Coated products
Abstract
The invention relates to barrier coatings to prevent migration of alkali metal ions from a glass surface. The barrier coatings are deposited by pyrolysis of a silane gas on the glass surface above 600 DEG C in the presence of a gaseous electron donating compound, whereby oxygen from the glass is incorporated with silicon to form a transparent barrier coating up to 50 nm thick on the glass surface. The barrier coatings are used to prevent migration of alkali metal ions into overlying layers sensitive to alkali metal ions e.g. in glass coated with electroconductive or infra red reflecting coatings, and in liquid crystal displays.

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Expired 9 August 2005, 21.1 years ago.
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18 claims: 5 independent, 13 dependent
- 1Patentkrav Patenttivaatimukset The claims 1. A method for reducing the diffusion of alkali metal ions from an alkali metal-containing glass to a top layer by applying a transparent barrier coating containing silicon and oxygen between the glass and the top layer and applying pyrolysis of silane gas, characterized in that the silane is pyrolyzed on the glass in the presence of an electron donating compound, when the ratio of the electron donating compound to the silane is such that that the oxygen from the glass combines with the silicon and a transparent barrier coating of not more than 50 nm is formed on the surface of the glass. 1. Förfarande för att minska diffusion av alkalimetalljoner frän glas innehällande alkalimetalljoner tili ett ovanpä beläget skikt genom att anordna mellan glaset och det ovanpä beläget skikt ett genomskinligt spärröverdrag, vilket innehäller kisel och syre och appliceras medelst pyrolys av en silangas, kännetecknat därav, att silanet pyrolyseras pä glasytan vid en temperatur över 600 °C i närvaro av en elektroner donerande gasformig förening, när förhällandet mellan den elektroner donerande föreningen och silanet är sädant, att syre frän glaset införlivas med kisel och pä glasytan bildas ett genomskinligt, högst 50 nm tjockt spärröverdrag. 1. Menetelmä alkalimetalli-ionien diffuusion vähentämiseksi alkalimetalleja sisältävästä lasista päällä olevaan kerrokseen sovittamalla lasin ja päällä olevan kerroksen väliin läpinäkyvä sulkupäällyste, joka sisältää piitä ja happea ja joka levitetään pyrolysoimalla silaanikaasua, tunnettu siitä, että silaani pyrolysoidaan lasin pinnalle yli 600 °C:n lämpötilassa kaasumaisen, elektroneja luovuttavan yhdisteen läsnäollessa, kun elektroneja luovuttavan yhdisteen suhde silaaniin on sellainen, että lasista peräisin olevaa happea yhtyy piin kanssa ja lasin pinnalle muodostuu läpinäkyvä, enintään 50 nm:n vahvuinen sulkupäällyste.
- 12Electrically conductive flat glass comprising a glass substrate containing alkali metal ions coated 12. Sähköä johtava tasolasi, joka käsittää alkalimetalli-ioneja sisältävän lasipohjan, joka on päällystetty 12. Elledande planglas, vilket omfattar ett glassubstrat, som innehäller alkalimetalljoner och som belagts 20 a transparent barrier coating not exceeding 50 nm in thickness containing silicon and oxygen by pyrolysis of silane gas, and an electrically conductive metal oxide layer on top of the transparent barrier coating having a resistivity of less than 500 ohms per square meter, characterized in that the silica gas is more than .25 ° C in the presence of a gaseous electron donating compound, when the ratio of electron donating compound to silane is such that oxygen from the glass coincides with silicon and forms. 30 guarantees a transparent barrier coating on the surface of the glass. 20 läpinäkyvällä sulkupäällysteellä, jonka paksuus on enintään 50 nm ja joka sisältää piitä ja happea, pyrolysoimalla silaanikaasua, ja läpinäkyvän sulkupäällysteen päällä olevalla sähköäjohtavalla metallioksidikerroksella, jonka ominaisvastus on alle 500 ohmia neliötä kohden, t u n .25 n e t t u siitä, että silaanikaasu on pyrolysoitu lasin pinnalle yli 600 °C lämpötilassa kaasumaisen, elektroneja luovuttavan yhdisteen läsnäollessa, kun elektroneja luovuttavan yhdisteen suhde silaaniin on sellainen, että lasista peräisin olevaa happea yhtyy piin kanssa ja muodos. 30 taa lasin pinnalle läpinäkyvän sulkupäällysteen. 20 med ett genomskinligt spärröverdrag, vilket har en tjocklek av högst 50 nm och innehäller kisel och syre, genom att pyrolysera en silangas och med ett ovanpä det genomskinliga spärröverdraget beläget elledande metalloxidskikt vars specifika ledningsförmäga är under 500 ohm per kva25 drat, kännetecknat därav, att silangasen pyrolyserats pä glasytan vid en temperatur över 600 °C i närvaro av en gasformig, elektroner donerande förening, när förhällandet mellan den elektroner donerande föreningen och silanet är sädant, att syre frän glaset införlivas 30 med kisel och bildar pä glasytan ett genomskinligt spärröverdrag .
- 13IR-reflecting flat glass comprising a glass substrate containing alkali metal ions coated with a transparent barrier coating to a thickness of not more than 50 nm containing silicon and oxygen by 13. IR-heijastava tasolasi, joka käsittää alkalimetalli-ioneja sisältävän lasipohjan, joka on päällystetty läpinäkyvällä sulkupäällysteellä enintään 50 nm:n paksuuteen, joka sisältää piitä ja happea, suorittamalla si- 13. IR-reflekterande planglas, vilket omfattar ett glassubstrat, som innehäller alkalimetalljoner och som belagts med ett genomskinligt spärröverdrag i en tjocklek av 35 pyrolysis of lane gas, and with a layer of IR-reflective doped metal oxide on top of a transparent barrier coating, characterized in that the silane gas is pyrolyzed on the glass surface at a temperature above 600 ° C in the presence of a gaseous electron donating compound when the ratio of electron donating compound to silicon the oxygen in combination with the silicon and forms a transparent barrier coating on the surface of the glass. 35 laanikaasun pyrolyysi, ja läpinäkyvän sulkupäällysteen päällä olevalla, IR-heijastavalla seostetun metallioksidin kerroksella, tunnettu siitä, että silaanikaasu pyrolysoidaan lasin pinnalle yli 600 °C:n lämpötilassa kaasumaisen, elektroneja luovuttavan yhdisteen läsnäollessa, kun elektroneja luovuttavan yhdisteen suhde silaaniin on sellainen, että lasista peräisin olevaa happea yhtyy piin kanssa ja muodostaa lasin pinnalle läpinäkyvän sulkupäällysteen. 35 högst 50 nm, vilket innehäller kisel och syre, medelst py rolys av en silangas, och med ett ovanpä det genomskinliga spärröverdraget beläget IR-reflekterande metalloxidskikt med tillsats, kännetecknat därav, att silangasen pyrolyseras pä glasytan vid en temperatur över 600 ° C i närvaro av en gasformig, elektroner donerande förening, när förhällandet mellan den elektroner donerande föreningen och silanet är sädant, att syre frän glaset införlivas med kisel och bildar pä glasytan ett genomskinligt spärröverdrag.
- 14Use of a transparent barrier coating containing up to 50 nm of silicon and oxygen applied by pyrolysis of silane gas to reduce the diffusion of alkali metal ions from glass up to 2 mm thick, characterized in that the silane is pyrolyzed on the glass surface above 600 ° C in the presence of a gaseous electron donating compound the ratio of gaseous electron-donating compound to silane is such that that the oxygen from the glass combines with the silicon and forms a transparent barrier coating on the surface of the glass. 14. Enintään 50 nm paksun, piitä ja happea sisältävän, silaanikaasua pyrolysoimalla levitetyn, läpinäkyvän sulkupäällysteen käyttö vähentämään alkalimetalliionien diffuusiota enintään 2 mm paksusta lasista, tunnettu siitä, että silaani on pyrolysoitu lasin pinnalle yli 600 °C:n lämpötilassa kaasumaisen, elektroneja luovuttavan yhdisteen läsnäollessa, kun kaasumaisen, elektroneja luovuttavan yhdisteen suhde silaaniin on sellainen, että lasista peräisin olevaa happea yhtyy piin kanssa ja muodostaa lasin pinnalle läpinäkyvän sulkupäällysteen. 14. Användning av ett högst 50 nm tjockt, kisel och syre innehällande, medelst pyrolys av en silangas applicerat genomskinligt spärröverdrag för att minska diffusion av alkalimetalljoner frän ett högst 2 mm tjockt glas, kännetecknad därav, att silanet pyrolyserats pä glasytan vid en temperatur över 600 °C i närvaro av en gasformig, elektroner donerande förening, när förhällandet mellan den elektroner donerande föreningen och silanet är sädant, att syre frän glaset införlivas med kisel och bildar pä glasytan ett genomskinligt spärröverdrag.
- 18A liquid crystal display device comprising two opposing electrically conductive layers with a liquid crystal material therebetween and an alignment layer on each electrically conductive layer in contact with the liquid crystal material, the at least one electrically conductive layer resting on a glass substrate having a thickness of 2 mm or less and containing alkali metal ions, a transparent, not more than 50 nm thick, is arranged between the electrically conductive layer and the glass, silicon and oxygen barrier coating by pyranysis of silane gas, characterized in that the transparent barrier coating is applied to the glass surface by pyrolysis of silane gas at a temperature above 600 ° C in the presence of a gaseous electron donating compound when the ratio of electron donating compound to silane is the head coincides with the silicon and forms a transparent barrier layer on the surface of the glass. 18. Nestekidenäyttölaite, joka käsittää kaksi vastakkaista sähköä johtavaa kerrosta, joiden välissä on nestekideainetta, ja kohdistuskerroksen kummankin sähköä johtavan kerroksen päällä kosketuksessa nestekideaineen kanssa, jolloin vähintään toinen sähköä johtava kerros on lasipohjan varassa, jonka paksuus on enintään 2 mm ja joka sisältää alkalimetalli-ioneja, jolloin sähköä johtavan kerroksen ja lasin väliin on sovitettu läpinäkyvä, enintään 50 nm paksu, piitä ja happea sisältävä sulkupäällyste suorittamalla silaanikaasun pyrolyysi, tunnettu 5 siitä, että läpinäkyvä sulkupäällyste on levitetty lasin pinnalle pyrolysoimalla silaanikaasua yli 600 °C:n lämpötilassa kaasumaisen, elektroneja luovuttavan yhdisteen läsnäollessa, kun elektroneja luovuttavan yhdisteen suhde silaaniin on sellainen, että lasista peräisin olevaa hap10 pea yhtyy piin kanssa ja muodostaa lasin pinnalle läpinäkyvän estokerroksen. 18. Vätskekristallvisningsanordning, som omfattar tvä elledande skikt med ett vätskekristallämne mellan dessa och ett inriktningsskikt ovanpä vardera elledande skikt i kontakt med vätskekristallämnet, varvid ätminstone det ena av de elledande skikten är beläget pä ett glassubstrat, som har en tjocklek av högst 2 mm och som innehäl ler alkalimetalljoner, varvid ett genomskinligt, högst 50 nm tjockt, kisel och syre innehällande spärröverdrag anordnats mellan det elledande skiktet och glaset medelst pyrolys av en silangas, kännetecknad därav, 5 att det genomskinliga spärröverdraget applicerats ρΔ glasytan genom att pyrolysera silangasen vid en temperatur Over 600 °C i närvaro av en gasformig, elektroner donerande förening, när förhällandet mellan den elektroner donerande föreningen och silanet är sädant, att syre frän gla10 set införlivas med kisel och bildar ρΔ glasytan ett genomskinligt spärröverdrag.
Independent claims5
381 paragraphs in 13 sections, as filed
A method for reducing the diffusion of alkali metal ions from a glass to a layer on top thereof by means of a barrier coating containing silicon and oxygen, the use of a barrier coating and an electrically conductive flat glass containing a barrier coating, a reflective flat glass and a liquid crystal display device
The invention relates to the manufacture and use of glass having a coating which prevents the migration of alkali metal ions out of the surface of the glass, and to products containing such coated glass.
It is known that certain coatings on glass are degraded because alkali metal ions migrate from the surface of the glass to the coating. For example, GB patent 705934 describes the appearance of a veil on a transparent, electrically conductive coating on soda lime silicon glass. This veil can be reduced by removing alkali metal ions from the surface of the glass before attaching the electrically conductive coating or by attaching an intermediate film, e.g., silicon or titanium oxide film, before attaching the electrically conductive coating. Silicon films are prepared either by placing silicon tetrachloride or tetrabromide or silichloroform in a volatile, non-aqueous solution on glass and exposing it to the atmosphere until the coating is dry, and then rubbing it until the coating is clear, or by immersing the glass sheet in a solution containing partially hydrolyzed silicon. ethyl orthosilicate and drying.
EP 0 071 865 A3 also relates to the contamination of an electrically conductive coating on soda-lime silicon glass because alkali metal ions scatter on the surface of the glass and react with the alkali metal-sensitive layers on top. It addresses white turbidity in the electrically conductive layer, deterioration of transparency, increase in electrical resistance and deterioration of physicochemical resistance as possible consequences of such dispersion. It also addresses the pollution of liquid crystal display devices, electrochromic devices, and amorphous electrolyte photocells as a result of alkali metal ions migrating away from the glass substrate. Such devices generally have electrically conductive layers, e.g. indium tin oxide, on the glass, but EP 0 071 865 A3 refers to the effects (in addition to the possible direct effect that alkali metal ions have on the electrically conductive layer) following alkali metal ions and electrically the effect between the layers on top of the conductive layer. EP 0 071 865 A3 proposes to prevent the migration of alkali metal ions from a glass substrate by using a barrier layer which is silica containing hydrogen bound to silicon. The barrier layer can be prepared by vacuum evaporation, sputtering, ion plating, sol / gel methods or CVD methods, i.e. chemical evaporation. In the CVD methods described, the silica layers are vaporized on glass substrates under oxidizing conditions and temperatures of 300 to 550 ° C from oxygen gas and monosilane gas (SiH<sub>4</sub>) in relation to O<sub>2</sub>: SiH<sub>4</sub> in the range of 10: 1 to 60: 1.
GB Patent 2,031,756B discloses the use of layers of metal oxide, including silica, as color-damping layers that reduce the glare reflection colors of reflective infrared coatings on semiconductor metal oxides on glass. The semiconductor metal oxide may be tin oxide to which fluorine has been added, and the publication refers to the known effect of amorphous silica layers when used to prevent alkali metal ions from migrating through the glass, thereby avoiding the formation of a mist when the tin oxide layer is subsequently vaporized. The color attenuation layers used according to GB patent 2,031,756B have a refractive index of 1.7 to 1.8 and a thickness of 64 to 80 nm. Silica-containing layers can be prepared by chemical gas coating on hot glass at 300-500 °
At C using silane in combination with oxidizing gas.
GB Patent 1,507,465 describes a process for forming a reflective silicon coating on a flat glass to obtain an au5 rinko control glass having an aesthetically pleasing silver reflective color. The coating is formed by discharging silane gas into a hot zone open toward the surface of the glass and maintaining non-oxidizing conditions in this hot zone so that pyrolysis of the silicon and evaporation of the reflective silicon coating on the glass surface occurs. GB Patent 1,573,154 describes an improvement in the method described in GB Patent 1,507,645 for making a reflective sunglasses glass; in the improved process, an electron donating gas mixture, e.g., ethylene, is added to the silane-containing gas, resulting in a surprising increase in the durability of the coated glass with respect to the effects of external alkalis. The ratio of electron donating compound to silane is generally 0.1 to 2.0, preferably 0.2 to 0.5, although the publication mentions the use of a ratio of more than 2.5, e.g. 5, to obtain an alkali-resistant silicon coating which lasts consumption very well, but does not have the high reflection of visible light obtained in the absence of the electron donating mixture. These coatings are used on building glass and Examples 25 describe the preparation of a coating for 6 mm soda lime silicon glass and rolled glass. Examining the coatings obtained using ethylene as the electron donating compound, it was found that although they were prepared under non-oxidizing conditions, they contained some 30 oxygen.
It has now been found that thin, transparent coatings made in an environment involving a high proportion of an electron donating compound, such as that described in GB Patent 1,573,154, contain oxygen from glass and are surprisingly effective as examples of alkali metal removal from glass surfaces. against ion migration. The coated glasses thus obtained can be used as bases for overlay layers (which are either directly on top of the barrier layer or the interlayer) which are sensitive to alkali metal ions.
According to the invention, there is provided a method of reducing the diffusion of an early metal ion from an alkali metal-containing glass to a top layer by applying a transparent barrier coating containing silicon and oxygen between the glass and the top layer and applying pyrolysis of silane gas, which method is characterized by pyrolyzing At a temperature of C in the presence of a gaseous electron-donating compound, when the ratio of electron donating compound to silane is such that oxygen from the glass combines with silicon and a transparent barrier coating of up to 50 nm is formed on the surface of the glass.
As used herein, a transparent barrier coating refers to coatings which, when formed on clear float glass of a thickness not exceeding 6 mm, result in a coated glass having a light transmittance of at least 75%.
A layer sensitive to the diffusion of alkali metal ions from the glass can be subsequently applied to the barrier coating formed by the method according to the invention.
The layer sensitive to the diffusion of alkali metal ions from the glass may be a light-transmitting layer which is an alloyed metal oxide.
Electron donating compounds are compounds that contain electrons that can be delivered to the electronic structure of suitable acceptor molecules, either in bonds or as separate pairs of electrons. Electron-donating compounds containing electron-linked bonds include, for example, unsaturated hydrocarbons, especially olefins (alkenes) and acetylenes (alkynes), e.g., ethylene, butadiene, pentene, difluoroethylene and acetylene (C<sub>2</sub>B<sub>2</sub>), and aromatic hydrocarbons such as benzene and xylene. Electron donating compounds containing their donated electrons in separate pairs include, for example, ethers, amines, aldehydes, ketones, alcohols, nitrogen hydrides, carbon monoxide and carbon dioxide. For simplicity, it is preferred to use electron donor compounds that are gaseous under ambient conditions, but other electron donor mixtures may be used without great difficulty provided that their vapor pressure is at least 5 kPa at 60 ° C.
When an electron donating compound is used, the result is that, in an unknown manner, the oxygen from the glass combines with the silicon from the silane to form a transparent barrier coating on the glass. Although the mechanism is not understood, it is believed to involve the adsorption of an electron donating compound on the glass surface.
Thus, although the pyrolysis can be performed in the absence of oxygen-containing gases, a transparent coating containing silicon and oxygen from the glass is obtained, and not a reflective silicon coating.
The efficiency of the migration of oxygen-containing components from the glass depends on the temperature of the glass and the coating is therefore formed on the glass at a temperature above 600 ° C in order to make more oxygen-containing components available from the glass. Not all of the oxygen in transparent barrier coatings is necessarily from the glass, but may be in part from the electron donating compound, and some oxidation may still occur when the coated glass is exposed to atmospheric oxygen after coating. However, it is preferred to use electron donating compounds that are oxygen-free or oxygen-free, although slightly oxygenated, and are generally considered to be reducing agents, e.g., carbon monoxide and alcohols. It is generally preferred to avoid the use of oxygen-containing gases that react with the silane before it reaches the hot glass surface to form powdery layers of silica. In particular, the presence of molecular oxygen should be avoided.
In a preferred embodiment of the invention, the electron donating compound is oxygen-free. Useful oxygen-free, electron-donating compounds include e.g.
unsaturated hydrocarbons, aromatic hydrocarbons and amines and nitrogen hydrides.
Due to the limited amount of oxygen-containing components derived from glass, the thickness of transparent coatings made using oxygen-free electron donating compounds is limited, and silicon and oxygen-containing transparent barrier coatings having a thickness of up to 50 nm are obtained according to the invention.
The ratio of electron donating compound to silane required to obtain a transparent coating depends on the electron donating compound used and can be easily determined by a simple experiment in which the ratio of electron donating compound to silane is increased until a satisfactory light-transmitting coating is obtained. Suitable ratios of electron donating gaseous compound and silane are generally in the range of 0.5: 1 to 15: 1 by volume. It has been found that the best results are obtained when using an olefin when the ratio of olefin: silane is in the range of 3: 1 to 10: 1.
It has been found that the use of too many certain oxygen-free, electron-donating compounds relative to the silane prevents the formation of a coating, so this should be avoided. The proportion that is too high depends on the electron donating compound used, but can be easily determined experimentally.
Since the transparent barrier layers used in the present invention can be made in the absence of free oxygen and compounds generally considered oxidizing agents, a barrier coating can be formed on the floating glass strip as it is fed forward over the molten metal bath in which it is formed without significant risk of molten metal oxidation. . It is preferably formed when the temperature of the glass is in the range of 600 to 750 ° C, especially 600 to 700 ° C.
Barrier coatings can be formed using the laminar flow method and apparatus described in GB Patent 1,507,465. The silane used is preferably a monosilane and is mixed with an inert gas, e.g., nitrogen.
The coatings used in the invention are very effective barriers to the migration of alkali metal ions, with coatings as thin as 15 nm giving excellent results, and even thinner coatings, e.g. 5 nm thick or even thinner, have useful barrier properties.
In some applications, high transparency is required, and coatings that provide at least 80% light transmission with clear float glass up to 6 mm thick are preferred. In addition, in some applications, it is desirable for the barrier coating to be highly resistant to external alkalis. It has been found that coatings prepared in the presence of organic, electron donating compounds contain significant amounts of carbon and are highly resistant to external alkalis.
Once the barrier coating is vaporized, a layer is formed on it that is sensitive to the migration of alkali metal ions from the glass. Such a layer can be prepared in a known manner, e.g. by sputtering, chemical evaporation or by spraying liquid or solid reactants on the coated surface.
Barrier-coated glasses are used in accordance with the invention to reduce the migration of alkali metal ions from alkali metal ions to an overlay layer that is sensitive to alkali metal ions and may be directly on top of the barrier coating or on the interlayer. The topsheet may be a light transmissive, electrically conductive metal oxide coating. The resistivity of such commercially used coatings is generally less than 500 ohms per square; some applications require much lower resistivity, e.g., less than 50 ohms per square, and use coatings with the lowest resistivity possible, taking into account satisfactory optical properties. According to the above-mentioned EP 0 071 865 A3, such coatings are susceptible to contamination when alkali metal ions diffuse from the underlying glass base, which impairs light transmission and electrical conductivity. Light-transmitting, electrically conductive metal oxides include, for example, doped metal oxides, including tin-doped indium oxide, which is usually prepared by sputtering, and doped tin oxides, especially fluorine-doped tin oxide, which can be prepared by sputtering or chemical vapor deposition or chemical vapor deposition. The thickness of the electrically conductive layer depends on the desired conductivity, but is generally in the range of 50 to 1500 nm.
Transparent, electrically conductive metal oxides, e.g., tin-doped indium oxide and fluorine-doped tin oxide, usually reflect infrared radiation, so they can be used as window glass coatings to reflect heat back into the building. When these coatings are used as infrared reflective layers, their thickness is generally in the range of 200 to 1000 nm.
According to the invention, there is thus further provided an electrically conductive flat glass comprising a glass substrate containing alkali metal ions coated with a transparent barrier coating having a thickness of not more than 50 nm.
89160 and containing silicon and oxygen, by pyrolysis of silane gas, and an electrically conductive metal oxide layer on a transparent barrier coating having a resistivity of less than 500 ohms per square, characterized by the presence of silane gas pyrolyzed on the surface of the glass , when the ratio of electron donating compound to silane is such that that the oxygen from the glass combines with the silicon and forms a transparent barrier coating on the surface of the glass. The electrically conductive metal oxide layer may be a light-transmitting layer and consist of a doped metal oxide.
In addition, according to the invention, there is provided an infrared reflective flat glass comprising a glass substrate containing alkali metal ions coated with a transparent barrier coating to a thickness of up to 50 nm containing silicon and oxygen by pyrolysis of a silane gas with a metal barrier layer characterized by flat glass, that the silane gas is pyrolyzed on the glass surface at a temperature above 600 ° C in the presence of a gaseous electron donating compound, the ratio of the electron donating compound to the silane being such that the oxygen from the glass combines with silicon to form a transparent barrier coating on the glass surface.
Barrier-coated glasses have additional advantages when used in more complex systems, e.g., as substrates for electrically conductive metal oxide coatings in liquid crystal display devices. Accordingly, the invention also relates to a liquid crystal display device comprising two opposing electrically conductive layers with a liquid crystal material therebetween and an alignment layer on each electrically conductive layer in contact with the liquid crystal material, the at least one electrically conductive layer resting on a glass substrate having a thickness of up to 2 mm -ions with a transparent thickness not exceeding 50 nm between the electrically conductive layer and the glass, a silicon and oxygen barrier coating by performing pyrolysis of the slag gas, wherein the transparent barrier coating is applied to the glass surface by pyrolyzing silane gas at a temperature above 600 ° C in the presence of a gaseous electron donating compound when the ratio of electron donating compound to silane is such that forms a transparent barrier layer on the glass surface. In such cases, the barrier coating not only protects the electrically conductive metal oxide layer from the direct action of alkali metal ions from the glass, but also prevents harmful electrochemical reactions resulting from the dispersion of alkali metal ions through the electrically conductive metal oxide layer into the liquid crystal material.
Transparent, barrier-coated glasses can also be used as transparent outer layers in amorphous silicon solar cells, where the migration of alkali metal ions out of the glass surface into the amorphous silicon reduces the efficiency of the cell.
The barrier coatings made in accordance with the present invention are very effective in controlling the migration of alkali metal ions, and because they are effective in very thin layers, they can be formed into a barrier-coated glass that transmits visible light well. Because the coatings contain oxygen from the glass, they do not require the use of strongly oxidizing conditions and are suitable for commercial manufacture directly on the float glass strip as it passes over the bath.
Transparent barrier coatings prepared according to the invention using ethylene were examined by infrared spectroscopy to detect Si-H bonds, in which no infrared absorptions corresponding to Si-H bonds were observed.
The following examples illustrate the invention but do not limit it. Unless otherwise stated, gas volumes were measured at ambient conditions, i.e. at a temperature of about 20 ° C and 1 atmospheric pressure.
Examples A 1-4 mm float glass strip was coated to a width of 3 m with a barrier coating as it progressed over the bath by passing a mixture of a mixture of monosilane (10% v / v) and nitrogen (90% v / v) fed at 50 l / min and 10 l / min fed ethylene, parallel to the glass surface under laminar flow conditions, as described in GB Patent 1,507,996. The temperature of the glass at the coating station was 625 ° C and the Lehr velocity of the glass strip was 350 m / h. The ethylene flow rate was then increased and barrier coatings were made at ethylene flow rates of 20, 30, 40 and 50 l / min.
Table 1 shows the ethylene: silane ratios of the coating gases and the measurement results of the prepared coatings.
The use of ethylene causes a reduction in light reflection and a rapid increase in light transmission up to an ethylene: silane ratio of about 4: 1. When the ethylene: silane ratio is further increased, the result is a continuous but slower increase in light transmission in the product.
The effectiveness of the coatings as barriers to the diffusion of alkali metal ions from the glass surface was determined as described below.
Two samples of coated glass, each 10 x 10 cm<sup>2</sup>, were cut and compressed with a silicone rubber ring therebetween having an inner diameter of 8.5 cm to form a cylindrical cell whose walls formed the coated surface of the glass and the inner surface of the silicone rubber ring. The cell was filled with deionized ve
891 60 through the hole in the rubber ring, the hole was closed and the sealed cell was immersed in a water bath at 96 ° C for 48 hours. The solution was removed and analyzed for sodium content by flame emission spectroscopy. The amount of dissolved sodium was determined and expressed as Na<sub>2</sub>0 micrograms of glass dm exposed to water in the cell<sup>2</sup>per.
The test was also performed with several commercially available soda-lime silica glasses with ion-blocking surface layers of silica. The results obtained were 60 micrograms of Na<sub>2</sub>O / dm<sup>2</sup> more than 1000 micrograms Na2O / dm<sup>2</sup>. In addition, uncoated, commercially available glass that was nominally alkali-free was tested to give a result of 13 mg Na2O / dm<sup>2</sup>.
It can be seen from the results that the coated glass according to the invention is advantageous over commercially available, nominally alkali-free glasses and coated glasses, which are believed to be made by separate methods which cannot be easily adapted for direct coating of float glass.
91 60
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<td>s</td><td> «.</td><td> 0.</td><td></td><td>K</td>
<td>V</td><td>(OF</td><td>rH</td><td>CD</td><td>C/O</td>
<td>CD</td><td>rH</td><td>T-1</td><td></td><td></td>
<td>m</td><td>C/O</td><td>in</td><td>o</td><td></td>
<td>o-</td><td>pH</td><td>CD</td><td>C/O</td><td> >*</td>
<td><o</td><td>C/O</td><td>C/O</td><td> 00</td><td> 00</td>
c φ Ό x:: (0 C
Φ CO Φ Φ PP • H oca • H ac • H
CO to i P • HO cc • H o.
<0 Λ c ω Φ 3 Φ 3 P CO \ -H
I -HC -H Φ C <0 H Ό φ (0 O JS Φ HO 3 P -HX CO Φ CO e • H
CO w
<td>o</td><td>o</td><td>CD</td><td>o</td><td></td>
<td>in</td><td>in</td><td>C/O</td><td>C/O</td><td>pH</td>
o
XO PP Φ Ό x: «o rI coi — I <0>
I ω HO
Cd V
<img file="FI89160B_D0003.tif" />
<img file="FI89160B_D0004.tif" />
<img file="FI89160B_D0005.tif" />
rd rl <0 P ρ Φ>
<img file="FI89160B_D0006.tif" />
<img file="FI89160B_D0007.tif" />
m
XO PP> 1 X0>.
PP Φ P • rl P X0 X0 X on the opposite side.
39160
The product of Example 3 was examined by electron spectroscopy of chemical studies. In this method, the surface to be examined is irradiated with X-rays and the elements on the surface are identified and quantified by examining the energy spectrum of the primary electrons emitted from the surface. The surface atomic layers are then removed by argon etching to expose the atoms below the surface, and then these are identified and quantified as described above. The etching and examination10 steps are repeated to form a profile of the composition of the surface layers to a depth that exceeds the thickness of the coating.
The results obtained for the product of the example are given below.
<td>L5</td><td>etching (Seconds)</td><td> 0</td><td> 300</td><td> 600</td><td> 900</td><td> 1200</td><td> 1500</td>
<td></td><td>Atomic% silicon</td><td> 20</td><td> 35</td><td> 36</td><td> 37</td><td> 37</td><td> 35</td>
<td></td><td>Atomic% oxygen</td><td> 31</td><td> 45</td><td> 39</td><td> 35, 5</td><td> 37</td><td> 43</td>
<td> 20</td><td>Atomic% carbon</td><td> 45, 5</td><td> 17</td><td> 22</td><td> 24</td><td> 20</td><td> 15</td>
The coating was found to contain silicon, oxygen and carbon. The ratio of oxygen to silicon on the surface of the coating is about 3: 2. It drops to about 1: 1 after 900 seconds of etching and increases later. The carbon content in the surface is 45% and varies by about 20% over the entire thickness of the coating.
Examples 5 and 6 mm A float glass strip was coated with a transparent barrier coating of silicon and oxygen as it progressed over the bath by applying a mixture of monosilane, nitrogen and ethylene parallel to the glass surface under laminar flow conditions as described in GB Patent 1,507,996. ° C and the Lehr speed of the glass strip was 1030 m / h.
Table 2 shows the gas flows and the characteristics of the products obtained.
The resulting coatings had useful ion barrier properties. The light transmittance increased with increasing ratio of ethylene to silane 5, giving a light transmittance of 84.9% at a ratio of 3.3: 1. The calculations showed that the light transmission of 1 mm glass with a similar coating would be 85.4% compared to 91.4% light transmission of uncoated 1 mm glass.
CM
Table
I
I -rl
<td>•B</td><td>r-1</td><td>c</td><td>•B</td><td><n</td>
<td>rH</td><td>i <</td><td>Φ</td><td>P</td><td>E</td>
<td> <0</td><td> <0</td><td>•B</td><td>c</td><td>Ό</td>
<td>X</td><td>P</td><td>c</td><td> <0</td><td> \</td>
<td>r-i</td><td>Φ</td><td> 0</td><td><Ö</td><td>CD</td>
<td> <</td><td>E</td><td>•B</td><td>CD</td><td>E</td>
<td>c</td><td>1 CD <0</td><td> <*></td><td></td><td></td>
Ο τι.
rH Ή CD CO Φ 3> x -pco r-4 (0>
<img file="FI89160B_D0008.tif" />
<td colspan="2"></td><td>•B</td><td>• HG</td>
<td>•B</td><td>Φ</td><td>c</td><td> (0</td>
<td>"B</td><td> 75</td><td>Φ</td><td> <0</td>
<td colspan="2"> 0 £</td><td>Φ</td><td>r-1</td>
<td> 0</td><td> 3</td><td>• P</td><td>•B</td>
<td></td><td>CD</td><td>Φ</td><td>CD</td>
<td></td><td> 1</td><td></td><td>E</td><td></td><td></td>
<td>c</td><td>CD</td><td></td><td> \</td><td></td><td> <·></td>
<td>B</td><td> 5</td><td>CD</td><td>G</td><td></td><td>CD</td>
<td>c</td><td> (0</td><td> 3</td><td>•B</td><td>G</td><td></td>
<td>Φ</td><td>P</td><td>Φ</td><td>E</td><td>•B</td><td>Φ</td>
<td>Φ</td><td>P</td><td colspan="2">a \</td><td>CD</td><td> ></td>
<td>P</td><td>•B</td><td> 0</td><td>rH</td><td>C/O</td><td>Φ</td>
<td>ω</td><td> ></td><td>c</td><td></td><td> <—1</td><td>r-1</td>
<td>G</td><td> 1</td><td></td><td>E</td><td></td>
<td>•B</td><td>CD</td><td></td><td>X0 \</td><td>^ * X</td>
<td>G</td><td> 3</td><td>CD</td><td>CD G</td><td>CD</td>
<td> (0</td><td> (0</td><td> 5</td><td>CD Ή G</td><td> >1</td>
<td> <0</td><td>• P</td><td>Φ</td><td>Φ E -H</td><td>Φ</td>
<td>r-1</td><td>P</td><td colspan="2">aa \ cd</td><td> ></td>
<td>•B</td><td>•B</td><td> 0</td><td> (0</td><td>Φ</td>
<td>ω</td><td> ></td><td>G</td><td></td><td>B</td>
<td> 1</td><td colspan="2">CD 3</td>
<td>•B</td><td> 3</td><td>xo</td>
<td>G</td><td>C/O</td><td>CD dp</td>
<td> (0</td><td>rl</td><td>CD 1</td>
<td> <0</td><td> 0</td><td>Φ H</td>
<td> <—1</td><td>P</td><td>am</td>
<td>B</td><td>rl</td><td>> iP</td>
<td>ω</td><td colspan="2">ap -</td>
£ • rl CD ω
<img file="FI89160B_D0009.tif" />
<img file="FI89160B_D0010.tif" />
<img file="FI89160B_D0011.tif" />
<img file="FI89160B_D0012.tif" />
LD 0 \ xxo <1 · O 00 n co
C4 CO
<img file="FI89160B_D0013.tif" />
<img file="FI89160B_D0014.tif" />
oo co co in in
<img file="FI89160B_D0015.tif" />
<img file="FI89160B_D0016.tif" />
C a) Ό x: * oc
<img file="FI89160B_D0017.tif" />
Φ Φ PP • H • H a
C • rl
CD <0
O
X0 PP Φ 75 £ X0 i — I co r-1 io> I ω H o
<img file="FI89160B_D0018.tif" />
Determined as described in Examples 1-4.
Examples 7-9
The 1.3 mm float glass strip was coated with a barrier coating containing silicon and oxygen as it progressed over the bath by passing a mixture of monosilane, nitrogen and ethylene parallel to the glass surface under laminar flow conditions as described in GB Patent 1,507,996. The glass temperature at the coating station was 640 ° C. and the leaf speed of the glass strip was 1200 m / h.
Table 3 shows the gas flows and the properties of the products obtained.
Although the deionization performance (measured by alkali metal ion uptake tests) was not the same as the excellent performance of the previous examples, it was comparable to commercially available glasses and satisfactory in commercial application. The light transmission of the products was high (about 90%).
Examples Static samples of 10-13 mm float glass were coated in the laboratory by applying a coating gas consisting of a mixture of nitrogen, 10% monosilane on nitrogen and an electron donating gaseous compound over a heated glass surface. Table 4 shows the compositions of the coating gases used, the glass temperatures and evaporation times, and the properties of the coated glass products.
It can be seen that the use of other electron donating gaseous compounds instead of ethylene gives transparent coatings with the same deionizing properties. The coatings are transparent and contain silicon and oxygen from glass.
39160 -I
B
B
O * /
H (0
<img file="FI89160B_D0019.tif" />
<td></td><td></td><td> 1</td><td>Ή</td><td> ♦</td>
<td></td><td></td><td>Ή</td><td>rd</td><td>GH rs</td>
<td></td><td></td><td>rd</td><td>r-1</td><td>Φ -PE</td>
<td></td><td></td><td> <0</td><td> <0</td><td>• HC Ό</td>
<td></td><td></td><td>Λ</td><td>P</td><td>C (0</td>
<td>iO</td><td>O</td><td>r-1</td><td>Φ</td><td>0 <0 O</td>
<td>C/O</td><td>o</td><td> <</td><td>E</td><td>• h ω E</td>
<td></td><td></td><td></td><td></td><td></td>
<td colspan="3"></td><td>B</td><td>CD</td>
<td>C/O</td><td></td><td>m</td><td> 1 (0</td><td></td>
<td>K</td><td>K</td><td></td><td>to Jd</td><td></td>
<td> 00</td><td>C/O</td><td> 00</td><td>> D'H</td><td></td>
<td></td><td></td><td></td><td colspan="2">p ro x</td>
<td></td><td></td><td></td><td>> d CD</td><td>Φ</td>
<td></td><td></td><td></td><td colspan="2">O CD</td>
<td></td><td></td><td></td><td>XP</td><td></td>
<td>O</td><td>rH</td><td></td><td></td><td></td>
<td>S</td><td>K</td><td>K</td><td></td><td>o</td>
<td>σ></td><td>o</td><td>o</td><td>c</td><td>1 O</td>
<td>C/O</td><td>I do not</td><td>I do not</td><td>c ro</td><td>•• o</td>
<td></td><td></td><td></td><td>• H c</td><td>a ro</td>
<td></td><td></td><td></td><td>to c</td><td>EH</td>
<td></td><td></td><td></td><td>ro -h</td><td>• CO -H</td>
<td></td><td></td><td></td><td colspan="2">P) QH p</td>
<td></td><td></td><td></td><td>1 • rl 1</td><td></td>
<td>i-1</td><td>rH</td><td>F-I</td><td>ω -h</td><td>Φ</td>
<td></td><td></td><td></td><td>\ c</td><td>Ό</td>
<td>ω</td><td>C/O</td><td>LO</td><td>o ro</td><td>Λ</td>
<td>K</td><td>K</td><td></td><td>Q ro</td><td> 3</td>
<td>C/O</td><td>C/O</td><td></td><td>ω h</td><td>CD</td>
CO Cd <-1 Cd
O CO
O> D cr>
CO rd r — i co <D CO
00 o <o
<td>o</td><td>O</td><td>C/O</td><td>in</td>
<td>C/O</td><td>C/O</td><td>m</td><td>CD</td>
<td>ID</td><td>vD</td><td>\ O</td><td><D</td>
o rd O in
- o ID rd
<td>"-B</td><td>o</td><td>ID</td><td>m</td>
<td>rH</td><td>o</td><td>O</td><td>o</td>
<td></td><td> «.</td><td>K</td><td></td>
<td>o</td><td>o</td><td>o</td><td>o</td>
<img file="FI89160B_D0020.tif" />
<img file="FI89160B_D0021.tif" />
No '
<img file="FI89160B_D0022.tif" />
<img file="FI89160B_D0023.tif" />
o 'rd in rd ID o' o '
<td colspan="4" rowspan="2"></td><td colspan="2">CM ® X0</td>
<td>df</td><td>ω w</td>
<td>in</td><td>tn</td><td>in</td><td>in</td><td></td><td></td>
<td>K</td><td></td><td></td><td>K</td><td>O</td><td>CM</td>
<td>kD</td><td>iD</td><td>iD</td><td>twist r</td><td>i-1</td><td>z</td>
<td></td><td>CD</td><td></td>
<td> 1</td><td> 5</td><td></td>
<td>•B</td><td> 3</td><td>.ro</td>
<td>c</td><td>CD</td><td>CD <*></td>
<td> (0</td><td>•B</td><td>CD 1</td>
<td> (0</td><td> 0</td><td>Φ rd</td>
<td>T-1</td><td>P</td><td>Ο. Ή</td>
<td>• rl</td><td>• rl</td><td>> P</td>
<td>ω</td><td colspan="2">O. P -</td>
e • H en ω
Co 'co en
E • H (D ω • rd <D Φ i »0 Φ CD Φ m rd φ> ι a 0)> <λ: p <*>« j • H rd C • H Jd Ji <0 • rd co (0
<img file="FI89160B_D0024.tif" />
o
<img file="FI89160B_D0025.tif" />
<img file="FI89160B_D0026.tif" />
Cd CO., LTD
<img file="FI89160B_D0027.tif" />
<img file="FI89160B_D0028.tif" />
Determined using a CIE light source C on the opposite side of the glass coating.
Determined as described in connection with Examples 1-4.
Examples Static samples of 14-16 mm float glass were coated in the laboratory by passing a coating gas containing 6.6 l / min nitrogen, 0.4 l / min 10% v / v monosilane in nitrogen and 0.4 l / min ethylene over a heated glass surface at 630 ° C for 10 to 40 seconds. Table 5 shows the times used and the properties of the coatings obtained.
The observed light reflection of the coated glass increases with the coating time, so that the coating obtained after 80 seconds has the same appearance as reflective coatings made using only small amounts of ethylene.
Table 5
Eg Coating - Light transmission * Thickness nm time (sec)%
<td> 14</td><td> 10</td><td> 89,0</td><td> 19</td>
<td> 15</td><td> 20</td><td> 85,2</td><td> 28</td>
<td> 16</td><td> 40</td><td> 79,2</td><td> 39</td>
<td>COMPARATIVE</td><td> 80</td><td> 55,2</td><td> 74</td>
Determined using CIE light source C on the side opposite to the glass coating
This series of experiments shows that as the coating time increases and the thickness of the coating increases, the oxygen obtained from the glass becomes consumed and the vaporized coating loses its transparency. This is believed to be due to the deposition of non-oxidized silicon on its first formed, transparent coating containing silicon and oxygen from glass. The resistance of all coatings to the effect of extraneous alkali was tested by immersing them in 1N NaOH solution at 80 ° C. In any case, there was no visible sign of effect after 50 minutes.
Examples Static samples of 17-33 mm float glass were coated in the laboratory by passing the coating gas over a hot glass surface at a temperature of 630 ° C. Table 6 shows the composition of the coating gas used, the coating time and the properties of the coated products. In each case, the ratio of the electron donating gaseous compound to the silane was adjusted to obtain a transparent coating.
r O
0) PO □ a
Eg Electrons Gas flow- Mole- Coating- Light thickness Alkali- Alkali-donating backgrounds (1 / min) ratio time of transmission * nm metal resistance
<td>s</td><td></td>
<td>Φ</td><td>Fri</td>
<td>P</td><td>C Ό</td>
<td>a</td><td>C/O</td>
<td>o</td><td>CO 0 £</td>
<td>B</td><td>me</td>
•B
W -H ·· co rt Q rt M rt
CM Z
O
QS oa) en
<img file="FI89160B_D0029.tif" />
<td rowspan="2"></td><td rowspan="2">and m</td><td colspan="7">σ σ mm <ro <N</td><td colspan="2" rowspan="2">00 1 CM</td><td colspan="6">· - <ooomo</td>
<td>I do not</td><td colspan="3">H (NN</td><td></td><td>CM</td><td>CM</td><td>CM</td><td>m</td><td><T</td><td>m</td><td>sr</td><td> <</td>
<td><r</td><td>o</td><td>O '</td><td>sr</td><td>o</td><td>ST</td><td>XD</td><td>un</td><td>O</td><td>O</td><td>un</td><td>Ό</td><td>o</td><td>un</td><td>o</td><td>o</td><td>un</td>
<td> 00</td><td>un</td><td> 00</td><td>O '</td><td>r *</td><td>O '</td><td>O '</td><td>o</td><td>O '</td><td>O</td><td>O '</td><td> 00</td><td>o</td><td>o</td><td>O '</td><td>B</td><td> 00</td>
<td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td> 00</td><td>O '</td><td> 00</td><td> 00</td><td>r * ·</td><td> 00</td><td> 00</td><td>O '</td><td> 00</td><td>O '</td><td> 00</td>
<td>o</td><td>m</td><td>P</td><td>R-4</td><td>CM</td><td>CM</td><td>CM</td><td>O</td><td>CM</td><td>O</td><td>CM</td><td>CM</td><td>O</td><td>«P</td><td>r *.</td><td>o</td><td>CM</td>
<td>"-B</td><td>»P</td><td>•-B</td><td>»P</td><td></td><td><P</td><td>tp</td><td>O '</td><td>rd</td><td>r * ·</td><td><P</td><td>rH</td><td>Ό</td><td>• P</td><td></td><td><T</td><td></td>
<td></td><td></td><td></td><td>r</td><td></td><td>un</td><td>xO</td><td></td><td>O</td><td>un</td><td>m</td><td>r</td><td><r</td><td>un</td><td>o</td><td>o</td><td>Γ, χ</td>
<td>O</td><td>m</td><td>xO</td><td>M</td><td> ·></td><td> •</td><td>M</td><td>CM</td><td>F-F</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>rp</td><td></td><td>»P</td><td>Ό</td><td><r</td><td>r * ·</td><td>»P</td><td></td><td></td><td>un</td><td>o</td><td>O</td><td>o</td><td>CM</td><td>CM</td><td> <</td><td>CM</td>
<td></td><td></td><td></td><td></td><td>«P</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>xO</td><td> 00</td><td>un</td><td> 00</td><td>xO</td><td>e **</td><td> 00</td><td>O</td><td>r *</td><td>un</td><td> 00</td><td>O '</td><td>xO</td><td>O '</td><td>un</td><td>un</td><td>O '</td>
<td>xO</td><td>xO</td><td>xO</td><td>xO</td><td>Ό</td><td>Ό</td><td>Ό</td><td>r</td><td>xO</td><td>xO</td><td>xO</td><td>O</td><td>xO</td><td>xO</td><td>xO</td><td>xO</td><td>XO</td>
<td>O</td><td>CM</td><td>Ό</td><td> <</td><td>O</td><td>O</td><td>Ό</td><td>CM</td><td>un</td><td>xO</td><td>m</td><td>un</td><td>ST</td><td>O</td><td>un</td><td> 00</td><td>p.m</td>
<td></td><td>»P</td><td>un</td><td>CM</td><td>un</td><td>m</td><td>O</td><td>CM</td><td>m</td><td>O</td><td></td><td>CM</td><td>O</td><td></td><td>• P</td><td>o</td><td>p.m</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td><td>o</td><td>O</td><td>O</td><td> •</td><td> ·></td><td> •</td><td> *</td>
<td>O</td><td>O</td><td>o</td><td>O</td><td>o</td><td>o</td><td>O</td><td> «·</td><td>o</td><td>O</td><td> •</td><td> ·></td><td></td><td>O</td><td>O</td><td>o</td><td>O</td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>O</td><td></td><td></td><td>o</td><td>O</td><td>O</td><td></td><td></td><td></td><td></td>
<td></td><td></td><td>un</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>o</td><td>O</td><td>m</td><td>xO</td><td>ST</td><td>o</td><td> 00</td><td> »—1</td><td>un</td><td>«P</td><td> 00</td><td> 00</td><td> 1—<</td><td>o</td><td>un</td><td>o</td><td>o</td>
<td><r</td><td><T</td><td> *</td><td>m</td><td>m</td><td><T</td><td>m</td><td>•-B</td><td>m</td><td>P</td><td>m</td><td>I do not</td><td>rH</td><td><T</td><td></td><td>CM</td><td><T</td>
<td></td><td></td><td>o</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>o</td><td>o</td><td></td><td>o</td><td>o</td><td>o</td><td>o</td><td>O</td><td>o</td><td>O</td><td>o</td><td>o</td><td>O</td><td>o</td><td>O</td><td>O</td><td>o</td>
<td></td><td></td><td>M</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td></td><td>Φ</td><td></td><td>•B</td><td>• rl</td><td></td><td></td><td></td><td></td><td></td><td>•B</td><td></td><td></td><td></td><td></td><td></td>
<td>•B</td><td></td><td>P</td><td></td><td>Ό</td><td>G</td><td></td><td></td><td></td><td></td><td>•B</td><td>Ό</td><td></td><td></td><td>•B</td><td></td><td>•B</td>
<td>Ί3</td><td></td><td>P</td><td></td><td>•B</td><td>•B</td><td></td><td></td><td></td><td></td><td>p.m</td><td> >1</td><td></td><td></td><td>rP</td><td>•B</td><td>Π3</td>
<td>•B</td><td></td><td>Φ</td><td></td><td>W</td><td>s</td><td></td><td></td><td></td><td></td><td>o</td><td>of</td><td></td><td>•B</td><td>G</td><td>O</td><td>•B</td>
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Example 34
A sample prepared by a method similar to that described in Examples 1-4 with a 5: 1 ratio of ethylene to silane and a sample of uncoated, clear 6 mm float glass were coated with fluorine-doped tin oxide. Ammonium difluorotetrachlorostannate (NH<sub>4</sub> )<sub>2</sub>SnCl<sub>4</sub>F<sub>2</sub> ground to a particle size of up to 50 microns, dispersed in a stream of air, and the stream of air containing the dispersed powder was directed onto heated glass samples at a temperature of about 580 ° C at a rate of 80 g / m<sup>2</sup>. The thickness of the obtained fluorine-doped tin oxide coatings and their electrical resistances were measured. The following results were obtained:
Tin oxide thickness (nm)
Specific resistance (ohm cm)
Base with barrier coating 58
Uncoated base 56
1.7 x 10 '<sup>3</sup> x 10 '<sup>3</sup>
The significantly lower resistivity of the coating on the barrier-coated substrate illuminates the value of the barrier coating in preventing the migration of alkali metal ions from the glass, as these degrade the resistivity of the doped tin oxide layer.
Example 35
Liquid crystal display devices as described herein were made using a glass with a transparent barrier coating made substantially as described in Example 8 and were subjected to durability tests. They were found to last for more than 1000 hours at 60 ° C and 95% relative humidity.
All of the electron donating compounds used in the examples were those having a vapor pressure in excess of
760 mm at 60 ° C, with the exception of the following
<td></td><td colspan="3">the pressure at 60 ° C was as follows:</td>
<td></td><td>isopropanol</td><td> 40</td><td>kPa</td>
<td></td><td>xylene</td><td> 8</td><td>kPa</td>
<td> 5</td><td>Water</td><td> 20</td><td>kPa</td>
Contents13
29 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29
57 members in 28 offices
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 8420534 | United Kingdom | A | |
| 8420534P | – | – | – |
| GB19840020534 | – | – | – |
Members57
| Document | Office | Kind | |
|---|---|---|---|
| GB8420534D0 | United Kingdom | D0 | |
| IT8521891A0 | Italy | A0 | |
| IT8521891D0 | Italy | D0 | |
| FI853064A0 | Finland | A0 | |
| SE8503777D0 | Sweden | D0 | |
| GB8520102D0 | United Kingdom | D0 | |
| GB8520183D0 | United Kingdom | D0 | |
| GB8519275D0 | United Kingdom | D0 | |
| BE903052A | Belgium | A | |
| FI853064L | Finland | L | |
| FR2568871A1 | France | A1 | |
| SE8503777L | Sweden | L | |
| GB2163144A | United Kingdom | A | |
| GB2163146A | United Kingdom | A | |
| AU4577485A | Australia | A | |
| DE3528600A1 | Germany | A1 | |
| EP0174727A1 | European Patent Office (EPO) | A1 | |
| ZA855927B | South Africa | B | |
| JPS6163545A | Japan | A | |
| JPS6176274A | Japan | A | |
| ZA855896B | South Africa | B | |
| BR8503814A | Brazil | A | |
| DD237501A5 | German Democratic Republic (until 1990) | A5 | |
| ES546099A0 | Spain | A0 | |
| ES8609170A1 | Spain | A1 | |
| CN85106620A | China | A | |
| KR870002029A | Republic of Korea | A | |
| US4670025A | United States of America | A | |
| GB2163146B | United Kingdom | B | |
| GB2163144B | United Kingdom | B | |
| IT1200709B | Italy | B | |
| AU582178B2 | Australia | B2 | |
| HK21589A | Hong Kong, China | A | |
| CA1255976A | Canada | A | |
| SG62888G | Singapore | G | |
| TR23260A | Türkiye | A | |
| IN165410B | India | B | |
| SE461771B | Sweden | B | |
| EP0174727B1 | European Patent Office (EPO) | B1 | |
| AT62897T | Austria | T | |
| ATE62897T1 | Austria | T1 | |
| DE3582636D1 | Germany | D1 | |
| MY101631A | Malaysia | A | |
| FR2568871B1 | France | B1 | |
| KR920010068B1 | Republic of Korea | B1 | |
| KR920010093B1 | Republic of Korea | B1 | |
| US5165972A | United States of America | A | |
| DE3528600C2 | Germany | C2 | |
| FI89160BThis record | Finland | B | |
| AR242944A1 | Argentina | A1 | |
| FI89160C | Finland | C | |
| MX171998B | Mexico | B | |
| CN1026779C | China | C | |
| RU2057730C1 | Russian Federation | C1 | |
| CZ584985A3 | Czechia | A3 | |
| CZ281584B6 | Czechia | B6 | |
| JP2585514B2 | Japan | B2 |
3 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Patent lapsedLapsedMM | MM | |
| Patent lapsedLapsedMM | MM | |
| Publication of examined applicationBB | BB |
Numbers
- Publication, DOCDB
- 89160
- Publication, EPODOC
- FI89160B
- Application
- 853064
- Application, DOCDB
- 853064
- Application, EPODOC
- FI19850003064
Titles2
- English
- FOERFARANDE Før ATT Minska DIFFUSION audio ALKALIMETALLJONER FRAON GLAS TILL ETT OVANPAO BELAEGET cover layer by means of a SPAERROEVERDRAG INNEHAOLLANDE Kisel Syré OCH, OCH ANVAENDNING audio SPAERROEVERDRAGET electrically conductive PLANGLAS EN, EN IR REFLEKTERANDE PLANGLAS OCH ... I VAETSKEKRISTALLVISNINGSANORDNING
- Finnish
- FOERFARANDE FOER ATT MINSKA DIFFUSION AV ALKALIMETALLJONER FRAON GLAS TILL ETT OVANPAO BELAEGET SKIKT MEDELST ETT SPAERROEVERDRAG INNEHAOLLANDE KISEL OCH SYRE, ANVAENDNING AV SPAERROEVERDRAGET OCH EN ELLEDANDE PLANGLAS, EN IR-REFLEKTERANDE PLANGLAS OCH EN VAETSKEKRISTALLVISNINGSANORDNING...
Classification
- CPC, 3
- C03C17/3417
- G02F1/1333
- G02F2001/133337
- IPC, 8
- C03C17 245
- C03C17 23
- C03C17 30
- C03C17 34
- C23C16 40
- G02F1 133
- G02F1 1333
- H01B5 14