US3919441A - Panel-styled calorific devices and a process for manufacturing the same - Google Patents

Panel-styled calorific devices and a process for manufacturing the same Download PDF

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US3919441A
US3919441A US42659673A US3919441A US 3919441 A US3919441 A US 3919441A US 42659673 A US42659673 A US 42659673A US 3919441 A US3919441 A US 3919441A
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resins
rubber
calorific
substrate
metal powder
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Seinosuke Horiki
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Priority claimed from JP4254173A external-priority patent/JPS5652479B2/ja
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/26—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base
    • H05B3/262—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base the insulating base being an insulated metal plate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/101—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/04—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/02—Noble metals
    • B32B2311/08—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/14—Lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/16—Tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/20—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • 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

Definitions

  • a calorific material for panel-soled calorific devices is prepared by mixing a paste of a metal powder with a synthetic oil and firing the mixture to a temperature sufficient to melt and partialh oxidize the metal.
  • a panel-styled calorific device coated with the calorific material is prepared h coating a substrate with a paste of a metal powder and a s nthetic oil. firing the coated substrate at a temperature sufficient to melt and partially oxidize the metal and coating the fired substrate with a protective material.
  • the present invention relates to panel-styled calorific devices. More particularly. the invention relates to panel-styled calorific devices are well suited for heating both large and small areas because there is a lesser risk of disconnection with these devices and because they have a simpler construction than other line-styled calorifie materials.
  • calorific panels are known in the prior art.
  • One style comprises a sub strate coated with a mixture of carbon powder in a binder.
  • the relative uniformity of the film of this type of panel is poor which results in turbulance of the electric resistance and the calorification process.
  • Another style of panel comprises a substrate which has been coated with a metal film by vacuum evaporation of a metal.
  • the cost of this type of panel is high.
  • Yet another style of panel comprises a substrate which is covered with sheafs of fine metal wires.
  • the manufacturing cost of this type of panel is high since a series of complicated process steps must be used which involve the fabrication of metal into the proper sized wire. a step of braiding the wire and sheafing it into panel form and other complicated steps.
  • conductive inks which comprise a mixture of a metal such as silver or some other noble metal in a vitreous glass frit. This ma tcrial can then be spread over the substrate and then fired to form a conductive layer over the substrate.
  • the metal used in the conductive ink should be one which is resistant to oxidation during the firing of the substrate. Thus. silver or another noble metal is required which greatly raises the expense of the device.
  • a conductive metal layer can be formed over a substrate by spreading a conductive ink which comprises a metallic powder such as copper suspended with a glass frit in a fugitive or temporary or ganic binder preferably ith a reducing compound on a refractory substrate.
  • a conductive ink which comprises a metallic powder such as copper suspended with a glass frit in a fugitive or temporary or ganic binder preferably ith a reducing compound on a refractory substrate.
  • one object of the present invention is to provide a panel-styled calorific device which is easily produced at low cost.
  • Another object of the present invention is to provide a panel-styled calorific device which is durable and useful in many applications.
  • Yet another object of the present invention is to provide a panel-styled calorific device which has substantial heat retaining properties and regenerative capacitics.
  • Still another object of the present invention is to provide an efficient method for producing panel-Sty led calorific devices.
  • a calorific material for panelstyled calorific devices which is prepared by mixing a paste of a metal powder with a synthetic oil and firing the mixture to a temperature sufficient to melt and partially oxidize the metal.
  • a panel-styled calorific device coated with the calorific material is prepared by coating a substrate with a paste of a metal powder and a synthetic oil. firing the coated substrate at a temperature sufficient to melt and partially oxidize the metal and coating the fired substrate with a protective material.
  • FIG. 1 is an illustration of the longitudinal section of the panelstyled calorific devices of the present invention'.
  • FIG. 2 is a partial sectional view of the calorific device of the present invention:
  • FIG. 3 is a partial sectional view of another embodi ment of the calorific device of the present invention.
  • FIG. 4 illustrates an example of a circuit plan used to activate the panel-styled calorific device of the present invention.
  • the preferred metals which are used in the calorific material of the invention are those which have practical firing temperatures. i.e.. a melting point of less than l.1(]OC. Since the protective coating films which are applied over the calorific layers are used to prevent the calorific layer from contacting air and oxidizing. plastic or vitreous glass meterials should primarily be employed. The most preferred materials are silicone resins. melamine resins. low melting point glass frits and the like. The application of certain types of porous layers placed over the film substantially improve the heatretaining properties and regenerative capacity of panelstyled calorific layers.
  • the calorific devices are fabricated from a paste which is formed by milling a mixture of a metal powder and a glass powder with a synthetic oil which contains an undiluted synthetic resin solution.
  • the paste which is formed is applied to a substrate as a film 3 of paste. Thereafter. the film is tired to form a calorific lay er on the substrate. Subsequently. a paint containing a plastic or a plastic film is applied over the calorific layer to form an insulating coating lay er.
  • Two procedures are used for applying a film of paste to the substrate.
  • One procedure employs the direct spreading of the paste on the substrate.
  • the other procedure involves the transfer of the paste from a printing paper covered with the paste.
  • a uniform film can be rather easily obtained by the transfer method. especially when the surface of the substrate is curved.
  • the film be flexible in order to exactly adapt to the curved surface.
  • the synthetic resins which comprise the synthetic oil have a glass transition point below 20C.
  • the panel-styled calorific device consists of a substrate 1 l. a calorific lay er 12 formed thereon. and a coating lay er 13 which protects the calorific layer 12. Both ends of the calorific layer 12 are equipped with zonal electrodes l4 and electric wires 15 connected to electrodes 14. Calorific layer 12. as shown in FIG. 3. may also be arranged as strips of material on the surface.
  • Substrate 11 is fabricated from insulating materials which are capable of being fired at temperatures at which calorific lay er 12 is formed.
  • Suitable substrates include ceramics. glass. bricks. pottery material. gypsum. calcium carbonate. calcium silicate. asbestos and the like. These materials are usually formed in the shape of boards or other desired shapes such as dishlike. cap-like. or tube-like forms. Also suitable for use are fibers of ceramic or glass materials which are knitted or bonded. Further. if the panel is to have only one calorific layer 12.
  • the structure of the substrate ll can be modified to comprise an ordinary metal panel which is enameled with a glass or ceramic coating on the side of the metal surface which has the calorific layer. Such enameled metal panels are the most preferred materials for substrates.
  • the glass or ceramic layer is reinforced by the metal base. and the calorific layer 12 which coats the enamel layer. readily adheres to the substrate.
  • the glass or ceramic laycr serves as a buffer zone between calorific layer 12 and its metal base. This being the case. the use of enameled metal panels as substrates yields products of good durability. great mechanical strength and which are capable of being rapidly heated and cooled.
  • the materials which are used in calorific layer 12 are fired products ofmetals or mixtures of metals and glass. Any kind of metal can be used to produce the mixtures to be fired if they have the proper conductivity. However. it is preferred that materials have a melting point of less than l.l()UC. preferably about 400C. as far as possible in order to facilitate the firing process hereinafter described. Suitable metals include copper. silver. gold. zinc cadmium. aluminum. indium. thallium. tin. lead. antimony. bismuth. and the like. Some of these metals have melting points greater than l.lO()C. However. the objective of the invention can still be achieved with the high melting metals if the firing termperatures are elevated.
  • Another way to circumvent the problem of the high melting metals is to blend a metal with a melting point below l.100C with a metal having a melting point above l.l0()C.
  • the combined metals will then have a eutectic or melt-adhesive temperature Ill 4 below l.lUUC.
  • Ill 4 melt-adhesive temperature
  • Zinc. tin. and lead are the most preferred from the view-point of their behavior when fired and their cost. lt has been found tha when the metals are partially oxidized during the firim process. thereby achieving the desired electrical resistance. better results are attained when the metal is blended with an amount of metal oxide before tht metal is fired.
  • any kind of ordinary glass can be used if it contains a skeletal component of silicic acid. phos phoric acid. boric acid or the like and an additive such as an alkali metal. and alkali earth metal. lead. an: or the like.
  • the metal component is the conductive component. and the metal oxide and glass components constitute the insulating materials.
  • the metal component in the mixed fired product exceeds this range. the resistance becomes smaller and it will be all the more difficult to achieve good calorification. On the other hand. if the metal content is below this range. the resistance increases and the free flow of the electric current is diffi cult. In view of the fact that voltages between 100 and 200 volts are commonly used in the home. it is generally desirable that the metal content of the mixed fired products be within the range of to 40%. lt is especially preferred that the metal content range from 90 to 70% by weight.
  • the resistance of the mixed fired product or calorific layer also depends upon the thickness of the calorific film. By taking into consideration such factors as the case of production as hereinafter will be more fully described and the durability of the final products. the most favorable thickness of the calorific film ranges from several ten up to several hundred microns. By considering all of these factors. the desired resistance values for the calorific devices can be attained.
  • the protective coating layer 13 is formed from various insulating. heat-resistant materials. and therefore includes the same materials which are used for substrate 11. Since the protective coating is applied after calorific layer 12 is applied to the substrate. it is not necessary to fire the calorific layer. nor to use such heat-resistant materials as used for substrate 11. Consequently. it is possible to use many kinds of heat-resist ant plastic materials such as tcflon resins. silicon resins. aminoplast resins. epoxide resins. urethane resins. polyamid resins. polyimide resins. polydiphenyl ether resins. and polymers which contain copper. boron. titanium or aluminum and so on. Moreover. in the case when the calorific material is required to retain heat at temperatures less than C.
  • plastic materials such as polyvinyl chloride. polyvinylidene chloride. nylon. acrylic resins. synthetic rubber. natural rubber and the like are suitable as protective materials.
  • inorganic foaming materials such as ceramics. glass. gypsum board. calcium carbonate board. calsium silicate board. sirasu board and the like or inorganic heat-resisting porous materials such as inorganic textile fabrics. knitted from glass and ceramic fibers are very suitable materials.
  • arnino plast resins such as melamine resins. urea resins. benzoguanamine resins and the like are also very desirable.
  • a metal powder or a mixture of glass powder and a metal powder is suspended in a synthetic oil which is composed of a synthetic resin solution.
  • the particle size of the metal powder be about to 50 u and that the particle size of the glass powder be about l0 to uv If the particle size of the powders is too fine. trouble will be encountered in the milling operation and films of uniform thickness will be difficult to attain.
  • Suitable synthetic resins which can be used for synthetic oils include many different types of resins such as vinyl. polymers or denatured vinylpolymers such as acryl resins. methacrylic resins. vinyl acetate resins. styrol resins. vinyl ether resins. vinyl chloride resins. vinylidene chloride resins. vinyl pyrrolidone resins. polyethylene. polypropylene. polyvinyl alchohol. acetal resins. butyryl resins and the like; condensation polymers such as phenol resins. alkyd resins. melamine resins. polyamide resins. polyurethan resins. and the like. cellulose derivatives such as methylcellulose. hydroxyethyl cellulose. carboxymethyl cellulose.
  • ethylcellulose cellulose nitrate. cellulose acetate. cellulose butyrate and the like.
  • rubbers such as styrenebutadiene rubber. acrylonitrile-butadiene rubber. isoprene rubber. butyl rubber. polybutadiene polychloroprene. ethylene-propylene rubber. thiokol rubber. natural rubber.
  • the synthetic resins mentioned above as synthetic oils are readily available on the market in many different solutions of organic solvents such as toluene. xylene. ethyl acetate. butyl acetate. cellosolve acetate. butyl cellosolv'e. acetone. methyl ethyl ketone. naphtha. pine oil and the like and emulsified aqueous solutions. These solutions or emulsions are usually applied to the substrate with synthetic resin concentrations of about 30 to 609! by weight.
  • the composition of the paste may be altered to conform to the resistance levels required for the resultant calorific layer. Specifically. it must be taken into consideration that when the coated device is fired. the resistance value of the calorific layer will decrease with increasing metal content. However. even when the metal content of the paste is substantial. the resistance value of the layer will increase as the yield of metal oxidation product increases under more and more severe firing conditions.
  • the calorific layers which are produced under the firing conditions of the invention i.e.. as a result of firing at a temperature of about l.(J00C for about I hour in air.
  • the quantity of miscible glass powder should be kept below 60% by weight. At these levels of glass powder. it doesn't matter if only metal powder is pres ent without relatively large amounts of glass powder.
  • the ratio of synthetic oil to metal or a mixture of metal and glass depends on the film thickness. substrate species and the like. Usually. however. a ratio of 10 to 60 parts by weight synthetic oil per 700 parts by weight of the metal or metal-glass mixture is employed. The ratio is determined by the plastering working property of the paste. lfthe amount of synthetic oil exceeds the indicated ratio. slackening of the paste will result and the paste will turn up when applied during plastering because of the low ⁇ iscosity of the mixture. If the amount of the oil is less than the indicated ratio. the oilmetal mixture is difficult to paint because the viscosity is too high.
  • the paste may be applied directly to the substrate surface by means of. for instance. silk screen printing.
  • the substrate surface is curved. however. it is more advantageous to adopt the so-called decal transferring method in order to more easily obtain a uniform paste film.
  • the film of paste plastered on the printing paper be flexible for good working properties during the transfer process.
  • the glass transition point (Tg) of the synthetic resins which comprise the synthetic oil should be less than 20C in order that said film may be flexible. because if the synthetic resin having a glass transition temperature of more than 20C is used. the printing layer is likely to loose its flexibility. readily crack. and loose its adaptability to various shapes of substrate surfaces. For the same reasons it is desired that the Tg of the mixture be below 20C when the synthetic resins are mixed.
  • Tga the glass transition point of component A
  • Tgb the glass transition point of component B
  • Ma the molar fraction of component A:
  • Mb the molar fraction of component B.
  • ordinary paper can be used.
  • the more preferable substrates are releasing papers or papers painted with a water soluble glue.
  • Nor- 7 mally screen printing is used to print the paste on the transfer papers.
  • an over-print laquer may be further applied on the surface of the printed layer to protect it.
  • a synthetic resin from the same group of synthetic resins with Tg temperatures below 20C if possible as the raw material for the synthetic oil of the present invention.
  • the printing layer thus obtained can then be transferred onto a substrate which is insulated. on its surface by a material such as a ceramic. steatite. forsterite. an aluminum coated oxidized film. glass. ceramic enamel or the like.
  • the insulated substrate is made by a procedure such as the pressure sensitive adhesion method. the heabsensitive adhesion method. the adhesive varnish undercoating method. the water-sliding method or the like.
  • the insulated substrate After the insulated substrate is formed it is normally fired at a temperature of from 600 to l.000C for about 1 hour in air. The process does not require an inert atmosphere.
  • the synthetic resins are decomposed to fugacity within the printing layer and the metals are melted and partially oxidized to form a calorific layer having a resistance of several il/sq cm to several KH/sq
  • the coating operation is performed either by spreading a paint of a plastic solution on the calorific lay er or by covering the calorific layer with a plas tic film coated with an adhesive which optionally can be a heat melting adhesive. lf glass.
  • glaze or the like is to be used as a coating material.
  • a film of the paste which has been treated in advance with a dispersed solution of the material may be subjected as a composite to firing.
  • porous inorganic materials it may be adhesively applied to the calorific layer with a bonding agent.
  • glass. ceramics. tefion. silica or the like which are subject to evaporation at the firing temperature employed. can be coated by means of a vacuum evaporation method.
  • the panel-styled calorific layer 10 can be incorporated in a circuit containing variable resistance 16 and switch 17. If switch 17 is turned ON" and current flows through the circuit. the panelstyled calorific device 10 commences to generate heat. Induction heating by high frequency waves is also available by use of the panel-styled calorific device 10.
  • the calorific device of the present invention has many various and wide-ranging uses such as in electric heating appliances for cooking which includes toasters. electric heaters. electric frying pans. electric heating plates. electric hot plates. table grills (home grill). electric ovens. electric cookpots. egg boilers. electric ranges. electric hot reservoirs. table ware dryers and the like: electrical apparatuses for heating such as electric stoves. electric foot warmers. electric blankets. electric hot-air-heaters. floor heaters. panel heaters. electric hot seats for toilets. electric heating chairs. electric heating desks and the like: household appliances such as electric irons. trousers pressers (creas- 8 ers). electric water heaters. immersion-type hot-water heaters. electric soldering irons. electric hair curlers. towl steamers. electric heating mirrors. ceramic tablets. tablet dishes and the like: and other uses such as in steam baths. sauna baths. electric dryers for industrial and laboratory uses. heating furnaces. heat retainers for hot houses. and the like.
  • a glass powder of a mixed. fired product of barium carbonate and boric acid in the ratio of 1:1 by weight was prepared; zinc powder (300 mesh free) was used as a metal powder; A polyacrylmethyl lacquer (Stlr by weight naphtha solution) was used as the synthetic oil.
  • the raw materials were milled in a roller mill in the ratio below to form a paste:
  • the surface of the calorific layer was painted with a 57% by weight butanol-xylol mixed solution of butyrated methylolmelamine resin. After the layer was painted. the product was cured by heating at 150C for minutes. The film on the coated panel had a thickness of about I00 u. In this manner. a panel-styled calorific device A was formed.
  • EXAMPLE 2 A calorific paste was formed from a pulverized silica glass powder and a synthetic oil comprising a mixture of 30 parts by weight of ethyl cellulose. 70 parts by weight. of pine oil and 10 parts by weight of dioctyl phthalate. The raw materials with silver were milled in a masher in the following ratio to prepare the paste.
  • a ceramic plate was used as a substrate.
  • the paste was painted on the substrate to a thickness of about 200u with a knife coater. After the plate was painted. it was dried. Subsequently. the conductive paste was ap plied in a belt-shape to both ends of the paste film. Thereafter. the device was fired at a maximum temper ature of 850C for l hour. After the firing operation. the device was cooled and a panel-styled calorific layer having belt-shaped electrodes on either end was formed.
  • a polyvinyl chloride film of 0.5 mm in thickness was adhered to the surface of a calorific layer with an epoxide resin adhesive.
  • a paneLstyled calorific material B was obtained.
  • COMPARISON EXAMPLE 2 Several paste compositions containing various ratios of glass powder to silver powder were prepared as described in Example 2. The ratios are shown in Table 3.
  • EXAMPLE 3 A paste was prepared from a mixture of l5 parts by weight of phosphate glass powder. parts by weight of a metal powder mixture of tin to copper to silver of 2:414 and 30 parts by weight of a synthetic oil comprising 40% by weight solvesso No. I50 solution of TUF PRENE (Trade name of styrenebutadiene rubber. pre pared by the ASAHl KASEI CO). The raw materials were milled in an attriter.
  • the paste prepared by the above procedure was printed on a pasteboard which was painted with water soluble dextrin by a screen printing procedure. and was left to dry in air.
  • the resulting dehydrated printing layer was of a thickness of about 100 to u.
  • the transfer which was paper cured in this manner had a flexible printing layer and was easy to keep and transport.
  • the paste was transferred to a ceramic plate substrate by a water sliding method in which the coated paper was dipped in water with its printed surface upward. This configuration permitted the water soluble dextrin to dissolve. which allowed the printing layer to separate from the pasteboard. The separated printing layer which had risen to the surface of the water was removed from the water either by the substrate itself or by the use of a pincette. Thereafter. it was transferred to the surface of the substrate.
  • the transfer-printed substrate was fired at a temperature of 600 to 700C. After the substrate was cooled. belt-shaped aluminum foil was applied to both ends of the calorific layer as electrodes.
  • a glass fiber mat was applied on the surface of the calorific layer with a urethane resin adhesive.
  • panel-styled calorific material C was obtained. which had a metal content of 48% by weight and a resistance value of 30 fl/sq cm. It had substantial heat retaining properties.
  • EXAMPLE 4 A paste was prepared from 40 parts by weight of a synthetic oil prepared from 5 parts by weight of ethyl ene glycol and 20 parts by weight of a hydroxyl-ethylcellulose solution which was added to I00 parts by weight of a Copolymer emulsion of acryl-n-butyl and methacryl n-butyl in mole ratio of l:3. 90 parts by weight of Zinc metal powder and l0 parts by weight of barium oxide glass powder. These raw materials were milled in a ball mill.
  • the paste was coated on a release paper with a roller coater. Thereafter, the paste was dried leaving a film of 50 in thickness.
  • a cylindrically shaped enameled metal vessel was used as a substrate.
  • the release paper upon which the film was coated was scrupulously fitted on the circumferential wall of the enameled metal vessel. whereby the film was pressure-adhered thereon. After removing the release paper after the pressure-adhering steps. the film adhered firmly to the circumferential wall and re mained there. Thereafter. a conductive paste was coated in a belt-shape configuration on the upper and lower rims of the film. and a glaze was coated on the surface of the film. After the coating had dried. the film was fired at 700 to 800C. By this procedure a glaze covered panel-styled calorific material D was obtained. The calorific material D had a metal content of 84)? and a resistance of 2 Q/sq cm.
  • a panel-styled calorific device which comprises:
  • a synthetic oil comprising an organic solvent and at least one synthetic resin selected from the group consisting of acr resins. methacrylic resins. vinyl acetate resins. styrol resins. vinyl ether resins. vinyl chloride resins. vinylidene chloride resins. vinyl pyrrolidone resins. polyethylene. polypropylene. polyvinyl alcohol. acetal resins. butyral resins. phenol resins. alkyol resins. melamine resins. polyamide resins. polyurethane resins. mcthylcellulose. hydroxyethyl cellulose. carboxymethyl cellulose. ethyl cellulose. cellulose nitrate. cellulose acetate. cellulose butyrate.
  • styrene butadiene rubbers acrylonitrile-butadiene rubber. isoprene rubber. butyl rubber. polybutadiene rubber. polychloroprene rubber. ethylenepropylene rubber. thiokol rubber. natural rubber and reclaimed rubbers thereof. petroleum resins. cumarone resins. terpeno resins. rosin and derivatives thereof. starch. denatured starch. proteins and denatured proteins. and firing the mixture at a temperature above the melting point of sand metal powder thereby partially oxidizing said metal powder on said substrate. and
  • a method for fabricating a panel-styled calorific device which comprises:
  • melamine resins polyamide resins. polyurethane resins. methylcellulosc. hydroxyethyl cellulose. carboxymethyl cellulose. ethyl cellulose. cellulose nitrate. cellulose acetate. cellulose buty rate. sty rene butadiene rubbers. acrylonitrilebutadiene rubber. isoprene rubber. butyl rubber. polybutadiene rubber. polychloroprene rubber. ethylene-propylene rubber. thiokol rubber. natural rubber and reclaimed rubbers thereof. pctroleum resins. cumarone resins. terpeno resins. rosin and derivatives thereof. starch. denatured starch. proteins and denatured proteins.
  • step (b) coating the tired mixture of step (b) with a protective material said metal powder being present in said mixture in an amount of from 86 to 27% by weight.
  • said paste comprises a mixture of l() to parts by weight of said synthetic oil per parts by weight of a mixture of 0 to 60% by weight of said glass and 100 to 40% by weight of said metal powder.

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Abstract

A calorific material for panel-styled calorific devices is prepared by mixing a paste of a metal powder with a synthetic oil and firing the mixture to a temperature sufficient to melt and partially oxidize the metal. A panel-styled calorific device coated with the calorific material is prepared by coating a substrate with a paste of a metal powder and a synthetic oil, firing the coated substrate at a temperature sufficient to melt and partially oxidize the metal and coating the fired substrate with a protective material.

Description

United States Patent 1191 Horiki 1 1 PANEL-STYLED CALORIFIC DEVICES AND A PROCESS FOR MANUFACTURING THE SAME [76] Inventor: Seinosuke Horiki. 57-134 Horagai.
Narumi. Midori. Nagoya. Japan [221 Filed: Dec. 20. 1973 1211 Appl. No.; 426.596
130] Foreign Application Priority Data Dec. 211 1972 Japan v.--17-1-17139 Dec. 26. 1972 Japan t v v 48-1831 Apr. 15. 1973 Japan 48-42541 1521 Us. C1. 428/426; 427/1231427/125; 428/457 [511 int. (11. 8323 17/06; 344D 1H8. B44D 1/16 [58] Field of Search 117/217. 218, 227'. 219/543. 338/308. 309
[561 References Cited UNITED STATES PATENTS 2.882.187 4/1959 1\'\\ate.....v.,,,..... 117/215 2.8911228 6/1959 Smithdohannsenh... 117/227 3.048.914 8/1962 Kohriligmnnu. 117/2115 3.052.573 9/1962 Dumesnil i .7 117/221 1 1 Nov. 11,1975
3.079.282 2/1963 Haller et 111.... 117/227 3.11)).75-1 11/ 1963 Tielens et a1. v 117/218 3.20 7116 /1965 Hoffman 117/227 3.277.419 111/1966 But1..,..,...,...,..... 338/314 3.296.415 1/1967 Eisler 219/385 3.374.111) 3/1968 Miller 117/227 3.385.799 5/1968 Hoffman... H 117/227 3.3961155 7 /1968 Hedden et a1, 117/227 3.679.473 7/1972 Blatcht'ord et a1v 117/217 3.808.046 4/1974 Dine) 117/227 Primal) limminvr-Cameron K. weiffenlmch Artur/1e Age/i1. or l-'1'rmOh1on. Fisher. Spit-alt. McClelland it Maier 1571 ABSTRACT A calorific material for panel-soled calorific devices is prepared by mixing a paste of a metal powder with a synthetic oil and firing the mixture to a temperature sufficient to melt and partialh oxidize the metal. A panel-styled calorific device coated with the calorific material is prepared h coating a substrate with a paste of a metal powder and a s nthetic oil. firing the coated substrate at a temperature sufficient to melt and partially oxidize the metal and coating the fired substrate with a protective material.
8 Claims. 4 Drawing Figures US. Patent Nov. 11, 1975 3,919,441
FIG. I
PANEL-STYLED CALORIFIC DEVICES AND A PROCESS FOR MANUFACTURING THE SAME BACKGROUND OF THE INVENTION l. Field of the Invention The present invention relates to panel-styled calorific devices. More particularly. the invention relates to panel-styled calorific devices are well suited for heating both large and small areas because there is a lesser risk of disconnection with these devices and because they have a simpler construction than other line-styled calorifie materials.
2. Description of the Prior Art Hitherto a wide variety of paneI-sty led calorific devices have been known. Many types of calorific panels are known in the prior art. One style comprises a sub strate coated with a mixture of carbon powder in a binder. However. the relative uniformity of the film of this type of panel is poor which results in turbulance of the electric resistance and the calorification process. Another style of panel comprises a substrate which has been coated with a metal film by vacuum evaporation of a metal. However. it is difficult to obtain calorific panels of relatively large areas because of difficulties encountered with vacuum evaporation of the metal. Also the cost of this type of panel is high. Yet another style of panel comprises a substrate which is covered with sheafs of fine metal wires. However. the manufacturing cost of this type of panel is high since a series of complicated process steps must be used which involve the fabrication of metal into the proper sized wire. a step of braiding the wire and sheafing it into panel form and other complicated steps.
Currently in use on the market are conductive inks which comprise a mixture of a metal such as silver or some other noble metal in a vitreous glass frit. This ma tcrial can then be spread over the substrate and then fired to form a conductive layer over the substrate. The metal used in the conductive ink should be one which is resistant to oxidation during the firing of the substrate. Thus. silver or another noble metal is required which greatly raises the expense of the device.
To overcome this difficulty. it is disclosed in US. Pat. No. 3.647.532 that a conductive metal layer can be formed over a substrate by spreading a conductive ink which comprises a metallic powder such as copper suspended with a glass frit in a fugitive or temporary or ganic binder preferably ith a reducing compound on a refractory substrate. The use of this procedure eliminates the need for a noble metals and oxidation and an otherwise inert atmosphere can be avoided. Thus. this technique permits the use of lower cost metals such as copper. nickel. cobalt and the like. This latter observation has led to the present invention which satisfies the need for low cost and easily constructed panel-styled calorific devices by the discovery that if the metal in the applied calorific layer is allowed to partially oxidize during firing of the substrate. a calorific layer of a high degree of resistance can be obtained because of the partially oxidized metal. Thus. it is quite unnecessary in the present invention to deliberately use a metal resistant to oxidation. or to fire the coated substrate in a non-oxidizing atmosphere.
SUMMARY OF THE INVENTION Accordingly. one object of the present invention is to provide a panel-styled calorific device which is easily produced at low cost.
Another object of the present invention is to provide a panel-styled calorific device which is durable and useful in many applications.
Yet another object of the present invention is to provide a panel-styled calorific device which has substantial heat retaining properties and regenerative capacitics.
Still another object of the present invention is to provide an efficient method for producing panel-Sty led calorific devices.
Briefly. these objects and other objects of the present invention as hereinafter will become more readily apparent can be attained by a calorific material for panelstyled calorific devices which is prepared by mixing a paste of a metal powder with a synthetic oil and firing the mixture to a temperature sufficient to melt and partially oxidize the metal. A panel-styled calorific device coated with the calorific material is prepared by coating a substrate with a paste of a metal powder and a synthetic oil. firing the coated substrate at a temperature sufficient to melt and partially oxidize the metal and coating the fired substrate with a protective material.
BRIEF DESCRIPTION OF THE DRAWINGS A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings. wherein:
FIG. 1 is an illustration of the longitudinal section of the panelstyled calorific devices of the present invention'.
FIG. 2 is a partial sectional view of the calorific device of the present invention:
FIG. 3 is a partial sectional view of another embodi ment of the calorific device of the present invention; and
FIG. 4 illustrates an example of a circuit plan used to activate the panel-styled calorific device of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred metals which are used in the calorific material of the invention are those which have practical firing temperatures. i.e.. a melting point of less than l.1(]OC. Since the protective coating films which are applied over the calorific layers are used to prevent the calorific layer from contacting air and oxidizing. plastic or vitreous glass meterials should primarily be employed. The most preferred materials are silicone resins. melamine resins. low melting point glass frits and the like. The application of certain types of porous layers placed over the film substantially improve the heatretaining properties and regenerative capacity of panelstyled calorific layers.
Generally. the calorific devices are fabricated from a paste which is formed by milling a mixture of a metal powder and a glass powder with a synthetic oil which contains an undiluted synthetic resin solution. The paste which is formed is applied to a substrate as a film 3 of paste. Thereafter. the film is tired to form a calorific lay er on the substrate. Subsequently. a paint containing a plastic or a plastic film is applied over the calorific layer to form an insulating coating lay er.
Two procedures are used for applying a film of paste to the substrate. One procedure employs the direct spreading of the paste on the substrate. The other procedure involves the transfer of the paste from a printing paper covered with the paste. Of the two ways. a uniform film can be rather easily obtained by the transfer method. especially when the surface of the substrate is curved. Thus. it is essential that the film be flexible in order to exactly adapt to the curved surface. It is desired that the synthetic resins which comprise the synthetic oil have a glass transition point below 20C.
With reference to FlG. l and FIG. 2. the panel-styled calorific device consists of a substrate 1 l. a calorific lay er 12 formed thereon. and a coating lay er 13 which protects the calorific layer 12. Both ends of the calorific layer 12 are equipped with zonal electrodes l4 and electric wires 15 connected to electrodes 14. Calorific layer 12. as shown in FIG. 3. may also be arranged as strips of material on the surface.
Substrate 11 is fabricated from insulating materials which are capable of being fired at temperatures at which calorific lay er 12 is formed. Suitable substrates include ceramics. glass. bricks. pottery material. gypsum. calcium carbonate. calcium silicate. asbestos and the like. These materials are usually formed in the shape of boards or other desired shapes such as dishlike. cap-like. or tube-like forms. Also suitable for use are fibers of ceramic or glass materials which are knitted or bonded. Further. if the panel is to have only one calorific layer 12. the structure of the substrate ll can be modified to comprise an ordinary metal panel which is enameled with a glass or ceramic coating on the side of the metal surface which has the calorific layer. Such enameled metal panels are the most preferred materials for substrates. because the glass or ceramic layer is reinforced by the metal base. and the calorific layer 12 which coats the enamel layer. readily adheres to the substrate. In addition. because the problem of thermal strain is not always avoidable for calorific devices. the glass or ceramic laycr serves as a buffer zone between calorific layer 12 and its metal base. This being the case. the use of enameled metal panels as substrates yields products of good durability. great mechanical strength and which are capable of being rapidly heated and cooled.
The materials which are used in calorific layer 12 are fired products ofmetals or mixtures of metals and glass. Any kind of metal can be used to produce the mixtures to be fired if they have the proper conductivity. However. it is preferred that materials have a melting point of less than l.l()UC. preferably about 400C. as far as possible in order to facilitate the firing process hereinafter described. Suitable metals include copper. silver. gold. zinc cadmium. aluminum. indium. thallium. tin. lead. antimony. bismuth. and the like. Some of these metals have melting points greater than l.lO()C. However. the objective of the invention can still be achieved with the high melting metals if the firing termperatures are elevated. Another way to circumvent the problem of the high melting metals is to blend a metal with a melting point below l.100C with a metal having a melting point above l.l0()C. The combined metals will then have a eutectic or melt-adhesive temperature Ill 4 below l.lUUC. Thus. the problem presented by the high melting metals can be solved by either technique.
Of the suitable metals mentioned. Zinc. tin. and lead are the most preferred from the view-point of their behavior when fired and their cost. lt has been found tha when the metals are partially oxidized during the firim process. thereby achieving the desired electrical resistance. better results are attained when the metal is blended with an amount of metal oxide before tht metal is fired.
With reference to the glass used in the mixture which is fired. almost any kind of ordinary glass can be used if it contains a skeletal component of silicic acid. phos phoric acid. boric acid or the like and an additive such as an alkali metal. and alkali earth metal. lead. an: or the like.
In the metal-glass fired products. the metal component is the conductive component. and the metal oxide and glass components constitute the insulating materials. In order to achieve the desired level of resistance- -normally from several Kit/sq cm and to several Sl/sq cm on the metallic component of the mixed components should be present in quantities between 97 to 27% by weight. If the metal component in the mixed fired product exceeds this range. the resistance becomes smaller and it will be all the more difficult to achieve good calorification. On the other hand. if the metal content is below this range. the resistance increases and the free flow of the electric current is diffi cult. In view of the fact that voltages between 100 and 200 volts are commonly used in the home. it is generally desirable that the metal content of the mixed fired products be within the range of to 40%. lt is especially preferred that the metal content range from 90 to 70% by weight.
Of course. the resistance of the mixed fired product or calorific layer also depends upon the thickness of the calorific film. By taking into consideration such factors as the case of production as hereinafter will be more fully described and the durability of the final products. the most favorable thickness of the calorific film ranges from several ten up to several hundred microns. By considering all of these factors. the desired resistance values for the calorific devices can be attained.
The protective coating layer 13 is formed from various insulating. heat-resistant materials. and therefore includes the same materials which are used for substrate 11. Since the protective coating is applied after calorific layer 12 is applied to the substrate. it is not necessary to fire the calorific layer. nor to use such heat-resistant materials as used for substrate 11. Consequently. it is possible to use many kinds of heat-resist ant plastic materials such as tcflon resins. silicon resins. aminoplast resins. epoxide resins. urethane resins. polyamid resins. polyimide resins. polydiphenyl ether resins. and polymers which contain copper. boron. titanium or aluminum and so on. Moreover. in the case when the calorific material is required to retain heat at temperatures less than C. plastic materials such as polyvinyl chloride. polyvinylidene chloride. nylon. acrylic resins. synthetic rubber. natural rubber and the like are suitable as protective materials. In view of the heat-retaining and exothermic properties of the calorific device inorganic foaming materials such as ceramics. glass. gypsum board. calcium carbonate board. calsium silicate board. sirasu board and the like or inorganic heat-resisting porous materials such as inorganic textile fabrics. knitted from glass and ceramic fibers are very suitable materials.
As far as the cost and heat-resisting properties of the protective layer are concerned. arnino plast resins such as melamine resins. urea resins. benzoguanamine resins and the like are also very desirable.
For the manufacture of the panel-styled calorific materials of the present invention it is preferred that the manufacturing process hereinafter described be used.
Initially. a metal powder or a mixture of glass powder and a metal powder is suspended in a synthetic oil which is composed of a synthetic resin solution. In the suspension it is preferred that the particle size of the metal powder be about to 50 u and that the particle size of the glass powder be about l0 to uv If the particle size of the powders is too fine. trouble will be encountered in the milling operation and films of uniform thickness will be difficult to attain.
Suitable synthetic resins which can be used for synthetic oils include many different types of resins such as vinyl. polymers or denatured vinylpolymers such as acryl resins. methacrylic resins. vinyl acetate resins. styrol resins. vinyl ether resins. vinyl chloride resins. vinylidene chloride resins. vinyl pyrrolidone resins. polyethylene. polypropylene. polyvinyl alchohol. acetal resins. butyryl resins and the like; condensation polymers such as phenol resins. alkyd resins. melamine resins. polyamide resins. polyurethan resins. and the like. cellulose derivatives such as methylcellulose. hydroxyethyl cellulose. carboxymethyl cellulose. ethylcellulose. cellulose nitrate. cellulose acetate. cellulose butyrate and the like. rubbers such as styrenebutadiene rubber. acrylonitrile-butadiene rubber. isoprene rubber. butyl rubber. polybutadiene polychloroprene. ethylene-propylene rubber. thiokol rubber. natural rubber.
and their reclaimed rubbers; and petroleum resins. cumarone resins. terpene resins. rosin and derivatives thereof. starch. denatured starch. proteins. denatured protein and the like. Other resins. too numerous to mention are also suitable resinous materials.
Of the synthetic resins mentioned. it is possible to mix two or more of the resins together to form a suitable oil. If desired. other components such as plastisiz ers. decomposition promotors. reducing agents and others can be added to the oil.
When the calorific layer is applied to or printed on the substrate. the presence of one of the resinous materials in the applied composition tends to cause tackiness of the printed layer which makes handling troublesome. In order to remedy this difficulty the use of materials which have a Tg (glass transition temperature) greater than 30C is recommended. In view of the firing and oxidation temperatures employed for the metals in the process of making the calorific devices. resinous substrates which decompose below 600C are preferred. However. none of these limitations are critical because. for example. the tackiness of the resin used can be eliminated from resins having a Tg of 30C or lower by the use of bridging.
The synthetic resins mentioned above as synthetic oils are readily available on the market in many different solutions of organic solvents such as toluene. xylene. ethyl acetate. butyl acetate. cellosolve acetate. butyl cellosolv'e. acetone. methyl ethyl ketone. naphtha. pine oil and the like and emulsified aqueous solutions. These solutions or emulsions are usually applied to the substrate with synthetic resin concentrations of about 30 to 609! by weight.
The previously described metal and glass powder mixtures and a synthetic oil are blended together by a ball mill. a roller mill. an attriter. a masher. or the like until a paste is formed.
The composition of the paste may be altered to conform to the resistance levels required for the resultant calorific layer. Specifically. it must be taken into consideration that when the coated device is fired. the resistance value of the calorific layer will decrease with increasing metal content. However. even when the metal content of the paste is substantial. the resistance value of the layer will increase as the yield of metal oxidation product increases under more and more severe firing conditions.
In order that the calorific layers which are produced under the firing conditions of the invention. i.e.. as a result of firing at a temperature of about l.(J00C for about I hour in air. have a quantity of metal which is sufficient to maintain the resistance values of the layer within the range of from several Q/sq cm to several KQ/sq cm. the quantity of miscible glass powder should be kept below 60% by weight. At these levels of glass powder. it doesn't matter if only metal powder is pres ent without relatively large amounts of glass powder.
The ratio of synthetic oil to metal or a mixture of metal and glass depends on the film thickness. substrate species and the like. Usually. however. a ratio of 10 to 60 parts by weight synthetic oil per 700 parts by weight of the metal or metal-glass mixture is employed. The ratio is determined by the plastering working property of the paste. lfthe amount of synthetic oil exceeds the indicated ratio. slackening of the paste will result and the paste will turn up when applied during plastering because of the low \iscosity of the mixture. If the amount of the oil is less than the indicated ratio. the oilmetal mixture is difficult to paint because the viscosity is too high.
The paste may be applied directly to the substrate surface by means of. for instance. silk screen printing. When the substrate surface is curved. however. it is more advantageous to adopt the so-called decal transferring method in order to more easily obtain a uniform paste film. In this'case. it is desirable that the film of paste plastered on the printing paper be flexible for good working properties during the transfer process. The glass transition point (Tg) of the synthetic resins which comprise the synthetic oil should be less than 20C in order that said film may be flexible. because if the synthetic resin having a glass transition temperature of more than 20C is used. the printing layer is likely to loose its flexibility. readily crack. and loose its adaptability to various shapes of substrate surfaces. For the same reasons it is desired that the Tg of the mixture be below 20C when the synthetic resins are mixed.
When the synthetic resins are being mixed. Tg temperatures of the mixtures less than 20C are satisfactory. In order to determine the Tg of the mixtures. the following formula is used:
TgaMa+TgbMb Tga+b.
wherein:
Tga the glass transition point of component A; Tgb the glass transition point of component B; Ma the molar fraction of component A: and Mb the molar fraction of component B. In the transfer step ordinary paper can be used. However. the more preferable substrates are releasing papers or papers painted with a water soluble glue. Nor- 7 mally screen printing is used to print the paste on the transfer papers.
After paste printing. an over-print laquer may be further applied on the surface of the printed layer to protect it. For the base material of the over-print lacquer. it is advisable to choose a synthetic resin from the same group of synthetic resins with Tg temperatures below 20C if possible as the raw material for the synthetic oil of the present invention. The printing layer thus obtained can then be transferred onto a substrate which is insulated. on its surface by a material such as a ceramic. steatite. forsterite. an aluminum coated oxidized film. glass. ceramic enamel or the like. The insulated substrate is made by a procedure such as the pressure sensitive adhesion method. the heabsensitive adhesion method. the adhesive varnish undercoating method. the water-sliding method or the like. After the insulated substrate is formed it is normally fired at a temperature of from 600 to l.000C for about 1 hour in air. The process does not require an inert atmosphere. In the firing treatment the synthetic resins are decomposed to fugacity within the printing layer and the metals are melted and partially oxidized to form a calorific layer having a resistance of several il/sq cm to several KH/sq When the previously mentioned plastics are used as coating materials over the calorific layer with the insulating layer. the coating operation is performed either by spreading a paint of a plastic solution on the calorific lay er or by covering the calorific layer with a plas tic film coated with an adhesive which optionally can be a heat melting adhesive. lf glass. glaze or the like is to be used as a coating material. a film of the paste which has been treated in advance with a dispersed solution of the material may be subjected as a composite to firing. Also. if one of the previously mentioned porous inorganic materials is used. it may be adhesively applied to the calorific layer with a bonding agent. Moreover. glass. ceramics. tefion. silica or the like which are subject to evaporation at the firing temperature employed. can be coated by means of a vacuum evaporation method.
As shown in FIG. 4. the panel-styled calorific layer 10 can be incorporated in a circuit containing variable resistance 16 and switch 17. If switch 17 is turned ON" and current flows through the circuit. the panelstyled calorific device 10 commences to generate heat. Induction heating by high frequency waves is also available by use of the panel-styled calorific device 10.
The calorific device of the present invention has many various and wide-ranging uses such as in electric heating appliances for cooking which includes toasters. electric heaters. electric frying pans. electric heating plates. electric hot plates. table grills (home grill). electric ovens. electric cookpots. egg boilers. electric ranges. electric hot reservoirs. table ware dryers and the like: electrical apparatuses for heating such as electric stoves. electric foot warmers. electric blankets. electric hot-air-heaters. floor heaters. panel heaters. electric hot seats for toilets. electric heating chairs. electric heating desks and the like: household appliances such as electric irons. trousers pressers (creas- 8 ers). electric water heaters. immersion-type hot-water heaters. electric soldering irons. electric hair curlers. towl steamers. electric heating mirrors. ceramic tablets. tablet dishes and the like: and other uses such as in steam baths. sauna baths. electric dryers for industrial and laboratory uses. heating furnaces. heat retainers for hot houses. and the like.
Having generally described this invention. a further understanding can be obtained by reference to certain specific examples which are provided hereinfor purpose of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLE 1 The following materials were mixed in the quantities indicated below:
A glass powder of a mixed. fired product of barium carbonate and boric acid in the ratio of 1:1 by weight was prepared; zinc powder (300 mesh free) was used as a metal powder; A polyacrylmethyl lacquer (Stlr by weight naphtha solution) was used as the synthetic oil. The raw materials were milled in a roller mill in the ratio below to form a paste:
glass powder: 20 parts by weight zinc powder: 80 parts by weight synthetic oil: 12 parts by weight An enameled steel panel was used as a substrate. The paste was plastered on the substrate to a thickness of about 150 u by means of a silk screen printing procedure. After the coated panel had dried. it was subjected to firing at a maximum temperature of 600 to 700C for 1 hour. After firing. it was allowed to cool and a calorific layer was formed. At both ends of the calorific layer were attached electrodes of belt-shaped aluminium foil.
The surface of the calorific layer was painted with a 57% by weight butanol-xylol mixed solution of butyrated methylolmelamine resin. After the layer was painted. the product was cured by heating at 150C for minutes. The film on the coated panel had a thickness of about I00 u. In this manner. a panel-styled calorific device A was formed.
COMPARISON EXAMPLE l Several pastes were prepared using glass powder and zinc powder similar to the procedure of Example 1 in a variety of ratios as shown in Table l.
TABLE 1 Paste No. l I 3 4 5 Glass powder (part/wt) 3t) S0 60 Zinc powder (partlwtl 70 60 50 40 30 From the data in Table 2. it is clear that calorific devices for practical purposes can not be obtained when the content of the glass powder in the paste exceeds 60% by weight because the resistance becomes too great. At glass powder contents less than 20% by weight the resistance values are also unsatisfactory.
EXAMPLE 2 A calorific paste was formed from a pulverized silica glass powder and a synthetic oil comprising a mixture of 30 parts by weight of ethyl cellulose. 70 parts by weight. of pine oil and 10 parts by weight of dioctyl phthalate. The raw materials with silver were milled in a masher in the following ratio to prepare the paste.
glass powder parts by weight silver powder 1 25 parts by weight synthetic oil parts by weight A ceramic plate was used as a substrate. The paste was painted on the substrate to a thickness of about 200u with a knife coater. After the plate was painted. it was dried. Subsequently. the conductive paste was ap plied in a belt-shape to both ends of the paste film. Thereafter. the device was fired at a maximum temper ature of 850C for l hour. After the firing operation. the device was cooled and a panel-styled calorific layer having belt-shaped electrodes on either end was formed.
A polyvinyl chloride film of 0.5 mm in thickness was adhered to the surface of a calorific layer with an epoxide resin adhesive. By this procedure a paneLstyled calorific material B was obtained.
COMPARISON EXAMPLE 2 Several paste compositions containing various ratios of glass powder to silver powder were prepared as described in Example 2. The ratios are shown in Table 3.
Using the various pastes shown in Table 3. several diverse panel-styled calorific devices were fabricated by the same procedure as used in Example 2. The firing procedure. however. was accomplished in a nitrogen atmosphere to prevent oxidation of the silver. Resistance values and silver metal contents of the panelstyled calorific material B of Example 2 and the panelstyled calorific materials of Comparison Example 2. are Shown in Table 4.
TABLE 3 Resistance Value 8 fr 7 t4 9 fli'sqcml Siher Metal content ratio l'ipwt) 10 From the data in Table 4. it is clear that calorific materials can not be effectively attained for practical purposes when the metal content exceeds 97% by weight because the resistance values are too small.
EXAMPLE 3 A paste was prepared from a mixture of l5 parts by weight of phosphate glass powder. parts by weight of a metal powder mixture of tin to copper to silver of 2:414 and 30 parts by weight of a synthetic oil comprising 40% by weight solvesso No. I50 solution of TUF PRENE (Trade name of styrenebutadiene rubber. pre pared by the ASAHl KASEI CO). The raw materials were milled in an attriter.
The paste prepared by the above procedure was printed on a pasteboard which was painted with water soluble dextrin by a screen printing procedure. and was left to dry in air. The resulting dehydrated printing layer was of a thickness of about 100 to u. The transfer which was paper cured in this manner had a flexible printing layer and was easy to keep and transport.
The paste was transferred to a ceramic plate substrate by a water sliding method in which the coated paper was dipped in water with its printed surface upward. This configuration permitted the water soluble dextrin to dissolve. which allowed the printing layer to separate from the pasteboard. The separated printing layer which had risen to the surface of the water was removed from the water either by the substrate itself or by the use of a pincette. Thereafter. it was transferred to the surface of the substrate. The transfer-printed substrate was fired at a temperature of 600 to 700C. After the substrate was cooled. belt-shaped aluminum foil was applied to both ends of the calorific layer as electrodes.
A glass fiber mat was applied on the surface of the calorific layer with a urethane resin adhesive. By this procedure panel-styled calorific material C was obtained. which had a metal content of 48% by weight and a resistance value of 30 fl/sq cm. It had substantial heat retaining properties.
EXAMPLE 4 A paste was prepared from 40 parts by weight of a synthetic oil prepared from 5 parts by weight of ethyl ene glycol and 20 parts by weight of a hydroxyl-ethylcellulose solution which was added to I00 parts by weight of a Copolymer emulsion of acryl-n-butyl and methacryl n-butyl in mole ratio of l:3. 90 parts by weight of Zinc metal powder and l0 parts by weight of barium oxide glass powder. These raw materials were milled in a ball mill.
The paste was coated on a release paper with a roller coater. Thereafter, the paste was dried leaving a film of 50 in thickness.
A cylindrically shaped enameled metal vessel was used as a substrate. The release paper upon which the film was coated was scrupulously fitted on the circumferential wall of the enameled metal vessel. whereby the film was pressure-adhered thereon. After removing the release paper after the pressure-adhering steps. the film adhered firmly to the circumferential wall and re mained there. Thereafter. a conductive paste was coated in a belt-shape configuration on the upper and lower rims of the film. and a glaze was coated on the surface of the film. After the coating had dried. the film was fired at 700 to 800C. By this procedure a glaze covered panel-styled calorific material D was obtained. The calorific material D had a metal content of 84)? and a resistance of 2 Q/sq cm.
Having now fully described this invention. it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
What is claimed as new and desired to be secured by Letters Patent of the United States is:
l. A panel-styled calorific device which comprises:
a. a substrate b. a layer of calorific material prepared by mixing l. glass powder 2. a metal powder selected from the group consisting of copper. silver. gold. zinc. cadmium. aluminum. indium. thallium. tin. lead. antimony and bismuth. and
3. a synthetic oil comprising an organic solvent and at least one synthetic resin selected from the group consisting of acr resins. methacrylic resins. vinyl acetate resins. styrol resins. vinyl ether resins. vinyl chloride resins. vinylidene chloride resins. vinyl pyrrolidone resins. polyethylene. polypropylene. polyvinyl alcohol. acetal resins. butyral resins. phenol resins. alkyol resins. melamine resins. polyamide resins. polyurethane resins. mcthylcellulose. hydroxyethyl cellulose. carboxymethyl cellulose. ethyl cellulose. cellulose nitrate. cellulose acetate. cellulose butyrate. styrene butadiene rubbers. acrylonitrile-butadiene rubber. isoprene rubber. butyl rubber. polybutadiene rubber. polychloroprene rubber. ethylenepropylene rubber. thiokol rubber. natural rubber and reclaimed rubbers thereof. petroleum resins. cumarone resins. terpeno resins. rosin and derivatives thereof. starch. denatured starch. proteins and denatured proteins. and firing the mixture at a temperature above the melting point of sand metal powder thereby partially oxidizing said metal powder on said substrate. and
c. a protective coating over said calorific layer. said metal powder being present in the mixture in an amount ranging from 97 to 2 5% by weight.
2. The panel-styled calorific device of claim 1, wherein said substrate is an enameled metal panel.
3. The panel-styled calorific device of claim 1. wherein said protective coating is a film formed from a synthetic composition whose major component is a melamine resin.
4. A method for fabricating a panel-styled calorific device which comprises:
a. coating a substrate with a paste comprising a mixture of a glass powder. a metal powder selected from the group consisting of Copper. zinc. silver gold. cadmium. chromium. indium. thallium. tin. lead. antimony and bismuth. and a synthetic oil comprising an organic solvent and at least one synthetic resin selected from the group consisting of acryl resins. methacrylic resins. vinyl acetate resins. styrol resins. vinyl ether resins. vinyl chloride resins. vinylidene chloride resins. vinyl pyrrolidone resins. polyethylene. polypropylene. polyvinyl alcohol. acetal resins. butyral resins. phenol resins. alkyol resins. melamine resins. polyamide resins. polyurethane resins. methylcellulosc. hydroxyethyl cellulose. carboxymethyl cellulose. ethyl cellulose. cellulose nitrate. cellulose acetate. cellulose buty rate. sty rene butadiene rubbers. acrylonitrilebutadiene rubber. isoprene rubber. butyl rubber. polybutadiene rubber. polychloroprene rubber. ethylene-propylene rubber. thiokol rubber. natural rubber and reclaimed rubbers thereof. pctroleum resins. cumarone resins. terpeno resins. rosin and derivatives thereof. starch. denatured starch. proteins and denatured proteins.
. firing the mixture at a temperature above the melting point of said metal powder thereby partially oxidizing said metal powder on said substrate. and
c. coating the tired mixture of step (b) with a protective material said metal powder being present in said mixture in an amount of from 86 to 27% by weight.
5. The method of claim 4, wherein said paste is coated on said substrate by coating the paste on a transfer paper and then transferring said coated paste to said substrate.
6. The method of claim 4. wherein said protective material is a film of melamine resin.
7. The method of claim 4, wherein said paste comprises a mixture of l() to parts by weight of said synthetic oil per parts by weight of a mixture of 0 to 60% by weight of said glass and 100 to 40% by weight of said metal powder.
8. The method of claim 7, wherein the glass transition temperature of the synthetic resin of said synthetic oil is less than 20C.

Claims (13)

1. A PANEL-STYLED CALORIFIC DEVICE WHICH COMPRISES: A. A SUBSTRATE B. A LAYER OF CALORIFIC MATERIAL PREPARED BY MIXING
1. GLASS POWDER
2. A METAL POWDER SELECTED FROM THE GROUP CONSISTING OF COPPER, SILVER, GOLD, ZINC, CADMIUM, ALUMINUM, INDIUM, THALLIUM, TIN, LEAD, ANTIMONY AND BISMUTH, AND
2. The panel-styled calorific device of claim 1, wherein said substrate is an enameled metal panel.
2. a metal powder selected from the group consisting of copper, silver, gold, zinc, cadmium, aluminum, indium, thallium, tin, lead, antimony and bismuth, and
3. a synthetic oil comprising an organic solvent and at least one synthetic resin selected from the group conSisting of acryl resins, methacrylic resins, vinyl acetate resins, styrol resins, vinyl ether resins, vinyl chloride resins, vinylidene chloride resins, vinyl pyrrolidone resins, polyethylene, polypropylene, polyvinyl alcohol, acetal resins, butyral resins, phenol resins, alkyol resins, melamine resins, polyamide resins, polyurethane resins, methylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, ethyl cellulose, cellulose nitrate, cellulose acetate, cellulose butyrate, styrene butadiene rubbers, acrylonitrile-butadiene rubber, isoprene rubber, butyl rubber, polybutadiene rubber, polychloroprene rubber, ethylene-propylene rubber, thiokol rubber, natural rubber and reclaimed rubbers thereof, petroleum resins, cumarone resins, terpeno resins, rosin and derivatives thereof, starch, denatured starch, proteins and denatured proteins, and firing the mixture at a temperature above the melting point of sand metal powder thereby partially oxidizing said metal powder on said substrate, and c. a protective coating over said calorific layer, said metal powder being present in the mixture in an amount ranging from 97 to 27% by weight.
3. The panel-styled calorific device of claim 1, wherein said protective coating is a film formed from a synthetic composition whose major component is a melamine resin.
3. A SYNTHETIC OIL COMPRISING AN ORGANIC SOLVENT AND AT LEAST ONE SYNTHETIC RESIN SELECTED FROM THE GROUP CONSISTING OF ACRYL RESINS, METHACRYLIC RESINS, VINYL ACETATE RESINS, STYROL RESINS, VINYL ETHER RESINS, VINYL CHLORIDE RESINS, VINYLIDENE CHLORIDE RESINS, VINYL PYRROLIDONE RESINS, POLYETHYLENE, POLYPROPYLENE, POLYVINYL ALCOHOL, ACETAL RESINS, BUTYRAL RESINS, PHENOL RESINS, ALKYOL RESINS, MELAMINE RESINS, POLYAMIDE RESINS, POLYURETHANE RESINS, METHYLCELLULOSE, HYDROXYETHYL CELLULOSE, CARBOXYMETHYL CELLULOSE, ETHYL CELLULOSE, CELLULOSE NITRATE, CELLULOSE ACETATE, CELLULOSE BUTYRATE, STYRENE BUTADIENE RUBBERS, ACRYLONITRILE-BUTADIENE RUBBER, ISOPRENE RUBBER, BUTYL RUBBER, POLYBUTADIENE RUBBER, POLYCHLOROPRENE RUBBER, ETHYLENE-PROPYLENE RUBBER, THIOKOL RUBBER, NATURAL RUBBER AND RECLAIMED RUBBERS THEREOF, PETROLEUM RESINS, CUMARONE RESINS, TORPENO RESINS, ROSIN AND DERIVATIVES THEREOF, STARCH, DENATURATED STARCH, PROTEINS AND DENATURATED PROTEINS, AND FIRING THE MIXTURE AT A TEMPERATURE ABOVE THE MELTING POINT OF SAND METAL POWDER THEREBY PARTIALLY OXIDIZING SAID METAL POWDER ON SAID SUBSTRATE, AND C. A PROTECTIVE COATING OVER SAID CALORIFIC LAYER, SAID METAL POWDER BEING PRESENT IN THE MIXTURE IN AN AMOUNT RANGING FROM 97 T 27% BY WEIGHT.
4. A METHOD FOR FABRICATING A PANEL-STYLED CALORIFIC DEVICE WHICH COMPRISES: A. COATING A SUBSTRATE WITH A PASTE COMPRISING A MIXTURE OF A GLASS POWDER, A METAL POWDER SELECTED FROM THE GROUP CONSISTING OF COPPER, ZINC, SILVER, GOLD, CADMIUM, CHROMIUM, INDIUM, THALLIUM, TIN, LEAD, ANTIMONY AND BISMUTH, AND A SYNTHETIC OIL COMPRISING AN ORGANIC SOLVENT AND AT LEAST ONE SYNTHETIC RESIN SELECTED FROM THE GROUP CONSISTING OF ACRYL RESINS, METHACRYLIC RESINS, VINYL ACETATE RESINS, STYROL RESINS, VINYL ETHER RESINS, VINYL CHLORIDE RESINS, VINYLIDENE CHLORIDE RESINS, VINYL PYRROLIDONE RESINS, POLYETHYLENE, POLYPROPYLENE, POLYVINYL ALCOHOL, ACETAL RESINS, BUTYRAL RESINS, PHENOL RESINS, ALKYOL RESINS, MELAMINE RESINS, POLYAMIDE RESINS, POLYURETHANE RESINS, METHYLCELLULOSE, HYDROXYETHYL CELLULOSE, CARBOXYMETHYL CELLULOSE, ETHYL CELLULOSE, CELLULOSE NITRATE, CELLULOSE ACETATE, CELLULOSE BUTYRATE, STYRENE BUTADIENE RUBBERS, ACRYLONITRILEBUTADIENE RUBBER, ISOPRENE RUBBER, BUTYL RUBBER, POLYBUTADIENE RUBBER, POLYCHLOROPRENE RUBBER, ETHYLENEPROPYLENE RUBBER, THIOKOL RUBBER, NATURAL RUBBER AND RECLAIMED RUBBERS THEREOF, PETROLEUM RESINS, CUMARONE RESINS, TERPENO RESINS, ROSIN AND DERIVATIVES THEREOF, STARCH, DENATURED STARCH, PROTEINS AND DENATURED PROTEINS, B. FIRING THE MIXTURE AT A TEMPERATURE ABOVE THE MELTING POINT OF SAID METAL POWDER THEREBY PARTIALLY OXIDIZING SAID METAL POWDER ON SAID SUBSTRATE, AND C. COATING THE FIRED MIXTURE OF STEP (B) WITH A PROTECTIVE MATERIAL SAID METAL POWDER BEING PRESENT IN SAID MIXTURE IN AN AMOUNT OF FROM 86 TO 27% BY WEIGHT.
5. The method of claim 4, wherein said paste is coated on said substrate by coating the paste on a transfer paper and then transferring said coated paste to said substrate.
6. The method of claim 4, wherein said protective material is a film of melamine resin.
7. The method of claim 4, wherein said paste comprises a mixture of 10 to 75 parts by weight of said synthetic oil per 100 parts by weight of a mixture of 0 to 60% by weight of said glass and 100 to 40% by weight of said metal powder.
8. The method of claim 7, wherein the glass transition temperature of the synthetic resin of said synthetic oil is less than 20*C.
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CN104270841A (en) * 2014-10-17 2015-01-07 无锡中车创想科技有限公司 Electric blanket of motor train unit
CN106799877A (en) * 2016-12-09 2017-06-06 东莞珂洛赫慕电子材料科技有限公司 A kind of flexible electrothermal membrane and preparation method thereof
CN106863970A (en) * 2016-12-22 2017-06-20 东莞珂洛赫慕电子材料科技有限公司 A kind of fast startup large-power flexible Electric radiant Heating Film and preparation method thereof

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AU6342573A (en) 1975-06-12
GB1463317A (en) 1977-02-02
FR2211832A1 (en) 1974-07-19
CS186780B2 (en) 1978-12-29
CA1014429A (en) 1977-07-26
DD109281A5 (en) 1974-10-20
DE2363650A1 (en) 1974-06-27
FR2211832B1 (en) 1978-11-10

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