EP3068738A1 - Vitre teintée pour véhicules - Google Patents

Vitre teintée pour véhicules

Info

Publication number
EP3068738A1
EP3068738A1 EP14737342.7A EP14737342A EP3068738A1 EP 3068738 A1 EP3068738 A1 EP 3068738A1 EP 14737342 A EP14737342 A EP 14737342A EP 3068738 A1 EP3068738 A1 EP 3068738A1
Authority
EP
European Patent Office
Prior art keywords
glass
selenium
privacy glass
weight
range
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Withdrawn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
EP14737342.7A
Other languages
German (de)
English (en)
Inventor
Fehiman Akmaz
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.)
TUERKIYE SISE VE CAM FABRIKALARI AS
Original Assignee
Tuerkiye Sise Ve Cam Fabrikalari AS
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 Tuerkiye Sise Ve Cam Fabrikalari AS filed Critical Tuerkiye Sise Ve Cam Fabrikalari AS
Publication of EP3068738A1 publication Critical patent/EP3068738A1/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Withdrawn legal-status Critical Current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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Definitions

  • the present invention relates to privacy glasses with low visible and solar transmission preferably in order to be used in sunroofs of vehicles.
  • the roofs of vehicles with sunroof are made of glass, and these glasses are called "privacy glass” in the literature.
  • These glasses provided in said ceiling section, shall be light-proof and heat-proof for driver and passenger health particularly during long-term voyages. Therefore, in obtaining such glasses, color additives are used having absorption both in the visible region and in the infrared region.
  • color additives are used having absorption both in the visible region and in the infrared region.
  • pluralities of oxides are added to the batch.
  • One of the most frequently used oxides in coloring is the iron oxide.
  • the iron oxide can be in the form of Fe +2 and Fe +3 in the glass. Fe +2 provides blue-green color to the glass, and Fe +3 provides yellow-green color to the glass.
  • Coloring by means of iron oxide is mostly used in production of green glasses used in automotive sector.
  • green glasses In order to obtain Fe +2 form in glass, green glasses shall be melted in reducing conditions.
  • the reducing agents comprising carbon enter into reaction with oxygen provided in the melted glass, and thereby they decrease partial pressure of oxygen. Therefore, carbon is frequently used as the reducing agents.
  • the performance of carbon on glass changes depending on the size of the particle. This creates a problem in the provision of standardization in production.
  • carbon provides sulphate to react at low temperatures, and leads to beforetime consumption of sulphate, and leads to silica problem.
  • said glass comprises Si0 2 in proportion of 69-75 %, Al 2 0 3 in proportion of 0-3 %; B 2 0 3 in proportion of 0-5 %, CaO in proportion of 2-10 %, MgO in proportion of 0-2 %, Na 2 0 in proportion of 9-17 %, K 2 0 in proportion of 0-8 %, Fe 2 0 3 in proportion of 0.2-4 % and Se, CoO, Cr 2 0 3 , NiO, CuO in proportion of 0-0.45 %.
  • the iron proportion is 1.5 % and lower, the amount of the coloring agents except iron is minimum 0.0002 %.
  • Said composition may comprise florin, zinc, zircon, cerium and titanium oxides; and may comprise barium oxide less T -than 4 % and the total percent of soil alkali acids is maximum 10 %.
  • the amount of Se used in said invention is maximum 0.008 %. However, since the amount of Se in the glass is low, this has a negative effect on the stability of the glass color desired to be obtained.
  • EP1218302 there is a green colored, infrared and ultraviolet absorbing glass article having a visible transmittance of up to 60 %.
  • the composition of the glass article uses a standard soda-lime-silica glass base composition and additionally iron oxide in proportion of 0.13-0.9 % in weight, cobalt oxide in proportion of 0.004-0.05 % in weight, selenium in proportion of 0.0005-0.007 % in weight, and chromium oxide in proportion of 0.0015-0.08 % in weight, and preferably titanium oxide in proportion of 0-1 % in weight, as infrared and ultraviolet radiation absorbing materials and colorants.
  • the visible transmittance of said glass in the thickness range 1 mm-10 mm and in the wavelength range 480-565 is maximum 60 % and total solar energy transmittance 50 % and lower.
  • the highest transmittance values given in the invention with publication number EP1218302 are desired to be lower in privacy glasses.
  • the present invention relates to dark-colored glasses used in vehicle sunroofs, for eliminating the above mentioned disadvantages and for bringing new advantages to the related technical field.
  • An object of the present invention is to provide a glass whose visible transmittance, UV and solar transmittance are low, in order to decrease the air-conditioner load of the vehicle and in order to prevent deformation of the textile and plastic material in the inner space particularly for use in sun-roofs of vehicles.
  • the present invention is to provide a glass which is grey colored.
  • the present invention is a dark-colored privacy glass having thickness in the range of 2 mm - 6 mm and having low transmission, preferably for use in vehicles, and comprising the main composition whose component proportions are given below and comprising selenium in the range of 11-25 ppm in the glass, which is the final product, in order to provide color in grey tones to the glass by being used together with cobalt oxide: Component Weight, %
  • the present invention comprises tin oxide in the range of 0.05-1.0 % in weight reducing Fe +3 , obtained from iron oxide, to Fe +2 and increasing selenium retention, when compared to glass without tin, in the dark colored glass which is the final product.
  • the glass color can be obtained in pinkish grey tones.
  • L value of said dark colored glass is minimum in the range of (48.1) - (52.2); value “a” is between (-7.90) - (- 5.98) and value “b” is between (-4.47) - (+3.97).
  • the visible transmission value (Tv) of said dark colored special glass is minimum 7.5 % and maximum 43 %.
  • the solar transmittance value (Te) of said dark colored special glass is minimum 5 % and maximum 34 %.
  • the transmission value (Tuv) of said dark colored special glass measured in the ultraviolet region is lower than 11 %.
  • the transmission value (Tuv) of said dark colored special glass measured in the ultraviolet region is lower than 8 %.
  • FIGURES In Figure 1 , the % transmision graphics for 4 mm glass thickness in the presence of 11 ppm and 25 ppm selenium for the crucible melting experiments of the privacy glass are given.
  • Iron, cobalt, selenium, tin and sodium nitrate are added to the subject matter glass batch, whose main composition is given above, as colorant agents for providing the desired optic properties.
  • the iron in the batch is provided in iron oxide form; and cobalt is provided in cobalt oxide form.
  • sulphate is used against the affination problem met in glass production.
  • Zinc selenide is used as the selenium source.
  • Cobalt provides blue color to glass and shows very strong absorption in the visible region wavelength range 530 nm- 590 nm and 650 nm. This decreases visible transmission and solar transmission value, since solar transmission can be calculated in the 350 nm-2100 nm wavelength range.
  • Cobalt is in divalent ionic form normally in soda-lime-silica glass or in other glasses.
  • Selenium decreases transmittance of glass.
  • the melting point of selenium providing pink color to soda-lime-silica glasses by means of the absorption band centered at 490 nm wavelength in neutral or light oxidant conditions is 217 °C and the boiling point thereof is 685 °C, and therefore, 70-90 % of selenium given to the furnace together with the batch vaporizes during melting.
  • Fe +2 provides blue-green color to the glass and Fe +3 provides yellow-green color to the glass.
  • the color provided by Fe +2 to the glass is 10 times stronger than the color provided by Fe +3 provided that they are in the same concentration.
  • Fe +2 has a strong absorption centered at 1050 nm wavelength in the infrared region. This absorption band continues up to 500 nm wavelength in the visible region and provides solar control function.
  • Fe +3 has absorption band centered at 440-430 and 380 nm wavelengths in the visible region and absorption band continuing in the ultraviolet region.
  • the concentration of reducing agents added to the glass batch decreases since some of the agents vaporize and some of the agents react due to the increase of the melting duration, and there remains no reducing agent in the glass melting after certain duration. Meanwhile, the partial pressure of the oxygen in the glass melting becomes lower than the partial •' pressure of the furnace atmosphere. When all of the agents are consumed, the partial pressure of the oxygen in the glass melting begins increasing and it is balanced with the partial pressure of the oxygen in the furnace atmosphere.
  • the Fe +2 concentration forming as a result of this is the present concentration. In order to keep the present iron in Fe +2 form, redox pair is required whose oxygen affinity is higher than Fe +2 and having low valence.
  • Tin is a suitable redox pair (Sn +2 - Sn +4 ) for keeping iron in Fe +2 form.
  • the standard reducing potential of tin redox pair (Sn +2 - Sn +4 ) is 0.15 eV in aqueous solutions and this value is 0.77 eV in iron (Fe +2 - Fe +3 ). From here, it is seen that Sn +2 ions have more oxygen affinity than the Fe +2 ions.
  • tin oxide is added into the glass in order to reduce iron oxide and in order to decrease transmittance in the infrared region.
  • experiments, with and without Sn0 2 in different proportions, are realized in two different iron oxide levels.
  • the results are given in Table 2.
  • Table 2 the increase in tin oxide reduces iron.
  • Selenium is added to the batch together with cobalt oxide in order for the glass to be in grey tones. Because of the volatility of selenium, the addition amount of selenium to the batch and the remaining amount thereof in the final product are important. The decrease of volatility of selenium is an important factor in obtaining a more stable color in glass. In the present invention, it is observed that the tin addition used for reducing iron decreases the volatility of selenium provided in glass batch and observed that tin addition increases selenium retention in the glass surprisingly. Thus, tin addition affects in a positive manner in obtaining pinkish grey tones which is the desired glass color.
  • CoO amount is 250 ppm
  • Fe 2 0 3 amount is 1.40 % in weight
  • the tin amount is between 0.5-1 %.
  • sodium nitrate added to the batch in the proportion range 0.3-0.5 (kg/100 kg glass) supports the glass color to be more stable. In the preferred application, sodium nitrate in proportion of 0.3 is used.
  • the amount of selenium entering into the batch as can be seen in Table 4 is 50-150 (ppm/100 kg glass) from ZnSe0 3 added to the batch as the selenium source in proportions given in Table 6, and the remaining amount in the glass after heat process is 11-25 (ppm/100 kg glass).
  • the transmission values of glass in the thickness range of 2 mm - 6 mm comprising the additives in the proportions given in Table 7 are given in Table 8 and Table 9.
  • Table 8 (Se: 25 ppm) Transmittance of glass with tin between 2 mm - 6 mm thickness
  • Tin oxide is not volatile since it has a stable structure and thus supports the stability of production. At the same time, from the studies realized, it is clearly seen that tin addition increases selenium retention in glass more than anthracite, and thus, glass color can be obtained in pinkish grey tones as given in the color analysis results in Table 10. Moreover, the standardization problem faced in productions with anthracite which may exist in various particle sizes in every usage is not faced in production with tin which may be used in close particle size range in every usage. Additionally, since tin oxide does not volatilize from the body even if the particle size is various, it has a positive effect on selenium retention.

Landscapes

  • 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)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne une vitre spéciale de couleur foncée ayant une épaisseur située dans la plage allant de 2 mm à 6 mm et ayant une faible transmittance, à utiliser de préférence dans les véhicules, et comprenant la composition principale dont les proportions des constituants sont présentées ci-dessous et qui comprend du sélénium dans la plage allant de 11 à 25 ppm dans la vitre, qui est le produit final, afin de fournir la couleur dans des tons fumés au verre en l'utilisant conjointement avec de l'oxyde de cobalt : % en poids du constituant SiO2 60-75 Na2O 10-25 CaO 5-20 MgO 3,5 - 5 Al2O3 0-5 K2O 0-5 et comprenant les colorants suivants en poids: quantité en % du constituant Fe2O3 (en poids) (dans la vitre) 1,35-1,45 CoO (ppm)(dans la vitre) 245-255 NaNO3 (dans le mélange) (kg/100kg de vitre) 0,3 - 0,5 caractérisé en ce qu'il comprend de l'oxyde d'étain dans la plage de 0,05-1,0 % en poids en réduisant du Fe3+, obtenu à partir d'oxyde de fer, en Fe2+ et en augmentant en permanence le sélénium, comparativement à la vitre sans étain, dans la vitre colorée foncée qui est le produit final.
EP14737342.7A 2013-11-16 2014-03-12 Vitre teintée pour véhicules Withdrawn EP3068738A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR201313333 2013-11-16
PCT/TR2014/000072 WO2015072939A1 (fr) 2013-11-16 2014-03-12 Vitre teintée pour véhicules

Publications (1)

Publication Number Publication Date
EP3068738A1 true EP3068738A1 (fr) 2016-09-21

Family

ID=51168325

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14737342.7A Withdrawn EP3068738A1 (fr) 2013-11-16 2014-03-12 Vitre teintée pour véhicules

Country Status (3)

Country Link
EP (1) EP3068738A1 (fr)
RU (1) RU2016123396A (fr)
WO (1) WO2015072939A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140309099A1 (en) 2013-04-15 2014-10-16 Ppg Industries Ohio, Inc. Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same
US11261122B2 (en) 2013-04-15 2022-03-01 Vitro Flat Glass Llc Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same
TW201803816A (zh) * 2016-03-16 2018-02-01 維托玻璃製造公司 低鐵含量、高氧化還原比及高鐵含量、高氧化還原比之碳酸鈉－氧化鈣－氧化矽玻璃及其製備方法
JP7120021B2 (ja) * 2016-10-21 2022-08-17 Ａｇｃ株式会社 ソーダライムガラス板

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393593A (en) * 1990-10-25 1995-02-28 Ppg Industries, Inc. Dark gray, infrared absorbing glass composition and coated glass for privacy glazing
JPH10101369A (ja) * 1996-10-01 1998-04-21 Nippon Sheet Glass Co Ltd 紫外線赤外線吸収ガラス
US6408650B1 (en) * 1997-12-10 2002-06-25 Ford Global Technologies, Inc. Nitrate/nitrite-free manufacturing of glass with selenium
US6524713B2 (en) * 1998-03-25 2003-02-25 Nippon Sheet Glass Co., Ltd. Ultraviolet-infrared absorbent low transmittance glass
JP2001206731A (ja) * 2000-01-24 2001-07-31 Nippon Sheet Glass Co Ltd 紫外線赤外線吸収低透過ガラス

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015072939A1 *

Also Published As

Publication number Publication date
RU2016123396A3 (fr) 2019-03-27
WO2015072939A1 (fr) 2015-05-21
RU2016123396A (ru) 2019-03-27

Similar Documents

Publication Publication Date Title
JP3127201B2 (ja) 濃い灰色のソーダライムガラス
JP4169394B2 (ja) 濃い緑色のソーダライムガラス
CA2139334C (fr) Verre neutre a facteur de transmission peu eleve
JP4213227B2 (ja) 窓ガラスの製造用のガラス組成物
US5411922A (en) Neutral gray-green low transmittance heat absorbing glass
JP4546646B2 (ja) 青色相のソーダライムガラス
JP5183600B2 (ja) 青緑色ガラス
KR101062878B1 (ko) 짙은 중성 녹회색의 소다라임 유리 조성물
JPH0264038A (ja) 黒ずんだ、濁った灰色でニッケルを含まないガラス組成物
NZ248851A (en) Uv-absorbing glass containing iron and titanium oxides
JPH10101369A (ja) 紫外線赤外線吸収ガラス
IE63124B1 (en) Infrared and ultraviolet radiation absorbing green glass composition
JPH09110464A (ja) 極めて濃い灰色のソーダライムガラス
JPH0859287A (ja) グレイソーダライムガラス
MXPA06010675A (es) Composicion de vidrio de silice de cal sodada gris oscuro que se pretende para la produccion de vidrieria.
KR20140089788A (ko) 짙은 녹회색 저투과 유리 조성물
WO1997011036A1 (fr) Verre neutre a faible facteur de transmission
BR112012030648B1 (pt) Composição de vidro escuro para controle solar
WO2015072939A1 (fr) Vitre teintée pour véhicules
JP2005512932A (ja) ウィンドウガラスの製造を目的とする青色ガラス組成物
CZ20004846A3 (cs) Zeleně zabarvené sodnovápenaté sklo
EP0976691B1 (fr) Verre absorbant les rayons ultraviolets
CZ301046B6 (cs) Sodnovápenatokremicité zabarvené sklo
GB2304710A (en) Clear grey soda-lime glass
JPH1072239A (ja) 紫外線赤外線吸収ガラス

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160614

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TUERKIYE SISE VE CAM FABRIKALARI A.S.

17Q First examination report despatched

Effective date: 20190321

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190801