In a specific embodiment, the glass substrate, is mechanically durable during handling and transportation, prior to heat treatment.
  • the glass substrate, wherein enamel coating is hydrophobic with a static contact angle between a water droplet and the coating is greater than 90 degrees. In a specific embodiment, the glass substrate, wherein the enamel coating is hydrophobic with an advancing contact angle between a water droplet and the coating is greater than 100 degrees.
  • a method for manufacturing a heat treatable glass substrate as claimed in claim 1, comprising the steps of: providing a glass substrate having a first surface and a second surface; applying an enamel coating comprising 0.01 to 10 wt% of non-wetting additive to extend partially on at least one surface of the glass substrate; drying the enamel coating so that the enamel coating is cured/dried; processing the enamel coated glass substrate to obtain final cut sizes; and heat-treating the processed enamel coated glass to fuse the coating to the glass; characterized in that the glass substrate coated with the enamel has a non-zero receding contact angle between a water droplet and the coating prior to heat-treatment.
  • the method wherein the processing includes cutting, washing, edge grinding, beveling, hole drilling, etc.
  • Table 1 discloses a base enamel coating including a non-wetting additive methoxy silicone, according to an inventive Example 1: Table 1 Component Composition P l i 121
  • the glass substrate is cleaned with distilled water, then polished with ceria powder and then dried.
  • the glass substrate on the first surface is provided with the adhesion promoter and over which the enamel coating is provided.
  • the glass substrate is further cured/dried at a temperature ranging from 150 to 200 °C.
  • the glass substrate post curing is processed (that includes cutting, edge grinding, hole drilling, etc.,) and subjected to heat treatment.
  • different non-wetting additives were added to base enamel coating as per Inventive examples 2 to 3, produced below.
  • Table 2 Component Composition Titania pigment 30-35 wt.% Glass frits 50-65 wt.%
  • Table 3 Component Composition P l bi d 1213 % Comparative Example 1
  • Table 4 discloses a base enamel coating without a non-wetting additive, according to comparative Example 1: Table 4 Component Composition Same method as disclosed under inventive example 1 has been followed. Similarly, another comparative examples 2 is produced below.
  • Table 5 Component Composition Polymer binder 12-13 wt.% g ventive and comparative examples.
  • Static and dynamic water contact angles are measured using a Goniometer.
  • Static contact angle A water droplet (0.5 ml) was added on the surface of the coating. An image of the drop was obtained and contact angle was measured from the drop image.
  • Advancing contact angle For measurement of advancing contact angle, a water droplet was deposited on the surface. The volume of the drop was increased at a constant rate through a needle that was inserted in the droplet.
  • the advancing contact angle was measured as the basal width of the droplet increases in size.
  • Receding contact angle For measurement of receding contact angle, at the end of the sequence adopted for measurement of advancing contact angle, the volume of the droplet was reduced at a constant rate through a needle that was inserted in the droplet. The receding angle was measured as the basal width of the droplet decrease in sizes.
  • Table 7 Contact Angle Comparative Ex 1 Inventive Ex 1 Receding CA(°) 0 21 ⁇ 5 Ta on the base enamel coating (comparative ex 1) and the enamel coating with a non-wetting additive (inventive ex 1), prior to heat treatment.
  • Table 8 as produced below indicated a comparison of the advancing water contact angles and receding water contact angle on the inventive enamel coatings with different non-wetting additive.
  • Table 8 Examples Advancing CA Receding CA It is clearly indicated form Table 8 that the incorporation of a non-wetting additive in the enamel coating, as per the inventive examples 1 to 3, increase in the static and the advancing contact angles, but more importantly, results in a non-zero receding angle. This is crucial to ensure an unstable wetting film on the enamel coated glass substrate surface and reduced interaction between water and the underlying coating.
  • the receding contact angle produced in Table 5 clearly demonstrates that an additive increases the advancing contact angle above 90 but does not ensure a non-zero receding angle (Comparative example 2).
  • Enamel coated samples were soaked in water for 10 to 15 minutes and then retrieved just prior to the testing process.
  • the sample was placed horizontally at the bottom of the felt plug.
  • the linear abrader fitted with the felt plug moves in a straight line to and fro across the surface of the enamel coating gently abrading the surface.
  • a load of 50g was applied on the sample during the abrasion studies.
  • the number of cycles required to delaminate the coating was then recorded.
  • Table 9 Example De-wetting nature No of cycles Com arative Exam le 1 Film on surface ⁇ 20 c cles st Table 9 as produced above indicates a comparison of the coating resistance to linear abrasion.
  • the difference in the water wettability of the comparative example 1, comparative example 2 and Inventive example 2 was also manifested as the resistance to delamination under an abrasive force.
  • the enamel coating as per the comparative example 1 to 2 and the enamel coating as per Inventive Example 2 were soaked in water for 10 minutes, retrieved and then subjected to repeated linear abrasion cycles with a 120-grit emery paper. The number of cycles needed to completely break through the coatings was recorded.
  • Table 6 shows linear abrasion cycles for delamination for the standard and modified enamel coatings. It is noted that the enamel coating as per the comparative example 1, and comparative example 2 show a zero receding contact angle.
  • the enamel coated glass substrate is heat treatable as such, and can withstand all processing steps prior to heat treatment.
  • the enamel coated glass substrate in accordance with the present disclosure ensures avoiding 100% delamination of the coating.
  • the coated glass substrate in accordance with the present disclosure having non-zero receding water contact between the water droplet and the coating, finds its application in various commercial and residential places such as office, interiors residential spaces, community halls, spandrels, facades, Panels, Kitchen Splash backs, Furniture (Wardrobes, Tabletops, workstations), claddings, lift lobbies, etc. Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • the use of “a” or “an” is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. For example, when a single item is described herein, more than one item may be used in place of a single item. Similarly, where more than one item is described herein, a single item may be substituted for that more than one item.

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

Abstract

La présente demande concerne un substrat de verre avec un revêtement d'émail pouvant être traité thermiquement. Ledit substrat de verre est pourvu d'un revêtement d'émail pouvant être traité thermiquement comprenant de 0,01 à 10 % en poids d'un additif non mouillant. Spécifiquement, le substrat de verre revêtu de l'émail, avant le traitement thermique, a un angle de contact sortant non nul entre une gouttelette d'eau et le revêtement d'émail. En outre, la présente invention concerne également un procédé de fabrication d'un substrat de verre pouvant être traité thermiquement.
PCT/IN2023/050717 2022-08-12 2023-07-27 Substrat de verre ayant un revêtement d'émail pouvant être traité thermiquement et son procédé de fabrication WO2024033936A1 (fr)

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IN202241045983 2022-08-12

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2029497A1 (fr) * 2006-05-24 2009-03-04 AGC Flat Glass Europe SA Vitre avec revetement
WO2015031555A1 (fr) * 2013-08-30 2015-03-05 Guardian Industries Corp. Substrat de verre peint apte au traitement thermique, et/ou son procédé de fabrication
WO2020161733A1 (fr) * 2019-02-06 2020-08-13 Saint-Gobain Glass France Revêtement protecteur temporaire à base d'eau pour articles en verre revêtus pouvant être traités thermiquement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2029497A1 (fr) * 2006-05-24 2009-03-04 AGC Flat Glass Europe SA Vitre avec revetement
WO2015031555A1 (fr) * 2013-08-30 2015-03-05 Guardian Industries Corp. Substrat de verre peint apte au traitement thermique, et/ou son procédé de fabrication
WO2020161733A1 (fr) * 2019-02-06 2020-08-13 Saint-Gobain Glass France Revêtement protecteur temporaire à base d'eau pour articles en verre revêtus pouvant être traités thermiquement

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