CN1175935A - Process for producing protecting coating on surface of glass or ceramic article - Google Patents
Process for producing protecting coating on surface of glass or ceramic article Download PDFInfo
- Publication number
- CN1175935A CN1175935A CN96192020A CN96192020A CN1175935A CN 1175935 A CN1175935 A CN 1175935A CN 96192020 A CN96192020 A CN 96192020A CN 96192020 A CN96192020 A CN 96192020A CN 1175935 A CN1175935 A CN 1175935A
- Authority
- CN
- China
- Prior art keywords
- precursor
- coating
- temperature
- oxide
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2453—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/211—SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
Abstract
The invention relates to a process for producing a protecting coating on a surface of a glass or ceramic article, said coating having an improved resistance to caustic wash treatments. In carrying out the inventive process a stream of an oxygeneous carrier gas containing a thermodecomposable precursor of tin oxide (SnO2) and a thermodecomposable precursor of silicon oxide (SiO2) in a molar ratio of the former precursor to the latter between 0.6 and 3.0, said precursors being present in evaporated form, and further containing water vapor in an amount of at least 1 mole per 100 moles of carrier gas, said surface having a temperature which is above the decomposition temperatures of said precursors and amounts to at least 550 DEG C, to deposit a mixed oxide protecting coating comprising tin oxide and silicon oxide, and the deposition is continued until a coating thickness of between 240 and 1,500 ANGSTROM is obtained.
Description
The present invention relates to surface-coated glass or ceramic, particularly Glass Containers, for example after with the basic solution washing, want reusable vial.
People have known the surface of glasswork have been handled to improve its wear resistance.For example US4144362 has described the technology with SnO 2 thin film coated glass bottle.It is by will be at oxygen-containing atmosphere that this stannic oxide applies, and for example is heated to 450-600 ℃ glass surface and is exposed in the organo-tin compound of vapor form or finely divided form and obtains in air.When contacting with hot glass surface, described tin compound can decompose and oxidation forms doped tin oxide coatings.Thickness by the doped tin oxide coatings of said paint-on technique acquisition among the US4144362 is the 45-120 dust.
According to US4130673, after the goods that will apply stannic oxide are cooled to 350 ℃ or lower temperature, the natural cured or synthetic polymer of skim is coated to the outside of the stannic oxide top coat that makes as mentioned above.The combination of these two kinds of coatings has allegedly reduced cut and the fragmentation of glasswork in processing and operation process.
Reuse at present Glass Containers, increase day by day as the trend of vial.Before the new charging of this receptacle, carry out the severe carrying out washing treatment to them, for example use basic solution.Use the basic solution of 1-4% to wash after 5-15 time down at 80 ℃, Zhi Bei doped tin oxide coatings will be completely removed as mentioned above.At first, after through washing several times, the thick point of doped tin oxide coatings can become ugly darkcyan.In the washing of back, gray spot and last the disappearance can appear in this coating.
The purpose of EP0485646 is to prepare the vial that can repeat to feed, and has on this vial to bear the coating of metal oxides of 4% basic solution 80 ℃ of following processing of 8 hours.This coating is made up of stannic oxide or titanium oxide and thickness is the 400-1000 dust.This coating is by with tin compound, as tin tetrachloride or dimethyl tin dichloride or titanium compound, is that 550-700 ℃ vial contacts and forms as titanium tetrachloride and hull-skin temperature.
The thicker doped tin oxide coatings that makes according to EP485646 with compare than shallow layer by above-mentioned United States Patent (USP) is known, can provide at alkali and wash 2-6 washing better protection.But the test of being undertaken by the present inventor shows that these can become quite fuzzyly than thick coating afterwards wash hour (carrying out with 4% basic solution) under 80 ℃, and this vial not too can be reused for a long time.For titania coating, can see that the titanium initial compounds is more difficult and very inefficent in the use.
WO93/13393 has described a kind of employing by stannic oxide precursor, silica precursors and a kind of accelerator, and the composition that is preferably the mixture composition of triethyl-phosphite comes the method for coated glass by chemical vapour sedimentation method (CVD).Said composition is to be higher than a kind of coating of speed formation of deposits of about 350 dust/seconds, and according to embodiment, its thickness is the 2000-4930 dust.Thus obtained coating can combine with other coating, thereby produces a kind of goods with specified property, for example has controlled radiation rate, specific refractory power, wear resistance or outward appearance.In embodiment 7, apply clear-glass bottle with a kind of steam mixture, this mixture is made up of stannic oxide precursor, silica precursors, triethyl-phosphite and warm air, and the mol ratio of stannic oxide precursor and silica precursors is 0.2.This steam mixture deposited for 10 seconds with the speed of about 200 dust/seconds, was the magenta-Lan Se film of about 2000 dusts thereby produce thickness.When not having triethyl-phosphite to exist, sedimentation velocity is about 50 dust/seconds.
The invention provides a kind of method for preparing supercoat on glass or ceramic, said coating can height alkali resistance carrying out washing treatment.
Method of the present invention also provides a kind of improved coating for Glass Containers, handles that said coating still keeps transparent and basically do not change when using next time Glass Containers being carried out repeatedly alkaline washing.
According to further purpose of the present invention, apply wax coating in described supercoat outside, thereby make this glass or ceramic mar-proof better.
The present invention also provides a kind of simple method effectively and reliably, is used for a kind of improved supercoat is provided on glass or ceramic surface, wherein adopt easy-to-handle can the pyrolysated precursor.
When on glass or ceramic surface, preparing supercoat according to the present invention, on the surface that will apply, spray a kind of air-flow that contains oxygen carrier gas equably, this air-flow contains heat decomposable stannic oxide (SnO
2) precursor and heat decomposable silicon oxide (SiO
2) precursor; preceding a kind of precursor is 0.6-3.0 with the mol ratio of a kind of precursor in back; said precursor is to exist with the form of evaporating; this air-flow also contains the water vapor of at least 1 mole/100 moles of vector gas; the temperature on said surface is higher than the decomposition temperature of said precursor and is at least 550 ℃; thereby deposit a kind of mixed oxide supercoat of forming by stannic oxide and silicon oxide, and till this deposition process lasts till that always obtaining thickness is the coating of 240-1500 dust.
CTU (coat-thickness unit) is that commonly used being used for of glass industry determined the optical unit of coat-thickness and based on the reflection of incident light measurement result.For oxide coating of the present invention, the thickness of 1CTU is approximately corresponding to 3 dusts.For practical reason and according to the convention in this area, in the description and embodiment of back, all adopt CTU thickness unit usually.
When the supercoat that will make according to the present invention was compared with known coating with identical CTU thickness, coating of the present invention obviously demonstrated the goodish alkali resistance washup rational faculty of having improved, and this coating keeps transparent outward appearance simultaneously.The high-performance that is obtained makes coating of the present invention also be highly suitable for protecting ceramic, for example pottery as the detergency of good anti-50 times even more times 8-10 minute.In addition, when conventional wax coating is coated to the outside of coating of the present invention, can obtain fabulous scratch-resistant.
The possible explanation that the supercoat that makes according to the present invention is had a high-performance is the silicon oxide that makes in this coating and the silicon oxide that contains in coated matrix fuses together mutually to small part on interface; and/or the coexistence of silicon oxide produces coating more closely or the film that the breach that alkali attacks does not almost take place, and/or the coexistence of silicon oxide has increased the anti-mechanical impact property of coating when contacting with tableware or in washing plant.At present, cause improved mechanism it be unclear that, therefore, above-mentioned possible explanation should think it only is a kind of constraint of supposing and should not being subjected to this theory.
Preferably, the method that is used to prepare the supercoat of being made up of stannic oxide and silicon oxide of the present invention is to carry out in the hot junction that produces glass or Ceramic Production line, and the still enough heat of product surface this moment is so that precursors decompose.In addition, to be that preparation has the coating of required superperformance necessary at least 550 ℃ surface temperature.Decomposition by precursor and oxidation prepare supercoat can be undertaken by CVD (chemical vapour deposition) method, and this method comprises that the precursor with the steam form contacts with the hot surface that will apply.
According to the CVD method, precursor is with vector gas, and the air-flow that is generally air is used together, air-flow is ejected on the surface that will apply and contains the precursor of steam form.For the short resolving time, as be lower than about 10 seconds, sedimentation velocity is directly proportional with depositing time.But when adopting long depositing time, the temperature on surface will reduce, and cause the corresponding reduction of sedimentation velocity and coating processes efficient.Therefore, according to required coat-thickness, must under quite high surface temperature, begin to apply or in coating procedure, provide additional heat to the surface that will apply.The quite high temperature on the surface that applies is owing to following said reason also is useful.
According to the present invention, as the tin compound of precursor can be any can the pyrolysated tin compound under the temperature on glass that will apply or ceramic surface.Cause the decomposition of stannic oxide with the decomposition reaction that is present in the oxygen in the vector gas.Suitable can be selected from the trichlorine monoalkyltin by the pyrolysated tin compound, for example trichlorine monomethyl tin and trichlorine Monobutyltin, tribromo monoalkyltin, and dichloro dialkyl tin, for example dimethyl tin dichloride, dibromo dialkyl tin and tin tetrachloride.The trichlorine Monobutyltin is most preferred stannic oxide precursor, and its reason is its easy handling and uses very effective.
As the silicon compound of precursor also should be can pyrolysated, then as above to produce silicon oxide in the face of the described form of tin compound.Suitable silicon compound is to have general formula R
nSiX
(4-n)Compound, R is alkyl, alkenyl, alkynyl or the alkoxyl group with 1-5 carbon atom in the formula, or phenyl; X is halogen atom or hydroxyl; N is the numeral of 0-4.Tetramethoxy-silicane, tetraethoxysilane and tetrapropoxysilane are the examples of suitable silicon compound.
Described tin compound is preferably with 0.5 * 10
-4-2 * 10
-2The amount of moles/mole vector gas exists.The mol ratio of tin compound and silicon compound is chosen as 0.6-3.0 according to desired high alkali resistance detergency.Verified in said scope, when said mol ratio is at most 2.0, preferably be at most at 1.5 o'clock, can obtain optimal results.In addition, vector gas (preferably as above said is air) must contain water vapour, and its amount is 1-50 mole/100 mole vector gas.When preparing supercoat of the present invention by normal atmosphere CVD, in as the air that contains oxygen carrier gas, contain the water vapor of capacity usually according to embodiment preferred.This vector gas is in the temperature that precursor is the steam form obviously.Usually, the temperature of this vector gas is 100-210 ℃, is preferably 120-180 ℃.The speed that the gas flow that will contain said components is ejected into the surface that will apply is selected from the 1-10 meter per second usually, is most preferably the 3-5 meter per second.
It is highly important that the glass that will apply or the temperature of ceramic surface must be on the decomposition temperatures of used precursor, but be starkly lower than the softening temperature of the goods that will apply.Usually, supercoat is at production line, as the hot junction coating of vial production line.The quite high temperature on the surface that applies has not only increased sedimentation velocity as mentioned above, and is found the weather resistance of in fact having improved coated surface, particularly concerning neutralizing treatment.Therefore, in coating procedure, the surface temperature of goods is at least 550 ℃, and preferred temperature is at least 570 ℃, and most preferred temperature is at least 600 ℃, for example between 600-650 ℃.For surface temperature being remained under the required high temperature, can in coating procedure, provide additional heat to goods.Any suitable the device of additional heat is provided all is easily, as flame spraying etc.
Described coating processing can last till always and obtains required coat-thickness for extremely.In fact, coat-thickness and above-mentioned tin compound provide good especially alkaline-resisting detergency with the mol ratio and the sufficiently high application temperature of silicon compound, and this coating keeps transparent appearance simultaneously.According to the present invention, the thickness of supercoat should be at least 80CTU.Have been found that at 150CTU at least, be preferably under the thickness of 180CTU at least, as long as the temperature height on the surface that applies, this coating can bear 12 hours severe carrying out washing treatment of 4% basic solution under 80 ℃, and can not show any fuzzy or unwanted color.Preferably, coat-thickness is 150CTU (450 dust)-900 dusts.
Among the said below embodiment that only is used for illustrating, tin compound and silicon compound import in the hot blast so that these compound evaporations by injector.The temperature of air is about 150 ℃.This gaseous mixture is by the lead surface of glasswork to be processed of known pipe.In this embodiment, the opening of pipe is 15 * 35mm.2/3rds height of 50ml glass bottle are following processed.They are heated to required temperature in stove.This temperature is measured occasionally by the thermoelectricity of putting into this glass bottle.This glass bottle is fixed by any suitable device, for example by rod, so that bottle can be operated and be rotated when they are exposed in the processing gas stream.
The temperature of glass is measured by the infrared thermometer (model C HINO IR-AHOT/-50 ℃～+ 1000 ℃) that radiant ratio is 0.93, the sensitive wave length scope is the 4-13 micron when beginning to form coating.Measure the test of scratch-resistant
To be horizontal positioned through two bottles of same treatment, one they can pressurize mutually on another, and they are slided mutually.When pressure increased, obviously, the time that cut forms must increase applied force just so that bottle continues the mutual time of sliding.Applied force is limited to 450N, because bigger power can make one or two bottles break.Bottle with suitable coating can bear the power of 450N, and can not produce cut.Measure the test of alkali resistance solution washing
Test conditions is corresponding with the condition of bottle Filling Station.
Bottle is immersed in 4% sodium hydroxide solution that remains under 80 ℃.At duration of test, will the container nitrogen purging of basic solution be housed, to avoid owing to the carbonic acid gas that is present in the ambient air makes sodium hydroxide change into yellow soda ash.Because identical, the sodium hydroxide solution of new system is adopted in test each time, this is because yellow soda ash can make coating be subjected to less damage.
During test, adopting diameter is 2 liters of borosilicate glass containers of 150mm.These containers can hold 4 bottles.These bottles are placed on container bottom separate on the plate of 20mm, each bottle is that 6mm, length are that the nail of 15mm is fixed with 3 diameters, and they are fixed in the hole on this plate.The hole of a 30mm diameter is arranged in the center of this plate, is the hole of 15mm and 8 diameters are arranged on its periphery.With length is that 40mm, diameter are that the agitator of 10mm stirs this basic solution, this agitator with magnetic stirring heating plate with 500 rev/mins of drivings.
Adopt the thickness of the device mensuration coating of the American Glass Research Co. (AGR).This device that is usually used in the bottle production is measured the reflectivity of handled glass surface, then this reflectance value is transformed into CTU (coat-thickness unit).For the mixed oxidization tin/silica coating that makes according to the present invention by above-mentioned CVD method, 1CTU is corresponding to about 3 dusts.
Following non-limiting examples be used for illustrating of the present invention.Embodiment 1 and 2 is comparative examples.
In embodiment 1, said according to US4130673, apply doped tin oxide coatings and wax coating on the bottle.
In embodiment 2, bottle handled making it to have thicker doped tin oxide coatings.For fear of bad bluring, adopt higher tin compound concentration and higher vector gas speed to form these coatings.Embodiment 1 (contrast)
Adopt above-mentioned technology, on four bottles, deposit doped tin oxide coatings by the trichlorine Monobutyltin.For this reason, be on 600 ℃ the glass bottle surface, to use the gaseous mixture of forming as vector gas by air to spray in temperature, the ratio of tin compound is 1.5 * 10
-4Moles/mole air, the concentration of water vapour are 2.3 moles/100 mole air.Air velocity is 3 meter per seconds.Deposition was carried out 2.5 seconds.The result obtains the doped tin oxide coatings of thickness for about 35CTU.
Make it to apply the cured layer of one deck according to the described method of US4130673 by handling then with the aqeous suspension powdered of polyethylene oxide and to two in these bottles.These two bottles show superior scratch-resistant under 450 newton.Apply wax coating at the bottle of the coating described in the following example in the same manner at them and also show superior scratch-resistant later on.
These two bottles are carried out the severe washing with 4% basic solution down at 80 ℃.After washing 15 minutes, doped tin oxide coatings is impaired serious, washs after 30 minutes, and coating is destroyed fully.Embodiment 2 (contrast)
Employing is at the conventional coating processes described in the embodiment 1, and the temperature that comprises the surface of glass bottle is 600 ℃.Forming thickness with the gaseous mixture that contains trichlorine Monobutyltin and water vapour is the doped tin oxide coatings of 100CTU, 150CTU and 200CTU, and the ratio of said trichlorine Monobutyltin is 1 * 10
-3The moles/mole air, and the concentration of said water vapour is 2.3 moles/100 mole air.Air velocity is 5 meter per seconds.Depositing time was respectively 3 seconds, 4.5 seconds and 6 seconds.The thickness of these coatings is thicker than embodiment's 1.In washing under the condition identical with embodiment 1 after 1 hour, all doped tin oxide coatings are all impaired and be partly removed.Embodiment 3
Employing is said general coating processes in embodiment 1, and the temperature that comprises the vial surface is 600 ℃.In this embodiment, preparation has the bottle of two kinds of different coating thickness.Be used on bottle, forming the gaseous mixture of coating by 1 * 10
-3The trichlorine Monobutyltin of moles/mole air, ratio are the tetraethoxysilane of 50% (mole) of the mixture of these two kinds of metallic compounds and the water vapour composition that concentration is 2.3 moles/100 mole air.Air velocity is 5 meter per seconds.Depositing time was respectively 4.5 seconds and 6 seconds.
The coat-thickness that is obtained is respectively 150CTU and 200CTU.They do not show any fuzzy.For the test of the alkali resistance solution washing that carries out under the condition described in the embodiment in front, after washing in 12 hours, it is slight fuzzy that thickness is that the coating of 150CTU shows, and thickness to be the coating of 200CTU any damage do not occur.Embodiment 4
As embodiment 3, on bottle, form coating, but adopt tetrapropoxysilane to replace tetraethoxysilane.Obtain the result similar with embodiment 3.Embodiment 5
Form the coating that thickness is 150CTU as described in example 3 above.But, the water vapor concentration difference in the used gaseous mixture.These concentration are respectively 8 mole of water steams and 14 mole of water steams in per 100 mole air.All coatings that obtained thickness in embodiment 3 is to have fabulous alkali resistance solution washing the coating of 200CTU.Embodiment 6
Technology is identical with embodiment 3, and its difference is to adopt tin tetrachloride or trichlorine monomethyl tin to replace the trichlorine Monobutyltin.All obtain the result identical in both cases with embodiment 3.Embodiment 7
Technology is identical with embodiment 3, and its difference is to adopt different vial surface temperatures, is respectively 575 ℃ and 625 ℃.Because under these high temperature, sedimentation velocity is identical, therefore, depositing time is respectively 4.5 seconds to obtain the coating that thickness is 150CTU and to be the coating of 200CTU to obtain thickness in 6 seconds.For these two kinds of coat-thicknesses, when the glass surface temperature was 575 ℃, the alkali resistance solution washing was better, when the glass surface temperature is 625 ℃, and this superior performance.Embodiment 8
Employing is said technology in embodiment 3, and the surface temperature that comprises vial is 600 ℃.In this embodiment, preparation thickness is the coating of 200CTU, changes the ratio of tin compound and silicon compound in the gaseous mixture be used for forming coating simultaneously.The consumption of trichlorine Monobutyltin is 1 * 10
-3The moles/mole air.Change the concentration of tetraethoxysilane.Water vapour is that 11.5 amount exists with the mol ratio with tin compound and silicon compound sum.Corresponding to 1.3-3.45 mole of water steam/100 mole air.
As described in the previous embodiment, to carry out basic solution washing in 6 hours through the bottle that applies.The ratio of tin compound and silicon compound and the result of washing test in following table, have been provided.
The mol ratio washing test result 0.5 (contrast) of table tin compound and silicon compound is seriously fuzzy, coating is subjected to havoc 0.6 slight fuzzy 0.9 not to be had fuzzy (=full impregnated is bright) 1.2 slight fuzzy 1.5 slight fuzzy 3.4 (contrasts) and blurs, coating is damaged, and 10.1 (contrasts) are serious blurs, and coating is subjected to havoc
Because " do not have fuzzy " is the result who needs most and " slight fuzzy " also is the acceptable result, therefore, the mol ratio of tin compound and silicon compound preferably should be selected from the 0.6-1.5 scope obviously.
Claims (14)
1. a method for preparing supercoat on glass or ceramic surface is wherein sprayed a kind of air-flow that contains oxygen carrier gas equably on the coated surface of desire, and this air-flow contains heat decomposable stannic oxide (SnO
2) precursor and heat decomposable silicon oxide (SiO
2) precursor; preceding a kind of precursor is 0.6-3.0 with the mol ratio of a kind of precursor in back; said precursor exists with evaporated form; this air-flow also contains the water vapour of at least 1 mole/100 moles of vector gas; the temperature on described surface is higher than the decomposition temperature of described precursor and is at least 550 ℃; thereby deposit a kind of mixed oxide supercoat that comprises stannic oxide and silicon oxide, and this deposition process lasts till always till the coating that obtains 240-1500 dust thickness.
2. according to the process of claim 1 wherein that the mol ratio of stannic oxide precursor and silica precursors mostly is 2.0 most.
3. according to the method for claim 2, wherein the mol ratio of stannic oxide precursor and silica precursors mostly is 1.5 most.
4. according to the described method of any one claim among the claim 1-3, wherein said vector gas contains 0.5 * 10
-4-2 * 10
-2The oxide precursor of moles/mole vector gas.
5. according to the described method of any one claim among the claim 1-4, the temperature of wherein said vector gas is 100-210 ℃, is preferably 120-180 ℃.
6. according to the described method of any one claim among the claim 1-5, wherein gas flow is injected into the coated surface of desire with the speed of 1-10 meter per second.
7. according to the described method of any one claim among the claim 1-6, wherein in coating procedure, the temperature on the surface that desire is coated remains at least 570 ℃.
8. according to the method for claim 7, wherein in coating procedure, the temperature on the surface that desire is coated remains at least 600 ℃.
9. according to the said method of any one claim among the claim 1-8, wherein can be selected from the trichlorine monoalkyltin by pyrolysated stannic oxide precursor, tribromo monoalkyltin, dichloro dialkyl tin, dibromo dialkyl tin and tin tetrachloride.
10. according to the method for claim 9, wherein can be selected from trichlorine monomethyl tin, trichlorine Monobutyltin and dimethyl tin dichloride by pyrolysated stannic oxide precursor.
11. according to the said method of any one claim among the claim 1-10, wherein heat decomposable silicon oxide parent substance is to have general formula R
nSiX
(4-n)Compound, R is alkyl, alkenyl, alkynyl or the alkoxyl group with 1-5 carbon atom in the formula, or phenyl; X is halogen atom or hydroxyl; N is the numeral of 0-4.
12. according to the said method of any one claim among the claim 1-11, till wherein deposition process lasts till that always obtaining thickness is the coating of 450-900 dust.
13. according to the said method of any one claim among the claim 1-12, wherein said deposition process adopts air to be undertaken by barometric point CVD method as vector gas.
14. according to the said method of any one claim among the claim 1-13, wherein said supercoat is to form on the outside surface of wanting reusable Glass Containers or pottery.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95200440 | 1995-02-22 | ||
| EP95200440.6 | 1995-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1175935A true CN1175935A (en) | 1998-03-11 |
Family
ID=8220042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96192020A Pending CN1175935A (en) | 1995-02-22 | 1996-02-22 | Process for producing protecting coating on surface of glass or ceramic article |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0810980A1 (en) |
| JP (1) | JPH11504610A (en) |
| KR (2) | KR19980702384A (en) |
| CN (1) | CN1175935A (en) |
| AR (1) | AR000999A1 (en) |
| AU (1) | AU4849096A (en) |
| BR (1) | BR9607269A (en) |
| CA (1) | CA2211940A1 (en) |
| CO (1) | CO4560356A1 (en) |
| CZ (1) | CZ260497A3 (en) |
| GT (1) | GT199600008A (en) |
| HU (1) | HUP9801366A3 (en) |
| NO (1) | NO973829L (en) |
| NZ (1) | NZ302437A (en) |
| PE (1) | PE61596A1 (en) |
| PL (1) | PL321863A1 (en) |
| TR (1) | TR199700841T1 (en) |
| UY (1) | UY24173A1 (en) |
| WO (1) | WO1996026163A1 (en) |
| ZA (1) | ZA961390B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153600A (en) * | 2016-05-12 | 2019-01-04 | 东洋佐佐木玻璃株式会社 | Glass container and its manufacturing method, manufacturing device |
| CN110183111A (en) * | 2019-06-19 | 2019-08-30 | 广东健诚高科玻璃制品股份有限公司 | A kind of coating by vaporization device of domestic glass ceramics, coating by vaporization coating and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9920758D0 (en) * | 1999-09-03 | 1999-11-03 | Nycomed Amersham Plc | Improved container composition for diagnostic agents |
| GB9920772D0 (en) * | 1999-09-03 | 1999-11-03 | Nycomed Amersham Plc | Improved container composition for radiopharmaceutical agents |
| EP1236705A1 (en) * | 2001-02-22 | 2002-09-04 | Atofina Vlissingen B.V. | Coated glazed articles and method for producing the same |
| KR20040033869A (en) * | 2002-10-16 | 2004-04-28 | 권원선 | Electronic oven type cooker, and process method of cooker |
| US20080152804A1 (en) * | 2006-07-28 | 2008-06-26 | Gulbrandsen Chemicals, Inc. | Method for depositing a metal-containing coating on a substrate |
| MX2009010674A (en) * | 2007-04-03 | 2009-12-01 | Ppg Ind Ohio Inc | Coated ceramic article. |
| KR100858704B1 (en) * | 2007-10-29 | 2008-09-17 | 에스아이디주식회사 | Method for coating high-resistance thin film of case appearance |
| GB201523156D0 (en) * | 2015-12-31 | 2016-02-17 | Pilkington Group Ltd | High strength glass containers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853257A (en) * | 1987-09-30 | 1989-08-01 | Ppg Industries, Inc. | Chemical vapor deposition of tin oxide on float glass in the tin bath |
| JP2672391B2 (en) * | 1989-07-26 | 1997-11-05 | 麒麟麦酒 株式会社 | Glass bottle and its manufacturing method |
| JPH03115139A (en) * | 1989-09-29 | 1991-05-16 | Hitachi Ltd | Antireflection film and its formation |
| RU2091340C1 (en) * | 1991-12-26 | 1997-09-27 | ЕЛФ Атокем Норт Америка, Инк. | Article made by applying at least one layer of silicon and tin oxides mixture on glass backing |
-
1996
- 1996-02-20 CO CO96007867A patent/CO4560356A1/en unknown
- 1996-02-21 PE PE1996000121A patent/PE61596A1/en not_active Application Discontinuation
- 1996-02-21 ZA ZA961390A patent/ZA961390B/en unknown
- 1996-02-21 GT GT199600008A patent/GT199600008A/en unknown
- 1996-02-21 AR ARP960101463A patent/AR000999A1/en unknown
- 1996-02-22 TR TR97/00841T patent/TR199700841T1/en unknown
- 1996-02-22 CZ CZ972604A patent/CZ260497A3/en unknown
- 1996-02-22 EP EP96904367A patent/EP0810980A1/en not_active Withdrawn
- 1996-02-22 PL PL96321863A patent/PL321863A1/en unknown
- 1996-02-22 WO PCT/NL1996/000087 patent/WO1996026163A1/en not_active Application Discontinuation
- 1996-02-22 CN CN96192020A patent/CN1175935A/en active Pending
- 1996-02-22 KR KR1019970705783A patent/KR19980702384A/en not_active Application Discontinuation
- 1996-02-22 HU HU9801366A patent/HUP9801366A3/en unknown
- 1996-02-22 BR BR9607269A patent/BR9607269A/en not_active Application Discontinuation
- 1996-02-22 AU AU48490/96A patent/AU4849096A/en not_active Abandoned
- 1996-02-22 NZ NZ302437A patent/NZ302437A/en unknown
- 1996-02-22 CA CA002211940A patent/CA2211940A1/en not_active Abandoned
- 1996-02-22 JP JP8525581A patent/JPH11504610A/en active Pending
- 1996-02-22 UY UY24173A patent/UY24173A1/en unknown
-
1997
- 1997-08-20 NO NO973829A patent/NO973829L/en unknown
- 1997-08-21 KR KR19977005783A patent/KR19987002384A/ko unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109153600A (en) * | 2016-05-12 | 2019-01-04 | 东洋佐佐木玻璃株式会社 | Glass container and its manufacturing method, manufacturing device |
| CN110183111A (en) * | 2019-06-19 | 2019-08-30 | 广东健诚高科玻璃制品股份有限公司 | A kind of coating by vaporization device of domestic glass ceramics, coating by vaporization coating and preparation method thereof |
| CN110183111B (en) * | 2019-06-19 | 2024-02-02 | 广东健诚高科玻璃制品股份有限公司 | Steaming coating device and steaming coating material for daily glass ceramic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11504610A (en) | 1999-04-27 |
| KR19987002384A (en) | 1998-07-15 |
| HUP9801366A2 (en) | 1998-08-28 |
| TR199700841T1 (en) | 1998-02-21 |
| NO973829D0 (en) | 1997-08-20 |
| AR000999A1 (en) | 1997-08-27 |
| WO1996026163A1 (en) | 1996-08-29 |
| CZ260497A3 (en) | 1998-01-14 |
| GT199600008A (en) | 1997-08-14 |
| UY24173A1 (en) | 1996-08-06 |
| BR9607269A (en) | 1998-12-15 |
| KR19980702384A (en) | 1998-07-15 |
| EP0810980A1 (en) | 1997-12-10 |
| NO973829L (en) | 1997-08-20 |
| AU4849096A (en) | 1996-09-11 |
| CA2211940A1 (en) | 1996-08-29 |
| MX9706302A (en) | 1998-06-28 |
| PL321863A1 (en) | 1997-12-22 |
| PE61596A1 (en) | 1997-02-01 |
| CO4560356A1 (en) | 1998-02-10 |
| ZA961390B (en) | 1996-07-16 |
| HUP9801366A3 (en) | 1998-12-28 |
| NZ302437A (en) | 1998-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3485918B2 (en) | Glass substrate coating method | |
| EP0627391B1 (en) | Neutral, low emissivity coated glass articles and method for making | |
| JP2003501338A (en) | Method for producing photocatalytic coating on substrate | |
| CN1175935A (en) | Process for producing protecting coating on surface of glass or ceramic article | |
| EP1608793A1 (en) | Titania coatings | |
| JP2820646B2 (en) | Solutions and methods for coating glass, glass-ceramic and enamel products by pyrolysis | |
| US5730771A (en) | Method of manufacturing a corrosion resistant pyrolytically coated glass | |
| US20040028911A1 (en) | Process for coating glass | |
| WO2005087678A1 (en) | Process for the deposition of aluminium oxide coatings | |
| CZ379996A3 (en) | Method of making transparency reducing layers on glass and glass ceramics by employing pyrolysis | |
| JP3821963B2 (en) | COATING AGENT FOR GLASS AND METHOD FOR COATING GLASS MATERIAL USING THE SAME | |
| US20030205169A1 (en) | Inorganic film-forming coating composition, preparation method thereof and inorganic film-forming method | |
| JPH08245242A (en) | Coating method and coating solution | |
| GB2139997A (en) | Surface treatment of glassware | |
| GB2067540A (en) | Improved method for applying an inorganic titanium coating to a glass surface | |
| MXPA97006302A (en) | Process to produce a protective coating on a surface of a glass or ceramic article | |
| EP0038863A1 (en) | Method of treating glassware with an aqueous solution containing coordination compounds | |
| JPH08231244A (en) | Method of hot-finishing glass balloon and chemical used for applying metal oxide layer on glass balloon by heat decomposition | |
| NZ264561A (en) | Method for coating a glass object with tin oxide | |
| JP2003226523A (en) | Titanium oxide coating film and method for forming the same | |
| JP2001253730A (en) | Metal oxide coated glass bottle and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |