US3906139A - Insulated wire - Google Patents

Insulated wire Download PDF

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Publication number
US3906139A
US3906139A US394611A US39461173A US3906139A US 3906139 A US3906139 A US 3906139A US 394611 A US394611 A US 394611A US 39461173 A US39461173 A US 39461173A US 3906139 A US3906139 A US 3906139A
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Prior art keywords
acid
insulated wire
polyacryl
group
resin
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US394611A
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English (en)
Inventor
Yukio Hiraoka
Sadao Nakao
Yoshinobu Noda
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Dainichi Nippon Cables Ltd
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Dainichi Nippon Cables Ltd
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Priority to US05/551,447 priority Critical patent/US3953310A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
    • C09D5/4411—Homopolymers or copolymers of acrylates or methacrylates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/065—Insulating conductors with lacquers or enamels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/308—Wires with resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/447—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from acrylic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0208—Cables with several layers of insulating material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2947—Synthetic resin or polymer in plural coatings, each of different type

Definitions

  • ABSTRACT An insulated wire suitable as a magnet wire having a baked layer of a specific polyacryl resin as an underlayer and a baked layer of a specific polyester resin as an upper-layer on the conductor as well as a process for producing the insulated wire are disclosed.
  • the insulated wire according to the present invention exhibits well-balanced overall properties necessary for use as a magnet wire and has an excellent heat resistance.
  • This invention relates to an insulated wire useful as a magnet wire for use in electric equipment such as motors, transformers and the like, and to a process for producing the insulated wire.
  • the multiple coating insulating layer exhibits some advantages, i.e., the excellent properties possessed by specific layers included in the layers of multiple coatings compensate for the defects of the other layers.
  • the excellent properties possessed by the layers sometimes can be masked by the presence of other layers and, in some cases, the presence of other layers adversely affects the properties.
  • the difficulty of operations for uncovering the tip of the wire coated with a polyamideimide resin due to an excessively strong chemical resistance of the resin to a remover can be solved by provid ing a polyester layer under the polyamide-imide layer, but, due to the presence of the polyester layer the abrasion resistance, the heat resistance, etc., of the polyester-polyamide-imide dual coated wire are inferior to those of a wire coated with the polyamide-imide alone.
  • the thermoplastic polyester layer of the insulated wire wherein the thermoplastic polyester layer is coated on a baked thermosetting polyester layer functions to improve the heat-shock resistance and the abrasion resistance properties of the baked polyester layer, but it lowers the cut through temperature of the insulated wire.
  • a dual insulating coating comprising a specific polyacryl resin layer having coated thereon a specific polyester resin layer exhibits excellent heat resistance properties over a coating of each of the above described resins and further it possesses well-balanced overall properties required for a coating of magnet wires.
  • the present invention has been completed by a further investigation of the above unexpected finding.
  • a primary object of this invention is to provide an insulated wire having excellent heat resistance and wellbalanced overall properties required for magnet wires.
  • Another object of this invention is to provide a process for improving the heat resistance of the magnet wires.
  • a further object of this invention is to provide a process for producing a magnet wire having excellent heat resistance and well-balanced overall properties for magnet wires.
  • the present invention comprises an insulated wire having a baked layer of a specific polyacryl resin on a conductor and a baked layer of a specific thermosetting polyester resin on the above polyacryl resin layer and to a process for producing such an insulated wire.
  • FIG. 1 is an enlarged schematic sectional view of the dual coated wire prepared according to an embodiment of this invention.
  • FIG. 2 illustrates an example of the processing line for producing the dual coated wire according to the present invention.
  • the dual coated wire having an excellent heat resistance and well-balanced overall properties can be obtained by providing a baked insulating layer 2 of the polyacryl resin as hereinafter speciand (b) at least one compound (hereinafter, the bcomponent) of the formula (II):
  • an unsaturated organic acid hereinafter, the c-component having 3 to about 30 carbon atoms and at least one double bond which is reactable with the double bond of the a-component or b-component.
  • R represents hydrogen atom and an alkyl group having 1 to about 30 carbon atoms, such as methyl, ethyl, propyl, butyl and the like
  • R represents a cyano group, an aldehyde group and a carboxyalkyl ester group having 2 to about 30 carbon atoms, such as carboxymethyl ester, carboxyethyl ester, carboxypropyl ester, carboxybutyl ester and the like
  • R and R each represents a hydrogen atom, an amide group, a glycidyl ester group, glycidyl ether group and an organic group having 1 to about 30 carbon atoms selected from the group consisting of an alkyl group, such as methyl, ethyl, propyl, butyl and the like, an N-alkylamide group, such as N-methylamide, N-ethylamide, N-propylamide and the like, and an alkylol group,
  • the heat resistance of the resulting polyacryl resin tends to decrease and, therefore, the maximum number of carbon atoms of the c-component and the above R R R or R organic groups preferably does not exceed about 20.
  • Examples of the c-cqmponent are monobasic unsaturated acids, such as acrylic, crotonic, vinylacetic acid, methacrylic, tiglic, a-ethylacrylic, B-methylcrotonic, 2-pentenoic, 2-hexenoic, 2-heptenoi c, 2-octenoic, lundecenoic, 9-octadecenoic, cinnamic, atro'pic, a-benzylacrylic, methyl atropic, 2,4-pentadienoic, 2,4- hexadienoic, 2,4-dodecadienoic acid, 9,12 octadecadienoic acid; dibasic unsaturated acids, such as maleic, fumaric, itaconic, citraconic, mesaconic, glutaconic, dihydromuconic, muconic; and-tribasic unsaturated acids, such as l,2',4-tricarbox
  • the polyacryl resin used in the present invention can be prepared by the well-known polymerization procedures such as an emulsion polymerization, a solution polymerization, a suspensionpolymerization and the like as described, for example, in US. Pat. Nos. 2,787,561 and 3,509,033, and in Acryl-Resin by Kou Asami, published by Nikkan Kogyo Shinbun, Tokyo, 1970, p. 25 to p.
  • more preferred examples are those components in which the total number of carbon atoms is less than from the standpoint of the heat resistance of the polyacryl resin obtained. More preferred examplesof the a-component are acrylonitrile, methacrylonitrile, methylacrylate, ethylacrylate, propylacrylate, butylacrylate, methylmethacrylate, ethylmethacrylate,
  • propylmethacrylate and acrolein. More preferred examples of the b-component are glycidylacrylate, glycidylmethacrylate, allylglycidylether, acrylamide,
  • methylolacrylamide and ethylolacrylamide. More preferred examples of the c-component are acrylic acid, methacrylic acid, a-ethylacrylic acid, crotonic acid, maleic acid, and fumaric acid.
  • the polyacryl resin employed in the present invention may also be those modified with one or more of styrene and its derivatives or diolefins.
  • the derivatives of styrene there are employed those compounds in which the phenyl group of styrene is substituted with at least one group selected from the group consisting of a cyano group, a nitro group, a hydroxy group, an amine group, a vinyl group, a phenyl group, a halogen atom such as chlorine, bromine, etc., an organic group having 1 to carbon atoms, such as an alkyl group, an aralkyl group,.an N-alkylamine group.
  • Examples ofthe above alkyl groups are methyl, ethyl, propyl, butyl, etc., and examples of the above aralkyl groupsare benzyl, 01- or B-phenylethyl, etc., and examples of the above N-alkylamine' groups are N-methylamine, N- ethylamine, N-propylamine, etc.
  • examples of the styrene derivatives those which have 1 to 3 substituent groups are preferable because of their ready reactivity with the ato c-components.
  • Preferableexamples are methyl styrenes, ethyl styrenes, divinyl benzenes, chlorostyrenes.
  • the diolefins used as a modifying agent those compounds are used whose total number of carbon
  • Polyacryl resin's modified with those modifying agents can be prepared using well-known polymerization methods previously described using a starting material mixture containing one or more of the above modifying materials in addition to a-, b-, and ccomponents'.
  • the amount of styrene and its derivatives ordiolefins should be restricted to about 2 moles or one mole or less, respectively, per one mole of the a-component, since use of the modifying materials in an amount greater than thatdescribed above results in the formation of a polyacryl resin poor in flexibility. in the case of styrenes, and in'the formation of polyacryl resinpoor in the cut through temperature in the .case of the diolefins. Y
  • a polyacryl resin (including the modified resin) having a degree of polymerization of approximately about 10,000 to-about 1,000,000 is used, since a polyacryl resin having too low a degree of polymerization is lacking in toughness, and, in turn a polyacryl resin having toohigh a degree of polymerization tends to vresult in a somewhat uneven coating surface due to a, poor fluidity of the resin in the uncured state. Therefore, more preferable polyacryl resins are those having a degree of polymerization of about 100,000 to about.500,000.
  • the polyacryl resin employable in this invention prepared by any one of the-prior art processes can be coated on a conductor in ,the form ofa dispersion or a solution in water or in an appropriate,organicsolvent such as N-methyl- Z-pyrrolidone, N,N-dimet hylformamide, N,N-dimethylacetamide, dimethylsulfoxide and the like using a polymer concentration of about 5 to about 50, preferably about 10 to about 30% by weight and subsequently the fcoating can be baked at a temperature ranging from about 100 C to about 600C, preferably about 200C to 500C, whereby atough insulating film can be formedon the conductor by crosslinking.
  • V an appropriate,organicsolvent
  • the polyesterresin-used in the present invention is a copolymerof (d) atleast one terephthalic acid compound and its derivatives, generally represented by the Formula (lll);.
  • atoms is 3 to about 20, preferably 4 to about l0.
  • diolefins are the butadienes, pentadienes, methyl-butadienes and the like.
  • R and R groups are hydroxyl groups, amino groups, halogen atoms, such as chlorine, bromine, etc., alkoxy groups, such as methoxy, ethoxy, propoxy, butoxy, etc., N-alkylamino groups, such as N- methylamino, N-ethylamino, etc.,.aryloxy groups such as phenoxy groups.
  • n is a positive integer of 2 to 4
  • R represents saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms.
  • n in the. Formula (1V) is 2, 3, or 4
  • the valency of R becomes divalent, trivalent, or tetravalent, respectively.
  • Examples of divalent R groups are alkylene, alkenylene, alkylidene or alkenylidene groups alkylene or alkenylene groups of which one or two hydrogen atoms on one or both end carbon atoms can be replaced by one or two alkyl groups or alkenyl groups, alkylidene or alkenylidene groups of which one hydrogen atom of the end carbon atom having two free valencies can be substituted with one alkyl group or alkenyl group, and the like.
  • Examples of trivalent R groups are alkane-yl ylidene groups or alkane-yl-ylidene groups, the above groups of which one hydrogen atom of the end carbon atom -having two free valencies. can be replacedby one alkyl group or alkenyl group, or of which one or two hydrogen atoms of another end carbon atom can be replaced by one or two alkyl or alkenyl groups, alkylene or alkenylene groups of which a hydrogen atom of one end carbon atom is replaced by one alkylene, alkenylene, alkylidene, or alkenylidene group, or of which a hydro gen atom of both end carbon atoms are replaced by one alkyl or alkenyl group and one alkylidene or alkenylidene group, alkylene or alkenylene group of which an inner carbon atom between both end carbon atoms is substituted with one alkylene or alkenylene group and one alkyl or alkenyl group and the like
  • Examples of tetravalent R groups are alkenediylidene groups or alkene-diylidene groups, the above groups of which one hydrogen atom of one or both end carbon atoms is replaced by one alkyl group or alkenyl group, alkaneyl-ylidene or alkene-yl-ylidene groups of which a hydrogen atom of one end carbon atom are replaced by one alkylene, alkenylene, alkylideneor alkenylidene group, alkylene or alkenylene groups of which a hydrogen atom of an end carbon atom andanother end carbon atom, are substituted with one alkylene, alkenylene, alkylidene or alkenylidene group, or of which an inner carbon atom between the both end carbon atom is substituted with two alkylene or alkenylene groups, and the like.
  • the above hydrocarbon group may contain in its carbon chain a hetero atom such as oxygen, nitrogen and the like or at least one, preferably 1 to 5, four to eight membered heterocyclic ring, such as a pyrazine ring, a pyrazole ring, a triazine ring, etc., or 1 to 5 benzene type rings, such as phenylene, phenylene ether, and may also be substituted with at least 1, preferably 1 to 5, phenyl groups and/or aralkyl groups having about 7 to 10 carbon atoms such as benzyl groups.
  • a hetero atom such as oxygen, nitrogen and the like or at least one, preferably 1 to 5, four to eight membered heterocyclic ring, such as a pyrazine ring, a pyrazole ring, a triazine ring, etc., or 1 to 5 benzene type rings, such as phenylene, phenylene ether, and may also be substituted with at least
  • aliphatic diols such as ethylene glycol, propylene. glycol, butane diol and the like
  • aromatic ring-containing diols such as 2,2- bis(p-hydroxyethoxyphenyl)propane and the like
  • triols such as glycerine, l,l,l-trimethylolethane,
  • the polyol mixture preferably contains about 45 to equivalents of the diols.
  • the polyester resins can be prepared using well-known polymerization techniques, e.g., a solution polymerization as described in U.S. Pat. No. 3,296,024.
  • isophthalic acid or its derivatives in an amount less than about 60 moles per 100 moles of terephthalic acid of the Formula (Ill) may be added in the polymerization reaction.
  • derivatives of isophthalic acid those corresponding to the derivatives of terephthalic acid described above can be employed.
  • Particularly preferred polyester resins are those obtained by reacting about 25 to 56 equivalents of terephthalic acid or a derivative thereof with about 15 to 46% equivalents of ethylene glycol and about 7 to 22% equivalents of glycerine and about 7 to 22% equivalents of tris-2-hydroxyethyl isocyanurate.
  • the proportion of glycerine and tris-2-hydroxyethyl isocyanurate can be varied as long as the sum of equivalents of glycerine plus tris-2-hydroxyethyl isocyanurate is about 14 to 44%.
  • the polyester resins which can be used in the present invention can be a modified polyester resin containing not greater than.70 imide groups or the sum of the amide groups plus the imide groups per 100 ester linkages in the resin.
  • Modified polyester resins can be prepared by using an imideor amide-imide-containing substance in the reaction between terephthalic acid or a derivative thereof and a polyol mixture. Altemativ'ely, the modified polyester resins can also be prepared by reacting an imideor amide-imide-containing substance with a polymerization product having a low degree of polymerization of about 1 to about 10 between terephthalic acid or a derivative thereof and the polyol mixture.
  • Such an imideor amide-imidecontaining substance can be obtained, for example, by reacting a polybasic acid or its anhydride higher than tribasic acid as disclosed in U.S. Pat. Nos; 3,489,696, 3,471,444 and 3,485,796 such as trimellitic anhydride, pyromellitic dianhydride, butane tetracarboxylic dianhydride, with a diamine as disclosed in U.S. Pat. No. 3,480,588 such as 4,4-diaminodiphenyl methane, 4,4- diaminodiphenyl ether, hexamethylenediamine, and/or a diisocyanate as disclosed in U.S. Pat. No. 3,489,696
  • imideor amide-imide-containing sub stances are those having a low degree of polymerization, containing imide groups or the sum of amide and imide groups of l to 2, to a degree of polymerization about 10. Substances having such a degree of polymerization can easily be prepared by adjusting the molar ratio of starting materials and polymerization conditions suchas temperature and period of polymerization.
  • An alternative procedure of introducing the imide groups or amide and imide groups into the poly ester resin comprises dissolving the above described imideor amide-imide-containing substance, a polyamide-imide resin, or a polyamic acid resin which is a precursor of the polyimide together with the polyester resin in a suitable solvent, such as phenol, cresol,-xylenol, N-methyl-2-pyrollidone, N,N-dimethylacetamide and the like, applying the resulting varnish on a conductor, and baking the varnish.
  • a suitable solvent such as phenol, cresol,-xylenol, N-methyl-2-pyrollidone, N,N-dimethylacetamide and the like
  • a polyester resin (including the modified resins) having a degree of polymerization of approximately about 2 to 200 is used, since a polyester resin having too low a degree of polymerization lacks toughness, and a polyester resin having too high a degree of polymerization tends to gel in the preparation of a varnish thereof. Therefore, more preferable polyester resins are those having a degree of polymerization ranging from about to 50.
  • the polyester resin used in the present invention forms a tough insulating layer by crosslinking when a dispersion or solution thereof in a solvent such as water, phenol, cresol, xylenol, N-methyl-2-pyrollidone, N,N-dimethylacetamide and the like in a polymer concentration of about 5 to about 50%, preferably about to about 45% by weight is applied to a conductor and baked at a temperature ranging from about 100C to about 600C, preferably about 200C to about 500C.
  • a solvent such as water, phenol, cresol, xylenol, N-methyl-2-pyrollidone, N,N-dimethylacetamide and the like in a polymer concentration of about 5 to about 50%, preferably about to about 45% by weight
  • the layer thickness of both the under-layer and the upper-layer can be varied freely, but the layer thickness of the under-layer is preferably from about 1 to 300 u, particularly, from about 5 to 100 p. and the thickness of upper-layer is preferably from about 0.3 to 100 ,u., particularly, from about 2 to 50 ,u..
  • the particularly preferred heat resistance and the well-balanced overall properties as an insulated wire for coils can be obtained when the thickness ratio of the under-layer to the upper-layer is within the range of from about 0.1 to 30, preferably from about 7 to 15.
  • the layer of the polyacryl resin and the layer of the polyester resin can be formed on a conductor using any conventional procedure such as, for example, by a well-known coating method such as dipcoating, spray-coating, brush-coating or using electrodeposition coating as described in Wire World, vol. 13, May/June, page 69, 1971, and Wire, vol. 40, No. 6, page 832, 1965, followed by baking according to a conventional baking procedures.
  • the polyester resin varnish can be applied onto an uncured or cured polyacryl resin layer, and baked together with the uncured or already cured polyacryl resin layer.
  • the baking can generally be carried out at a temperature ranging from about 200C to 600C. It is preferred to dry the coated wire at a temperature below about 200C prior to the baking since the tendency of blistering of the coating layers which is frequently observed in baking without previous drying, can effectively be prevented.
  • the above described drying prior to the baking is desirable when the insulated wire is produced at a rate higher than about 50 m per minute.
  • the polyacryl resin is first electrodeposited on a conductor, and then the polyester resin film is formed thereon using electrodeposition coating or the dip-coating of a polyester resin varnish.
  • the process for producing the insulated wire according to the present invention is hereinafter described in greater detail by reference to FIG. 2 in a preferred embodiment comprising coating a conductor with a polyacryl resin-by electrodeposition coating and then applying a polyester varnish by dip-coating to the polyacryl resin film.
  • a conductor W such as copper, aluminum and the like which is connected to the positive terminal of a DC. power supply (not shown) is passed through an electrodeposition bath 6 filled with a polyacryl resin varnish 4 in the form of an aqueous solution or an aqueous dispersion.
  • a cylindrical cathode 8 is mounted in the electro-deposition bath 6, and the polyacryl resin particles from the varnish are deposited uniformly on the conductor W by electro-phoresis due to the potential difference between the conductor, as the anode, and the cathode while the conductor passes through the cathode.
  • suitable varnishes may be used, such as the emulsified product per se of a polyacryl resin prepared by the emulsion polymerization process described in US. Pat. Nos. 2,787,561 and 3,509,033, an aqueous-solution of a polyacryl resin together with, if necessary, an amine disclosed in US. Pat. No. 3,230,162, and a water dispersion of a polyacryl resin having particle size of about 0.01 p. to about 1.0 p. in diameter with a well-known surface active agent.
  • the electrodeposition coating using the above described polyacryl resin in the present invention can be carried out under the conditions well-established in the art as described in US. Pat. No. 3,378,477. That is, the polyacryl resin varnish containing from about 5 to 50% by weight of a polyacryl resin can be used with a load voltage of from about 10 to 200 V for the aqueous solution varnish and from about 1 to 50 vV for the aqueous dispersion varnish. In the electrodeposition coating, an AC. current can be superposed on the DC. current.
  • the conductor W having coated thereon the electrodeposited coating of the polyacryl resin can then be dried and baked, or can be directly subjected to the overcoating of the polyester resin varnish.
  • the polyacryl resin varnish is in the form of an aqueous dispersion
  • that the polyacryl resin coated conductor be passed through an organic solvent bath 12 filled with an organic solvent 10 which is capable of dissolving water to an extent of at least about 1% by weight, preferably at least about 10% by weight and which is capable of at least swelling, preferably, dissolving the polyacryl resin deposited on the conductor prior to the heat-drying or the crosslinking of the resin.
  • the water contained in the polyacryl resin deposited on the conductor is eluted into the organic solvent and, at the same time, a portion of the organic solvent penetrates into the deposited polyacryl resin layer during the passage of the conductor through the organic solvent bath, whereby the penetrated solvent retained in the resin layer serves to render the film more uniform with less pinholes by swelling or dissolving the resin until it is removed in a subsequent evaporation step.
  • the treatment with the organic solvent should preferably be accomplished while the polyacryl resin deposited on the conductor remains wet by a medium for the polyacryl resin varnish (in this embodiment, water), or a poor result will be obtained if the treatment is carried out after the deposited polyacryl resin is dried.
  • the organic solvent used be capable of at least swelling the polyacryl resin before the semi-cured stage.
  • organic solvents both dissolving water and swelling and/or dissolving the resin are monohydride or polyhydric alcohols such asmethanol, ethanol, propanol, ethylene glycol, glycerine and the like, cellosolves such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monophenyl ether and the like, nitrogen-containing organic solvents such as N,N-dimethylformamide, N,N- dimethylacetamide, N-2methylpyrrolidone-" and the like, sulfur-containing organic solvents such as dimethylsulfoxide, etc.
  • monohydride or polyhydric alcohols such asmethanol, ethanol, propanol, ethylene glycol,
  • N,N-dimethylacetamide, N-Z-methylpyrrolidone and dimethylsulfoxide are preferred.
  • a DC. voltage of from about 30 to 500 V with or without an A.C. voltage superposed thereupon lower than the D.C. voltage is applied between a cathode (not shown) mounted in the bath l2 and the conductor W passing through the cathode.
  • a cathode not shown mounted in the bath l2 and the conductor W passing through the cathode.
  • the deposited resin layer can be exposed to an organic solvent vapor or the organic solvent can be sprayed on the deposited resin layer, etc. as described in British Pat. No. 1,169,447.
  • a wiping means such as an airwiper, roll-wiper and the like at the outletof the electrodeposition bath 4 and the organic solvent bath 12.
  • the adhering liquid sometimes prevents a high speed operation of the clectrodeposition coating of the polyacryl resin, because of blistering of the adhering liquid in the baking process and such a wiping means eliminates the liquid so as to permit a conductor line speed of greater than about 50 m per minute.
  • the conductor from the organic solvent bath 12 is then introduced into a drying means 14 where the conductor is heated and the organic solvent from the bath l2 and water remaining in the resin layer in those methods retaining water are removed by evaporation.
  • the drying temperature in the drying means 14 varies somewhat depending upon the type of the organic solvent, but generally ranges from about 60 to 200C, preferably from about 100 to 200C.
  • an elevated temperature for example, about 200C to .uids and at the same time for curing or semi-curing the polyacryl resin deposited on the conductor.
  • the last portion of the drying means 14 can be maintained at the temperature required for curing the polyacryl resin or a baking means can be provided separatelyat the end of the drying means, whereby the polyacryl resin layer is first dried at a relatively low temperature, i.e., about C and then cured or semicured at a high temperature.
  • a relatively low temperature i.e., about C
  • cured or semicured at a high temperature i.e., about C
  • the conductor from the drying means 14 is then passed on the bath 18 filled with a polyester resin varnish 16 while contacting a roll 20 which 'is mounted in the bath l8 and rotates freely.- While passing on the roll 20, the polyacryl resin layer on the conductor is over-coated with a polyester resin varnish 16 by the roll 20, and an excess of the varnish 16 is wiped by a metering device 22 such as a metal die which is fixedly mounted downstream of the roll 20.
  • the conductor W which has been dual coated with the polyacryl resin and the polyester resin is sent to a baking oven 24 and both layers (or the polyesterlayer alone when the polyacryl resin layer has already been baked) are baked and cured.
  • the baking temperature of the baking oven 24 can be approximately the same whether both polyacryl and polyester layers are baked simultaneously or only the polyester resin layer is baked and generally is in the range of from about 200 to 600C.
  • the conductor from the baking oven can be immediately wound on a reel 26 or, if necessary, the conductor may be repeatedly passed several times through the polyester resin bath l8 and the baking oven 24 in order to obtain a desired layer thickness of the polyester resin layer.
  • the polyester resin can be coated on the polyacryl resin layer using clectrodeposition coating under conditions and procedures similar to those described for the electrodeposition of the polyacryl resin layer using an clectrodeposition varnish of the polyester resin in the form of anv aqueous dispersion or an aqueous solution containing about 5 to 50% by weight of the polyester resin.
  • the coating materials containing polyacryl resins or polyester resins were prepared according to the following procedures.
  • Acryl-A to Acryl-L and Polyester-A to Polyester-l are polyacryl resins and polyester resin coating materials, respectively, suitable for the present invention, and Acryl-M and Polyester-J were prepared for the purpose of comparison.
  • Polyacryl-A A monomer mixture consisting of 5 moles of acrylonitrile, 1 mole of acrylic acid, 0.3 mole of glycidylmethacrylate, 760 gof deionized water, 7.5 g of sodium lauryl sulfate, and 0.13 g of sodium persulfate were charged into a flask, and stirredunder a nitrogen stream at room temperature for 15 to 30 minutes.
  • Polyacryl-B The acryl varnish was prepared in the same manner as described in the preparation 1 of Polyacryl-A but using a monomer mixture consisting of 5 moles of acrolein, 1 mole of methacrylic acid and 0.3 mole of acrylic amide in place of the monomer mixture of Polyacryl A.
  • the acryl varnish was prepared in the same manner as described in the preparation of Polyacryl-A but using 5 moles of acrylonitrile, 1 mole of maleic acid, 0.3 mole of glycidyl methacrylate, 840 g of deionized water, 8 g of sodium lauryl sulfate and 0.15 g of sodium persulfate.
  • the acryl varnish was prepared in the same manner as described in the preparation of Polyacryl-A but using 5 moles of methacrylonitrile, 1 mole of maleic acid, 0.3 mole of allyl glycidyl ether, 970 g of deionized water, 10 g of sodium lauryl sulfate and 0.15 g of sodium persulfate.
  • the acryl varnish was prepared in the same manner as described in the preparation of Polyacryl-A but using 5 moles of methylmethacrylate, 0.5 mole of acrylic acid, 0.5 mole of methacrylic acid, 0.2 mole of glycidyl methacrylate, 0.1 mole of acrylamide, 1200 g [Polyacryl-J] I I the acryl varnish was prepared in the same manner as described in the preparation of Polyacryl-A but using 5 moles of butyl acrylate, 0.5 mole of acrylic acid, 0.5 mole of methacrylic acid, 0.2 mole of glycidyl methacrylate, 0.1 mole of acrylamide, 1500. g of deionized water, 15 g of sodium lauryl sulfate and 0.25 g of sodium persulfate.
  • the acryl varnish was prepared in the same manner as described in the preparation of 'Pol-yacryl-A but using 3' moles of acrylonitrile, 2 moles of'ethyl acrylate, 0.5 mole of acrylic acid, 0.5 mole of methacrylic acid, 0.2 mole of glycidyl methacrylate, 0.1 mole of acrylamide, 1 mole of 1,3-butadiene, 1100 gof deionized water, 11 g of sodium lauryl sulfate and 0.18 g of sodium persulfate.
  • the acryl varnish was prepared in the same manner as described in the preparation of Polyacryl-A but using 2 moles of styrene, 5 moles of ethyl acrylate, 1400 g of deionized water, 14g of sodium lauryl sulfate and 0.2g of sodium persulfate. i
  • the concentration of a polyacryl resin each of the above Polyacryl-A to Polyacryl-M vamishes was about 30% by weight
  • polyester-A The polyester resin was prepared from the following composition:
  • Dimethyl Terephthalate i Ethylene'Gl'ycol Glycerin A mixture of the above composition and 50 g of xylol was charged into a four-necked flaskequipped with a thermometer, a stirrer and a Liebig condenser. The flask was then heated to a temperature of about 1 30C over 30 minutes while introducing nitrogen gas through an additional inlet, with the methyl alcohol formed in the course of the reaction being removed continuously from the flask as an azeotropic mixture with thexylol.
  • polyester-C The polyester varnish was prepared in the same manner as described in the preparation of Polyester-A but using 43.5 g (10% equivalents) of tris-2-hydroxyethyl isocyanurate and 19.9 g (13% equivalents) of glycerin in place of 35.2 g (23% equivalents) of glycerin to obtain a varnish having a solids content of 40% by weight.
  • polyester varnish was prepared in the same manner as described in the preparation of Polyester-B but using 33.6 g of hexamethylene diisocyanate in place of 52.4 g of 4,4'-di-isocyanate-dicyclohexylmethane and 51.6 g of butane tricarboxylic anhydride in place of 57.6 g of trimellitic anhydride.
  • polyester varnish was prepared in the same manner as described in the preparation of Polyester-F but using g (22.5% equivalents) of ethylene glycol and 51 g (13.3% equivalents) of propylene glycol in place of 163 g (36.0% equivalents) of 1,4-butanediol and 45 g (14.6% equivalents) of glycerin and 85 g l (9.8% equivalents) of tris-2-hydr0xyethylisocyanurate in place of g (24.2% equivalents) of glycerin to obtain a varnish having a solids content of 37% by weight.
  • polyester-H The polyester varnish was prepared in the same manner as described in the preparation of Polyester-A but using 195.0 g (40.2% equivalents) of dimethyl terephthalate, 28.1 g (5.8% equivalents) of dimethyl isophthalate, 31.0 g (20.0% equivalents) of ethylene glycol, 13.5 g (6.0% equivalents) of 1,4-butanediol and 42.9 g (28% equivalents) of'glycerin to obtain a varnish having a solids content of 43% by weight.
  • polyester varnish was prepared in the same manner as described in the preparation of Polyester-A ,but using 223.1 g (46.0% equivalents) of dimethyl terephthalate, 38.8 g (25.0% equivalents) of ethylene glycol, 13.5 g (6.0% equivalents) of 1,4-butanediol, 30.7 g (20.0% equivalents) of glycerin, 5.1 g (3.0% equivalents) of pentaerythritol to obtain a varnish having a solids content of 30% by weight.
  • Polyester-J 98 g (23.8% equivalents) of maleic anhydride, 148 g (23.8% equivalents) of phthalic anhydride and 233 g (52.4% equivalents) of diethylene glycol were reacted in a manner similar to that described in the preparation of Polyester-A but using about 0.02 g of vhydroquinone as a polymerization inhibitor anda sufficient amount of styrene to obtain a polyester resin solution having a solids content of 50% by weight.
  • EXAMPLE 1 A copper conductor having a diameter of 0.3 mm was coated with Polyacryl-A by the conventional dipcoating procedure using a horizontal coating machine and a metal die, and the coated conductor was then baked at a line speed of 40 m/minute at a temperature of 400C. The above procedure was repeated five times to form an insulating under-layer having a layer thickness of 22 p. on the copper conductor. Polyester-A was then coated on the insulating under-layer at a lined speed of 40 m/minute and the coated conductor was baked one time at a temperature of 450C to form an insulating upper-layer having a layer thickness of 3 u to obtain a dual coated wire having a total insulating coating thickness of 25 ,u.
  • EXAMPLE 2 A copper conductor having a diameter of 0.3 mm as an anode was coated with Polyacryl-B by employing conventional electrodeposition coating using a horizontal coating machine at a line speed of 40 m/minute under the following conditions:
  • Cathode A copper cylindrical tube of 6 cm in diameter and 30 cm in length Distance between Electrodes: 3 cm Electrodeposition Voltage: 5V D.C.
  • Varnish Temperature 30 1C
  • the coated conductor was then passed through a chamber having a length of l m filled with a saturated vapor of N,N-dimethylformamide at 155C to provide a vapor of N,N-dimethylformamideon the acryl varnish resin layer deposited on the copper conductor, and the deposited layer thus treated with the vapor was dried at 200C to from a smooth insulating under-layer having a layer thickness of 22 1.1..
  • Polyester-B was then coated one time on the above insulating under-layer at a line speed of 40 m/minute and a simultaneous baking of the insulating under-layer and the upper-layer was carried out at a temperature of 450C to form an insulating upper-layer having a layer thickness of 3 [.L whereby a dual coated wire having a total coating thickness of 25p. was obtained.
  • EXAMPLE 3 A copper conductor having a diameter of 0.3 mm as an anode was coated with Polyacryl-C by employing conventional electrodeposition coating using a horizontal coating machine at a line speed of 60 m/minute under the following conditions:
  • Cathode A copper cylindrical tube of 6 cm in diameter and 30 cm in length Distance between Electrodes: 3 cm Electrodeposition Voltage: 7V D.C.
  • Cathode A copper cylindrical tube of 6 cm in diameter and 30 cm in length Distance between Electrodes: 3 cm Voltage Applied: 200V D.C.
  • Polyester-C was then coated one time on the above insulating under-layer at a line speed of 60 m/minute, and a simultaneous baking of the insulating underlayer and the upperlayer was carried out at a temperature of 550C to form an insulating upper-layer having a layer
  • EXAMPLES 4 TO 12 AND COMPARATIVE EXAMPLES 1 TO 5 Similar preparation methods for producing a dual coated wire as described in Example 3 were repeated in Examples 4 to 12, and in Comparative Examples 3 and 4, whereas similar preparation of Example 1 in Comparative Examples 1, 2 and 5, were conducted but using the varnishes shown in Table l in place of the Polyacryl-B and Polyester-B, or Polyacryl-A and Polyester-A, respectively, employed in these examples.
  • the polyvinyl formal (PVF) varnish used in Comparative Examples 4 and 5 is composed of 100 parts (by weight) of a polyvinyl formal resin (trade name: BIN I- REKKU-FL, manufactured by Chisso Co.'), parts of trimer of toluene diisocyanate stabilized with glycerin and phenol, 15 parts of a resole type phenolformaldehyde resin (trade name: Plyophen 5030, manufactured by Japan Reichhold Chemicals Inc.), 5 parts of butylated melamine, 200 parts of m-cresol, and 300 parts of solvent naphtha.
  • a polyvinyl formal resin trade name: BIN I- REKKU-FL, manufactured by Chisso Co.'
  • trimer of toluene diisocyanate stabilized with glycerin and phenol 15 parts of a resole type phenolformaldehyde resin (trade name: Plyophen 5030, manufactured by Japan Reichhold Chemicals Inc.)
  • Each insulated wire prepared in Examples 1 to 12, and Comparative Examples 1 to 5 was subjected to several tests including heat resistance as well as general test evaluations for determining the characteristics and properties of the insulated magnet wire.
  • polyester-A to Polyester-J 10 kinds of polyester single coated wires were prepared, wherein a copper conductor, 0.3 mm in diameter, was coated with apolyester varnish aforementioned by the conventional dip-coating using a horizontal coating machine and a metal die, thenafter the coated conductor was introduced into an oven maintained at a temperature of 400C in a line speed of 40 m/minute to bake the coating layer at that temperature.
  • the above procedure was repeated six times to form a baked coating layer having of the corresponding single coated wires as well as that of any of the dual coated insulating wires of the Comparative Examples, but also has well-balanced propera coating thickness of ,u.. i
  • Example I Example 2
  • Example 3 Example 4
  • Example 5 Under Layer Polyacryl Polyacryl Polyacryl Polyacryl Polyacryl Polyacryl Wire -A -B -C -D -E -F Structure Polyester Polyester Polyester Polyester Polyester Upper Layer A -B -C -D Continuity* (number of 0 O 0 0 0 pinholes/5m) Mandrel Diameter* good for good for good for good for good for good for good for good for IX IX 1X 1X 1X IX Breakdown Voltage* (KV) 9.0 8.8 9.0 9.5 9.0 8.5 Abrasion Resistance* 30 43 38 5I (strokes) Cut Through Tempera- 180 I78 I78 I72 I63 I83 ture** (C) Heat Shock.
  • An insulated wire comprising a conductor having thereon a coating of a baked insulating layer of a polyacryl resin and a baked layer of a polyester resin overcoated on said polyacryl resin layer,
  • said polyacryl resin comprising a copolyrner of (a) at least one compound represented by the formula F i F? H 2 (b) at least one compound represented by the formula (ll) i i i? H R and (c) at least one unsaturated organic acid, said acid having from 3 to about 30 carbon atoms and at least one double bond which is reactable with the double bond of said compound of the formula (I or ll), wherein R represents a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms, R represents .a.cyano group, an aldehyde groupor a carboxyalkyl ester group having from 2 to about 30 carbon atoms, and R and R each represents a hydrogen atom, an organic group having 1 to about 30 carbon atoms selected from the group consisting of an alkyl group, an amide group, an N-alkylamide group, an alkylol group, a glycidyle ther group and a glycidylester group, except that
  • the insulated wire of claim 1 wherein the total number of carbon atoms in'each of said compound of the formula (I), said compound of the formula (ll) and said unsaturated organic acid is less than about 15 carbon atoms.
  • said polyacryl resin comprises from I .to about- 20 moles of said compound of the formula (I) per mole of said com-1 pound of the forumula (ll) and from about 0.01 to about 0.2 mole of said unsaturated organic acid per mole of the total moles said compound of the formula (I) and said compound of the formula (II).
  • com pound of the formula (I) is acrylonitrile, methacrylonitrile, methylacrylate, ethylacrylate, propylacrylate, butylacrylate, methylmethacrylate, ethylmethacrylate, propylmcthacrylate, or acrolein
  • said compound of the formula (II) is glycidylacrylate, glycidylmethacrylate, allylglycidylether, acrylamide, methlolacrylamide, or ethylacrylamide
  • said unsaturated organic acid is acrylic acid, methacrylic acid, oz-ethylacrylic acid, crotonic acid, maleic acid, or fumaric acid.
  • polyacryl resin is a copolymer of said components (a), (b), (c) and additionally styrene or a derivative thereof, said styrene or a derivative thereof being present at a level of no more than about 2 mole per mole of said component (a).
  • styrene derivative is styrene in which the phenyl group is substituted with at least one substituent, said substituent being an organic group having 1 to about 20 carbon atoms or a halogen atoms.
  • styrene derivative is methylstyrene, ethylstyrene, dimethylstyrene, benzylstyrcnc, dibenzylstyrene, divinylbenzene, chlorostyrene, or dichlorostyrene.
  • the insulated wire of claim 1 wherein said unsaturated organic acid is a monobasic unsaturated acid, a dibasic unsaturated acid, a tribasic unsaturated acid or a mixture thereof.
  • said unsaturated organic acid is acrylic acid, crotonic acid, vinylacetic acid, methacrylic acid, tiglic acid, a-ethylacrylic acid, ,Bmethylcrotonic acid, Z-pentenoic acid, 2-hexenoic acid, Z-heptenoic acid, 2-octenoic acid, undecenoic acid, 9-octadecenoic acid, cinnamic acid, atropic acid, oz-benzylacrylic acid, methyl atropic acid, 2,4-pentadienoic acid, 9,12-octadecadienoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, dihydromuconic acid, muconic acid, or 1,2,4-tricarboxybutene.
  • said unsaturated organic acid is acrylic acid, crotonic acid, vinylacetic acid, methacrylic acid, tiglic acid,
  • polyacryl resin is a copolymer of said components (a), (b), (c) and additionally a diolefin, said diolefin being present at a level of no more than about 1 mole per mole of said component (a).
  • diolefm is butadiene, pentadiene, or methyl-butadiene.
  • the insulated wire of claim 1 wherein said derivative of terephthalic acid is represented by the formula (Ill) COR (III) wherein R represents a hydrocarbon group having 1 to about 10 carbon atoms and n is a positive integer of 2' 18.
  • R represents a hydrocarbon group having 1 to about 10 carbon atoms and n is a positive integer of 2' 18.
  • said hydrocarbon group is selected from the group consisting of a saturated hydrocarbon group and an unsaturated hydrocarbon group.
  • said saturated hydrocarbon group contains at least one ring selected from the group consisting of a four to eight membered heterocyclic ring and a benzene type ring in the carbon chain thereof.
  • polyester resin comprises the polymerization product of said terephthalic acid, said polyol mixture and additionally an imideor amide-imide-containing substance comprising the reaction product of a tribasic or higher polybasic acid and a diamide, a diisocyanate or a mixtue of said diamine and said diisocyanate.
  • the insulated wire of claim 1 wherein the thickness of said polyacryl resin layer ranges from about 1 to 300 p. and the thickness of said polyester resin layer ranges from about 0.3 to 100 u, and wherein the thickness ratio of said polyacryl resin layer to said polyester resin layer ranges from about 0.1 to 30.
  • divalent R groups are alkylene or alkenylene groups of which one or two hydrogen atoms on one i or two end carbon atoms can be replaced by one or two alkyl groups or alkenyl groups and the like.
  • trivalent .R groups are alkylene or al-: kenylene groups of which a hydrogen atom of one end carbon 6 atom is replaced by one alkylene, or alkenylene group, or of which one hydrogen atom of both end carbon atoms is replaced by one alkyl or alkenyl group and one alkylene or alkenylene group or of which an inner carbon atom between both end carbon atoms is substituted with one alkylene or alkenylene group and one alkyl or alkenyl group.
  • R groups are alkylene or alkenylene groups of which a hydrogen atom of an end carbon atom and another end carbon atom, are subsituted with one alkylene or alkenylene group, or of which an inner carbon atom between both end carbon atoms is substituted with two alkylene or alkenylene groups.

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975571A (en) * 1974-10-25 1976-08-17 Sumitomo Electric Industries, Ltd. Self-bonding magnet wire
US4143238A (en) * 1977-02-28 1979-03-06 Belden Corporation Shielded ultra-miniature cable
US4163826A (en) * 1977-02-28 1979-08-07 Sumitomo Electric Industries, Ltd. Self-bonding magnet wires and coils made therefrom
US4208464A (en) * 1974-09-26 1980-06-17 Nitto Electric Industrial Co., Ltd. Article coated with baked layer of water-soluble heat-resistant insulating varnish
US4239814A (en) * 1977-09-19 1980-12-16 Herberts Gesellschaft Mit Beschrankter Haftung Method of producing electrically insulating, highly flexible and/or solderable coatings
US4537804A (en) * 1982-05-05 1985-08-27 General Electric Company Corona-resistant wire enamel compositions and conductors insulated therewith
US5091028A (en) * 1985-03-30 1992-02-25 Totoku Electric Co., Ltd. Method for manufacturing a heat resistant voice coil
US6161520A (en) * 1999-03-22 2000-12-19 The Gasket King Multiple spark ignition gasket
US20050084674A1 (en) * 2003-10-16 2005-04-21 American Wire Tie Inc. Textured wire tie and methods of making same
EP1623438A4 (en) * 2003-05-12 2008-07-09 Nippon Paint Co Ltd METHOD FOR APPLYING A COATING ON A SQUARE WIRE AND INSULATED WIRE PRODUCED FROM A SQUARE WIRE
USD616292S1 (en) * 2008-12-16 2010-05-25 Martinson Daniel J Twist tie
US20110042120A1 (en) * 2008-01-31 2011-02-24 Ibiden Co., Ltd. Wiring and composite wiring
US20130026316A1 (en) * 2008-10-08 2013-01-31 Nite Ize, Inc. Tie wrap for bundling objects
CN103500617A (zh) * 2013-09-26 2014-01-08 露笑科技股份有限公司 一种双烘炉漆包机
US8776322B2 (en) 2008-10-08 2014-07-15 Nite Ize, Inc. Tie wrap for bundling objects
US8806723B2 (en) 2008-10-08 2014-08-19 Nite Ize, Inc. Tie wrap for bundling objects
USD714278S1 (en) 2013-07-29 2014-09-30 Nite Ize, Inc. Mobile phone case
US20150170796A1 (en) * 2012-09-10 2015-06-18 Yazaki Corporation Wire harness
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USD774879S1 (en) * 2008-10-08 2016-12-27 Nite Ize, Inc. Tie wrap for bundling objects
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US10991481B2 (en) 2019-08-23 2021-04-27 Zeus Industrial Products, Inc. Polymer-coated wires

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191581A (en) * 1938-06-18 1940-02-27 Gen Electric Insulating resinous compositions and electrical conductors coated with the same
US2787561A (en) * 1953-07-23 1957-04-02 Du Pont Cross-linkable acrylonitrile interpolymers and coating compositions derived therefrom
US3112223A (en) * 1960-06-09 1963-11-26 Bayer Ag Method for coating a wire with a heatcured acrylonitrile copolymer and coated article
US3220882A (en) * 1961-05-22 1965-11-30 Monsanto Co Metal conductor having alternate layers of epoxy enamel and polyamid enamel coatings
US3242036A (en) * 1962-12-31 1966-03-22 Du Pont Coating composition comprising an interpolymer of acrylonitrile, cyanoalkyl acrylate and an unsaturated carboxylic acid
US3406045A (en) * 1964-09-16 1968-10-15 Westinghouse Electric Corp Cross-linked polyethylene terephthalate overcoat for insulated electrical conductors
US3503918A (en) * 1965-12-07 1970-03-31 Rohm & Haas Aqueous dispersion of thermosettable acrylonitrile copolymers and articles coated therewith

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191581A (en) * 1938-06-18 1940-02-27 Gen Electric Insulating resinous compositions and electrical conductors coated with the same
US2787561A (en) * 1953-07-23 1957-04-02 Du Pont Cross-linkable acrylonitrile interpolymers and coating compositions derived therefrom
US3112223A (en) * 1960-06-09 1963-11-26 Bayer Ag Method for coating a wire with a heatcured acrylonitrile copolymer and coated article
US3220882A (en) * 1961-05-22 1965-11-30 Monsanto Co Metal conductor having alternate layers of epoxy enamel and polyamid enamel coatings
US3242036A (en) * 1962-12-31 1966-03-22 Du Pont Coating composition comprising an interpolymer of acrylonitrile, cyanoalkyl acrylate and an unsaturated carboxylic acid
US3406045A (en) * 1964-09-16 1968-10-15 Westinghouse Electric Corp Cross-linked polyethylene terephthalate overcoat for insulated electrical conductors
US3503918A (en) * 1965-12-07 1970-03-31 Rohm & Haas Aqueous dispersion of thermosettable acrylonitrile copolymers and articles coated therewith

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4208464A (en) * 1974-09-26 1980-06-17 Nitto Electric Industrial Co., Ltd. Article coated with baked layer of water-soluble heat-resistant insulating varnish
US3975571A (en) * 1974-10-25 1976-08-17 Sumitomo Electric Industries, Ltd. Self-bonding magnet wire
US4143238A (en) * 1977-02-28 1979-03-06 Belden Corporation Shielded ultra-miniature cable
US4163826A (en) * 1977-02-28 1979-08-07 Sumitomo Electric Industries, Ltd. Self-bonding magnet wires and coils made therefrom
US4239814A (en) * 1977-09-19 1980-12-16 Herberts Gesellschaft Mit Beschrankter Haftung Method of producing electrically insulating, highly flexible and/or solderable coatings
US4537804A (en) * 1982-05-05 1985-08-27 General Electric Company Corona-resistant wire enamel compositions and conductors insulated therewith
US5091028A (en) * 1985-03-30 1992-02-25 Totoku Electric Co., Ltd. Method for manufacturing a heat resistant voice coil
US6161520A (en) * 1999-03-22 2000-12-19 The Gasket King Multiple spark ignition gasket
EP1623438A4 (en) * 2003-05-12 2008-07-09 Nippon Paint Co Ltd METHOD FOR APPLYING A COATING ON A SQUARE WIRE AND INSULATED WIRE PRODUCED FROM A SQUARE WIRE
US20050084674A1 (en) * 2003-10-16 2005-04-21 American Wire Tie Inc. Textured wire tie and methods of making same
US7250213B2 (en) * 2003-10-16 2007-07-31 American Wire Tie Inc. Textured wire tie and methods of making same
US20110042120A1 (en) * 2008-01-31 2011-02-24 Ibiden Co., Ltd. Wiring and composite wiring
US10549895B2 (en) 2008-10-08 2020-02-04 Nita Ize, Inc. Tie wrap for bundling objects
US20130026316A1 (en) * 2008-10-08 2013-01-31 Nite Ize, Inc. Tie wrap for bundling objects
US8776322B2 (en) 2008-10-08 2014-07-15 Nite Ize, Inc. Tie wrap for bundling objects
US8806723B2 (en) 2008-10-08 2014-08-19 Nite Ize, Inc. Tie wrap for bundling objects
US9174781B2 (en) * 2008-10-08 2015-11-03 Nite Ize, Inc. Tie wrap for bundling objects
USD863946S1 (en) 2008-10-08 2019-10-22 Nite Ize, Inc. Tie
USD774879S1 (en) * 2008-10-08 2016-12-27 Nite Ize, Inc. Tie wrap for bundling objects
USD863945S1 (en) 2008-10-08 2019-10-22 Nite Ize, Inc. Tie
USD616292S1 (en) * 2008-12-16 2010-05-25 Martinson Daniel J Twist tie
USD745866S1 (en) 2011-08-02 2015-12-22 Nite Ize, Inc. Cantilevered snap fit case
US20150170796A1 (en) * 2012-09-10 2015-06-18 Yazaki Corporation Wire harness
US9947439B2 (en) * 2012-09-10 2018-04-17 Yazaki Corporation Dark exterior wire harness with heat-reflection and identification portion
USD714278S1 (en) 2013-07-29 2014-09-30 Nite Ize, Inc. Mobile phone case
CN103500617A (zh) * 2013-09-26 2014-01-08 露笑科技股份有限公司 一种双烘炉漆包机
CN103500617B (zh) * 2013-09-26 2016-06-01 露笑科技股份有限公司 一种双烘炉漆包机
US10991481B2 (en) 2019-08-23 2021-04-27 Zeus Industrial Products, Inc. Polymer-coated wires
US11631504B2 (en) 2019-08-23 2023-04-18 Zeus Company Inc. Polymer-coated wires

Also Published As

Publication number Publication date
JPS5120471Y2 (enrdf_load_stackoverflow) 1976-05-28
GB1412501A (en) 1975-11-05
JPS4960266U (enrdf_load_stackoverflow) 1974-05-27

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