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EP0823120A1 - Formulation de vernis pour fils metalliques a lubrifiant interne - Google Patents

Formulation de vernis pour fils metalliques a lubrifiant interne

Info

Publication number
EP0823120A1
EP0823120A1 EP96914118A EP96914118A EP0823120A1 EP 0823120 A1 EP0823120 A1 EP 0823120A1 EP 96914118 A EP96914118 A EP 96914118A EP 96914118 A EP96914118 A EP 96914118A EP 0823120 A1 EP0823120 A1 EP 0823120A1
Authority
EP
European Patent Office
Prior art keywords
wire enamel
polyethylene wax
wire
wetting agent
lubricant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96914118A
Other languages
German (de)
English (en)
Other versions
EP0823120B1 (fr
Inventor
Klaus-Wilhelm Lienert
Irmgart Gebert
Helmut Lehmann
Michael W. MÜLLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Altana Electrical Insulation GmbH
Original Assignee
Dr Beck & Co AG
Beck & Co AG Dr
Dr Beck & Co AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dr Beck & Co AG, Beck & Co AG Dr, Dr Beck & Co AG filed Critical Dr Beck & Co AG
Publication of EP0823120A1 publication Critical patent/EP0823120A1/fr
Application granted granted Critical
Publication of EP0823120B1 publication Critical patent/EP0823120B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a wire enamel formulation containing components known per se with an internal lubricant.
  • Lacquered copper wires are coated with a lubricant to improve their processability.
  • Classic lubricants consist of a 0.5 to 2% solution of paraffins or waxes in a volatile solvent. When applied to the wire, the solvent evaporates and the paraffin or wax film remains.
  • a disadvantage of this method is that the solvents commonly used can cause surface cracks in the wire enamel film.
  • DE 32 37 022A describes a lubricant which consists of an aliphatic hydrocarbon mixture as solvent and 1% paraffin wax and 1% hydrogenated triglyceride.
  • the paraffin wax has a melting point of 50-52 ° C.
  • the hydrogenated triglyceride is a commercial product with a melting point of 47 ° C to 50 ° C.
  • This solution is applied to a wire coated with a polyamideimide.
  • An internal lubricant can also be used. This is added to the polyamideimide in a concentration of 1%.
  • the internal lubricant consists of tall oil fatty acid esters. No information is given on the friction coefficients achieved.
  • EP 00 72 178A describes the modification of wire enamel binders in which a C21 hydrocarbon chain is incorporated into the polymer. This chain leads to an improved coefficient of friction for the enamelled wires. There is no information in the script about the thermal properties. It can be assumed that the softening of the lacquer film and the dielectric loss factor suffer from the introduction of the hydrocarbon chain.
  • EP 0 103 307A describes conventionally applied lubricants which tend to reduce outgassing on the wires in relays. This is achieved by substituting the terminal hydrogen in a polypropylene glycol with an organic residue.
  • JP 0524 7374A Another document (JP 0524 7374A) describes how the use of dispersions of fluorinated waxes in conventional wire enamels improves the lubricity of the wires produced therewith. However, such systems tend to separate the phases.
  • JP 0 521 7427A describes the use of a polyethylene wax dispersion in a polyamideimidic wire enamel. Experience shows that these systems are not stable in storage.
  • an optimal lubricant must be an internal lubricant.
  • the additive that improves lubricity should be a polymeric material and the formulation should be stable on storage.
  • the internal lubricant contains a polyethylene wax, preferably with a molecular weight [Mw] of 3000 to 6000 [g / mol], and a wetting agent, preferably fatty alcohol ethoxylate.
  • the lubricant can also consist exclusively of the polyethylene wax and the wetting agent.
  • wire enamels with a polyesterimide can be used as a binder.
  • polyesterimide resins are known and are described, for example, in DE-OS 1445263 and DE-OS 14 95 100.
  • the polyesterimides are prepared in a known manner by esterifying the polyhydric carboxylic acids with the polyhydric alcohols, optionally with the addition of oxycarboxylic acids, and using starting materials containing imide groups. Instead of the free acids and or alcohols, their reactive derivatives can also be used.
  • Terephthalic acid is preferably used as the carboxylic acid component, and ethylene glycol, glycerol and tris (2-hydroxyethyl) isocyanurate (THEIC) are preferably used as polyhydric alcohols, the latter being particularly preferred.
  • TEEIC 2,2-hydroxyethyl) isocyanurate
  • the use of tris (2-hydroxyethyl) isocyanurate leads to an increase in the softening temperature of the paint film obtained.
  • the starting materials containing imide groups can be obtained, for example, by reaction between compounds, one of which must have a five-membered, cyclic carboxylic anhydride group and at least one further functional group, while the other contains at least one further functional group in addition to a primary amino group.
  • These further functional groups are primarily carboxyl groups or hydroxyl groups, but they can also be further primary amino groups or carboxylic anhydride groups.
  • Carboxylic anhydride grouping with a further functional group are, above all, pyromellitic dianhydride and trimellitic anhydride.
  • aromatic carboxylic acid anhydrides are also possible, for example the naphthalene tetracarboxylic acid dianhydrides or dianhydrides of tetracarboxylic acids with two benzene nuclei in the molecule, in which the carboxyl groups are in the 3,3'-, 4- and 4'-position.
  • Examples of compounds having a primary amino group and a further functional group are, in particular, diprimeric diamines, for example ethylenediamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine and other aliphatic diprimeric diamines.
  • diprimeric diamines for example ethylenediamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine and other aliphatic diprimeric diamines.
  • Aromatic diprimary diamines such as benzidine, are also suitable.
  • Amino alcohol-containing compounds with a further functional group are also amino alcohols, z.
  • monoethanolamine or monopropanolamines furthermore amino carboxylic acids such as glycine, aminopropionic acids, aminocaproic acids or aminobenzoic acids.
  • polyesterimide resins for example heavy metal salts such as lead acetate, zinc acetate, organic titanates, cerium compounds and organic acids, such as, for. B. para-toluenesulfonic acid.
  • heavy metal salts such as lead acetate, zinc acetate, organic titanates, cerium compounds and organic acids, such as, for. B. para-toluenesulfonic acid.
  • Solvents suitable for the production of the polyesterimide wire enamels are cresolic and non-cresolic organic solvents such as, for example, cresol, phenol, glycol ethers such as, for. B. methyl glycol, ethyl glycol, isopropyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol; Glycol ether esters, such as methyl glycol acetate,
  • Aromatic solvents can also be used, if appropriate in combination with the solvents mentioned. Examples of such solvents are xylene, solvent naphtha®, toluene, ethylbenzene, cumene, heavy benzene, various types of Solvesso® and Shellsol® as well as Deasol®.
  • wire enamels with a polyamideimide can also be used as a binder.
  • polyamide-imides used in wire enamels are known and are described, for example, in US Pat. Nos. 3,554,984, DE-A-2441 020, DE-A-25 56 523, DE-A-1266427 and DE-A-1956512.
  • the polyamideimides are prepared in a known manner from polycarboxylic acids or their anhydrides, in which 2 carboxyl groups are in the vicinal position and which must have at least one further functional group, and from polyamines with at least one primary amino group capable of imid ring formation or from compounds with at least 2 Isocyanate groups.
  • the polyamideimides can also be obtained by reacting polyamides, polyisocyanates which contain at least 2 NCO groups and cyclic dicarboxylic anhydrides which contain at least one further group capable of condensation or addition.
  • a tricarboxylic anhydride can first be reacted with a diprimary diamine to give the corresponding diimidocarboxylic acid, which then reacts with a diisocyanate to give the polyamideimide.
  • Tricarboxylic acids or their anhydrides are preferably used for the preparation of the polyamideimides.
  • the corresponding aromatic tricarboxylic acid anhydrides e.g. Trimellitic anhydride, naphthalene tricarboxylic acid anhydrides, bisphenyltricarboxylic acid anhydrides and further tricarboxylic acids with 2 benzene nuclei in the molecule and 2 vicinal carboxyl groups, such as the examples listed in DE-OS 19 56 512.
  • Trimellitic anhydride is very particularly preferably used.
  • the diprimary diamines already described for the polyamido carboxylic acids can be used as the amine component.
  • Aromatic diamines containing a thiadiazole ring such as e.g. 2,5-bis- (4-aminophenyl) -1, 3,4-thiadiazole, 2,5-bis- (3-aminophenyl) -3,3,4-thiadiazole, 2- (4-amino ⁇ henyl) -5- (3-aminophenyl) -1, 3,4-thiadiazole and mixtures of the different isomers.
  • Suitable diisocyanates for the preparation of the polyamideimides are aliphatic diisocyanates, such as, for example, tetramethylene, hexamethylene, heptamethylene and trimethylhexamethylene diisocyanates; cycloaliphatic diisocyanates such as isophorone diisocyanate, ⁇ , ⁇ '-diisocyanate-1, 4-dimethylcyclohexane, cyclohexane-1, 3-, cyclohexane-1, 4-, 1-methylcyclohexane-2,4- and dicyclohexylmethane-4,4'- diisocyanate; aromatic diisocyanates such as phenylene, toluene, naphthylene and xylylene diisocyanates and substituted aromatic systems such as diphenyl ether, diphenyl sulfide, diphenyl sulfone and diphenyl methane diisocyanates; mixed aromatic-
  • 4,4'-Diphenylmethane diisocyanate, 2,4- and 2,6-tolylene diisocyanate and hexamethylene diisocyanate are preferably used.
  • Suitable polyamides are those polyamides which have been obtained by polycondensation of dicarboxylic acids or their derivatives with diamines or of aminocarboxylic acids and their derivatives, such as lactams.
  • polyamides may be mentioned by way of example: dimethylene succinic acid amide, pentamethylene pimelic acid amide, undecanemethylene tridecanedicarboxylic acid amide, hexamethylene adipic acid amide, polycaproic acid amide. Hexamethylene adipic acid amide and polycaproic acid amide are particularly preferred.
  • Heavy metal salts soluble in the wire enamels can be used as crosslinking catalysts in the curing of the polyamideimides.
  • Zinc octoate, cadmium octoate, tetraisopropyl titanate or tetrabutyl titanate in an amount of up to 3% by weight, based on the binder, can be used.
  • the internal lubricant is preferably composed of 0.1 to 4.5% by weight of polyethylene wax and 0.1 to 2.0% by weight of wetting agent. 1.0 to 2.2% by weight of polyethylene wax are very particularly preferred and 0.2 to 1.2 wt% wetting agent. The stated amounts are based on the binder content in the wire enamel.
  • polyethylene waxes which can be used according to the invention are commercially available under the name Luwax®. These polyethylene waxes are characterized by a narrow molar mass distribution. In addition, high hardness and high crystallinity can be specifically set.
  • phase separation takes place.
  • wetting agent is added, the phase separation can be suppressed to different extents.
  • wetting agents are accordingly added to the wire enamel formulation.
  • fatty alcohol ethoxylates are advantageously used for this.
  • Emulan® AF a product from BASF AG, is particularly well suited to stabilizing the polyethylene waxes described in a wire enamel.
  • the tested and approved wetting agents also include the BASF products Emulan® EL, Emulan® PO and Pluronic® 8100.
  • the present invention further relates to a method for producing the wire enamel formulation described.
  • a polyethylene wax preferably with a molecular mass of 3000 to 6000 [g / mol]
  • solvent Preferably 5 to 25% by weight of solvent based on the polyethylene wax are added.
  • a proportion of solvent of 8 to 11% by weight is particularly preferred. 10% by weight is very particularly preferred.
  • Can be used as a solvent especially aromatic fractions are used.
  • Xylene and toluene are particularly preferred.
  • polyethylene wax and solvent are heated, preferably to 70 to 100 ° C. A temperature of approximately 80 ° C. is very particularly preferred. After the polyethylene wax has completely dissolved, it is cooled again to room temperature.
  • a wetting agent preferably fatty alcohol ethoxylate, is then added.
  • the proportions are chosen so that preferably 0.1 to 4.5% by weight of polyethylene wax and 0.1 to 2.0% by weight of wetting agent, based in each case on the binder content in the wire enamel, are used. 1.0 to 2.2% by weight of polyethylene wax and 0.2 to 1.2% by weight of wetting agent are very particularly preferred.
  • wire enamel containing components known per se is mixed with the dispersion thus obtained.
  • wire enamels are particularly suitable which contain polyesterimides or polyesteramideimides described above as binders.
  • wire enamels according to the invention thus produced are used in particular in the coating of electrical conductors.
  • a polyamideimide is produced from 38.5 parts of trimellitic acid and 60.0 parts of diphenylmethane diisocyanate by the method described in DE-AS 12 66 427.
  • the wire enamel is a 25% solution of this polyamideimide in a mixture of 65 parts of N-methylpyrrolidone and 35 parts of xylene. This wire enamel has a viscosity of 230 mPas at 23 ° C.
  • Example 5 Production of a Polvesterimid wire enamel with internal lubricant
  • Example 6 Production of a polvamidimide wire enamel with internal lubricant
  • Example 2 1000 g of wire enamel from Example 2 are mixed with 50 g of dispersion from Example 4.
  • the lacquer thus produced is lacquered as a topcoat over a commercially available THEIC polyester base lacquer.
  • the wires from Examples 5 and 6 were each operated as follows: A twist is produced from a piece of wire of approximately 750 mm in length, as described in IEC 851-5 / 4.3. 240 mm are cut out of the twist. This section has 10 turns. The opposite ends of the twist wires are clamped in a Lloyd M30K tearing machine. The force is measured in Newtons to pull the twist apart at a speed of 200 m / min.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Insulated Conductors (AREA)
  • Paints Or Removers (AREA)
  • Organic Insulating Materials (AREA)
  • Lubricants (AREA)
  • Metal Extraction Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP96914118A 1995-04-26 1996-04-25 Formulation de vernis pour fils metalliques a lubrifiant interne Expired - Lifetime EP0823120B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19515263A DE19515263A1 (de) 1995-04-26 1995-04-26 Drahtlackformulierung mit internem Gleitmittel
DE19515263 1995-04-26
PCT/EP1996/001723 WO1996034399A1 (fr) 1995-04-26 1996-04-25 Formulation de vernis pour fils metalliques a lubrifiant interne

Publications (2)

Publication Number Publication Date
EP0823120A1 true EP0823120A1 (fr) 1998-02-11
EP0823120B1 EP0823120B1 (fr) 2001-08-08

Family

ID=7760366

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96914118A Expired - Lifetime EP0823120B1 (fr) 1995-04-26 1996-04-25 Formulation de vernis pour fils metalliques a lubrifiant interne

Country Status (10)

Country Link
US (1) US6022918A (fr)
EP (1) EP0823120B1 (fr)
JP (1) JPH11504156A (fr)
KR (1) KR100382621B1 (fr)
AT (1) ATE204093T1 (fr)
BR (1) BR9608294A (fr)
DE (2) DE19515263A1 (fr)
ES (1) ES2163626T3 (fr)
TW (1) TW315387B (fr)
WO (1) WO1996034399A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010039169A1 (de) 2010-08-10 2012-02-16 Universität Paderborn Selbststrukturierende Oberflächen durch PDMS-Phasentrennungen in harten Polymerbeschichtungen
DE102010039168A1 (de) 2010-08-10 2012-02-16 Schwering & Hasse Elektrodraht Gmbh Elektroisolierlacke aus modifizierten Polymeren und daraus hergestellte elektrische Leiter mit verbesserter Gleitfähigkeit
EP4307322A1 (fr) * 2022-07-13 2024-01-17 Siemens Aktiengesellschaft Fil rond isolé par un vernis, procédé de fabrication et utilisation correspondante

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19648830A1 (de) * 1996-11-26 1998-05-28 Beck & Co Ag Dr Verfahren zur Herstellung carboxyl- und hydroxylgruppenhaltiger Polyesterimide und deren Verwendung in Drahtlacken
US6392000B1 (en) 2000-10-26 2002-05-21 E. I. Du Pont De Nemours And Company Binder for a coating composition for electrical conductors
US7099627B2 (en) * 2003-06-11 2006-08-29 Acco Brands Usa Llc Systems and methods for a wireless network connection point locator
US7396395B1 (en) * 2007-05-08 2008-07-08 Everest Textile Co., Ltd. Composition of a water-repellent agent
US10253211B2 (en) 2011-05-12 2019-04-09 Elantas Pdg, Inc. Composite insulating film
US10406791B2 (en) 2011-05-12 2019-09-10 Elantas Pdg, Inc. Composite insulating film

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US4450258A (en) * 1975-01-02 1984-05-22 General Electric Company Coating compositions
US4146499A (en) * 1976-09-18 1979-03-27 Rosano Henri L Method for preparing microemulsions
JPS5826409A (ja) * 1981-08-07 1983-02-16 住友電気工業株式会社 絶縁電線
US4390590A (en) * 1981-10-19 1983-06-28 Essex Group, Inc. Power insertable polyamide-imide coated magnet wire
US4605917A (en) * 1982-09-14 1986-08-12 Nec Corporation Coil wire
DE3635141C1 (de) * 1986-10-15 1988-03-03 Pelikan Ag Thermocarbonband mit einer kunststoffgebundenen Aufschmelzfarbe sowie ein Verfahren zur Herstellung dieses Bandes
EP0267736B1 (fr) * 1986-11-11 1990-10-03 Sumitomo Electric Industries Limited Fil de bobinage et relais électromagnétique l'utilisant
JPH05217427A (ja) * 1992-02-04 1993-08-27 Furukawa Electric Co Ltd:The 自己潤滑性絶縁電線
JPH05247374A (ja) * 1992-03-03 1993-09-24 Fujikura Ltd 潤滑塗料およびこれを用いた自己潤滑絶縁電線
DE4330342A1 (de) * 1993-09-08 1995-03-09 Basf Ag Stabile wäßrige Polyolefinwachsdispersionen

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010039169A1 (de) 2010-08-10 2012-02-16 Universität Paderborn Selbststrukturierende Oberflächen durch PDMS-Phasentrennungen in harten Polymerbeschichtungen
DE102010039168A1 (de) 2010-08-10 2012-02-16 Schwering & Hasse Elektrodraht Gmbh Elektroisolierlacke aus modifizierten Polymeren und daraus hergestellte elektrische Leiter mit verbesserter Gleitfähigkeit
WO2012020068A2 (fr) 2010-08-10 2012-02-16 Universität Paderborn Surfaces autostructurantes par séparations de phases de polydiméthylsiloxanes dans des revêtements polymères durs
WO2012020067A1 (fr) 2010-08-10 2012-02-16 Schwering & Hasse Elektrodraht Gmbh Vernis diélectriques à base de polymères modifiés et conducteurs électriques à capacité de glissement améliorée fabriqués avec ces vernis
EP4307322A1 (fr) * 2022-07-13 2024-01-17 Siemens Aktiengesellschaft Fil rond isolé par un vernis, procédé de fabrication et utilisation correspondante
WO2024012906A1 (fr) * 2022-07-13 2024-01-18 Siemens Aktiengesellschaft Fil de section circulaire émaillé, son procédé de fabrication et son utilisation

Also Published As

Publication number Publication date
TW315387B (fr) 1997-09-11
JPH11504156A (ja) 1999-04-06
BR9608294A (pt) 1999-05-11
ATE204093T1 (de) 2001-08-15
KR100382621B1 (ko) 2005-05-24
WO1996034399A1 (fr) 1996-10-31
DE59607451D1 (de) 2001-09-13
KR19990008063A (ko) 1999-01-25
US6022918A (en) 2000-02-08
DE19515263A1 (de) 1996-10-31
ES2163626T3 (es) 2002-02-01
EP0823120B1 (fr) 2001-08-08

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