# US 5,707,685 A · Process for forming ultrafine particle film, transparent plate and image display plate > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,707,685 A - Document ID: US5707685A - Status: Granted - Kind: A - Application number: 08/062,747 - Filed: 1993-05-18 - Granted: 1998-01-13 - Earliest claimed: 1991-03-19 - Assignees: Hitachi, Ltd. - Inventors: Yoshishige Endou; Masahiko Ono; Masahiro Miyazaki; Hiromitsu Kawamura; Katsumi Kobara; Toshihiro Yamada; Toshiaki Kawabata; Takao Kawamura - Web page: https://patentgrep.com/patent/US5707685A ## CPC - G02B 1/11: Anti-reflection coatings - C03C 17/007: {containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase} - H01J 9/20: Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel - H01J 29/868: {Screens covering the input or output face of the vessel, e.g. transparent anti-static coatings, X-ray absorbing layers} - H01J 29/896: {Anti-reflection means, e.g. eliminating glare due to ambient light} - C03C 2217/475: Inorganic materials - G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS - 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 - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) ## Abstract An ultrafine particle film which is effective for the prevention of electrostatic charge and reflection of visible light and can be applied to a large area at low cost, an image display plate such as the one adapted to a Braun tube to which the ultrafine particle film is applied, and a process for producing the ultrafine particle film which comprises attaching a coating solution bath 22 to a surface of a Braun tube 21, filling the bath with a coating solution 23 containing the antistatic SnO.sub.2 ultrafine particles so that the surface of the Braun tube 21 is covered with the coating solution, and then exposing the coated Braun tube surface at a predetermined rate to form an electrically conductive film on the Braun tube surface, the above process being repeated by using a coating solution containing the visible light anti-reflection ultrafine particles to form a visible light anti-reflection film on the electrically conductive film. ## Claims ### Claim 1 A process for forming films on a surface of a substrate, comprising the steps of: introducing a first coating solution containing antistatic ultrafine particles having an average particle size of 10 nm or less and a binder into a container in which is provided at least the surface of the substrate until said surface is covered with said first coating solution; subsequently discharging said first coating solution from said container to coat said surface with said first coating solution, thereby forming a first film containing antistatic ultrafine particles on said surface; subsequently introducing a second coating solution containing anti-reflection ultrafine particles having an average particle size of 80 to 150 nm and a binder into said container until said surface having said first film provided thereon is covered with said second coating solution; and subsequently discharging said second coating solution from said container to coat said surface having said first film provided thereon with said second coating solution, thereby forming a second film containing anti-reflection ultrafine particles on said first film, wherein the second coating solution is discharged at a rate sufficient to provide said second film in which said anti-reflection ultrafine particles are regularly arranged in a single layer in such a manner that any area not having said anti-reflection ultrafine particles present has a length less than visible light wavelength. ### Claim 2 (depends on 1) A process according to claim 1, wherein the anti-reflection ultrafine particles are selected from the group consisting of SiO.sub.2 (silicon dioxide) and MgF.sub.2 (magnesium fluoride). ### Claim 3 (depends on 1) A process according to claim 1, wherein the antistatic ultrafine particles are selected from the group consisting of SnO.sub.2 (tin dioxide), SnO.sub.2 +Sb.sub.2 O.sub.3 (antimony oxide), In.sub.2 O.sub.3 (indium oxide), and In.sub.2 O.sub.3 +SnO.sub.2. ### Claim 4 (depends on 1) A process according to claim 1, wherein the substrate is glass, the binder of the first and second coating solutions is Si(OR).sub.4 (wherein R is alkyl), and the substrate is pretreated with an alkali and/or hydrofluoric acid. ### Claim 5 (depends on 1) A process according to claim 1, wherein the substrate is a plastic, the binder of the first and second coating solutions is Si(OR).sub.3 (wherein R is alkyl), a coupling agent having a functional group capable of bonding with said plastic is used, and the substrate is pretreated with at least one selected from the group consisting of alkali and hydrofluoric acid. ### Claim 6 (depends on 5) A process according to claim 5, wherein the plastic is acryl resin, and the coupling agent is .gamma.-methacryloxypropyltrimethoxysilane. ### Claim 7 (depends on 5) A process according to claim 5, wherein the plastic is epoxy resin and the coupling agent is .gamma.-glycidoxypropyltrimethoxysilane. ### Claim 8 (depends on 1) A process according to claim 1, wherein said first and second films are formed on both sides of the substrate. ### Claim 9 (depends on 1) A process according to claim 1, wherein said first and second films are formed only on one side of the substrate. ### Claim 10 (depends on 1) A process according to claim 1, wherein the anti-reflection ultrafine particles are SiO.sub.2 ultrafine particles having a particle size of 80 to 150 nm. ### Claim 11 (depends on 1) A process according to claim 1, wherein the antistatic ultrafine particles comprise tin oxide. ### Claim 12 (depends on 1) A process according to claim 1, wherein said substrate is a transparent substrate. ### Claim 13 (depends on 12) A process according to claim 12, wherein the substrate is glass, the binder of the first and second coating solutions is Si(OR).sub.4 (wherein R is alkyl), and the substrate is pretreated with an alkali and/or hydrofluoric acid. ### Claim 14 (depends on 12) A process according to claim 12, wherein the substrate is a plastic, the binder of the first and second coating solutions is Si(OR).sub.3 (wherein R is alkyl), a coupling agent having a functional group capable of bonding with said plastic is used, and the substrate is pretreated with at least one selected from the group consisting of alkali and hydrofluoric acid. ### Claim 15 (depends on 14) A process according to claim 14, wherein the plastic is acryl resin, and the coupling agent is .gamma.-methacryloxypropyltrimethoxysilane. ### Claim 16 (depends on 14) A process according to claim 14, wherein the plastic is epoxy resin, and the coupling agent is .gamma.-glycidoxypropyltrimethoxysilane. ### Claim 17 (depends on 12) A process according to claim 12, wherein the anti-reflection ultrafine particles are selected from the group consisting of SiO.sub.2 and MgF.sub.2. ### Claim 18 (depends on 12) A process according to claim 12, wherein the anti-reflection ultrafine particles are SiO.sub.2 ultrafine particles. ### Claim 19 (depends on 12) A process according to claim 12, wherein the surface of the substrate is provided in said container such that said surface extends in a substantially vertical direction. ### Claim 20 (depends on 1) A process according to claim 1, wherein said first coating solution further contains infrared reflection ultrafine particles having an average particle size of 5 to 50 nm. ### Claim 21 (depends on 1) A process according to claim 1, wherein the infrared reflection ultrafine particles are selected from the group consisting of SnO.sub.2, SnO.sub.2 +Sb.sub.2 O.sub.3, In.sub.2 O.sub.3, In.sub.2 O.sub.3 +SnO.sub.2, TiO.sub.2 (titanium oxide), and ZrO.sub.2 (zirconium oxide). ### Claim 22 (depends on 1) A process according to claim 1, wherein the surface of the substrate is provided in said container such that said surface extends in a substantially vertical direction. ### Claim 23 (depends on 1) A process according to claim 1, further comprising firing the first and second films. ### Claim 24 (depends on 1) A process according to claim 1, wherein said substrate is a Braun tube.