HU0203217A2 - Transparent substrate provided with a silicon derivative layer - Google Patents

Transparent substrate provided with a silicon derivative layer Download PDF

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Publication number
HU0203217A2
HU0203217A2 HU0203217A HU0203217A HU0203217A2 HU 0203217 A2 HU0203217 A2 HU 0203217A2 HU 0203217 A HU0203217 A HU 0203217A HU 0203217 A HU0203217 A HU 0203217A HU 0203217 A2 HU0203217 A2 HU 0203217A2
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Hungary
Prior art keywords
silicon
coating layer
characterized
carrier according
glass
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HU0203217A
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Hungarian (hu)
Inventor
Marie-Jose Azzopardi
Anne Durandeau
Michel Simonet
Xavier Talpaert
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Saint Gobain
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Priority to FR9913937A priority Critical patent/FR2800731B1/en
Application filed by Saint Gobain filed Critical Saint Gobain
Priority to PCT/FR2000/003037 priority patent/WO2001032578A1/en
Publication of HU0203217A2 publication Critical patent/HU0203217A2/en

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225Nitrides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3441Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/213SiO2
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/28Other inorganic materials
    • C03C2217/281Nitrides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/28Other inorganic materials
    • C03C2217/282Carbides, silicides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/75Hydrophilic and oleophilic coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/77Coatings having a rough surface
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/113Deposition methods from solutions or suspensions by sol-gel processes
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/152Deposition methods from the vapour phase by cvd
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils
    • Y10T428/2651 mil or less
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Abstract

The present invention relates to a transparent substrate coated with a layer of silicon derivative, in particular glass, having at least one surface of a silicon-based derivative based on a silicon derivative, which is a silicon derivative of acrylic dioxide or silicon stoichiometric oxides, silicon oxide or silicon oxynitride. The present invention further relates to the use of this carrier for the manufacture of various glass products. HE

Description

EXTRACT

SUMMARY OF THE INVENTION The present invention relates to a transparent substrate coated with a layer of silicon derivative, in particular glass, which is provided with a coating layer made of at least a partially oxidized derivative of silicon on at least one surface, the silicon derivative being oxides of silicon dioxide or silicon having a stoichiometric ratio, silicon oxide or silicon oxide. is selected from silicon oxynitride and has an absorbent capacity

The invention also relates to the use of this carrier for the manufacture of various glass products.

96837-15265 Sps / str ρ 02032 ^ 7 d'd: '·

LI

TRANSPARENT CARTRIDGES, COMPLETELY GLASS LEATHER, COMPLETED BY SILICONE, AND THIS CARRIER \ t

APPLICATION FOR THE PRODUCTION OF GLASS PRODUCTS

The present invention relates to a transparent substrate coated with a layer of silicon derivative, particularly glass, which is coated with layers of thin, i.e., interferential thickness, which enable the specific applicability of the substrates and the use of this substrate for the production of glass products.

Transparent carriers may be made in various glazing, screen or mirror applications as described below, from organic polymers such as glass ceramic, or preferably glass.

The recurring problem of glass-type transparent (or semi-transparent) media is that, due to their gradual dirt, they need to be cleaned periodically by laborious work. Another problem is the condensation phenomenon, which causes unpleasant evaporation when the substrate is in contact with water vapor and causes the accumulation of water droplets in addition to simple evaporation, which hinders vision.

Various at least partially effective solutions have already been proposed in this regard: for example, fluorinated polymer-based coatings are known, the highly water-repellent surface of which facilitates removal of water and less adherence of impurities. Photocatalytic coatings are also known, which contain, for example, titanium dioxide crystallized in the form of anatase, which are effective at least by oxidation degradation of organic impurities.

These different types of coatings have good efficiency but are relatively complicated. In addition, none of them are optimal for solving all the problems raised above. For example, water-repellent coatings do not prevent the phenomenon of condensation, and vice versa, and photocatalytic coatings are not very effective only when exposed to ultraviolet radiation, and therefore can be used on the outside rather than on the exterior of a building.

It is therefore an object of the present invention to provide easy-to-use coatings that are suitable to facilitate cleaning of glass type or similar carriers and / or

96837-15265 Sps / str ···· «··· to eliminate or reduce the phenomenon of water vapor condensation, or at least to ensure that the condensation of water vapor does not coincide with evaporation or the appearance of a plethora of water droplets.

The object of the present invention is to achieve a transparent substrate coated with a layer of silicon derivative, particularly glass, characterized in that it has at least a partially coated base layer of silicon on the surface, which is a silicon derivative of silicon dioxide. is selected from silicon oxycarbide or silicon oxynitride and has an absorbent capacity.

In the present invention, silicon derivative S1O2 may contain only silicon and oxygen as the chemical element, silicon, oxygen and nitrogen for oxynitride, and silicon, oxygen and carbon for oxycarbide. However, according to the present invention, the silicon derivative may also include materials which contain a small amount of at least one metal, such as aluminum, zinc or zirconium, relative to silicon (by weight). The addition of a metal can have three advantages: reactive cathodic spray can "contaminate" the electrical conductivity of the silicon target, which accelerates / facilitates coating application. In addition, regardless of how the coating is applied (e.g., by pyrolysis), the addition of an aluminum type metal may increase the durability of the material, especially when it contains little or no carbon / nitrogen. Finally, the addition of this type of metal in a controlled amount to the layer allows the refractive index to be controlled, namely to increase it (the refractive index of aluminum oxide is about 1.65, while the refractive index of zinc oxide and zirconium oxide is about 2).

According to the present invention, the silicon derivative also includes silicon oxides having SiO x having less than the stoichiometric ratio, where x is less than 2.

Thus, the invention has discovered a new feature of this type of material, i.e. a certain absorbency, which imparts unexpected properties to this material: it has been discovered that a carrier having this type of coating layer, preferably glass, can be more easily cleaned than an uncoated glass (less frictional effort is needed to clean the glass with the cloth, the impurities being overwhelming) part of it is removed by itself, washed with a water jet, without any special force to be exerted). In addition, it has been found that the surface will become dirty later, which will allow the frequency of cleaning to be reduced,

96837-15265 Sps / str is more prominent when the glass is outside and is occasionally exposed to rain: rain water - naturally drops the stains of glass. The third unexpected effect is that the phenomenon of condensation of water on the surface of the glass thus coated does not, or only slightly, reduce transparency on the glass: water appears to be in the form of a liquid, homogeneous and transparent film, in an invisible manner, not in the form of drops.

The same improvements are seen when comparing a composite-coated glass with a coating layer according to the invention at the top, with a glass that has only a composite coating of other properties (e.g., with a sun protection function, low specific emission or a composite coating with optical function, which ends in a coating layer chemically different from the layer of the invention, such as a metal oxide, in a metal nitride layer).

These beneficial effects can be adjusted / modified by varying the chemical composition, the appearance of the surface, or the selected mode of coating.

The refractive index of the coating layer may be about 1.45 (pure SiO 2 ) or greater than 1.45 if it is a suboxide of silicon or if the derivative contains carbon or nitrogen. Preferably, in the latter cases, the refractive index is set between 1.45 and 1.80, more preferably between 1.50 and 1.75, or between 1.55 and 1.68. As used herein, "refractive index" or "refractive index" of a substance as used herein, when the composition of the coating layer and its refractive index is homogeneous along the thickness of the coating layer, or an average apparent refractive index thereof, when the composition and refractive index of the coating layer change along its thickness. A preferred embodiment of the invention relates to coating layers whose refractive index decreases from the base substrate to the outer surface of the coating layer.

There are two advantages to choosing a smaller refractive index:

on the one hand, it approaches the glass refractive index when it forms the substrate and thus avoids reflective properties of the glass, and on the other hand, the more the refractive index increases, the more the carbon or nitrogen ratio increases to the detriment of oxygen, and the coating layer has been shown to be absorbent to increase the oxygen ratio.

96837-15265 Sps / str

Another parameter capable of affecting the absorbency of the coating layer is the roughness of the surface, which in some embodiments of the invention is substantially greater than the standard uncoated glass.

The coating layer according to the invention may be applied by any method suitable for the application of thin films of this type: vacuum processes, such as cathodic spraying, which are used in combination with a magnetic field (for example, by a silicon contaminated with wine or aluminum) may be included. starting from a material target). In order to promote the formation of Si-OH clusters which are preferred for high absorbency on the surface, a reactive atmosphere can be used which contains, in addition to a purely oxidizing compound of type O 2 ,, for example, a hydrogen-containing compound and / or a compound that simultaneously contains hydrogen and oxygen. Thus, the reactive atmosphere may include O2 / H2, O2 / H2O or H 2 O 2 when a silicon oxide is produced. For example, when a silicon oxynitride is applied, reactive atmospheres include, for example, nitrogen-containing and / or hydrogen-containing compounds, such as amine, imine, hydrazine, ammonia. The refractive indices of S1O2 based (optionally contaminated with a small amount of metal or wine) reactive cathodic spray coatings may be quite variable. Depending on the selected application parameters, i.e., the pressure applied during spray application of the target, the refractive index of the coating layers (averaged between 380 and 780 nm) may be about 1.4 to 1.5, which means that the coating layers are sufficiently dense. The refractive index may be smaller, in the order of 1.25 to 1.40, preferably 1.28 to 1.35, e.g. 1.30 (± 0.05). Thus, in this case, lower density coating layers are obtained, but their surface will be somewhat porous and / or rough, which positively affects their absorbency.

Advantageously, a coating applied by a sol-gel process or by a pyrolysis process, preferably by vapor-phase pyrolysis (CVD or Chemical Vapor Deposition) is preferred. In the sol-gel process, the sol can contain TEOS tetraethyl orthosilicate-based precursors, and dipping, spraying or spin coating, or spin-coating, or more. in English it can be applied by methods known as "flow-coating". In the case of CVD application, a silane precursor of type S1H4 can therefore be used for silicon. The silicon precursor is an organic silane of type RS1X3

96837-15265 Sps / str »··· ···· can also be where X is a chlorine-type halo and R is an alkyl group (linear or branched alkyl, e.g. with 1 to 10 carbon atoms or more). RySiXi-y organic silane may also be contemplated by the same agreements for R and X, or a compound belonging to the ethoxysilane family. Other precursors / gases may also be added to the silicon precursor (s), such as ethylene, a nitrogen-containing derivative such as ammonia, or an amine (preferably a primary amine). The addition of an oxidizing agent may be present (O2, H2 O, H2 O2, ...).

It has also been observed that certain roughness on the surface of the coating layer is advantageously influenced by the effects described above, namely roughness that can be controlled by the application of the coating layer and by the preparation of the surface on which the coating layer itself is applied.

In the coating layers according to the invention, the angle of contact with water is preferably less than 35 °, or less than or equal to 25 °, for example between 15 ° and 25 °: this is indeed an absorbent property (in comparison: the standard uncoated glass contact angle usually 40 °). This is not necessarily a significant absorbent property that has the beneficial effects of the invention, but rather a modest absorbency, but better compared to an uncoated glass. We do not necessarily eliminate the phenomenon of condensation, but avoid the effect of water droplets (in practice, if the contact angle is 7 ° or less than 10 °, the evaporation remains invisible, even if it continues condensation exists).

In some embodiments, and for example, coatings applied with CVD, the contact angle may be less than 15 °, preferably less than 10 °.

The coating layer according to the invention may optionally have a variable chemical composition along its thickness. Preferably, its oxygen concentration can be increased in the direction of the "outer" surface (i.e., the furthest surface of the underlying substrate). Thus, a layer of silicon oxycarbide or oxynitride can be obtained which is much richer in C or N than the surface closest to the substrate, and is richer in O than its outer surface, until it has an almost pure SiO 2 (fine) layer forms a layer of C or N richer or even almost pure Si or S13N4 chemical compound. This gradient of oxygen concentration can be achieved by adjusting the application conditions or after surface application by surface oxidation, such as heat treatment.

96837-15265 Sps / Str ···· · ♦ · · · · · ···· · · · · · ···· · · · · ·· ·· · · ·

In practice, it is preferred that the surface of the coating layer have a high oxygen concentration, in the sense that it allows a higher proportion of Si-O-H hydroxyl bonds to be reached on the surface, which makes it absorbent.

The coating layer according to the invention preferably has a thickness of at least 5 nm, more preferably 5 to 100 nm, for example 10 to 60 nm.

The coating layer of the present invention may form part of a plurality of composite coatings arranged over one another, i.e. the last layer (or a further layer for a particular composite coating) which is furthest from the substrate. Here, for instance a non-reflective composite coating (high refractive index and low refractive index layers alternating such coating layer of 2 / Si0 2 / TiO 2 / invention Ti0, wherein the TiO 2 layer can be replaced by Nb 2 O 2, with a SriN ^ gel, SnO 2 with ). In addition, a composite coating of a sunscreen type, for example a coating with an arbitrary coating layer / TiN / coating according to the invention, or a sunscreen based on a mixture of TiO 2 or iron, cobalt, and chromium oxides may be contemplated: Coated glass products are marketed under the name "Vision-Lite", "Stareli" and "Antélio" by Saint-Gobain Glass France. In addition, composite coatings containing at least one silver-based layer with low emission or sun protection function (glass products with such coatings are marketed under the name "Planitherm" by Saint-Gobain Glass France) or small emissive composite coatings with a functional layer of fluorinated contaminated tin oxide (glass products with such coatings are marketed under the name "EKO" by Saint-Gobain Glass Francé) or composite coatings to protect against sunlight with a functional layer of steel or Ni / Cr Alloy (glass products with such coatings are marketed under the name "Cool-Lite" by Saint-Gobain Glass France). For more details on these, see EP-638,528, EP-718,250, EP511901, EP-728,712, WO97 / 43224, EP-638,527 and EP-573,325. patent documents

If the substrate is made of glass, it can be bent (embossed), hardened or softened before or after application of the layer or layers.

The invention further relates to the use of the above-described carriers for the production of glass products which are "dehumidifiers" and / or "dirt repellents" and / or are easy to clean (according to the invention, "condensation96837-15265 Sps / str.

Ítő Exemption ”means that there may be condensation on the glass product, but it does not or does not have much effect on the transparency of the glass product). Such glass products may be used in buildings, vehicles, mirrors, and especially in bathroom mirrors, rear-view mirrors, shower-glass bottles, glass doors and interior partitions, outdoor furniture, billboards, television or computer screen display screens.

The invention will now be described in more detail by way of non-limiting examples, with reference to the accompanying drawings:

1-3. Figs. 1 to 3 show a scanning electron microscope (MEB) negative of the surface of an exemplary coating layer.

In each example, 50 nm silicon oxycarbide layers (e.g., EP-518 755) were applied to a clean silicone-calcium calcium glass of the "Planilux" type marketed by Saint-Gobain Glass France. starting from S1H4, ethylene, and optionally an oxidizing agent, varying the precursor ratio and application temperature so that the refractive index of the coating layers is 1.58-1.75. It has been confirmed that those coated with SiOC coatings have the best absorbent properties and are the most effective in slowing down the dirt that have the lowest refractive indices. These are also the bottles that have the most pronounced "de-condensation" effect, even though their contact angle with water is not very small and is around 15-30 °. It should be noted that the properties of coatings with smaller refractive indexes are increasingly approaching the glass (refractive index 1.52), thus modifying only slightly the appearance of the glass: in other examples of the invention, the contact angle is below 15 ° or 10 °.

The advantage of pyrolysis coatings is that the coating is continuously applied directly to the "water line".

The coatings thus obtained are generally of high durability.

1-4. EXAMPLES

Table 1 below shows the refractive index of the four silicon oxycarbide-based coating layers obtained in Examples 1, 2, 3 and 4, as well as their contact angle with water after purification, and the results of an assay from it. the coatings coated with the coating layer for 18 hours at 30 ° C with 95% relative humidity

96837-15265 Sps / str was stored at atmospheric pressure. ("YES" indicates that there is a "de-evaporation" effect in the sense that no visible water droplets appear on the coating layer and "NO" that there are such drops visible to the naked eye). The purification was done with a surfactant in two steps, by rinsing with wired water, where the purification was completed with the last rinse with deionized water and then dried under a stream of nitrogen gas.

the refractive index Θ tested result Example 1 1:58 14 ° Yes Example 2 1.68 23 ° Yes Example 3 1.71 27 ° Yes No Example 4 1.75 31 ° No

TABLE 1

From these data, the most interesting coating layers are those with the lowest refractive index less than 1.70. These are the ones that have the best absorbency and most of which are oxygen.

5-7. EXAMPLES

In these examples, a Planilux-type glass was used to which a SiOC coating layer was applied at a thickness of 50 nm using the procedure of the previous example. Table 2 below shows these refractive indices (the glasses were cleaned before applying the coating layer, as above).

the refractive index Example 5 1.68 Example 6 1.58 Example 7 1.71

TABLE 2

96837-15265 Sps / str • ·

1-3. Fig. 5A shows a scanning electron microscope (MEB) negative of the surface of the coating layer of Example 5 at three different magnifications. We can see a special porous surface with small irregular bladder-like and quite flat-shaped blisters. The largest magnification of Figure 3 shows "blisters" based on the largest dimension between 60-80 and 100-110 nm.

These are compared to Comparative Example 8 from uncoated Planilux glass:

with a laboratory test ('lab test') where they were stored for 1.6 to 14 days at 1 -4. in the atmosphere described in Examples 1 to 5, at a relative humidity of 30 ° C and 95%, in an industrial site in an open-air environment ('industrial site test') where they were stored for 1 to 10 days at 30 ° C, 95% RH atmosphere.

The results (expressed as "YES" and "NO" as in Table 1) are summarized in Tables 3 and 4 below:

LABORATORY TEST

One day 6 days 14 days Example 5 Yes Yes Yes Comparative 8 example Yes No No

TABLE 3

INDUSTRIAL SITUATION TEST

One day 10 days Example 6 Yes Yes Example 7 Yes Yes Comparative Example 8 Yes No

TABLE 4

96837-15265 Sps / str

These results show that the coating layers according to the invention have a durable "de-icing" effect, with which the uncoated glass has only a very temporary character.

Another study was conducted on Examples 6 and 7 and Comparative Example 8: the opacity of the transparency of the glass with coating layer according to Examples 6 and 7 and the uncoated glass of Comparative Example 8 was measured on a 10-day industrial site. , after storage outdoors (the opacity of the transparency reflects the diffuse light transmittance, expressed as a percentage in a known manner).

The results are as follows: Examples 6 and 7 showed limited blurring after 10 days, which was below 1%, whereas Comparative Example 8 showed significant blur after 10 days (at least 5%) on the glass caused by the accumulation of dirt. This assay demonstrates the anti-dirt effect of the coating layers according to the invention.

EXAMPLE 9

This example refers to a glass with sun protection function, marketed under the name "Antélio clair" by Saint-Gobain Glass France.

This is a 6 mm Planilux glass, which is coated in a known manner in a liquid phase by pyrolysis with a coating of a mixture of Fe, Co, Cr oxides at a thickness of about 45 nm.

According to the invention, a thin coating layer based on SiO 2 is applied to the mixed oxide coating layer by a sol-gel process. In this case, the sol consists of 2 propanol as solvent and 0.3 M hydrochloric acid solution in water and tetraethyl orthosilicate (TEOS).

The coating layer is applied and solidified in a conventional manner. The resulting coating layer has a thickness of less than or equal to 20 nm and a refractive index of about 1.45.

The contact angle measurements were carried out in comparison with Comparative Example 10, which was formed by the single Antélio glass product with the glass / Fe, Co, Cr oxide composition.

In comparative examples 9 and 10, the following operations were performed in series:

(a) cleaning, as above, treatment with ozone and ultraviolet light to remove carbonaceous materials absorbed on the surface of the coating layer, (b) free-standing for 2 days,

96837-15265 Sps / Str • 9 · * * * * · ···· (c) 19 day aging in free space, (d) cleaning test as above.

After each step, changes in the angles of contact with water were measured. The results are shown in Table 5 below:

EXAMPLE 9 10. COMPARATIVE EXAMPLE 0 (a) 17 ° 5 ° Θ (b) 32 ° 53.1 ° © (c) 42 ° 79.3 ° Θ (d) 24 ° 71 °

TABLE 5

From these data, it can be seen that, in Comparative Example 10, the contact angle Θ is rapidly increasing in the open space, and that with standard cleaning we could not restore a smaller contact angle. On the contrary, Example 9 is much less dirty, its contact angle with water remains relatively low, even after several weeks, and, particularly interesting, impurities can be removed much faster after a standard cleaning: the glass product is easy to clean become.

EXAMPLE 11

This example relates to the application of a silicon-based and oxygen-based coating layer (optionally including other elements but only negligible amounts of contaminants). Applying the coating layer to "Planilux" glass as described in Figures 1-4. examples, starting with CVD, SiKt and an oxidizing compound, but without ethylene. This gave a 50 nm layer of silicon oxide coating and a refractive index of 1.50. The angle of contact with this water is shown in FIGS. measured by the measurements used in Examples 1 to 4, small (less than 10 °). The coating layer has the same "anti-evaporation" effect as the coating layers of Examples 1 and 2.

96837-15265 Sps / str

Claims (3)

PATIENT INDIVIDUAL POINTS
1/3
Ρ 0203217 • · · · · ··· ····
A transparent substrate coated with a layer of silicon derivative, particularly glass, characterized in that it comprises at least one of the base coating layers of a silicon-oxidized derivative of silicon on the surface, silicon oxide or silicon oxide containing less than stoichiometric silica, silicon oxide carbide. or is selected from silicon oxynitride and has an absorbent capacity.
Figure 2 · · · · · · · · · · · · · · · · · · ···· · · · ρ 020321>
• ·
3/3 βΗΙι iilei ββΙΙΙ. · <Ί υι # χ
300000 ΐοοηιβ Ο 5IOC BON 12 512
15KU 2mm * 5GR * Μ125Τ
3IOCBT4.TIF
2/3
A carrier according to claim 1, characterized in that the refractive index of the silicon derivative coating layer is from 1.45 to 1.80, preferably from 1.50 to 1.75, most preferably from 1.55 to 1.68.
Carrier according to claim 1 or 2, characterized in that the coating layer is applied by means of a slurry process or pyrolysis, preferably by pyrolysis by steam-phase CVD.
4. Referring to 1-3. Carrier according to one of Claims 1 to 3, characterized in that the outer surface of the coating layer is rough.
5. Carrier according to one of Claims 1 to 5, characterized in that the contact angle of the surface of the coating layer with water is less than 35 °, preferably less than or equal to 30 °, for example 15-20 'or less than or equal to 10 °.
6. Carrier according to one of Claims 1 to 3, characterized in that the oxygen concentration of the coating layer is increasing towards its outer surface.
7. A carrier according to any one of claims 1 to 4, characterized in that the outer surface of the coating layer has a high ratio of Si-O-H hydroxyl bonds.
8. Referring to Figures 1-7. A carrier according to any one of claims 1 to 3, characterized in that the coating layer has a thickness of at least 5 nm, preferably between 10 and 60 nm.
9. Carrier according to one of Claims 1 to 3, characterized in that the coating layer comprises the last coating layer in a composite coating comprising more than one thin layer, preferably non-reflective, sun protection or low specific emission.
10. References 1-9. A carrier according to any one of claims 1 to 3, characterized in that it is bent and / or hardened or softened before or after application of the coating layer.
96837-15265 Sps / str
11. Referring to Figs. Carrier according to one of Claims 1 to 3, characterized in that the silicon derivative contains at least one additive, preferably a metal such as aluminum, zinc or zirconium, relative to silicon.
12. Use of a carrier according to any one of claims 1 to 5 for the manufacture of glass products, comprising the use of "dewatering" and / or "degassing" and / or "dirt repellent" and / or easy-to-clean glass products, preferably for buildings and vehicles; and mirrors, in particular bathroom mirrors or rear-view mirrors, shower-glasses, glass doors and interior partitions, outdoor furniture, billboards, display screens.
The proxy;
Iroda Kft
96837-15265 Sps / str
20 02032 1 7
Figure 3
HU0203217A 1999-11-05 2000-10-31 Transparent substrate provided with a silicon derivative layer HU0203217A2 (en)

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