US2695275A - Silver paint - Google Patents

Silver paint Download PDF

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Publication number
US2695275A
US2695275A US74851A US7485149A US2695275A US 2695275 A US2695275 A US 2695275A US 74851 A US74851 A US 74851A US 7485149 A US7485149 A US 7485149A US 2695275 A US2695275 A US 2695275A
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United States
Prior art keywords
silver
film
firing
paint
water
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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
Application number
US74851A
Inventor
Robert B Gray
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Erie Resistor Corp
Original Assignee
Erie Resistor Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Priority to US74851A priority Critical patent/US2695275A/en
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Publication of US2695275A publication Critical patent/US2695275A/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14Conductive material dispersed in non-conductive inorganic material
    • H01B1/16Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/25Metals
    • C03C2217/251Al, Cu, Mg or noble metals
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/17Deposition methods from a solid phase
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/43Electric condenser making
    • Y10T29/435Solid dielectric type

Definitions

  • This invention is a metal paint for applying coatings to be fixed by heating or firing.
  • advantages are electrical conductivity permitting capacity measurement during application. dry film strength, freedom from bubble formation, and safety. Further objects and advantages appcar in the specification and claims.
  • Paints for producing metallized coatings on refractories such as ceramics, mica, quartz, and glass have heretofore consisted of a base. a vehicle, and a pigment and flux. These comprise a compatible mixture in which each ingredient performs its function independently of the others and at a difierent stage in the coating operation.
  • the base functions as a thinner providing the desired consistency for spreading, dipping or spraying.
  • the film forming vehicle functions as a temporary binder giving sufficient strength to the coating so that it will adhere until the firing or setting operation.
  • the pigment is reduced by firing to a metallic film held in place by the fiux which fuses or vitrifies.
  • Fluxes are well known. Common fluxes are bismuth, subnitrate, mercuric oxide, lead oxide. lead borate. lead silicate. These fluxes although known as ceramic fiuxcs are usable on other materials.
  • the function of the base starts with providing the desired consistency of the paint and ends with the drying of the applied film. After the film is dried, the base no longer has any function.
  • the function of the film forming vehicle starts with the application of the wet film and ends with the firing operation.
  • the vehicle provides the necessary adherence of the unfired film. During firing, the vehicle breaks down.
  • the present paint has the property of high electrical conductivity prior to drying of the applied film which permits the determination of the electrical properties of the film before firing.
  • the paint comprises an evaporating electrically conductive base, a film forming vehicle.'and a silver pigment and flux.
  • the vehicle or temporary bonding agent is from a large class of materials having the property of adhering in both the wet and dry state. Such materials include natural and synthetic gums, glue sizes, resins.
  • the vehicle is merely a compatible adhesive agent which holds the paint film until firing and which breaks down at firing temperature.
  • the base is water or water alcohol.
  • the film forming vehicle should be compatible with the base.
  • Polyvinyl alcohol. dextrin. methyl cellulose are common vehicles. thers are known.
  • the high electrical conductivity is obtained from the evaporating base. The high electrical conductivity may result The high electrical conductivity from ionizing of the base. ionizing of an electrolyte added to the base or ionizing of the pigment or to a combination of these effects. ideally the base should supply the 2,695,275 Patented Nov. 23, 1954 high electrical conductivity when the paint is wet and then evaporate completely.
  • Precipitated silver with or without silver chloride, an active impurity
  • Precipitated silver oxide 50 Ceramic flux 2 to 10 Purified dextrin 4 Silver nitrate O to 5 Water Balance (4) Finely divided silver (precipitated, flake,
  • Silver nitrate 3 Vehicle 2 to 4 Ceramic flux 2 to 10 10% solution of silver protein in water such as sold under the trade-mark Argyrol Balance
  • the pigment in the paint in Example (1) tends to settle so that the paint has to be stirred during application.
  • the paints in Examples (2), (3) and (5) are very stable and can stand for some hours during use without requiring stirring. There is no trace of reaction between the constituents of Example (2) in six months.
  • the silver nitrate should be added shortly before use to prevent breakdown of the vehicle.
  • the paints can have a very low electrical resistance and are therefore adapted to coating by the striping or brushing process where the capacity is high enough to make the series resistance more than a few percent of the capacitive reactance. With all of the paints the dried coating has too high an electrical resistance for capacity measurements.
  • the conductivity is due to the suspending medium and ions dissolved in it, since the pigments are insulated by the film forming material.
  • the constituents do not react chemically but form a mixture in which each of the constituents functions substantially independently of the other constituents.
  • the percentage of pigment depends upon the thickness of the coating to be applied. After heating or firing the pigment forms a uniform silver coating held in place by and alloyed with the ceramic flux. The remaining constituents are broken down during the firing.
  • the amount of ceramic flux necessary depends upon the type of ceramic or other dielectric. The amount and kind of flux for any particular dielectric is well known. Other bonding agents may be used.
  • the firing or baking temperature is primarily determined by the heat necessary to set the bonding agent. Firing is used to define the necessary setting heat.
  • the film forming vehicle (or protective colloid) holds firing after any Jr the pigment in suspension and upon drying, holds the coating against the ceramic surface until the firing operation.
  • the antifoaming agent ethyl alcohol
  • the purified dextrin requires no antifoarning agent.
  • the electrolyte or substance increasing the hydrogen ion concentration is selected from a known :iass of materials. Each of the constituents acts independently belongs to a class of materials hav ng well known U.FDI erties.
  • the constituents are chosen to have r action.
  • silver nitrate cles such as; polyi alcohol
  • do trio within the normal period of poly tyl alcohol, the silver nitrate should added immediately prior to use. Chlorides she be avoided as these nave a tendon v to form silty cltaricie w ich is undesirable in the fin .ed coating. "these factors well. understood iutheart.
  • a water base paint for producing a film having good electrical conductivity before drying and reducible by firing after drying to a metallic silver film comprising a finely divided metallic silver pigment, an aqueous solu- 5 tion of a protective colloid, and a water soluble agent increasing the hydrogen ion concentration.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Description

United States Patent i SILVER PAINT Robert B. Gray, Erie, Pa., assignor to Erie Resistor Corporation, Erie, Pa.. a corporation of Pennsylvania No Drawing. Application February 5, 1949, Serial No. 74,851
7 Claims. (Cl. 260-8) This application is a continuation in part of my application, Serial No. 592,946, filed May 10, 1945, now abandoned.
This invention is a metal paint for applying coatings to be fixed by heating or firing. Among its advantages are electrical conductivity permitting capacity measurement during application. dry film strength, freedom from bubble formation, and safety. Further objects and advantages appcar in the specification and claims.
Paints for producing metallized coatings on refractories such as ceramics, mica, quartz, and glass have heretofore consisted of a base. a vehicle, and a pigment and flux. These comprise a compatible mixture in which each ingredient performs its function independently of the others and at a difierent stage in the coating operation. The base functions as a thinner providing the desired consistency for spreading, dipping or spraying. The film forming vehicle functions as a temporary binder giving sufficient strength to the coating so that it will adhere until the firing or setting operation. The pigment is reduced by firing to a metallic film held in place by the fiux which fuses or vitrifies. Fluxes are well known. Common fluxes are bismuth, subnitrate, mercuric oxide, lead oxide. lead borate. lead silicate. These fluxes although known as ceramic fiuxcs are usable on other materials.
The function of the base starts with providing the desired consistency of the paint and ends with the drying of the applied film. After the film is dried, the base no longer has any function.
The function of the film forming vehicle starts with the application of the wet film and ends with the firing operation. The vehicle provides the necessary adherence of the unfired film. During firing, the vehicle breaks down.
The function of the pigment and fiux starts with the firing operation.
The prior paints have all had high electrical resistance until the firing operation. if the electrical properties of the coating were important, as is the case in electrical condensers. it has heretofore been necessary to wait until after the firing operation to learn whether the coating has the desired properties.
The present paint has the property of high electrical conductivity prior to drying of the applied film which permits the determination of the electrical properties of the film before firing. of the wet paint film makes the paint particularly applicable to the manufacture of condensers as disclosed in my application Serial No. 592,946, filed May 10, 1945. The paint comprises an evaporating electrically conductive base, a film forming vehicle.'and a silver pigment and flux. The vehicle or temporary bonding agent is from a large class of materials having the property of adhering in both the wet and dry state. Such materials include natural and synthetic gums, glue sizes, resins.
The vehicle is merely a compatible adhesive agent which holds the paint film until firing and which breaks down at firing temperature. it the base is water or water alcohol. the film forming vehicle should be compatible with the base. Polyvinyl alcohol. dextrin. methyl cellulose are common vehicles. thers are known. The high electrical conductivity is obtained from the evaporating base. The high electrical conductivity may result The high electrical conductivity from ionizing of the base. ionizing of an electrolyte added to the base or ionizing of the pigment or to a combination of these effects. ideally the base should supply the 2,695,275 Patented Nov. 23, 1954 high electrical conductivity when the paint is wet and then evaporate completely. This ideal result is achieved by a water or water alcohol base with or without an added evaporating electrolyte such as ammonia. Water also lonizcs silver oxide. in water alcohol mixtures, the water is the main source of high electrical conductivity. It is, however. equally satisfactory if the base contains nonevaporating solids so long as the residue is compatible with the pigment and flux. Water-silver nuclineate (silver protein e. g. Argyrol") solutions have the desired high electrical conductivity and the residue after evaporation is compatible with the silver pigment. The addition of electrolytes such as silver nitrate in reasonable quantities to increase the hydrogen ion concentration and thereby increase the conductivity does not affect the fired silver film.
The following are specific examples:
Per cent (1) Precipitated silver (with or without silver chloride, an active impurity) Ceramic flux 2 to 10 Polyvinyl alcohol 4 Ammonia .2 to 1 Water Balance (2) Precipitated silver oxide 50 Ceramic fiux 2 to 10 Polyvinyl alcohol 2 Ethyl alcohol 2 to 4 Water Balance (3) Precipitated silver oxide 50 Ceramic flux 2 to 10 Purified dextrin 4 Silver nitrate O to 5 Water Balance (4) Finely divided silver (precipitated, flake,
silver oxide) Silver nitrate 3 Vehicle 2 to 4 Ceramic flux 2 to 10 10% solution of silver protein in water such as sold under the trade-mark Argyrol Balance The pigment in the paint in Example (1) tends to settle so that the paint has to be stirred during application. The paints in Examples (2), (3) and (5) are very stable and can stand for some hours during use without requiring stirring. There is no trace of reaction between the constituents of Example (2) in six months. The silver nitrate should be added shortly before use to prevent breakdown of the vehicle. The paints can have a very low electrical resistance and are therefore adapted to coating by the striping or brushing process where the capacity is high enough to make the series resistance more than a few percent of the capacitive reactance. With all of the paints the dried coating has too high an electrical resistance for capacity measurements. The conductivity is due to the suspending medium and ions dissolved in it, since the pigments are insulated by the film forming material.
The constituents do not react chemically but form a mixture in which each of the constituents functions substantially independently of the other constituents. The percentage of pigment depends upon the thickness of the coating to be applied. After heating or firing the pigment forms a uniform silver coating held in place by and alloyed with the ceramic flux. The remaining constituents are broken down during the firing. The amount of ceramic flux necessary depends upon the type of ceramic or other dielectric. The amount and kind of flux for any particular dielectric is well known. Other bonding agents may be used. The firing or baking temperature is primarily determined by the heat necessary to set the bonding agent. Firing is used to define the necessary setting heat.
The film forming vehicle (or protective colloid) holds firing after any Jr the pigment in suspension and upon drying, holds the coating against the ceramic surface until the firing operation. The antifoaming agent (ethyl alcohol) is necessary with some vehicles but not with others. For example. the purified dextrin requires no antifoarning agent. The electrolyte or substance increasing the hydrogen ion concentration is selected from a known :iass of materials. Each of the constituents acts independently belongs to a class of materials hav ng well known U.FDI erties.
The constituents are chosen to have r action. For silver nitrate cles, such as; polyi alcohol, do trio within the normal period of poly tyl alcohol, the silver nitrate should added immediately prior to use. Chlorides she be avoided as these nave a tendon v to form silty cltaricie w ich is undesirable in the fin .ed coating. "these factors well. understood iutheart.
What i 1. A water b electrical co harmful resome velw attack {l xfinely divided meta" c L vinyl alcohol. water. and an anti 2. A paint for producing a film h. conductivity Lil drying to a vided metal 0i a water soluble AL.- in suspension.
3. A paint f' conductivity drying to a metallic. all solution or pigment in ring ocal electric l r an; reduciol firing af" lvr film comprising a finely (1 nt, and an aqueoue solution 4. A water base paint for producing a film having good electrical conductivity before drying and reducible by firing after drying to a metallic silver film comprising a finely divided metallic silver pigment, an aqueous solu- 5 tion of a protective colloid, and a water soluble agent increasing the hydrogen ion concentration.
5. The paint as claimed in claim 4 in which the increasing the hydrogen ion concentration is silver pro tein.
10 6. The paint as claimed in claim. 4 in which the agent en 50ft concentration is ammonia.
mud to claim 4 in, which the agent roe-en ton concentration 1s silver nitrate.
l5 file of this patent ATENTS

Claims (1)

1. A WATER BASE PAINT FOR PRODUCING A FILM HAVING GOOD ELECTRICAL CONDUCTIVITY BEFORE DRYING AND REDUCIBLE BY FIRING AFTER DRYING TO A METALLIC SILVER FILM COMPRISING A FINELY DIVIDED METALLIC SILVER PIGMENT, A VEHICLE OF POLYVINYL ALCOHOL, WATER, AND AN ANTIFOAMING AGENT.
US74851A 1949-02-05 1949-02-05 Silver paint Expired - Lifetime US2695275A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3262790A (en) * 1962-08-01 1966-07-26 Engelhard Ind Inc Decorating compositions containing silver carboxylate-amine coordination compounds and method of applying same
DE1226232B (en) * 1958-12-06 1966-10-06 Philips Patentverwaltung Coating agent for the production of electrically conductive silver layers on insulating bodies
US3286604A (en) * 1962-08-16 1966-11-22 Prismo Safety Corp Marking materials
US3305369A (en) * 1962-11-15 1967-02-21 Tesla Np Method of production of aqueous silver suspensions applied for only one stoving operation
US3350341A (en) * 1964-07-16 1967-10-31 Du Pont Silver compositions containing novel vitreous binders and a vehicle
US3394290A (en) * 1966-08-24 1968-07-23 Otis F. Boykin Thin film capacitor
US3419758A (en) * 1966-01-03 1968-12-31 Matsushita Electric Ind Co Ltd Ceramic capacitor comprising semiconductive barium titanate body and silver alloy electrodes containing minor amount of cu, ca or bi
US3419759A (en) * 1965-09-17 1968-12-31 Matsushita Electric Ind Co Ltd Capacitor comprising ferroelectric ceramic with oxidic silver electrodes and heterojunction barrier layer between electrodes and ceramic
US3515958A (en) * 1965-11-05 1970-06-02 Corning Glass Works Electrical component with attached leads
US3539392A (en) * 1966-06-14 1970-11-10 Plessey Co Ltd Resistors
US3988160A (en) * 1974-12-24 1976-10-26 Trexel James J Water-based flemishing composition
US5017638A (en) * 1987-10-21 1991-05-21 Toyota Jidosha Kabushiki Kaisha Metallic paint film
US5147453A (en) * 1987-11-03 1992-09-15 Basf Corporation Paint compositions containing silver metal flake pigment

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE130495C (en) *
FR407872A (en) *
GB189422191A (en) * 1894-11-16 1895-09-21 Oliver Imray Manufacture of a New Solid Silver Compound which is not Precipitated by Albumen or Salt.
GB189813690A (en) * 1898-06-20 1899-04-08 Friedrich Silberstein Improvements in and connected with the Manufacture of Soluble Products from Proteids.
US1002548A (en) * 1910-06-17 1911-09-05 Chem Fab Vorm E Schering Albumose-silver-ammonio products.
CH52475A (en) * 1910-07-05 1911-11-16 Chem Fab Vorm E Schering Process for the preparation of a therapeutic silver preparation
US2103598A (en) * 1935-02-11 1937-12-28 Corning Glass Works Metallizing composition for glass
GB566718A (en) * 1943-09-07 1945-01-10 Johnson Matthey Co Ltd Improvements in or relating to the silvering of non-metallic surfaces
US2385580A (en) * 1944-07-01 1945-09-25 Du Pont Vitrifiable flux and bonding composition containing same
US2550345A (en) * 1945-05-10 1951-04-24 Erie Resistor Corp Silver paint

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE130495C (en) *
FR407872A (en) *
GB189422191A (en) * 1894-11-16 1895-09-21 Oliver Imray Manufacture of a New Solid Silver Compound which is not Precipitated by Albumen or Salt.
GB189813690A (en) * 1898-06-20 1899-04-08 Friedrich Silberstein Improvements in and connected with the Manufacture of Soluble Products from Proteids.
US1002548A (en) * 1910-06-17 1911-09-05 Chem Fab Vorm E Schering Albumose-silver-ammonio products.
CH52475A (en) * 1910-07-05 1911-11-16 Chem Fab Vorm E Schering Process for the preparation of a therapeutic silver preparation
US2103598A (en) * 1935-02-11 1937-12-28 Corning Glass Works Metallizing composition for glass
GB566718A (en) * 1943-09-07 1945-01-10 Johnson Matthey Co Ltd Improvements in or relating to the silvering of non-metallic surfaces
US2385580A (en) * 1944-07-01 1945-09-25 Du Pont Vitrifiable flux and bonding composition containing same
US2550345A (en) * 1945-05-10 1951-04-24 Erie Resistor Corp Silver paint

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1226232B (en) * 1958-12-06 1966-10-06 Philips Patentverwaltung Coating agent for the production of electrically conductive silver layers on insulating bodies
US3262790A (en) * 1962-08-01 1966-07-26 Engelhard Ind Inc Decorating compositions containing silver carboxylate-amine coordination compounds and method of applying same
US3286604A (en) * 1962-08-16 1966-11-22 Prismo Safety Corp Marking materials
US3305369A (en) * 1962-11-15 1967-02-21 Tesla Np Method of production of aqueous silver suspensions applied for only one stoving operation
DE1259763B (en) * 1962-11-15 1968-01-25 Tesla Np Stoving water polishing silver suspension
US3350341A (en) * 1964-07-16 1967-10-31 Du Pont Silver compositions containing novel vitreous binders and a vehicle
US3419759A (en) * 1965-09-17 1968-12-31 Matsushita Electric Ind Co Ltd Capacitor comprising ferroelectric ceramic with oxidic silver electrodes and heterojunction barrier layer between electrodes and ceramic
US3515958A (en) * 1965-11-05 1970-06-02 Corning Glass Works Electrical component with attached leads
US3419758A (en) * 1966-01-03 1968-12-31 Matsushita Electric Ind Co Ltd Ceramic capacitor comprising semiconductive barium titanate body and silver alloy electrodes containing minor amount of cu, ca or bi
US3539392A (en) * 1966-06-14 1970-11-10 Plessey Co Ltd Resistors
US3394290A (en) * 1966-08-24 1968-07-23 Otis F. Boykin Thin film capacitor
US3988160A (en) * 1974-12-24 1976-10-26 Trexel James J Water-based flemishing composition
US5017638A (en) * 1987-10-21 1991-05-21 Toyota Jidosha Kabushiki Kaisha Metallic paint film
US5147453A (en) * 1987-11-03 1992-09-15 Basf Corporation Paint compositions containing silver metal flake pigment

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