EP0603941B1 - Anzeigevorrichtung mit einem Bildschirm ausgerüstet mit einer Filterschicht - Google Patents

Anzeigevorrichtung mit einem Bildschirm ausgerüstet mit einer Filterschicht Download PDF

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Publication number
EP0603941B1
EP0603941B1 EP19930203506 EP93203506A EP0603941B1 EP 0603941 B1 EP0603941 B1 EP 0603941B1 EP 19930203506 EP19930203506 EP 19930203506 EP 93203506 A EP93203506 A EP 93203506A EP 0603941 B1 EP0603941 B1 EP 0603941B1
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EP
European Patent Office
Prior art keywords
filtering layer
display screen
black
silicon dioxide
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.)
Expired - Lifetime
Application number
EP19930203506
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English (en)
French (fr)
Other versions
EP0603941A1 (de
Inventor
Emmanuel Wilhelmus Johannes Leonardus Oomen
Joseph Gijsbertus Van Lierop
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.)
Koninklijke Philips NV
Original Assignee
Koninklijke Philips Electronics NV
Philips Electronics NV
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Application filed by Koninklijke Philips Electronics NV, Philips Electronics NV filed Critical Koninklijke Philips Electronics NV
Priority to EP19930203506 priority Critical patent/EP0603941B1/de
Publication of EP0603941A1 publication Critical patent/EP0603941A1/de
Application granted granted Critical
Publication of EP0603941B1 publication Critical patent/EP0603941B1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/89—Optical or photographic arrangements structurally combined or co-operating with the vessel
    • H01J29/896—Anti-reflection means, e.g. eliminating glare due to ambient light

Definitions

  • the invention relates to a display device comprising a display screen which is provided with a filtering layer comprising silicon dioxide, a black dye, and a metal oxide.
  • the invention also relates to a method of manufacturing a filtering layer of silicon dioxide on a display screen of a display device.
  • Filtering layers serving to reduce the light transmission are used on the faceplates of display devices, such as cathode ray tubes (CRTs) and liquid crystal display devices (LCD and LC-TV), to improve the contrast of the reproduced image.
  • CTRs cathode ray tubes
  • LCD and LC-TV liquid crystal display devices
  • Such filtering layers reduce the transmission of both incident ambient light and light originating from CRT phosphors.
  • the filtering layers can be provided in a uniform manner, the transmission of the filtering layers is also uniform.
  • the incident ambient light passes through the filtering layer and the glass display screen, after which it reflects off the rough phosphor layer on the inside of the display screen and again passes through the display screen and the filtering layer.
  • T transmissivity of the filtering layer
  • the intensity of the reflected ambient light is reduced by a factor of T 2 .
  • Light originating from CRT phosphors passes through the filtering layer only once, so that the intensity of this light is reduced by only a factor of T, resulting in an increase of the contrast by a factor of T.
  • a disadvantage of the known filtering layer is its purplish-violet appearance which in the case of much ambient light leads to an undesired purplish background of the reproduced image.
  • a further disadvantage of the known dyes used is that they are not resistant to light, so that when the layer is exposed to ambient light the transmission of the layer increases with passage of time, and hence the contrast-increasing effect decreases.
  • European patent application EP-A-517.611 discloses a cathode ray tube having a screen provided with a nonglare film comprising silica, a black dye and a metal oxide such as tin oxide or indium oxide as a conductive agent in order to produce an antistatic effect.
  • the invention also aims at providing a simple method of manufacturing such a filtering layer on a display screen, which filtering layer may have, if desired, a high-gloss appearance.
  • a display device as described in the opening paragraph, which is characterized according to the invention in that the metal of the oxide is selected from the group formed by Ge, Zr, Al and Ti.
  • the metal of the oxide is selected from the group formed by Ge, Zr, Al and Ti.
  • Black dyes which are suitable for use in accordance with the invention are Orasol Black CNTM (Colour Index: Solvent Black 28) and Orasol Black RLTM (Colour Index: Solvent Black 29) available from Ciba Geigy; Zapon Black X51TM (Colour Index: Solvent Black 27) available from BASF and Lampronol Black” (Colour Index: Solvent Black 35) available from ICI. Said dyes enable high-gloss black filtering layers to be manufactured.
  • a very suitable dye is Orasol Black CNTM (Colour Index: Solvent Black 28) because it has a high resistance to light. The chemical structural formula of the latter dye is unknown; according to the information provided by the supplier it is a mono-azo chromium complex.
  • the filtering layer comprises dye stuff in a quantity of 1-15% by weight.
  • the transmission of the filtering layer comprising said dye is substantially constant and hence spectrally neutral. It has been found that these and other dyes can readily be leached when the filtering layer is in contact with customary cleaning liquids such as ethanol, acetone, diluted acetic acid, ammonium hydroxide, soap and salt water.
  • customary cleaning liquids such as ethanol, acetone, diluted acetic acid, ammonium hydroxide, soap and salt water.
  • the above metal oxides can be incorporated in the filtering layer on the basis of a mixture of an alkoxysilane and a corresponding alkoxy compounds of said metals, such as tetraethyl orthogermanate Ge(OC 2 H 5 ) 4 (TEOG), tetrabutyl orthozirconate Zr(OC 4 H 9 ) 4 (TBOZ), tetrapropyl orthozirconate Zr(OC 3 H 7 ) 4 (TPOZ), tripropyl orthoaluminate Al(OC 3 H 7 ) 3 (TPOAl) and tetraethyl orthotitanate Ti(OC 2 H 5 ) 4 (TEOTi) in an alcoholic solution.
  • the filtering layer is formed in the hereinafter described manner.
  • the filtering layer comprises 2-15 mole%, preferably 5-12 mole%, of germanium oxide or zirconium oxide in relation to silicon dioxide. Below 5 mole% the filtering layer is less resistant to cleaning liquids and above 15 mole% no further improvement of the resistance to leaching is obtained and the filtering layer becomes unnecessarily expensive. In addition, above 15 mole% of zirconium oxide, there is a greater risk of gellification of the alcoholic solution after a few hours at room temperature, which would render the solution unsuitable for further processing.
  • the object of providing a method of manufacturing a filtering layer of silicon dioxide on a display screen of a display device is achieved in that the filtering layer is manufactured by providing, on the display screen, an alcoholic solution of an alkoxysilane compound, an alkoxy compound of at least one metal selected from the group formed by Ge, Zr, Al and Ti, acidified water and a black dye, followed by a treatment at an increased temperature, thereby forming the filtering layer comprising silicon dioxide, an oxide of the metal and the dye.
  • a suitable alkoxysilane compound for use in the method in accordance with the invention is tetraethyl orthosilicate (TEOS).
  • TEOS tetraethyl orthosilicate
  • Other alkoxysilane compounds of the type Si(OR) 4 , which are known per se , and oligomers thereof can alternatively be used, wherein R represents an alkyl group, preferably a C 1 -C 5 alkyl group.
  • the alcoholic solution is applied to the display screen by spin coating. After drying and heating to, for example, 160°C for 30 minutes a grey to black, smooth and high-gloss filtering layer is obtained in this manner.
  • the solution may be beneficial to add a surface-active substance, for example in quantities of from 0.001 to 5% by weight, to the solution.
  • the alcoholic solution can be applied by spraying, thereby forming a mat filtering layer having anti-glare properties.
  • the alcohol use can be made of ethanol, propanol, butanol, diacetone alcohol or a mixture thereof.
  • acidified water the alkoxy groups of Si and the above-mentioned metals are converted into hydroxy groups by hydrolysis. Said hydroxy groups react with each other and with hydroxy groups of the glass surface of the display screen.
  • acetylacetone (2,4-pentanedione) per mole of alkoxy compound of Ge, Zr, Al or Ti is also added to the alcoholic solution.
  • This addition leads to an improved abrasion resistance of the filtering layer formed.
  • the enol form of acetylacetone forms a complex with the metal M, as a result of which the velocity of the hydrolysis reaction and condensation reaction of the relevant M compound is reduced by steric hindrance.
  • a filtering layer having antistatic properties can be obtained by adding a conductive metal oxide such as tin oxide, indium oxide or antimony oxide, the oxide being suspended in the alcoholic solution of the alkoxy compounds. It is alternatively possible to provide the filtering layer on a separate transparent front plate instead of on the display screen itself.
  • FIG. 1 is a partly exploded perspective view of an embodiment of a cathode ray tube in accordance with the invention.
  • TEOG tetraethoxygermanate
  • Orasol Black CNTM supplier Ciba Geigy
  • a solution is prepared which comprises 100 grams of ethanol, 50 grams of tetraethoxy silane (TEOS) and 8 grams of water acidified with 1 N of HCl. After a reaction time of 30 minutes the two solutions are mixed. After 15 minutes a mixture of 8 grams of water acidified with 1 mole/l of HCl, 50 grams of ethanol and 50 grams of diacetone alcohol is added. After a reaction time of 6 hours, the mixture obtained is passed through a PTFE-filter having a pore size of 0.2 ⁇ m.
  • TEOTi tetraethoxy titanate
  • Orasol Black CNTM a solution which comprises 100 grams of ethanol, 50 grams of TEOS and 8 grams of water acidified with 1 mole/l of HCl. After a reaction time of 30 minutes, the two solutions are mixed. After 15 minutes, a mixture of 8 grams of water acidified with 1 mole of HCl, 50 grams of ethanol and 50 grams of diacetone alcohol is added. After a reaction time of 6 hours, the mixture obtained is passed through a PTFE filter having a pore size of 0.2 ⁇ m.
  • TBOZ tetrabutoxy zirconate
  • the above solutions are spin coated on to clean glass plates of 10 x 10 cm at a speed of 200 r.p.m. for 1 minute.
  • the coated glass plates are heated to 150°C for 20 minutes, thereby forming the cured filtering layers.
  • All filtering layers thus formed are mirror bright, neutral black and exhibit an average transmission of 70 ⁇ 2% between 420 and 680 nm.
  • All filtering layers are resistant to washing with weak acid, weak base, ethanol, acetone, water and customary cleaning agents.
  • the resistance to light of the filtering layers is tested by means of the so-called Xenotest in accordance with DIN-standards 54003 and 54004, using a Heraeus Suntest CPS apparatus.
  • the filtering layers are exposed to artificial light corresponding to daylight under indoor conditions, in such a manner that a residence time of the filtering layer of 24 hours in this apparatus corresponds to 1 year of indoor conditions as tested according to DIN-wool standards.
  • the results after an exposure corresponding to 4 years of indoor use (DIN-wool scale 6) are listed in Table 1.
  • glass plates are provided with filtering layers of silicon dioxide into which zirconium oxide and black dye is incorporated, the zirconium oxide content varying between 5 and 15 mole% in relation to silicon dioxide.
  • coating liquids having varying TBOZ contents are prepared.
  • the filtering layer provided must be resistant to cleaning agents and other customarily used liquids.
  • drops of ethanol (100%), acetone (100%), acetic acid (50%), ammonium hydroxide (14%), soap solution and salt water are provided on the filtering layer. After the drops have dried the surface of the filtering layer is examined as to whether it has been attacked and/or any dye has been leached. The results regarding leaching are shown in Table 2. TABLE 2 mol.
  • Ammonium hydroxide slightly attacks the filtering layer, except when the filtering layer contains at least 10 mol. % of germanium oxide.
  • solution B a solution is prepared (solution B) from the following constituents:
  • the solution obtained is used to coat glass plates.
  • the Figure diagrammatically shows an exploded perspective view of a cathode ray tube which is known per se and which has a glass envelope 31 comprising a display screen 32, a cone 33 and a neck 34.
  • a glass envelope 31 comprising a display screen 32, a cone 33 and a neck 34.
  • an electron gun 35 for generating an electron beam 36.
  • This electron beam 36 is focused on to a target spot 38 on a phosphor layer 37 on the inner surface of the display screen 32.
  • the electron beam 36 is deflected across the display screen 32 in two mutually perpendicular directions x-y by means of the deflection coil system 39.
  • the outer surface of the display screen 32 is provided with a filtering layer 40 which is manufactured as described in any of the above exemplary embodiments.
  • the invention enables spectrally neutral filtering layers to be manufactured and provided on a display screen of a display device in a simple manner.
  • Said filtering layers may be mirror bright, are resistant to light and to customary cleaning liquids. Curing the filtering layer at 160°C, a temperature to which display tubes are resistant, results in scratch-resistant layers.

Landscapes

  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
  • Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
  • Optical Filters (AREA)

Claims (8)

  1. Bildwiedergabeanordnung mit einem Bildschirm mit einer Filterschicht mit Siliziumdioxid, einem schwarzen Farbstoff und mit einem Metalloxid, dadurch gekennzeichnet, daß das Metall des Oxids aus der Gruppe gewählt worden ist, die durch Ge, Zr, Al und Ti gebildet wird.
  2. Bildwiedergabeanordnung nach Anspruch 1, dadurch gekennzeichnet, daß der schwarze Farbstoff ein Mono-azo-chromkomplex mit einem Farbindex: Solvent Black 28 ist.
  3. Bildwiedergabeanordnung nach Anspruch 1, dadurch gekennzeichnet, daß die Filterschicht 2 - 15 Mol% Germaniumoxid gegenüber Siliziumdioxid aufweist.
  4. Bildwiedergabeanordnung nach Anspruch 1, dadurch gekennzeichnet, daß die Filterschicht 2 - 15 Mol% Zirkonoxid gegenüber Siliziumdioxid aufweist.
  5. Verfahren zum Anbringen einer Filterschicht aus Siliziumdioxid auf einem Wiedergabeschirm einer Bildwiedergabeanordnung, wobei die Filterschicht dadurch hergestellt wird, daß am Wiedergabeschirm eine Alkohollösung aus einer Alkoxysilanverbindung, einer Alkoxyverbindung von wenigstens einem Metall, selektiert aus der Gruppe, die durch Ge, Zr, Al und Ti gebildet wird, aus angesäuertem Wasser und aus einem schwarzen Farbstoff vorgesehen wird, wonach eine Behandlung bei erhöhter Temperatur folgt, wodurch die Filterschicht mit Siliziumdioxid, mit einem Oxid des Metalls und mit dem Farbstoff gebildet wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß ein Mono-azo-chromkomplex mit einem Farbindex: Solvent Black 28 als schwarzer Farbstoff verwendet wird.
  7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß als Alkoxyverbindung ein Tetraalkoxyzirkonat oder ein Tetraalkoxygermanat verwendet wird.
  8. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß 0,25 - 1 Mol Azetylazeton je Mol Alkoxyverbindung von Ge, Zr, Al oder Ti zu der Alkohollösung hinzugefügt wird.
EP19930203506 1992-12-21 1993-12-14 Anzeigevorrichtung mit einem Bildschirm ausgerüstet mit einer Filterschicht Expired - Lifetime EP0603941B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19930203506 EP0603941B1 (de) 1992-12-21 1993-12-14 Anzeigevorrichtung mit einem Bildschirm ausgerüstet mit einer Filterschicht

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP92204041 1992-12-21
EP92204041 1992-12-21
EP19930203506 EP0603941B1 (de) 1992-12-21 1993-12-14 Anzeigevorrichtung mit einem Bildschirm ausgerüstet mit einer Filterschicht

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EP0603941A1 EP0603941A1 (de) 1994-06-29
EP0603941B1 true EP0603941B1 (de) 1997-04-02

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69502671T2 (de) * 1994-03-03 1999-01-07 Philips Electronics N.V., Eindhoven Anzeigevorrichtung mit einem mit einer licht absorbierenden schicht versehenen bildschirm
DE69600957T2 (de) * 1995-02-20 1999-06-02 Koninklijke Philips Electronics N.V., Eindhoven Anzeigevorrichtung mit einem bildschirm mit einer lichtabsorbierenden schicht
US5523114A (en) * 1995-03-28 1996-06-04 Chung Picture Tubes, Ltd. Surface coating with enhanced color contrast for video display
CN1060586C (zh) * 1995-05-31 2001-01-10 中华映管股份有限公司 信息显示器面板及其涂布方法
TW382724B (en) * 1998-01-30 2000-02-21 Koninkl Philips Electronics Nv Method of manufacturing a coating on a display window and a display device comprising a display window provided with a coating
JP2000275409A (ja) * 1999-01-18 2000-10-06 Sumitomo Metal Mining Co Ltd 低透過率透明性基材とその製造方法およびこの基材が適用された表示装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62297142A (ja) * 1986-06-16 1987-12-24 尾池工業株式会社 ノングレア−フイルム
US4987338A (en) * 1988-03-31 1991-01-22 Kabushiki Kaisha Toshiba Cathode ray tube with film on face-plate
US5291097A (en) * 1990-05-14 1994-03-01 Hitachi, Ltd. Cathode-ray tube
JPH05299034A (ja) * 1991-06-07 1993-11-12 Sony Corp 陰極線管及びその表示面用塗布液

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