US20030104129A1 - Coating film, and method and apparatus for producing the same - Google Patents

Coating film, and method and apparatus for producing the same Download PDF

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Publication number
US20030104129A1
US20030104129A1 US10/254,884 US25488402A US2003104129A1 US 20030104129 A1 US20030104129 A1 US 20030104129A1 US 25488402 A US25488402 A US 25488402A US 2003104129 A1 US2003104129 A1 US 2003104129A1
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United States
Prior art keywords
substrate
silane
based compound
compound
coating
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Abandoned
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US10/254,884
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English (en)
Inventor
Norihisa Mino
Mitsuo Ebisawa
Yoshiaki Oono
Kazufumi Ogawa
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority to US10/254,884 priority Critical patent/US20030104129A1/en
Publication of US20030104129A1 publication Critical patent/US20030104129A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C1/00—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating
    • B05C1/02—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to separate articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C1/00—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating
    • B05C1/04—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to work of indefinite length
    • B05C1/06—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to work of indefinite length by rubbing contact, e.g. by brushes, by pads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/08—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation
    • B05C9/14—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation the auxiliary operation involving heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface

Definitions

  • the present invention relates to a coating film (hereinafter also referred to as “an organic thin film”), and a method and an apparatus for producing the same, in which a compound having a hydrolyzable group, e.g. a silane-based compound, is chemically bonded to a surface of a substrate.
  • a coating film hereinafter also referred to as “an organic thin film”
  • a compound having a hydrolyzable group e.g. a silane-based compound
  • the conventional immersion method is excellent when the shape of the object to be coated is not flat but is irregular. In this case, a film can be formed on the irregular surface, as a liquid reacts along the surface.
  • a large amount of liquid is required for immersion, and manipulations for removing and inserting a substrate are necessary. Thus, the operation becomes complex and requires a large amount of time, resulting in a high cost.
  • a chlorosilane-based compound reacts with water easily, its short pot life is a problem.
  • the method is inconvenient when the substrate has a surface which is not desirable to be coated with the chlorosilane-based compound.
  • the method in which a film is formed by roll coating has solved conventional problems in the immersion method, such as amount of liquid, complex operation, long operational time, dealing with a surface not needed to be coated, etc.
  • the object to be coated must be a flat plate.
  • the present invention provides a first method for producing a coating film using a compound (1) represented by a general formula (1) ABXn (where A is a carbon-containing group; B is at least one element selected from Si, Ge, Sn, Ti and Zr; X is a hydrolyzable group; and n is 1, 2 or 3) as a raw material, comprising: measuring the compound (1) in an amount required for one time application (a required amount) on a surface of a substrate having an active hydrogen on the surface, and supplying it to the surface of the substrate-at each time of application; in an atmosphere having a water vapor concentration of more than 0.0076 kg/m 3 , bringing the compound (1) into contact with the surface of the substrate, causing an elimination reaction between the active hydrogen on the surface of the substrate and the hydrolyzable group in parts of the molecules of the compound (1), thereby covalently bonding the parts of the molecules of the compound (1) to the surface of the substrate, as well as polymerizing parts
  • A is a carbon-containing group
  • B is at least
  • the present invention provides a second method for producing a coating film, comprising: applying a coating solution containing a silane-based compound having at least one reactive group selected from at least halogen atoms, an alkoxyl group and an isocyanate group to a surface of a substrate having an active hydrogen on the surface; causing an elimination reaction between the active hydrogen on the surface of the substrate and the reactive group of the silane-based compound, thereby covalently bonding the silane-based compound to the surface of the substrate, wherein the method comprises: conveying the substrate into a chamber in which a water vapor concentration in an atmosphere is maintained at more than 0.0076 kg/m 3 ; measuring a coating solution containing the silane-based compound and at least one solvent not having an active hydrogen in an amount required for one time application (a required amount), and supplying it to a coating device present in the chamber at each time of application; spreading and rubbing the coating solution uniformly on the surface of the substrate with the coating device; then changing the atmosphere in the chamber and increasing
  • an apparatus for producing a coating film of the present invention comprises: a device for transporting a substrate from an inlet to an outlet in a chamber; a device for measuring a coating solution containing a silane-based compound and at least one solvent not having an active hydrogen in an amount required for one time application (a required amount) and supplying it to a coating device present in the chamber at each time of application; a coating device for applying and spreading the coating solution uniformly, and for accelerating an elimination reaction between the reactive group of the silane-based compound in an amount required for one time application and the active hydrogen on the surface of the substrate; a device for controlling and maintaining a water vapor concentration in an atmosphere in the chamber; and a device for removing the solvent in the coating solution.
  • a coating film of the present invention is characterized in that: the film is transparent; the film has a thickness of 1 nm to 0.5 ⁇ m; the film has a durability of at least five times for an abrasion resistance test in which a mixture of sugar and soy source (1:1 by weight ratio) is applied, heated at a high temperature of 300° C. for 20 minutes, and cooled, then a fouling baked and adhered to the film can be removed by rubbing with a wet cloth by one's hand; parts of the molecules of the film are covalently bonded to a surface of a substrate via at least one element selected from Si, Ge, Sn, Ti and Zr; and parts of the molecules of the film are polymerized with one another.
  • FIG. 1 is a schematic diagram of a rotational coating film-forming apparatus according to Example 4 of the present invention.
  • FIG. 2 is a perspective view showing a coating method according to Example 4 of the present invention.
  • FIG. 3 is a perspective view showing a coating method according to Example 4 of the present invention.
  • FIG. 4 is a schematic diagram of a cross section of a substrate and a coating film formed on the substrate according to Example 4 of the present invention.
  • FIG. 5 is a schematic diagram of a coating device according to Example 5 of the present invention.
  • FIG. 6 is a schematic diagram of a coating device according to Example 5 of the present invention.
  • FIG. 7 is a perspective view showing a coating method according to Example 6 of the present invention.
  • FIG. 8 is a perspective view showing a coating method according to Example 7 of the present invention.
  • FIG. 9 is a perspective view showing a coating method according to Example 8 of the present invention.
  • FIG. 10 is a perspective view showing a coating method according to Example 9 of the present invention.
  • FIG. 11 is a perspective view showing a coating method according to Example 10 of the present invention.
  • FIG. 12 is a flow diagram showing a mechanism of a repair system for ceramic and glass products according to Example 11 of the present invention.
  • FIG. 13 is a schematic diagram of a product-repair system according to Example 11 of the present invention.
  • FIG. 14 is a diagram showing a mechanism of film repairing according to Example 11 of the present invention.
  • FIG. 15 is a diagram showing a vehicle loaded with a film-repairing apparatus according to Example 11 of the present invention.
  • FIG. 16 is a diagram showing the film-repairing apparatus in the vehicle according to Example 11 of the present invention.
  • a hydrogen chloride elimination reaction occurs as the elimination reaction.
  • an alcohol elimination reaction occurs as the elimination reaction.
  • an isocyanate compound an isocyanic acid elimination reaction occurs as the elimination reaction.
  • the silane-based compound contains an alkyl group or a fluoroalkyl group.
  • the silane-based compound when containing a fluoroalkyl group, it has improved water repellency, oil repellency, and anti-fouling property, etc., and thus it is preferable.
  • the coating device is operated so that a liquid containing the silane-based compound is further brought into contact with the surface of the substrate in the step of increasing the concentration of the silane-based compound and accelerating an elimination reaction between the reactive group of the silane-based compound at least in an amount required for one time application and the active hydrogen on the surface of the substrate. Accordingly, the elimination reaction can be ensured better, and a final organic thin film of a high density can be formed.
  • the solvent is removed either by changing the atmosphere in the chamber or by operating the coating device, or by both. Accordingly, the concentration of the coating solution can be increased, so that probability of occurrence of the elimination reaction may be increased further.
  • the atmosphere in the chamber is changed by changing the temperature in the chamber, changing the gas flow rate in the chamber, or changing the temperature of the substrate, or by a combination of these measures.
  • the solvent not having an active hydrogen is at least one selected from hydrocarbon compounds, siloxane based compounds, and halogenated hydrocarbons. If the solvent has an active hydrogen, it will react with the silane-based compound.
  • the coating device comprises a body in a form that makes it impregnated with the coating solution.
  • the coating device can absorb excess of the coating solution, so that the coating solution can be applied in a required minimum amount to the surface of the substrate.
  • the body of the coating device in a form that makes it impregnated with the coating solution is a porous material, such as a resin foam, a woven fabric, or a nonwoven fabric. Particularly, by using a flexible material, substrates of various forms can be handled.
  • the step of spreading the coating solution uniformly on the surface of the substrate is carried out by fixing the substrate, and rotating the coating device or moving it in longitudinal and transverse directions, or conducting both simultaneously.
  • substrates of various forms can be handled with flexibility.
  • the coating device for spreading the coating solution uniformly on the surface of the substrate is different from the coating device for increasing the concentration of the silane-based compound and accelerating the elimination reaction between the reactive group of the silane-based compound at least in an amount required for one time application and the active hydrogen on the surface of the substrate. Accordingly, production efficiency can be doubled.
  • the step of spreading the coating solution uniformly on the surface of the substrate and the step of accelerating the elimination reaction between the reactive group of the silane-based compound in an amount required for one time application and the active hydrogen on the surface of the substrate are carried out in two independent chambers.
  • the atmospheres in the chambers in these two steps are different, so that productivity of an organic thin film can be increased significantly by providing two chambers with different atmospheres, rather than changing the atmosphere in the chamber in each step.
  • the apparatus of the present invention includes a device for transporting a substrate from an inlet to an outlet in a chamber; a device for dropping a coating solution containing a silane-based compound and a solvent on a surface of the substrate; a coating device for applying and spreading the coating solution uniformly, in which an elimination reaction between a reactive group of the silane-based compound in an amount required for one time application and an active hydrogen on the surface of the substrate is accelerated; a device for controlling and maintaining a water vapor concentration in an atmosphere in the chamber; and a device for removing the solvent in the coating solution.
  • the device for transporting the substrate in the chamber is of a belting system or a roller system.
  • the device for dropping the coating solution containing a silane-based compound and a solvent on a surface of the substrate is of a nozzle system or a spray system.
  • the device for controlling and maintaining the water vapor concentration in the atmosphere controls and maintains it in the range of more than 0.0076 kg/m 3 .
  • the coating device comprises a body in a form that makes it impregnated with the coating solution.
  • the body in a form that makes it impregnated with the coating solution of the coating device is a porous material, such as a resin foam, a woven fabric, or a nonwoven fabric.
  • the coating device is rotated or moved in the longitudinal and transverse directions, or both rotated and moved simultaneously.
  • the coating device for spreading the coating solution uniformly on the surface of the substrate is different from the coating device for increasing the concentration of the silane-based compound and accelerating the elimination reaction between the reactive group of the silane-based compound at least in an amount required for one time application and the active hydrogen on the surface of the substrate.
  • the chamber in which the coating solution is spread uniformly on the surface of the substrate, and the chamber in which the elimination reaction between the reactive group of the silane-based compound in an amount required for one time application and the active hydrogen on the surface of the substrate is accelerated are two independent chambers.
  • the device for removing the solvent in the coating solution from the surface of the substrate is of at least one selected from gas blowing, heating evaporation, and evaporation under reduced pressure.
  • At least the surface of the portion of the substrate on which the organic thin film is to be formed is covered with a material comprising glass, a metal, a plastic, or a metal oxide.
  • the group having an active hydrogen is exposed on a surface of the plastic by oxygen plasma treatment, corona discharge treatment, ozone oxidation treatment, or ultraviolet oxidation treatment.
  • the substrate is at least one selected from glass, metals, metal oxides, ceramics, polymer compounds, and composites thereof.
  • the substrate is a product made from an inorganic oxide as a raw material, and is at least one selected from glass products including glass sheets and mirrors, ceramic products, enameled products, and composites thereof
  • a siloxane bond may be formed between the substrate and the silane-based compound, and a coating film having a thickness of at least 1 nm but not more than 1 ⁇ m may be formed on the substrate.
  • the silane-based compound contains an alkyl group or a fluoroalkyl group.
  • fluoroalkylsilane compounds represented by a general formula C n F 2n+1 (CH 2 ) 2 SiCl 3 (n is a positive integer of 1 to 30) such as heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane are available.
  • solvents not having an active hydrogen that is reactive with the chlorosilane-based compound may be used.
  • solvents not having an active hydrogen that is reactive with the chlorosilane-based compound may be used.
  • hydrocarbon based solvents include petroleum solvents represented by a general formula C n H 2n+2 (where n is a positive integer) or C n H 2n such as terpene oil.
  • Halogenated hydrocarbon based solvents include those represented by a general formula C n H 2n ⁇ m+2 X m (where n is a positive integer; m is a positive integer; X is a halogen) such as octadecafluorooctane.
  • linear silicone solvents represented by a general formula R 1 (R 2 R 3 SiO) n R 4 (where n is a positive integer; R 1 , R 2 , R 3 and R 4 are alkyl groups) such as hexamethyldisiloxane, cyclic silicone solvents represented by a general formula (R 1 R 2 SiO) n (where n is a positive integer; R 1 and R 2 are alkyl groups) such as octamethylsiloxane, or arbitrary mixtures of these preferably may be used.
  • silane-based compound that may be used in the present invention:
  • Y is a hydrogen, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxyl group.
  • isocyanate type silane-based compounds in which isocyanate groups are substituted for all chlorosilyl groups e.g. the following (12) to (16), may be used:
  • adsorptive compounds specified in the following (17) to (23) also may be used:
  • silane-based compound materials generally represented by SiY k (OA) 4 ⁇ k (where Y is the same as the above; A is an alkyl group; and k is 0, 1, 2 or 3) may be used.
  • substances represented by a formula CF 3 (CF 2 ) n (R) q SiY p (OA) 3 ⁇ p where n is an integer of at least 1, preferably 1 to 22; R is an alkyl, vinyl, ethynyl or aryl group, or a substituent containing a silicon or oxygen atom; q is 0 or 1; Y, A and p are the same as the above) are used, so that a more excellent anti-fouling coating film can be formed.
  • silane-based compound the following (24) to (47) may be used:
  • a glove box made of a transparent vinyl chloride was prepared, and was provided with a temperature sensor and a humidity sensor.
  • the water vapor concentration in the glove box was controlled constantly by measuring the temperature and relative humidity in the glove box.
  • the glove box had a construction in which dry air was introduced from a dry air generator as needed through a pipe so as to control the water vapor concentration. It also had a construction in which air passed through a humidifier was introduced as needed through a pipe.
  • Example 1 The same type of experiment as in Example 1 was carried out in an atmosphere having a high water vapor concentration of 20.3 g per m 3 . A phenomenon on a surface of a glass sheet suggesting a formation of an organic thin film was confirmed in the same way as in Example 1.
  • the surface of the substrate was rubbed with a nonwoven fabric containing anhydrous hexane.
  • an infrared absorption spectrum was measured by reflection method.
  • two spectra resulting from CH 2 stretching vibrations were observed near 2900 cm ⁇ 1 and 2850 cm ⁇ 1
  • a spectrum resulting from a CH stretching vibration of an alkene was observed near 1650 cm ⁇ 1 .
  • 18-nonadecenyltrichlorosilane caused a hydrogen chloride elimination reaction on the surface of the substrate to form a film.
  • the surface energy was 33 mN/m, and it was estimated that an organic compound different from a silicon oxide had been formed on the surface of the substrate.
  • Example 1 the system for controlling the water vapor concentration as shown in Example 1 is a very simple, laboratory one, and it has a satisfactory construction in which a gas having a controlled water vapor concentration is introduced.
  • a pre-chamber in which humidities of gases to be introduced are adjusted may be provided.
  • the glove box has a small size, it is preferably provided with a pre-chamber.
  • Example 1 Although excess agent, dirt etc. were removed from the surface by rubbing with a cloth (waste), if excess agent can be removed naturally, for example, by controlling viscosity of the agent or using an agent that can be evaporated easily, rubbing on the surface is of course unnecessary. Moreover, if there is any measure to drain a liquid from the agent using an air gun etc., rubbing on the surface also is unnecessary. The same also applies to Example 3.
  • This example describes a method and an apparatus for,producing a coating film, using a rotational coating film-forming apparatus as an example of an apparatus for producing a coating film of the present invention.
  • FIG. 1 is a schematic diagram of a rotational coating film-forming apparatus.
  • a substrate is moved from left to right, and during the process a coating film is formed on a surface of the substrate.
  • a chamber 1 air was supplied constantly through an air flow pipe 2 as shown by an arrow A so as to control and maintain the water vapor concentration in the chamber 1 in the range of higher than 0.0076 kg/m 3 .
  • a belt conveyor 3 was provided at an inlet for a substrate.
  • An enamel plate 4 as a substrate to be coated with an organic thin film was placed on the belt conveyor 3 , and automatically it was introduced into the chamber as shown by an arrow B. Then, the enamel plate 4 was positioned on a support 5 .
  • FIG. 2 is a perspective view showing selectively a rotational coating section in FIG. 1.
  • a nozzle 6 connected to a container for supplying a coating solution was moved as shown by an arrow C, and a coating solution was measured in an amount required for one time application, for example, in an amount of 0.6 ml to 0.8 ml per a plate with a diameter of 20 cm.
  • the measured coating solution which is described below, was dropped on the enamel plate 4 at each time of application.
  • the coating solution comprised a solution in which one weight part of heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane was dissolved in 100 weight parts of a cyclic silicone oil, both of which agents were produced by Shin-Etsu Chemical Co., Ltd.
  • an axis 7 a of a coating device was rotated, and a surface of the enamel plate 4 was rubbed uniformly with a nonwoven fabric 7 b.
  • the coating solution was applied on the entire surface of the enamel plate 4 .
  • a plate with a diameter of 20 cm application of the coating solution on the entire surface was able to be completed in several seconds.
  • the enamel plate was transported by a belt conveyor 8 and sent to another chamber 9 .
  • a warm air was supplied through an airflow pipe 10 as shown by an arrow D, and the temperature in the chamber was maintained at higher than room temperature.
  • the enamel plate 11 sent to the chamber 9 was positioned on a support 13 , and the coating device 12 a was rotated, so that a surface of the enamel plate was rubbed uniformly with a nonwoven fabric 12 b.
  • the coating solution spread uniformly on the enamel plate by this operation caused an elimination reaction with a vitreous component on the surface of the enamel plate.
  • an organic thin film 16 covalently bonded to an enamel plate 15 was formed.
  • the solvent in the coating solution was removed using the atmosphere in the chamber 9 , and only the organic thin film 16 remained on the enamel plate 15 .
  • the enamel plate 11 was discharged from the chamber 9 by a belt conveyor 14 as shown by an arrow E.
  • a finished product of the enamel plate 15 in which an organic thin film was formed on a surface, was obtained.
  • the agent was dropped directly on the enamel plate in this example, the same film also was able to be formed by dropping the agent to a nonwoven fabric and causing it to be absorbed by the nonwoven fabric, followed by rotating the axis of the coating device as shown in FIG. 3.
  • the state of the surface of the glass sheet after completing the film forming was measured by dropping water and using an angle formed by a water drop and the glass sheet (a contact angle).
  • Table 1 below shows results of comparison between Example 1 and Comparative Example 1.
  • Table 1 shows a comparison between the case in which a film was formed on an enamel plate by the method shown in the example and the case in which a film was formed on the same enamel plate by the method shown in the comparative example, with respect to contact angle, visual inspection of appearance, amount of solution prepared, and time for forming a film. Both of the contact angles of the formed films were 110 degree, and the states of the surfaces were the same. On the other hand, in the conventional method, because the specified condition of water vapor concentration after immersion was incomplete, many adhered white materials were generated on the glass sheet according to visual inspection of appearance. However, in the method of the present invention, such an adhered material was not confirmed.
  • the amount of the solution of the chlorosilane-based compound used per one enamel plate was 0.75 g.
  • the solution was prepared in an amount required for immersing the enamel plate, 1800 g of the solution, which was 2400 times larger than the amount in the present invention, was required.
  • the solution after preparing a film on a first substrate contains enough chlorosilane-based compound to form a film, so that of course a film can be formed when a second substrate is immersed in that solution, and films can be formed on a plurality of substrates. Thus, it cannot be generally said that an amount exceeding 2000 times is required.
  • the method of the present invention is more excellent than the conventional method to form a film depending on the requirements for each production. Accordingly, the cost required for forming a film can be reduced. Moreover, the method of the present invention is also more excellent than the conventional method in terms of storability of the solution, etc.
  • Another difference between the method of the present invention and the conventional immersion method is that while a film is formed on one side of a substrate in the present invention, a film is formed on both sides in the conventional method. If it is necessary to form a film only on one side by the conventional method, measures must be taken in advance to cover the side not needed to be coated, so that no reaction of forming a film may occur on that side. Moreover, when effect on only one side is sufficient, because films are formed on both sides in the conventional method, an excess film is formed on an unneeded side, and the cost of forming a film is doubled.
  • JP-10-180179 A shows details of this method.
  • the roll coating method is very excellent to form a film on a flat plate.
  • the substrate is not a flat plate as shown in Example 1, the roll coating method cannot be used. This indicates an obvious difference.
  • Durability was evaluated for the enamel plate coated with an organic thin film as produced in Example 1, and an enamel plate produced in an atmosphere having a water vapor concentration of less than 0.0076 kg/m 3 .
  • a mixture of sugar and soy source (1:1 by weight ratio) was applied to the enamel plate coated with an organic thin film, heated to a high temperature of 300° C. for 20 minutes and cooled, and then the fouling baked and adhered to the enamel plate was removed by rubbing it with a wet cloth by one's hand. This was because wiping off with one's hand was the most practical measure to remove a fouling. The operation was repeated until the fouling was not able to be removed, and the number of repeated cycles was counted.
  • Table 2 shows the result. TABLE 2 Water Vapor Concentration (kg/m 3 ) 0.0021 0.0060 0.0076 0.0150 0.0169 0.0203 Number of 0 2 6 8 6 5 Possible Fouling Removal Evaluation X X ⁇ ⁇ ⁇ ⁇ ⁇
  • ⁇ indicates at least 8 times of possible fouling removal (determined as the best durability and abrasion resistance with practicability); ⁇ indicates at least 5 but less than 8 times of possible fouling removal (determined as good durability and abrasion resistance with practicability); and ⁇ indicates less than five times of possible fouling removal (determined as poor durability and abrasion resistance without practicability).
  • the organic thin film formed on a substrate by the method of the present invention was free of a white adhered material, and had more durability than a film formed by the conventional method.
  • a coating device shown in FIG. 5 was placed in a room (chamber) in which a water vapor concentration in air was controlled and maintained in the range of more than 0.0076 kg/m 3 .
  • the coating device was provided with a cover 18 and an air supply pipe 19 for supplying air having an adjusted water vapor concentration, particularly in a section for forming an organic thin film, so that an artificial increase in the water vapor concentration was inhibited.
  • a glass sheet 20 having a bend in part (for example, a glass sheet having a bend extending upward only at the right lower angle is illustrated in FIG. 5) was set in the coating device by hand. The glass sheet was not placed horizontally as in Example 1, but was placed in an obliquely vertical direction.
  • a nozzle 21 extended from a side, and the same coating solution as in Example 1 was dropped from the nozzle 21 on a surface of the glass sheet.
  • the coating solution was spread uniformly on the surface of the glass sheet with a sponge coater 22 attached to a crossarm extending from a side.
  • the nozzle and the sponge coater were simultaneously moved up and down and right and left in concert as shown by an arrow in FIG. 5, spreading the solution uniformly on the glass sheet while dropping it.
  • the sponge coater was rotated to enable easy spreading of the coating solution.
  • the sponge coater dealt with the bend of the glass sheet by deforming, and made it possible to coat the bend smoothly.
  • a dryer 23 having an opening for blowing a dry warm air and a sponge coater 24 different from the above sponge coater were used to form an organic thin film.
  • a glass surface of the glass sheet 20 applied with a coating solution was rubbed with the sponge coater, and at the same time a dry warm air was applied thereto so as to form an organic thin film.
  • the dryer 23 having an opening for blowing a dry warm air and the sponge coater 24 were simultaneously moved up and down and right and left in concert as shown by an arrow in FIG. 6. Then, the glass sheet 20 was removed by one's hand.
  • an organic thin film comprising mainly carbon fluoride was able to be formed on a special shaped glass sheet having a bend in part (e.g. a windshield glass of an automobile).
  • Example 1 Although two chambers were used in Example 1, the treatment can be performed with one chamber, if the water vapor concentration can be controlled and maintained, and if the atmosphere does not change when warm air required in the next step is supplied.
  • the change of the atmosphere in the chamber also can be accomplished by changing the gas flow rate or the temperature of the substrate.
  • changing the gas flow rate it can be accomplished by providing a nozzle near the coating device and supplying air or the like from the nozzle.
  • changing the temperature of the substrate it can be accomplished by providing the support with a heating device to increase the temperature of the substrate.
  • Example 5 Although a method in which the water vapor concentration in the entire room is controlled and maintained is shown in Example 5, because a change from people coming in and out cannot be dealt with in practice, the cover was provided. The cover was necessary only in this example, and it is not required if the water vapor concentration in the entire room can be controlled with more precision.
  • the coating solution was supplied by dropping it with a nozzle in Examples 1 and 5, it also can be supplied as a spray or a mist.
  • a film can be formed on an irregular shaped substrate of a large size, and productivity can be improved considerably compared to the conventional immersion method, so that production cost can be reduced considerably. Thus, it has a large industrial value.
  • FIG. 7 is a schematic diagram of a rotational coating film-forming apparatus of one example of the present invention.
  • an organic thin film can be formed on the inner surface by using a sponge wiper 31 contacting the inner surface and rotating the wiper with a rotational axis 32 .
  • the hollow substrate is long in shape, an organic thin film can be formed by moving the rotational axis 32 up and down to move the wiper 31 up and down.
  • the water vapor concentration is controlled and maintained in the range of more than 0.0076 kg/m 3 .
  • the agent is supplied by causing it to be absorbed by the wiper as shown in Example 1.
  • FIG. 8 is a schematic diagram of a rotational coating film-forming apparatus of one example of the present invention.
  • a cylindrical substrate 33 such as a soup container or a glass tumbler as in Example 6
  • an organic thin film can be formed on the outer surface by using a cylindrical sponge wiper 34 contacting the outer surface and rotating the wiper with a rotational axis 35 .
  • a uniform organic thin film can be formed by moving the rotational axis 35 up and down to move the wiper 34 up and down as shown in FIG. 8.
  • the agent is supplied by causing it to be absorbed by the wiper as shown in Example 1.
  • the water vapor concentration is controlled and maintained in the range of more than 0.0076 kg/m 3 .
  • an organic thin film of the present invention is formed on a flat plate.
  • an organic thin film can be formed by using a sponge wiper 40 corresponding to the length of one side of a flat plate 41 and dropping an agent on the flat plate 41 or onto the wiper, and then moving the wiper 40 on the flat plate 41 as shown by an arrow in FIG. 9.
  • Other conditions are the same as in Example 1.
  • FIG. 10 A case in which an organic thin film of the present invention is formed on a flat plate is described. As shown in FIG. 10, a uniform organic thin film can be formed by dropping an agent on a flat plate 42 or onto the wiper, and then moving the flat plate 42 while rotating a sponge wiper 43 with a rotational axis 44 , or moving the rotational axis 44 back and forth and right and left. Other conditions are the same as in Example 1.
  • a uniform organic thin film can be formed by using a sponge wiper 46 as shown in FIG. 11, whose end is curved corresponding to the swelling of the plate, and a rotational axis 47 capable of moving back and forth and right and left as shown by an arrow in FIG. 11.
  • an organic thin film also can be formed by moving the flat plate 45 back and forth and right and left, instead of moving the rotational axis 47 back and forth and right and left as in Example 9. Other conditions are the same as in Example 1.
  • FIG. 12 shows a flow diagram to explain the following example.
  • a restaurant-managing company A owns ceramic and glass products for food and drink (plates ( 101 ) are exemplified here), which has been processed for a water repellent surface treatment. Because these products has generated irregularity in the surface treatment, the company A decides to proceed to repair the surface treatment of these products on the next regular holiday.
  • the company A transmits a request for repair treatment to a water repellent surface treatment company B through the Internet work 103 as an information transfer system, using a personal computer 102 as an information transmitter.
  • the company B receives the request from the company A using a personal computer 104 , which is an information receiver present in the company B.
  • the company B also can obtain information on the location and method of contact of the company A, and contents of the articles for treatment (e.g.
  • a personal computer 105 which is an information processing mechanism present in the company B.
  • the company B also prepares to send a product-repair system 106 to the company A on the date specified by the company A.
  • the company B provides the product-repair system 106 owned by the company B on the date and at the location specified by the company A.
  • the company carries out a surface treatment of the plates 101 , which are representative examples of the ceramic and glass products for food and drink requested for treatment by the company A. Then, right after the treatment, the company B delivers the products to the company A.
  • a personal computer also has been described as an example of an information transmitter, as long as the same function can be realized, a digital phone or a digital facsimile etc. also may be used as an information transmitter.
  • a personal computer has been described as an example of an information receiver, as long as the same function can be realized, a digital phone or a digital facsimile etc. also may be used as an information receiver.
  • FIG. 13 is a scheme of a product-repair system, which comprises a temperature and humidity controlling device 111 and a chlorosilane-based material reaction device 112 , and further provided with a product-for-repair supplying device 113 and a product-after-repair collecting device 114 .
  • the product-for-repair supplying device 113 has a mechanism for conveying a product for repair, which is usually of a belting system. A product for repair can be put in the chlorosilane-based material reaction device 112 by conveyance.
  • the chlorosilane-based material reaction device comprises a rubbing film-forming structure, a material-supplying structure, an exhauster and a ventilator.
  • the product-after-repair collecting device 114 is of a belting system, and can collect products after repair by conveyance.
  • the temperature and humidity controlling device controls the temperature and humidity of the entire product-repair system, and particularly controls strictly the temperature and humidity in the vicinity of the chlorosilane-based material reaction device.
  • product-for-repair supplying device 113 and the product-after-repair collecting device 114 have been described as being of a belting system, a roller system or a chuck system also may be employed as needed.
  • a rubbing system has been exemplified in the chlorosilane-based material reaction device 112
  • the device has a mechanism for spreading an agent uniformly on a substrate such as a spray system or a roll system, such may be substituted.
  • a ceramic plate 121 for a surface to be repaired (a plate is herein exemplified as a substrate) is placed on a carrier belt 122 , moved under an agent-dropping nozzle 123 , and a chlorosilane-based material is dropped from the nozzle 123 .
  • the dropped chlorosilane-based material is spread uniformly by rotating a rotational jig 124 for application and reaction (the portion of the jig contacting the plate is surrounded with a cloth). At this time, a hydroxyl group having an active hydrogen is exposed in a portion in which a film is peeled and the plate substrate is bared.
  • the hydroxyl group and the chlorosilane group of the material cause a hydrogen chloride elimination reaction to generate a chemical bonding with the substrate, so that a film of the material is formed on the portion in which a hydroxyl group is exposed.
  • the agent is put on the plate without causing a reaction between the material and the plate.
  • FIG. 15 is a scheme of a vehicle 131 loaded with a film-repairing apparatus.
  • FIG. 16 is a representative schematic diagram of the film-repairing apparatus in the vehicle 131 .
  • the vehicle loaded with a film-repairing apparatus can repair a film using a chlorosilane-based material, and is in a form of a vehicle, which is movable.
  • the film-repairing apparatus loaded on the vehicle 131 comprises a temperature and humidity controlling device and a chlorosilane-based material reaction device 141 , and further comprises a product-for-repair supplying device 142 and a product-after-repair collecting device 143 .
  • the chlorosilane-based material reaction device illustrates the film-forming system shown in FIG. 14 as an example.
US10/254,884 1999-08-31 2002-09-24 Coating film, and method and apparatus for producing the same Abandoned US20030104129A1 (en)

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KR102563917B1 (ko) 2015-03-20 2023-08-04 리달, 아이엔씨. 소유성 절연 차폐물 및 이의 제조 방법
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KR102119717B1 (ko) * 2020-03-17 2020-06-08 주식회사 나온씨에스 태양광 모듈의 오염방지를 위한 옥외 환경의 코팅장치와 그 방법
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DE60010994T2 (de) 2005-06-09
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EP1382400B1 (fr) 2010-03-10
JP2001137769A (ja) 2001-05-22
DE60044000D1 (de) 2010-04-22
EP1445034A2 (fr) 2004-08-11
EP1080794B1 (fr) 2004-05-26
EP1080794A2 (fr) 2001-03-07
EP1382400A3 (fr) 2004-11-17
EP1445034B1 (fr) 2006-06-21
DK1080794T3 (da) 2004-08-30
MY123514A (en) 2006-05-31
EP1080794A3 (fr) 2001-06-13
DE60029027D1 (de) 2006-08-03
DE60010994D1 (de) 2004-07-01
EP1382400A2 (fr) 2004-01-21
US6485785B1 (en) 2002-11-26
JP3494622B2 (ja) 2004-02-09
DE60029027T2 (de) 2006-10-19

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