EP0538937B1 - Antireflektive und antistatische Verkleidungsschicht insbesonder für eine Elektronenstrahlröhre - Google Patents

Antireflektive und antistatische Verkleidungsschicht insbesonder für eine Elektronenstrahlröhre Download PDF

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Publication number
EP0538937B1
EP0538937B1 EP19920203161 EP92203161A EP0538937B1 EP 0538937 B1 EP0538937 B1 EP 0538937B1 EP 19920203161 EP19920203161 EP 19920203161 EP 92203161 A EP92203161 A EP 92203161A EP 0538937 B1 EP0538937 B1 EP 0538937B1
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Prior art keywords
layer
coating
silicon dioxide
antistatic
antireflective
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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
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EP19920203161
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English (en)
French (fr)
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EP0538937A1 (de
Inventor
Johannes M.A.A. C/O Int. Octrooibureau Bv Compen
A.L.G. C/O Int. Octrooibureau Bv Van Den Eeden
Jürgen P.A. c/o INT. OCTROOIBUREAU BV Heymbeeck
Henricus A.A. C/O Int. Octrooibureau Bv Keetels
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Koninklijke Philips NV
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Koninklijke Philips Electronics NV
Philips Electronics NV
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Priority to EP19920203161 priority Critical patent/EP0538937B1/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
    • H01J29/867—Means associated with the outside of the vessel for shielding, e.g. magnetic shields
    • H01J29/868—Screens covering the input or output face of the vessel, e.g. transparent anti-static coatings, X-ray absorbing layers

Definitions

  • the invention relates to an antireflective and antistatic coating on a substrate, which coating comprises a double layer consisting of a layer of silicon dioxide and an antiglare layer.
  • the invention also relates to a cathode ray tube comprising a display screen having an antireflective and antistatic coating comprising a double layer which consists of a layer of silicon dioxide and an antiglare layer.
  • the invention further relates to a method of manufacturing an antireflective and antistatic coating on a substrate, which coating comprises a double layer consisting of an antistatic layer and an antiglare layer, said antistatic layer being manufactured by providing a suspension of at least one conductive metal oxide in an alcoholic solution of an alkoxysilane compound, followed by a treatment at an increased temperature to form a layer of a mixture of silicon dioxide and at least one conductive metal oxide.
  • the invention also relates to an alternative method of manufacturing an antireflective and antistatic coating on a substrate, which coating comprises a double layer consisting of a layer of silicon dioxide and an antiglare layer.
  • Antireflective coatings are used, for example, on display screens of display devices, on envelopes of light sources and on other optical elements such as windows, to reduce reflection losses of traversing light and to suppress disturbing reflections in images. Coatings as described above are more particularly used to reduce specular reflection (antiglare effect).
  • Antistatic coatings are used, for example, on display screens of display devices. Such layers are sufficiently electroconductive to ensure that a high electrostatic voltage present on the outside surface of the device is removed within a few seconds. Thus, it is precluded that a user upon touching a screen is unpleasantly shocked and, in addition, the attraction of atmospheric dust is reduced.
  • the silicon dioxide layer is an antistatic layer which contains, for example, a transparent conductive metal oxide, and which is disposed between the substrate and the antireflective layer and has a thickness of 5 to 50 nm.
  • the antireflective layer also contains silicon dioxide and comprises silicon dioxide particles having diameters of 10 to 1000 nm. If desired, the functions of both layers can be combined in a single layer.
  • Said United States Patent Specification also describes a method of manufacturing an antireflective and antistatic coating.
  • Both layers are manufactured by providing an alcoholic solution of an alkoxysilane compound, followed by a treatment at an increased temperature to form a layer of silicon dioxide.
  • a conductive metal oxide such as tin oxide, indium oxide or antimony oxide, is suspended in the alcoholic solution of the alkoxysilane compound.
  • silicon dioxide particles are suspended in the alcoholic solution of the alkoxysilane compound.
  • a disadvantage of this known method of manufacturing an antireflective and antistatic coating is that it utilizes a reactive, intrinsically unstable alcoholic solution of an alkoxysilane compound.
  • the solution is sensitive to moisture and has limited keeping qualities.
  • As the structure of the layer thus manufactured is governed, inter alia, by the degree of hydrolysis and polymerization of the alkoxysilane compound and by the viscosity of the solution, the reproducibility of the result leaves a lot to be desired. This is important, in particular, for the antireflective layer in which the microstructure substantially influences the optical properties, and it is only of minor importance for the much thinner antistatic layer.
  • a further disadvantage of the known method is formed by the use of an organic solvent which, when used on a large scale, requires a number of safety precautions to be taken.
  • the coating manufactured according to the known method is mechanically weak due to the presence of discrete silicon dioxide particles in the surface layer.
  • the invention aims to use stable starting materials having long keeping qualities.
  • a further object of the invention is to provide a mechanically strong layer having stable properties which are not subject to rapid deterioration due to damage, the attack of moisture or contamination.
  • a particular object of the invention is to provide a cathode ray tube comprising a display screen which is provided with such an antireflective and antistatic coating.
  • a still further object of the invention is to provide a simple and reliable method of providing an antireflective and antistatic coating. In this connection, the invention aims at minimizing the use of organic solvents.
  • an antireflective and antistatic coating as described in the opening paragraph, which coating comprises a double layer consisting of a layer of silicon dioxide and an antiglare layer, said coating according to the invention being characterized in that the antiglare layer consists of lithium silicate.
  • the layer of silicon dioxide is an antistatic layer which contains at least one conductive metal oxide.
  • Suitable transparent, conductive metal oxides are tin oxide, indium oxide, antimony oxide and mixtures of said oxides.
  • Other materials which are known per se, such as hygroscopic materials and metals and metal compounds, in particular palladium compounds, may alternatively be used to provide the antistatic layer with the required electric conductance.
  • the layer of silicon dioxide is located between the substrate and the layer of lithium silicate.
  • materials may be added to the layers to change the optical, mechanical or other properties.
  • dyes may be used to influence the light transmission properties.
  • the silicon dioxide layer contains at least one dye. This is preferred to the addition of a dye to the lithium silicate layer because the incorporation of the dye in such a layer is less durable.
  • the layer of lithium silicate is located between the substrate and the layer of silicon dioxide.
  • the layer of lithium silicate is an antistatic layer which contains at least one conductive metal oxide, said layer being located between the substrate and the layer of silicon dioxide.
  • the conductive metal oxides used, or if desired other materials imparting electric conductance, may be the same as those used in the two above-mentioned embodiments in the layer of silicon dioxide.
  • the layer of silicon dioxide serves to ensure that the materials which are added to the layer of lithium silicate are permanently incorporated therein.
  • dyes can be added to each of the layers at will.
  • at least one of the layers of the double layer contains a dye.
  • dyes are permanently incorporated, and the layer of lithium silicate according to these embodiments is covered with a layer of silicon dioxide, so that also in this case a definitely stable coating is obtained.
  • a substrate comprising a coating according to the invention may additionally be provided with antireflective layers, which are known per se, to reduce both the total specular reflection and the total diffuse reflection.
  • antireflective layers which are known per se, to reduce both the total specular reflection and the total diffuse reflection.
  • a layer of magnesium fluoride having a low refractive index may be provided as the outermost layer, or a stack of layers having alternately high and low refractive indices may be used.
  • the refractive index may be changed by adding, if desired, dopants to the coating according to the invention, in particular to the silicon dioxide layer.
  • a stack of layers which is suited to reduce total reflection consists, for example, of a first antistatic layer of silicon dioxide which is additionally doped with titanium dioxide (refractive index 1.7), and a second layer of titanium dioxide (refractive index 2.1, to be manufactured according to a method which is analogous to the method of manufacturing the silicon dioxide layer), and with an outermost antiglare layer of lithium silicate (refractive index 1.43).
  • the thickness of each of the layers is 100 to 150 nm.
  • the object of providing a method of manufacturing an antireflective and antistatic coating is achieved by a method as described in the opening paragraph, in which a double layer is manufactured comprising an antistatic layer and an antiglare layer, the antistatic layer being manufactured by providing a suspension of at least one conductive metal oxide in an alcoholic solution of an alkoxysilane compound, followed by a treatment at an increased temperature to form a layer of a mixture of silicon dioxide and at least one conductive metal oxide, which method according to the invention is characterized in that the antiglare layer is manufactured by providing a lithium oxide-stabilized silicon dioxide sol in water, followed by a treatment at an increased temperature to form a layer of lithium silicate.
  • the antistatic layer and the antiglare layer can be provided on a substrate, for example on the display screen of a cathode ray tube, in any desired relative order.
  • an alternative method in accordance with the invention is characterized in that an antiglare layer having an antistatic effect is manufactured by providing a suspension of at least one conductive metal oxide in a lithiumoxide-stabilized silicon dioxide sol in water, followed by a treatment at an increased temperature to form a layer of a mixture of lithium silicate and at least one conductive metal oxide, after which a protective layer is manufactured by providing an alcoholic solution of an alkoxysilane compound, followed by a treatment at an increased temperature to form a layer of silicon dioxide.
  • a layer of silicon dioxide is used which can be manufactured in accordance with a method described in United States Patent Specification US 4,945,282. According to the invention, this layer is used as an antistatic layer or as a protective layer. For both applications a relatively thin layer, having a thickness below 200 nm, preferably between 5 and 50 nm, can be used. By virtue thereof, the required quantities of reactive and, thus, unstable alkoxysilane compound and of the organic solvent are limited as compared with the method according to the state of the art. According to the invention, a layer of lithium silicate is used for the antiglare layer, which lithium silicate layer does not contain discrete particles and, hence, exhibits great mechanical strength.
  • Figs. 1 to 3 are diagrammatic cross-sectional views of different embodiments of a substrate comprising a coating layer according to the invention.
  • Fig. 4 is a partly cut-away perspective view of an embodiment of a cathode ray tube according to the invention.
  • Fig. 1 shows a substrate 2 having an antireflective and antistatic coating in accordance with a first embodiment of the invention, which coating consists of a double layer comprising an antistatic layer 4 of silicon dioxide with at least one conductive metal oxide, and an antiglare layer 6 of lithium silicate.
  • Such a coating was manufactured by the following method according to the invention.
  • the display screen of a cathode ray tube was thoroughly cleaned, after which a first, antistatic layer was provided by spin coating.
  • the coating material consisted of a solution of 2% by weight of tetraethyl orthosilicate Si(OC2H5)4 in ethanol, wherein 1% by weight of a 1:0.15 mixture of tin oxide SnO2 and antimony oxide Sb2O3 was dispersed as the conductive material.
  • the coating material contains a dye, for example 0.2% by weight of Rhodamine B, available from Merck.
  • the dimensions of the metal oxide particles and dyes present in the suspension are smaller than 50 nm to preclude light scattering.
  • the layer was dried at 60°C and had a thickness in the range between 50 and 100 nm.
  • a second, antiglare layer was provided by spin coating.
  • the coating material consisted of a lithium oxide-stabilized silicon dioxide sol in water having a solid content of 2% by weight and a SiO2:Li2O molar ratio of 8:1.
  • the layer thickness was approximately 1000 nm.
  • both layers were cured by a treatment at a temperature of 160° C for 30 minutes, in which treatment the first layer was converted to silicon dioxide and the second layer was converted to lithium silicate. Finally, the display screen was washed with running water and dried.
  • the display screen thus obtained was sufficiently electroconductive and antistatic.
  • the increase in diffuse reflection at the expense of specular reflection assists in the suppression of disturbing images of, for example, external light sources on a display screen.
  • alkoxysilane compounds of the type Si(OR)4, which are known per se can alternatively be used, where R is an alkyl group having preferably 1 to 5 carbon atoms.
  • R is an alkyl group having preferably 1 to 5 carbon atoms.
  • methanol may alternatively be used as the solvent.
  • a quantity of water having, for example, an inorganic acid may be added to the solution to enhance the conversion to silicon dioxide.
  • suitable compositions are described in, for example, United States Patent Specification US 4,945,282, wherein also suitable conductive metal oxides are mentioned in addition to other compounds which can suitably be used in an antistatic layer.
  • conductive metal oxides for example, compounds of palladium, platinum or gold may be used to obtain electric conductance, see United States Patent Specification US 4,563,612.
  • Compositions which are suitable for a lithium oxide-stabilized silicon dioxide sol in water, are described in United States Patent Specifications US 3,940,511 and US 4,563,612.
  • Fig. 4 diagrammatically shows a cathode ray tube, which is known per se , comprising a glass envelope 31 having a display window 32, a cone 33 and a neck 34.
  • an electron gun 35 for generating an electron beam 36.
  • Said electron beam 36 is focused on a display screen 37 to form a target spot 38.
  • the electron beam 36 is deflected across the display screen 37 in two mutually perpendicular directions x-y by means of the deflection coil system 39.
  • a layer of a luminescent material (phosphor) is present on the display screen 37.
  • the outside of the display window 32 is provided with an antireflective and antistatic coating 40 which was manufactured as described in exemplary embodiment 1.
  • Fig. 2 shows a substrate 12 having an antireflective and antistatic coating in accordance with a second embodiment of the invention, which coating consists of a double layer comprising an antiglare layer 16 of lithium silicate and an antistatic layer 14 of silicon dioxide containing at least one conductive metal oxide.
  • Such a coating was manufactured by using the materials and the method in accordance with exemplary embodiment 1, except that the sequence in which the layers were provided was reversed. After providing a first layer of a lithium oxide-stabilized silicon dioxide sol, said layer was dried at 60°C. After providing the second layer containing the alkoxysilane compound, both layers were annealed at a temperature of 160° C for 30 minutes, after which the display screen was washed with running water and dried. The result obtained was the same as described in exemplary embodiment 1.
  • Fig. 3 shows a substrate 22 having an antireflective and antistatic coating in accordance with a third embodiment of the invention, which coating consists of a double layer comprising an antiglare and antistatic layer 26 of lithium silicate containing at least one conductive metal oxide, and a protective layer 28 of silicon dioxide.
  • Such a coating was manufactured by using the materials and the method in accordance with exemplary embodiment 3, except that the conductive metal oxides were suspended in the lithium oxide-stabilized silicon dioxide sol in water instead of in the alcoholic solution of the alkoxysilane compound.
  • the quantities used, the process steps and the results were the same as in exemplary embodiment 3.

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  • Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Claims (10)

  1. Antireflektive und antistatische Verkleidungsschicht auf einem Träger (2), wobei diese Schicht aus einer Doppelschicht aus einer Siliziumdioxidschicht (4, 14, 28) und einer Blendschutzschicht (6, 16, 26) besteht, dadurch gekennzeichnet, daß die Blendschutzschicht aus Lithiumsilikat besteht.
  2. Verkleidungsschicht nach Anspruch 1, wobei die Siliziumdioxidschicht (4, 14) eine antistatische Schicht ist, die wenigstens ein leitendes Metalloxid aufweist.
  3. Verkleidungsschicht nach Anspruch 2, wobei die Siliziumdioxidschicht (4) zwischen dem Träger und der Lithiumsilikatschicht (6) liegt.
  4. Verkleidungsschicht nach Anspruch 3, wobei die Schicht aus Siliziumdioxid mindestens einen Farbstoff aufweist.
  5. Verkleidungsschicht nach Anspruch 2, wobei die Schicht aus Lithiumsilikat (16, 26) zwischen dem Träger und der Siliziumdioxidschicht (14, 28) liegt.
  6. Verkleidungsschicht nach Anspruch 1, wobei die Schicht aus Lithiumsilikat (26) eine antistatische Schicht ist, die mindestens ein leitendes Metalloxid aufweist, wobei diese Schicht zwischen dem Träger und der Schicht aus Siliziumdioxid (28) liegt.
  7. Verkleidungsschicht nach Anspruch 5 oder 6, wobei mindestens eine der Schichten der Doppelschicht einen Farbstoff aufweist.
  8. Elektronenstrahlröhre mit einem Bildschirm mit einer antireflektiven und antistatischen Verkleidungsschicht, wobei diese Schicht aus einer Doppelschicht aus einer Siliziumdioxidschicht und einer Blendschutzschicht besteht, dadurch gekennzeichnet, daß die Blendschutzschicht aus Lithiumsilikat besteht.
  9. Verfahren zum Herstellen einer antireflektiven und antistatischen Verkleidungsschicht auf einem Träger (2), wobei diese Schicht aus einer Doppelschicht aus einer Siliziumdioxidschicht und einer Blendschutzschicht besteht, wobei die antistatische Schicht (4, 14) dadurch hergestellt wird, daß eine Suspension aus mindestens einem leitenden Metalloxid in einer alkoholischen Lösung einer Alkoxysilanverbindung angebracht wird, wonach eine Behandlung bei erhöhter Temperatur unter Bildung einer Schicht aus einem Gemisch aus Siliziumdioxid und mindestens einem leitenden Metalloxid folgt, dadurch gekennzeichnet, daß die Blendschutzschicht (6, 16) dadurch hergestellt wird, daß ein mit Lithiumoxid stabilisiertes in Wasser hergestellt wird, wonach eine Behandlung bei erhöhter Temperatur unter Bildung einer Schicht aus Lithiumsilikat folgt.
  10. Verfahren zum Herstellen einer antireflektiven und antistatischen Verkleidungsschicht auf einem Träger (2), wobei diese Schicht aus einer Doppelschicht aus einer Siliziumdioxidschicht und einer Blendschutzschicht besteht, dadurch gekennzeichnet, daß eine Blendschutzschicht (26) mit antistatischer Wirkung dadurch hergestellt wird, daß eine Suspension aus mindestens einem leitenden Metalloxid in einem mit Lithium stabilisierten Siliziumdioxidsol in Wasser angebracht wird, wonach eine Behandlung bei erhöhter Temperatur unter Bildung einer Schicht aus einem Gemisch von Lithiumsilikat und mindestens einem leitenden Metalloxid folgt, wonach eine Abdeckschicht (28) dadurch hergestellt wird, daß eine alkoholische Lösung einer Alkoxysilanverbindung angebracht wird, wonach eine Behandlung bei erhöhter Temperatur zur Bildung einer Siliziumdioxidschicht folgt.
EP19920203161 1991-10-23 1992-10-15 Antireflektive und antistatische Verkleidungsschicht insbesonder für eine Elektronenstrahlröhre Expired - Lifetime EP0538937B1 (de)

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Application Number Priority Date Filing Date Title
EP19920203161 EP0538937B1 (de) 1991-10-23 1992-10-15 Antireflektive und antistatische Verkleidungsschicht insbesonder für eine Elektronenstrahlröhre

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP91202744 1991-10-23
EP91202744 1991-10-23
EP19920203161 EP0538937B1 (de) 1991-10-23 1992-10-15 Antireflektive und antistatische Verkleidungsschicht insbesonder für eine Elektronenstrahlröhre

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EP0538937A1 EP0538937A1 (de) 1993-04-28
EP0538937B1 true EP0538937B1 (de) 1996-01-03

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69428320T2 (de) 1993-10-18 2002-07-04 Koninkl Philips Electronics Nv Verfahren zur Herstellung einer Beschichtung auf einen Bildschirm und Anzeigevorrichtung die diese enthalt
BE1007855A3 (nl) * 1993-12-06 1995-11-07 Philips Electronics Nv Werkwijze voor het vervaardigen van een bekledingslaag op een beeldscherm en een beeldweergaveinrichting met een beeldscherm voorzien van een bekledingslaag.
EP0713240B1 (de) * 1994-11-17 2004-10-13 Sumitomo Metal Mining Company Limited Transparente Leiterschicht zur elektrischen Feldabschirmung
GB2389123B (en) 2002-05-29 2005-08-17 Unilever Plc Rechargeable dispensing device
US7166957B2 (en) * 2002-08-14 2007-01-23 Thomson Licensing CRT having a contrast enhancing exterior coating and method of manufacturing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3940511A (en) * 1973-06-25 1976-02-24 Rca Corporation Method for preparing haze-resistant lithium-silicate glare-reducing coating
US4563612A (en) * 1984-06-25 1986-01-07 Rca Corporation Cathode-ray tube having antistatic silicate glare-reducing coating
US4945282A (en) * 1987-12-10 1990-07-31 Hitachi, Ltd. Image display panel having antistatic film with transparent and electroconductive properties and process for processing same

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