EP0810980A1 - Procede de production d'un revetement de protection sur une surface d'un article en verre ou en ceramique - Google Patents

Procede de production d'un revetement de protection sur une surface d'un article en verre ou en ceramique

Info

Publication number
EP0810980A1
EP0810980A1 EP96904367A EP96904367A EP0810980A1 EP 0810980 A1 EP0810980 A1 EP 0810980A1 EP 96904367 A EP96904367 A EP 96904367A EP 96904367 A EP96904367 A EP 96904367A EP 0810980 A1 EP0810980 A1 EP 0810980A1
Authority
EP
European Patent Office
Prior art keywords
coating
tin
precursor
process according
oxide
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.)
Withdrawn
Application number
EP96904367A
Other languages
German (de)
English (en)
Inventor
Leendert Cornelis Hoekman
Stephen W. Carson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Vlissingen BV
Original Assignee
Elf Atochem Vlissingen BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elf Atochem Vlissingen BV filed Critical Elf Atochem Vlissingen BV
Publication of EP0810980A1 publication Critical patent/EP0810980A1/fr
Withdrawn legal-status Critical Current

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

Definitions

  • the invention relates to surface coating glass or ceramic articles, in particular glass containers such as bottles, which are intended for repeated use after having been washed with a caustic solution.
  • US-A-4 144 362 describes the coating of glass bottles with a thin film of tin oxide.
  • the tin oxide coatings are obtained by exposing the glass surface, heated at a temperature between 450°C and
  • a thin layer of a natural wax or a synthetic polymer is applied on top of a tin oxide surface coating produced as described above after the tin oxide coated article has been cooled to a temperature of 350°C or less.
  • the combination of the two coating layers is said to reduce scratching and breaking of the glass articles during handling and processing.
  • EP-A-0 485 646 aims at producing refillable glass bottles which are provided with a metal oxide coating which would resist an eight-hour treatment with a 4% caustic solution at 80°C.
  • the coating comprises tin oxide or titanium oxide and has a thickness of 400 to 1,000 A.
  • the coating is made by contacting a tin compound such as tin tetrachloride or dimethyl tin dichloride or a titanium compound such as titanium tetrachloride with a glass bottle which has an external surface temperature of 550 to 700°C.
  • the thicker tin oxide coatings prepared according to EP-A- 0 485 646 provide a better protection against caustic wash than the thinner coatings known from the US patents discussed above.
  • tests which have been carried out by the present inventors show that these thicker coatings become rather hazy after 2 to 6 hours of washing (using a 4% caustic solution at 80°C), making the bottles less acceptable for long lasting repeated use.
  • titanium oxide coatings it can be observed that the titanium starting compound is hard and difficult to handle and is very inefficient in use.
  • WO 93/13393 discloses a process for coating glass by chemical vapor deposition (CVD) using a composition comprising a mixture of a tin oxide precursor, a silicon oxide precursor and an accelerant, preferably triethyl phosphite.
  • the composition is deposited at a rate greater than about 350 A/sec to form a coating which according to the Examples has a thickness between 2,000 and 4,930 A.
  • the coating thus obtained can be combined with other layers to produce an article with specific properties such as controlled emissivity, refractive index, abrasion resistance or appearance.
  • Example 7 a clear glass bottle is coated with a vapor mixture comprising a tin oxide precursor, a silicon oxide precursor, triethyl phosphite and hot air, the molar ratio of the tin oxide precursor to the silicon oxide precursor being 0.2.
  • the vapor mixture is deposited for 10 seconds at an estimated deposition rate of about 200 A/second to produce a magenta-blue colored film having a thickness of about 2,000 A. Without the presence of triethyl phosphite the deposition rate is about 50 A/second.
  • the present invention provides a process for producing a protecting coating for glass or ceramic articles, said coating being highly resistant to caustic wash treatments.
  • the process of the present invention also provides an improved coating for glass containers, said coating remaining clear and substantially unchanged when the glass container is subjected many times to caustic wash treatments preparatory to a next use thereof.
  • a wax coating is applied on top of the protecting coating, thus making the glass or ceramic articles better resistant to scratches.
  • the present invention also provides a simple, efficient and reliable process for producing an improved protecting coating on a surface of a glass or ceramic article, wherein thermodecomposable precursors are used which are easy to handle.
  • CTU coating thickness unit
  • coating thickness unit is an optical unit which is frequently used in the glass industry for defining the thickness of coatings and is based on measurements of the reflection of incident light.
  • a thickness of 1 CTU may be estimated to correspond with about 3 A.
  • the CTU thickness units will generally be adopted throughout the description and the Examples to follow.
  • the inventive coating When a protective coating produced according to the invention is compared with a known coating having the same CTU thickness, the inventive coating strikingly shows a considerably improved resistance to caustic wash treatments, while the coating maintains its clear appearance.
  • the excellent properties which have been established e.g. a good resistance to 50 and even more wash cycles of 8 to 10 minutes, make the inventive coating also very suitable for protecting ceramic articles such as crockery. Further, after a usual wax coating has been applied on top of the inventive coating, an excellent scratch resistance is obtained.
  • Possible explanations for the excellent properties of the protecting coating produced according to the invention could be that the silicon oxide produced in the coating and the silicon oxide contained in the substrate to be coated, at least in part, melt together at the interface, and/or that the co-presence of silicon oxide results in a more tight coating or film having almost no openings through which caustic attack can take place, and/or that the co-presence of silicon oxide increases the resistance of the coating layer to the mechanical impact on contact with cutlery or occurring m washing equipement
  • the mechan ⁇ sm(s) causing the improvement is (are) not yet understood and therefore, the possible explanations detailed above have to be considered as hypothetical only and it is not intended to be bound by them
  • the present process for producing a protective coating comprising tin oxide and silicon oxide is preferably carried out at the hot end of the production line for producing the glass or ceramic article, while the surface of the article is still hot enough for the precursor to be decomposed. Moreover, a surface temperature of at least 550°C is essential for producing a coating having the desired good properties.
  • the production of the protecting coating by decomposition and oxidation of the precursors can be carried out by means of the CVD (Chemical Vapor Deposition) method comprising bringing the precursors in vapor form in contact with the hot surface to be coated.
  • the precursors are applied from a stream of a carrier gas, conveniently air, impinging onto the surface to be coated and containing the precursors in evaporated form.
  • a carrier gas conveniently air
  • the deposition rate s proportional to the deposition time
  • the temperature of the surface will decrease resulting in a correponding decrease of the deposition rate and of the efficiency of the coating process. Therefore, depending on the desired coating thickness, it can be necessary either to start the coating at a rather high surface temperature or to supply additional heat to the surface to be coated during the coating itself .
  • a rather high temperature of the surface to be coated is also advantageous for other reasons as will be discussed below.
  • the tin compound for use as a precursor according to the invention can be any tin compound which is capable of being thermally decomposed at the temperature of the surface of the glass or ceramic article to be coated. During decomposition reaction with oxygen present in the carrier gas results in the deposition of tin oxide.
  • Suitable thermodecomposable tin compounds can be selected from monalkyl tin trichlorides such as monomethyl tin trichloride and monobutyl tin trichloride, monoalkyl tin tribromides , dialkyl tin dichlorides such as dimethyl tin dichloride, dialkyl tin dibromides, and tin tetrachloride.
  • Monobutyl tin trichloride is most preferred for use as precursor of tin oxide, because it is easy to handle and very efficient in use.
  • the silicon compound for use as a precursor should also be capable of being thermally decomposed and then producing silicon oxide as described above with respect to the tin compounds.
  • Suitable silicon compounds are compounds having the formula R n SiX( 4 - n ) ⁇ wherein R is an alkyl, an alkenyl, an alkynyl or an alkoxy group having 1-5 carbon atoms, or a phenyl group; X is a halogen atom or a hydroxy group; and n s a number from 0 to 4.
  • Tetramethoxy silane, tetraethoxy silane and tetrapropoxy silane are examples of suitable silicon compounds .
  • the tin compound is preferably present in an amount of 0.5 x 10" 4 - 2 x 10 "2 mole per 1 mole of carrier gas.
  • the molar ratio of the tin compound to the silicon compound is chosen between 0.6 and 3.0 in view of the high caustic wash resistance aimed at. There has been established that, within the indicated range, the best results are obtained when said molar ratio is at most 2.0 and preferably at most 1.5.
  • the carrier gas preferably air as said before, contains water vapor, which is present in an amount of 1-50 mole(s) per 100 moles of the carrier gas.
  • a sufficient amount of water vapor is usually contained in the air employed as the oxygeneous carrier gas when producing the inventive protecting coating by atmospheri -pressure CVD according to a preferred embodiment.
  • the carrier gas is at a temperature at which the precursors are in evaporated form. In general the temperature of the carrier gas is between 100°C and 210°C and a preferred temperature range is between 120°C and 180°C.
  • the velocity at which the gas stream containing the components detailed above impinges onto the surface to be coated is usually selected in the range of 1-10 m/s and most preferably in the range of 3-5 m/s.
  • the temperature of the glass or ceramic surface to be coated is above the decomposition temperature of the precursors used, but evidently below the softening temperature of the article to be coated.
  • the protecting coating is applied at the hot end of the production line of e.g. glass bottles.
  • a rather high temperature of the surface to be coated not only increases the deposition rate, as has been discussed before, but has also been found to substantially improve the resistance of the coated surface, in particular to caustic wash. Therefore, the temperature at the surface of the article should be at least 550°C during the coating process, the preferred temperature being at least
  • 570°C and the most preferred temperature being at least 600°C, such as between 600°C and 650°C.
  • Additional heat can be supplied to the article during the coating process in order to keep the surface temperature at the desired high value. Any suitable means for supplying additional heat is convenient such as flame projection etc.
  • the coating treatment is continued until the desired coating thickness is obtained.
  • the coating thickness in combination with the molar ratio of the tin compound to the silicon compound and a sufficiently high coating temperature as discussed above, provides the excellent resistance to caustic wash, while the coating maintains a clear appearance.
  • the thickness of the protecting coating should be at least 80 CTU. At thicknesses of at least 150 CTU and preferably of at least 180 CTU the coatings have been found to withstand heavy wash treatments of 12 hours with 4% caustic solutions at 80°C without showing any haze or unwanted colors provided the temperature of the surface to be coated has been sufficiently high.
  • the coating thickness is between 150 CTU (450 A) and 900 A.
  • the compounds of tin and of silicon are introduced into a hot air stream by means of syringes in order to evaporate these compounds.
  • the temperature of the air is about 150°C.
  • the gas mixture is directed towards the surface of the glass articles to be treated by means of a tube, as is well known.
  • the opening of the tube is 15 x 35 mm.
  • Glass bottles of 50 ml are treated over two-thirds of their height. They are heated in an oven to the desired temperature. The temperature is measured by means of a thermocouple disposed inside the bottles.
  • the bottles are fixed by any appropriate means, for instance by means of a stick allowing the bottles to be handled and rotated during their exposure in the treatment gas stream.
  • the temperature of the glass at the start of the formation of the coating is measured by means of an infrared thermometer (type CHINO IR-AHOT/-50°C to + 1000°C) set at an emissivity of 0.93, sensitive over a wavelength range of from 4 to 13 ⁇ .
  • an infrared thermometer type CHINO IR-AHOT/-50°C to + 1000°C
  • the test conditions correspond with those of bottle filling stations .
  • the bottles are immersed in a 4% sodium hydroxide solution maintained at 80°C During the test, the container holding the caustic solution has to be purged with nitrogen to avoid any conversion of sodium hydroxide to sodium carbonate as a result of the presence of carbon dioxide present in the ambient air For the same reason, for each test a freshly prepared sodium hydroxide solution is used as sodium carbonate would cause less damage to the coating.
  • 2-liter borosilicate glass containers of 150 mm diameter are used. These containers can contain 4 bottles. The bottles are placed on a plate disposed 20 mm from the bottom of the container. Each bottle is retained by three pins of 6 mm diameter and 15 mm length, which are fixed in holes in the plate. The plate, in the middle thereof, has a hole of 30 mm diameter and 8 holes of 15 mm along its periphery The caustic solution is stirred using a stirrer of 40 mm length and 10 mm diameter, driven at 500 rpm by a magnetic stirring heating plate.
  • AGR American Glass Research Co
  • Example 1 bottles are covered with a tin oxide coating and with a wax coating according to the teaching of U.S. Patent 4,130,673.
  • Example 2 bottles are treated to provide them with a thicker tin oxide coating. To avoid an unacceptable haze, these coatings were formed utilizing higher tin compound concentrations and higher carrier gas velocities .
  • a tin oxide coating is deposited on 4 bottles, starting from monobutyl tin trichloride. To this end, there is impinged on the surface of the glass bottles brought to a temperature of 600°C, a gas mixture comprising air as carrier gas, the tin compound in a ratio of 1.5 x 10" 4 mole per mole of air and water vapor in a concentration of 2.3 moles per 100 moles of air. The air velocity is 3 m/sec. The deposition is effected in 2.5 sec. A tin oxide coating having a thickness of about 35 CTU is obtained.
  • Tin oxide coatings having thicknesses of 100 CTU, 150 CTU and 200 CTU were formed, starting from a gas mixture containing monobutyl tin trichloride in a ratio of 1 x 10 "3 mole per mole of air and water vapor in a concentration of 2.3 moles per 100 moles of air.
  • the air velocity is 5 m/sec.
  • the deposition periods are, respectively, 3 seconds, 4.5 seconds, and 6 seconds .
  • the thickness of these coatings is higher than that of the coating of Example 1. Yet, after one hour of washing under the conditions of Example 1, all the tin oxide films are damaged and partly removed.
  • the general coating procedure described in Example 1 is utilized, including the temperature of 600°C at the surface of the glass bottles .
  • bottles having two different coating thicknesses are prepared.
  • the gas mixture used for forming the coatings on the bottles comprises monobutyl tin trichloride in a ratio of 1 x 10 "3 moles per 1 mole of air, tetraethoxy silane in a ratio of 50 mole % of the mixture of the two metallic compounds, and water vapor in a concentration of 2.3 moles per 100 moles of air.
  • the air velocity is 5m/sec.
  • the deposition periods are, respectively, 4.5 seconds and 6 seconds.
  • the coatings obtained have thicknesses of 150 CTU and 200 CTU. They do not show any haze. As regards the resistance to washing with a caustic solution as realized in the conditions of the preceding Examples, after 12 hours of washing the coating having a thickness of 150 CTU shows only a slight haze and the coating of 200 CTU does not show any damage.
  • Example 5 Coatings are formed on bottles as in Example 3 , but tetrapropoxy silane is used instead of tetraethoxy silane. Similar results as in Example 3 are obtained.
  • Example 5 tetrapropoxy silane is used instead of tetraethoxy silane. Similar results as in Example 3 are obtained.
  • Coatings of a thickness of 150 CTU are formed as described in Example 3. However, the water vapor concentration in the gas mixtures used is varied. These concentrations are, respectively, 8 moles and 14 moles per 100 moles of air.
  • Example 3 The procedure is as in Example 3 , except that instead of monobutyl tin trichloride, tin tetrachloride or monomethyl tin trichloride is used. In both cases, similar results as those of Example 3 are obtained.
  • Example 3 The procedure is as in Example 3, except that different temperatures of the surface of the glass bottles are used: viz 575°C and 625°C. Since at these high temperatures the deposition rates are about the same the deposition periods are, respectively, 4.5 seconds for a coating thickness of 150 CTU and 6 seconds for a coating thickness of 200 CTU. For both coatings thicknesses the resistance to washing with the caustic solution is quite acceptable when the glass surface temperature is 575°C, and is excellent when the glass surface temperature is 625°C.
  • Example 3 The general coating procedure described in Example 3 is utilized, including the temperature of 600°C at the surface of the glass bottles.
  • coatings with a thickness of 200 CTU were prepared, while varying the ratio of the tin compound to the silicon compound in the gas mixture used for forming the coatings .
  • Monobutyl tin trichloride was used in a ratio of 1 x 10" 3 moles per 1 mole of air.
  • the tetraethoxy silane concentration was varied.
  • Water vapor was present at a molar ratio to the tin compound ⁇ * ⁇ the silicon compound of 11.5 , which corresponds with an amount of water vapor of 1.3 3.45 moles per 100 moles of air.
  • the coated bottles were subjected to a 6 hours washing with caustic solution as described in the preceding Examples .
  • the tin compound/silicon compound ratios and the results of the washing tests are given in the Table below.
  • the molar ratio of the tin compound to the silicon compound is preferably chosen in the range of 0.6 to 1.5.

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

Abstract

La présente invention concerne un procédé de production d'un revêtement de protection sur une surface d'un article en verre ou en céramique, le revêtement considéré faisant preuve d'une résistance améliorée aux traitements aux produits de lavage caustiques. Le procédé de l'invention consiste à projeter sur la surface à revêtir, de façon uniforme, de l'oxygène servant de gaz porteur chargé, d'une part d'un précurseur thermodécomposable d'oxyde d'étain (SnO2) ainsi que d'un précurseur thermodécomposable d'oxyde de silicium (SiO2) selon une proportion molaire entre SnO2 et SiO2 variant de 0,6 à 3,0, lesdits précurseurs étant présents sous forme évaporée, et d'autre part de vapeur d'eau à raison d'1 mole pour 100 moles de gaz porteur. En l'occurrence, la température de ladite surface, supérieure aux températures de décomposition desdits précurseurs, atteint au moins 550°C. Ce procédé permet de déposer un revêtement de protection à base d'un mélange d'oxydes comprenant l'oxyde d'étain et l'oxyde de silicium, le dépôt se poursuivant jusqu'à obtenir une épaisseur de couche de revêtement entre 240 et 1000 Å.
EP96904367A 1995-02-22 1996-02-22 Procede de production d'un revetement de protection sur une surface d'un article en verre ou en ceramique Withdrawn EP0810980A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95200440 1995-02-22
EP95200440 1995-02-22
PCT/NL1996/000087 WO1996026163A1 (fr) 1995-02-22 1996-02-22 Procede de production d'un revetement de protection sur une surface d'un article en verre ou en ceramique

Publications (1)

Publication Number Publication Date
EP0810980A1 true EP0810980A1 (fr) 1997-12-10

Family

ID=8220042

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96904367A Withdrawn EP0810980A1 (fr) 1995-02-22 1996-02-22 Procede de production d'un revetement de protection sur une surface d'un article en verre ou en ceramique

Country Status (20)

Country Link
EP (1) EP0810980A1 (fr)
JP (1) JPH11504610A (fr)
KR (2) KR19980702384A (fr)
CN (1) CN1175935A (fr)
AR (1) AR000999A1 (fr)
AU (1) AU4849096A (fr)
BR (1) BR9607269A (fr)
CA (1) CA2211940A1 (fr)
CO (1) CO4560356A1 (fr)
CZ (1) CZ260497A3 (fr)
GT (1) GT199600008A (fr)
HU (1) HUP9801366A3 (fr)
NO (1) NO973829D0 (fr)
NZ (1) NZ302437A (fr)
PE (1) PE61596A1 (fr)
PL (1) PL321863A1 (fr)
TR (1) TR199700841T1 (fr)
UY (1) UY24173A1 (fr)
WO (1) WO1996026163A1 (fr)
ZA (1) ZA961390B (fr)

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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 (fr) * 2001-02-22 2002-09-04 Atofina Vlissingen B.V. Article revetu émaillé et procédé de preparation
KR20040033869A (ko) * 2002-10-16 2004-04-28 권원선 전자렌지용 조리용기 및 그 제조방법
US20080152804A1 (en) * 2006-07-28 2008-06-26 Gulbrandsen Chemicals, Inc. Method for depositing a metal-containing coating on a substrate
MX2009010674A (es) * 2007-04-03 2009-12-01 Ppg Ind Ohio Inc Articulo de ceramica recubierto.
KR100858704B1 (ko) * 2007-10-29 2008-09-17 에스아이디주식회사 케이스 외관의 고저항 박막 코팅방법
GB201523156D0 (en) * 2015-12-31 2016-02-17 Pilkington Group Ltd High strength glass containers
DE112017002437B4 (de) * 2016-05-12 2025-01-30 Toyo-Sasaki Glass Co., Ltd. Glasbehälter und Verfahren und Vorrichtung zur Herstellung desselben
CN110183111B (zh) * 2019-06-19 2024-02-02 广东健诚高科玻璃制品股份有限公司 一种日用玻璃陶瓷的蒸涂装置、蒸涂涂料及其制备方法

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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 (ja) * 1989-07-26 1997-11-05 麒麟麦酒 株式会社 ガラス壜とその製造法
JPH03115139A (ja) * 1989-09-29 1991-05-16 Hitachi Ltd 反射防止膜およびその形成方法
AU651754B2 (en) * 1991-12-26 1994-07-28 Atofina Chemicals, Inc. Coated glass article

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Title
See references of WO9626163A1 *

Also Published As

Publication number Publication date
UY24173A1 (es) 1996-08-06
ZA961390B (en) 1996-07-16
NZ302437A (en) 1998-04-27
CO4560356A1 (es) 1998-02-10
NO973829L (no) 1997-08-20
MX9706302A (es) 1998-06-28
AR000999A1 (es) 1997-08-27
HUP9801366A3 (en) 1998-12-28
PL321863A1 (en) 1997-12-22
HUP9801366A2 (hu) 1998-08-28
WO1996026163A1 (fr) 1996-08-29
JPH11504610A (ja) 1999-04-27
KR19980702384A (ko) 1998-07-15
TR199700841T1 (xx) 1998-02-21
AU4849096A (en) 1996-09-11
CA2211940A1 (fr) 1996-08-29
PE61596A1 (es) 1997-02-01
KR19987002384A (fr) 1998-07-15
GT199600008A (es) 1997-08-14
BR9607269A (pt) 1998-12-15
CN1175935A (zh) 1998-03-11
CZ260497A3 (cs) 1998-01-14
NO973829D0 (no) 1997-08-20

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