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US2689802A - - layers -to reflecting metal - Google Patents

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US2689802A
US2689802A US2689802DA US2689802A US 2689802 A US2689802 A US 2689802A US 2689802D A US2689802D A US 2689802DA US 2689802 A US2689802 A US 2689802A
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Prior art keywords
lacquer
layer
metal
hardened
metal surface
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • 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
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • 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
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • 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
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B05D5/068—Metallic effect achieved by multilayers
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

  • 'Ih-is invention relates to methods of apply -'-protective'layersto reflecting metal surfaces and to mirrors-manufactured with the use of said methods.
  • a suitable method of providing the reflecting metal iayer consists in vaporizing metal in a vacuum.
  • the invention consists of a method of applying a protective layer to a reflecting metal surface, provided, for example, by vapourization of metal in a vacuum, on a hardened thermo-setting layer of lacquer, and is characterized in that the refleeting metal surface is covered with a layer of a thermo-setting lacquer which is subsequently hardened at a temperature lower than that at which the layer of lacquer which serves as a base for the metal mirror was hardened.
  • expression lower temperature is to be understood to mean a temperature which is atleast 15" C. and preferably at least 25C., lower than the temperature at which the supporting layer --of lacquer was hardened.
  • a-mufliing lacquer is chosen for this purpose.
  • the reflecting surface was "liable to damage during theoperation of hardening the protective layer unless said lower temperature was used; presumably due to deformation of the supporting layer of lacquer, bubbles and fissures were formed in the metal layer, thus usually the reflecting surface remains undamaged whenmuffiing the protective layer of lacquer at 125 to 130 C. It is to be preferred toohoose thetemperaturestill lower, for example C.
  • the time of hardening is still longer, for example, two hours.
  • a spraying method according to which an appropriate lacquer solution is sprayed on to the reflecting metal surface by means of a spray-gun.
  • the method is employed according to which a small quantity of lacquer solution is applied on to the reflecting metal surface which is subsequently rotated rapidly.
  • This method permits a very thin layer of lacquer to be applied by which the whole surface of the metal mirror is covered.
  • the lacquer solution should not be too viscous.
  • a lacquer solution having a viscosity of 9 to 9.5 degrees Engler at 20 C. is used.
  • thermo-setting protective lacquer use is preferably made of the same lacquer that has been employed for providing the supporting layer.
  • a very suitable solution consists, for example, of a mixture of an ureaformaldehyde condensation product and a non-drying alkyd resin in xylolbutanol. After mulfiing, a very hard, smooth and substantially colourless protective layer of lacquer is provided which firmly adheres to the metal mirror and which is substantially not discoloured by exposure to the atmosphere.
  • Example A layer of aluminium several thousandths of a millimeter thick is applied, by vaporisation in a vacuum, to a layer of hardened lacquer, mumed at 150 0., consisting of a hardened mixture of an ureaformaldehyde condensation product and a non-drying alkyd resin provided on a plate of dimensions 80 mms. by 65 mms. curved into part of a spherical surface.
  • the mirror is subsequently fitted to the turntable of a centrifuge, on to which is applied 1 cc. of a solution of an ureaformaldehyde condensation product and non-drying alkyd resin in a xylol-butanol mixture having a viscosity of 9 to 9.5 degrees Engler at C.
  • a solution of an ureaformaldehyde condensation product and non-drying alkyd resin in a xylol-butanol mixture having a viscosity of 9 to 9.5 degrees Engler at C On rotating the mirror rapidly the lacquer solution spreads over the metal mirror and dries to form a thin layer. This is followed by after-drying at 60 C. for
  • a method of applying a protective layer to a reflecting metal surface comprising the steps of forming a base for said metal surface by providing a first non-opaque thermo-setting layer of lacquer including a non-drying alkyd resin, applying a thin layer of highly reflective metal to said first layer of hardened lacquer, and covering said metal with a second layer of non-opaque thermo-setting lacquer including a non-drying alkyd resin which is subsequently hardened at a temperature that is at least 15 C. lower than that at which said first layer of lacquer was hardened.
  • a method of applying a protective layer to a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of aluminum to said first layer and covering said layer of aluminum with a second layer of lacquer 3.
  • a method as claimed in claim 1 wherein said 7 first and second layers of lacquer are distributed over said metal surface by the rapid rotation of said metal surface.
  • a method of applying a protective layer to a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of aluminum to said first layer by vaporization in a vacuum and covering said layer of aluminum with a second layer of lacquer comprising-an ureaformaldehyde condensation product and-a non-drying alkyd resin which is subsequently hardened at a temperature which is at least 15 C. lower than the temperature at which said first layer of lacquer was hardened.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)

Description

Patented Sept. 21, 1954 "METHOD OF APPLYING PROTECTIVE LAYERS T REFLECTING MET-AL SURFACE S 'Cornelis "iKorver, Eindhoven, Netherlands, -assigner: to Hartford National- Bank and Trust Company, Hartford, Conn., as trustee z N 0 Drawing. Application November 6, 1951, I Serial No.- 255,139
"Claims priority, application Netherlands December 5, 1950 "6 Claims. 1
'Ih-is inventionrelates to methods of apply -'-protective'layersto reflecting metal surfaces and to mirrors-manufactured with the use of said methods.
-It isknown to; provide areflecting' metal surface on a layen-of lacquer provided one rigid support, thus dispensing-with treatments otherconsist, forexample, of aluminium which, due to i itsconsiderable'reflecting power throughout the and of visible light is particularly suitable.
Wlternativelyf however; -other metals, e. g, silver, may be used. A suitable method of providing the reflecting metal iayerconsists in vaporizing metal in a vacuum.
Int-conjunction *With the requirements with respect to smoothness, hardness and thermal stability imposed on"the-support preferably a" lacquer capable of-being hardened by "heating (mufiling lacquer). is employed. Due to the heatingopera'tion necessary'for har'deningthe lacquer thoroughly,=residues.of solventsiaridzmoisture are vapour-ized from the layer of lacquer in order that stheyemaylnot later occasiontdamage to the re- J flecti-ng-metal surface provided thereon. As is known mufiling lacquers-.best-satisfy the requirements imposed.
It has, however, been found that such refiecting metal surfaces do not fulfil stringent requirements imposed with respect to durability, since they are relatively readily damaged by atmosphere influences, dust and handling. It has been suggested to enhance the durability of such reflecting metal surfaces by subjecting them to chemical treatment or by precipitation of quartz vapour on to the metal surface. For reflecting aluminium surfaces a known method is to form a protective layer by oxidizing the surface of the aluminium by electrical agency. When employing silver a protective layer may be formed by heating the mirror in an oxygen or hydrogen peroxide atmosphere.
However, these methods of applying a protective layer are expensive.
The invention consists of a method of applying a protective layer to a reflecting metal surface, provided, for example, by vapourization of metal in a vacuum, on a hardened thermo-setting layer of lacquer, and is characterized in that the refleeting metal surface is covered with a layer of a thermo-setting lacquer which is subsequently hardened at a temperature lower than that at which the layer of lacquer which serves as a base for the metal mirror was hardened. The
"expression lower temperature is to be understood to mean a temperature which is atleast 15" C. and preferably at least 25C., lower than the temperature at which the supporting layer --of lacquer was hardened.
'I'heprotectinglayer of lacquer is thin and in order to ensure thedesired adherence anddurability, a-mufliing lacquer is chosen for this purpose.
It was found that the reflecting surfacewas "liable to damage during theoperation of hardening the protective layer unless said lower temperature was used; presumably due to deformation of the supporting layer of lacquer, bubbles and fissures were formed in the metal layer, thus usually the reflecting surface remains undamaged whenmuffiing the protective layer of lacquer at 125 to 130 C. It is to be preferred toohoose thetemperaturestill lower, for example C.
-'In this event, however, the times duringwhich the article furnished with the reflecting surface -issi1bjected to the hardening temperature, are longer. Thus,'forexample, one'anda half hours -wouldbe-requiredto harden the lacquer at "C.
At 115 C. the time of hardening is still longer, for example, two hours.
To provide the protective layer of lacquer use may be made of a spraying method according to which an appropriate lacquer solution is sprayed on to the reflecting metal surface by means of a spray-gun. Preferably, however, the method is employed according to which a small quantity of lacquer solution is applied on to the reflecting metal surface which is subsequently rotated rapidly. This method permits a very thin layer of lacquer to be applied by which the whole surface of the metal mirror is covered. For use in this method and also for obtaining a very thin layer, the lacquer solution should not be too viscous. Preferably, a lacquer solution having a viscosity of 9 to 9.5 degrees Engler at 20 C. is used.
As a thermo-setting protective lacquer, use is preferably made of the same lacquer that has been employed for providing the supporting layer. A very suitable solution consists, for example, of a mixture of an ureaformaldehyde condensation product and a non-drying alkyd resin in xylolbutanol. After mulfiing, a very hard, smooth and substantially colourless protective layer of lacquer is provided which firmly adheres to the metal mirror and which is substantially not discoloured by exposure to the atmosphere.
Example A layer of aluminium several thousandths of a millimeter thick is applied, by vaporisation in a vacuum, to a layer of hardened lacquer, mumed at 150 0., consisting of a hardened mixture of an ureaformaldehyde condensation product and a non-drying alkyd resin provided on a plate of dimensions 80 mms. by 65 mms. curved into part of a spherical surface.
The mirror is subsequently fitted to the turntable of a centrifuge, on to which is applied 1 cc. of a solution of an ureaformaldehyde condensation product and non-drying alkyd resin in a xylol-butanol mixture having a viscosity of 9 to 9.5 degrees Engler at C. On rotating the mirror rapidly the lacquer solution spreads over the metal mirror and dries to form a thin layer. This is followed by after-drying at 60 C. for
20 minutes and muffling at 115 C. for more than 1 hours. In this manner, a hard, substantially colourless well-adhering layer of lacquer having a smooth surface is formed on the metal mirror. The decrease in the reflecting power of the mirror is at most reduced only by a few percent by said layer of lacquer.
What I claim is:
1. A method of applying a protective layer to a reflecting metal surface comprising the steps of forming a base for said metal surface by providing a first non-opaque thermo-setting layer of lacquer including a non-drying alkyd resin, applying a thin layer of highly reflective metal to said first layer of hardened lacquer, and covering said metal with a second layer of non-opaque thermo-setting lacquer including a non-drying alkyd resin which is subsequently hardened at a temperature that is at least 15 C. lower than that at which said first layer of lacquer was hardened.
2. A method as claimed in claim 1 wherein the composition of said first layer of lacquer is the same as said second layer of lacquer.
4. A method of applying a protective layer to a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of aluminum to said first layer and covering said layer of aluminum with a second layer of lacquer 3. A method as claimed in claim 1 wherein said 7 first and second layers of lacquer are distributed over said metal surface by the rapid rotation of said metal surface.
comprising an ureaformaldehyde condensation product and a non-drying alkyd resin having a viscosity of approximately 9 degrees Engler at 20 C., said second layer of lacquer being hardened at a temperature lower than that at which said first layer of lacquerwas hardened.
6. A method of applying a protective layer to a metal surface comprising the steps of forming a base for said metal surface by providing a first thermo-setting layer of lacquer comprising an ureaformaldehyde condensation product and a non-drying alkyd resin, applying a thin layer of aluminum to said first layer by vaporization in a vacuum and covering said layer of aluminum with a second layer of lacquer comprising-an ureaformaldehyde condensation product and-a non-drying alkyd resin which is subsequently hardened at a temperature which is at least 15 C. lower than the temperature at which said first layer of lacquer was hardened.
References Cited in the file of this patentv UNITED STATES PATENTS

Claims (1)

1. A METHOD OF APPLYING A PROTECTIVE LAYER TO A REFLECTING METAL SURFACE COMPRISING THE STEPS OF FORMING A BASE FOR SAID METAL SURFACE BY PROVIDING A FIRST NON-OPAQUE THERMO-SETTING LAYER OF LACQUER INCLUDING A NON-DRYING ALKYD RESIN, APPLYING A THIN LAYER OF HIGHLY REFLECTIVE METAL TO SAID FIRST LAYER OF HARDENED LACQUER, AND COVERING SAID METAL WITH A SECOND LAYER OF NON-OPAQUE THERMO-SETTING LACQUER INCLUDING A NON-DRYING ALKYD RESIN WHICH IS SUBSEQUENTLY HARDENED AT A TEMPERATURE THAT IS AT LEAST 15* C. LOWER THAN THAT AT WHICH SAID FIRST LAYER OF LACQUER WAS HARDENED.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2865787A (en) * 1955-03-09 1958-12-23 Heberlein Patent Corp Process for producing color effects on textile and other sheet-like material and products therefrom
US2974055A (en) * 1956-06-18 1961-03-07 Metal Film Company Inc Lustrous fabrics and methods of producing same
US2992125A (en) * 1958-01-09 1961-07-11 J Bocuze & Cie Soc Sheet material having a decorative appearance
US3308004A (en) * 1937-05-10 1967-03-07 Rhone Poulenc Sa Translucent panels having selective transmission and their manufacture
US3393087A (en) * 1955-04-22 1968-07-16 Monsanto Co Plastic vessel coated with epoxy resin containing lacquer
US3660138A (en) * 1969-02-05 1972-05-02 King Seeley Thermos Co Metallized article
US4535022A (en) * 1983-07-08 1985-08-13 Aluteck Co., Ltd. Decorative tile and method for manufacturing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296840A (en) * 1938-03-14 1942-09-29 Alexander J Faust Finishing process
US2375669A (en) * 1943-09-17 1945-05-08 Gen Motors Corp Reflector
US2382432A (en) * 1940-08-02 1945-08-14 Crown Cork & Seal Co Method and apparatus for depositing vaporized metal coatings

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296840A (en) * 1938-03-14 1942-09-29 Alexander J Faust Finishing process
US2382432A (en) * 1940-08-02 1945-08-14 Crown Cork & Seal Co Method and apparatus for depositing vaporized metal coatings
US2375669A (en) * 1943-09-17 1945-05-08 Gen Motors Corp Reflector

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308004A (en) * 1937-05-10 1967-03-07 Rhone Poulenc Sa Translucent panels having selective transmission and their manufacture
US2865787A (en) * 1955-03-09 1958-12-23 Heberlein Patent Corp Process for producing color effects on textile and other sheet-like material and products therefrom
US3393087A (en) * 1955-04-22 1968-07-16 Monsanto Co Plastic vessel coated with epoxy resin containing lacquer
US2974055A (en) * 1956-06-18 1961-03-07 Metal Film Company Inc Lustrous fabrics and methods of producing same
US2992125A (en) * 1958-01-09 1961-07-11 J Bocuze & Cie Soc Sheet material having a decorative appearance
US3660138A (en) * 1969-02-05 1972-05-02 King Seeley Thermos Co Metallized article
US4535022A (en) * 1983-07-08 1985-08-13 Aluteck Co., Ltd. Decorative tile and method for manufacturing the same

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