EP0066194A2 - Process for preparing an electrically insulating aqueous and thermosetting enamel, and its use - Google Patents

Process for preparing an electrically insulating aqueous and thermosetting enamel, and its use Download PDF

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Publication number
EP0066194A2
EP0066194A2 EP82104390A EP82104390A EP0066194A2 EP 0066194 A2 EP0066194 A2 EP 0066194A2 EP 82104390 A EP82104390 A EP 82104390A EP 82104390 A EP82104390 A EP 82104390A EP 0066194 A2 EP0066194 A2 EP 0066194A2
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Prior art keywords
weight
polyesterimide
ammonia
aqueous
lacquers
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EP82104390A
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German (de)
French (fr)
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EP0066194A3 (en
EP0066194B1 (en
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Udo Dr. Reiter
Hans-Uwe Dr. Schenck
Helmut Lehmann
Ferdinand Hansch
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Beck Dr and Co GmbH
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Beck Dr and Co GmbH
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    • 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
    • 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]
    • Y10T428/31721—Of polyimide

Definitions

  • the invention relates to a process for the production of aqueous thermosetting electrical insulating lacquers based on polyesterimides and their use as wire lacquers or as impregnating lacquers, e.g. for impregnating enamelled wire windings.
  • polyesterimide solutions In order to process polyesterimide solutions well, relatively low solids contents have to be produced. Due to the specific solubility properties of PEI, phenols, cresols, xylenols, N-methylpyrolidone, etc. must be used as solvents or as solvent mixtures. These solvents are mostly non-volatile, expensive and sometimes have a very unpleasant smell. In order to avoid unpleasant smells and environmental pollution from such solvents, very complex post-combustion systems are necessary.
  • aqueous systems In addition to coating electrical conductors with solvent-free resins from the melt, aqueous systems have also been proposed as environmentally friendly and economical alternatives.
  • DE-OS 23 51 077 and 23 51 078 describe aqueous PEI secondary dispersions. However, these secondary dispersions have too low a solids content and also require special application devices.
  • DE-OS 26 05 790 water-thinnable PEI electrical insulating lacquers are described, which can be obtained with the help of considerable Ls / P
  • Amounts (5 to 30% by weight, preferably 20 to 30%) of tertiary amine and with the use of 5 to 20% by weight of auxiliary solvent are converted into an aqueous form.
  • DE-OS 17 20 321 describes a process for the preparation of water-dilutable polyesterimide resins with the aid of ammonia.
  • aromatic tricarboxylic anhydrides are first reacted with up to 80% of the stoichiometric amount of primary diamines which are necessary for imide formation and condensed with an excess of di- and / or trial alcohols.
  • Anschlies- se nd the excess alcohol is distilled off and the condensation product with a small amount of aqueous ammonia, optionally with the addition of dialcohols heated to a temperature of about 80 ° C and then diluted the condensation product with water.
  • DE-OS 27 24 913 also shows water-soluble polyesterimide resins and processes for their preparation.
  • the products and manufacturing processes described herein result in products that must be adjusted to pH> 7 with amines, i.e. these products smell strongly of amines, which has an adverse effect on workplace hygiene.
  • larger amounts of auxiliary solvents are used (> 10%, as can be seen from the examples).
  • the present invention relates to a process for the preparation of aqueous thermosetting electrical insulating lacquers based on polyesterimides which have been obtained by condensation of aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their esterifiable derivatives, diamines, diols and a triols containing an isocyanurate ring, which is characterized in that hydroxyl group-containing Polyesterimides with kinematic viscosities from 16 to 30 mm 2 .
  • s - 1 (measured in a solution of 1 part polyesterimide in 2 parts N-methylpyrrolidone at 30 ° C) and acid numbers ⁇ 10 at temperatures between 80 and 130 ° C, optionally with the use of up to 5% by weight, based on polyesterimide , an organic solvent, treated with 5 to 15% by weight, based on polyesterimide, ammonia in the form of an aqueous ammonia solution with aminolysis and hydrolysis, so that a neutral to weakly acidic solution results, and by adding demineralized water to a viscosity between 100 and 10,000 mPa.s are diluted, with 0.1 to 5% by weight, based on polyesterimide, of a water-soluble curing catalyst optionally being added after the treatment with ammonia.
  • the present invention also relates to the use of these aqueous electrical insulating lacquers as wire lacquers or impregnating lacquers.
  • the process according to the invention gives completely clear, water-dilutable lacquers which have improved heat levels compared to the water-dilutable lacquers obtained with tertiary amines.
  • the electrical insulating varnishes according to the invention m more economical and much more environmentally friendly due to the use of cheap ammonia instead of ethanol amines. They can be applied to the substrates to be coated using customary application systems and, after baking, show that the technical properties of the conventional polyesterimide lacquers dissolved in the above-mentioned organic solvents and thus problematic with regard to their environmental impact are at least equivalent.
  • polyesterimides to be used for the process according to the invention and their structural components it should be stated that the basic structure of suitable polyesterimides can be found in DE-AS 14 45 263 and DE-AS 14 55 100.
  • the hydroxyl-containing polyester imide to be used according to the invention can preferably be prepared by the process described in DE-OS 14 55 182.
  • the PEI are condensation products from aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their derivatives, diamines, diols and triols with an isocyanurate ring.
  • aromatic tricarboxylic acid monoanhydrides are consider trimellitic anhydride, 3, 4, 3'-benzophenone tricarboxylic acid anhydride and hemimellitic acid anhydride, with trimellitic acid anhydride being preferred.
  • Suitable aromatic dicarboxylic acids and their esterifiable derivatives are, for example, terephthalic acid, isophthalic acid, benzophenone-4,4'-dicarboxylic acid, esters of aromatic dicarboxylic acids, such as, for example, the esters of terephthalic acid with alcohols containing 1 to 3 carbon atoms, for example dimethyl terephthalate, dinethyl isophthalate, diethyl terephthalate.
  • Suitable diamines are preferably those with primary amino groups which are bonded to aromatic groups, for example those of the general formula where X stands for a divalent radical, for example -CH 2 -, -0-, -CO-, -S- or -SO 2 -.
  • Examples of such diamines are diaminodiphenylmethane, diaminodiphenyloxide and benzophenonediamine.
  • Suitable diols are customary dihydric aliphatic alcohols, such as: 1,4-butanediol, trimethylene glycol, preferably ethylene glycol.
  • Tricarboxylic acid monoanhydride, dicarboxylic acid (derivative), diamine, diol and triol are generally in a molar ratio of 1.7-2.8 / 0.5-1.2 / 0.7-1.4 / 0.4-1.2 / 0.8-1.4, preferably 1.9-2.1 / 0.7-1.0 / 0.9-1.1 / 0.5-0.8 / 1.0-1.3.
  • the hydroxyl-containing polyester imides can procedures described 14 55 182 are produced for example by the in the D E-OS.
  • the condensation is carried out here in ethylene glycol, polyesterimides which do not
  • the hydroxyl group-containing polyesterimides to be used for the process according to the invention have acid numbers ⁇ 10, preferably ⁇ 5 and kinematic viscosities of 16 to 30, preferably 18 to 28 mm 2 .s -1 (measured in a solution of 1 part by weight of polyesterimide in 2 parts by weight . Parts N - methylpyrrolidone at 30 ° C).
  • the poly-hydroxyl-be it terimide at temperatures between 80 and 130 o C, preferably 90 and 110 ° C, optionally with the addition of up to 5 wt.%,
  • an organic solvent with from 5 to 15, preferably 7 , 5 to 10% by weight, based on PEI, of ammonia in the form of an aqueous ammonia solution, which may contain, for example, 5 to 25% by weight of ammonia, treated with aminolysis and hydrolysis.
  • pH values between 6 and 7, preferably 6.5 and 6.9.
  • Water-miscible solvents such as, for example, organic solvents to be used, optionally in amounts of up to 5% by weight, based on PEI.
  • N-methylpyrrolidone glycols, such as ethylene glycol, glycol ethers, such as butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol or other polar solvents, such as dimethylformamide or dimethylacetamide.
  • the PEI solution which is expediently cooled to 20 to 50 ° C., can also be mixed with 0.1 to 5, preferably 2 to 4,% by weight, based on PEI, of a water-soluble curing catalyst .
  • a water-soluble curing catalyst water-soluble titanates such as e.g. Titanium tetralactate.
  • polyesterimide solutions are diluted to viscosities between 100 and 10,000 mPa.s by adding deionized water.
  • polyesterimide solutions produced according to the invention can be used directly for coating wires, e.g. copper wires or as an impregnating varnish for impregnating enamelled wire windings.
  • Application methods and devices which are customary for this purpose are suitable.
  • the paintwork is generally baked at temperatures of 200 to 550, preferably 400 to 520 ° C.
  • the aqueous thermosetting polyesterimide lacquers produced according to the invention have good storage stability, are completely clear and have no ammonia odor.
  • the paintwork thus obtained also shows excellent properties with regard to the softening temperature, the thermal shock and the thermal aging behavior.
  • trimellitic anhydride (equivalent to 5.0 mol) 485 parts of diaminodiphenylmethane (equivalent to 2.5 mol) 815.5 parts of trishydroxyethyl isocyanurate (equivalent to 3.12 mol) 339.5 parts of dimethyl terephthalate (equivalent to 1.75 mol) 1375 Parts of ethylene glycol
  • the varnish is applied to a copper wire of 0.5 mm 0 in 8 passes using a conventional wire varnishing furnace 2.50 m long and baked at 460 ° C.
  • the take-off speed was 22 m / min.
  • the enamelled wire had the following properties when tested according to DIN 46 453:
  • Example 1 of DE-AS 17 20 321 was reworked.
  • the solution thus obtained was coated (baking temperature 460 ° C., take-off speed 22 m / min).

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Paints Or Removers (AREA)
  • Organic Insulating Materials (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Aqueous thermosetting electrical insulating varnishes are prepared by a process wherein hydroxyl-containing polyester-imides which have kinematic viscosities of from 16 to 30 mm2 x s-1 and acid numbers of <10, and which have been obtained by condensing aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their esterifiable or transesterifiable derivatives, diamines, diols, and triols containing an isocyanurate ring, are treated, at from 80 DEG to 130 DEG C., in the presence or absence of up to 5% by weight, based on polyester-imide, of an organic solvent, with from 5 to 15% by weight, based on polyester-imide, of ammonia in the form of an aqueous solution, thereby producing aminolysis and hydrolysis so that a neutral or slightly acidic solution results, which is diluted to a viscosity of from 100 to 10,000 mPa.s by adding demineralized water, from 0.1 to 5% by weight, based on polyester-imide, of a water-soluble curing catalyst being added, if desired, after the treatment with ammonia. The electrical insulating varnishes are used as wire enamels or as impregnating varnishes.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung wäßriger hitzehärtbarer Elektroisolierlacke auf Basis von Polyesterimiden und deren Verwendung als Drahtlacke oder als Tränklacke, z.B. zur Imprägnierung von Lackdrahtwicklungen.The invention relates to a process for the production of aqueous thermosetting electrical insulating lacquers based on polyesterimides and their use as wire lacquers or as impregnating lacquers, e.g. for impregnating enamelled wire windings.

Die Herstellung von Polyesterimiden (= PEI) und ihre Verwendung zur Elektroisolation ist schon lange bekannt und beispielsweise in den DE-AS 14 45 263, 14 95 100, 14 95 152 und 16 45 435 beschrieben.The production of polyesterimides (= PEI) and their use for electrical insulation has long been known and is described, for example, in DE-AS 14 45 263, 14 95 100, 14 95 152 and 16 45 435.

Um Polyesterimidlösungen gut zu verarbeiten, müssen verhältnismäßig niedere Feststoffgehalte hergestellt werden. Aufgrund der spezifischen Löslichkeitseigenschaften der PEI müssen als Lösungsmittel bzw. als Lösungsmittelgemische Phenole, Kresole, Xylenole, N-Methylpyrolidon usw. verwendet werden. Diese Lösungsmittel sind meistens schwerflüchtig, teuer und haben teilweise einen sehr unangenehmen Geruch. Um Geruchs- bzw. Umweltbelästigung durch derartige Lösungsmittel zu vermeiden, sind sehr aufwendige Nachverbrennungsanlagen notwendig.In order to process polyesterimide solutions well, relatively low solids contents have to be produced. Due to the specific solubility properties of PEI, phenols, cresols, xylenols, N-methylpyrolidone, etc. must be used as solvents or as solvent mixtures. These solvents are mostly non-volatile, expensive and sometimes have a very unpleasant smell. In order to avoid unpleasant smells and environmental pollution from such solvents, very complex post-combustion systems are necessary.

Als umweltfreundliche und wirtschaftliche Alternativen sind neben der Beschichtung elektrischer Leiter mit lösungsmittelfreien Harzen aus der Schmelze auch wäßrige Systeme vorgeschlagen worden. So werden in den DE-OS 23 51 077 und 23 51 078 wäßrige PEI-Sekundär-Dispersionen beschrieben. Diese Sekundärdispersionen weisen jedoch einen zu geringen Feststoffgehalt auf und benötigen zudem spezielle Applikationsvorrichtungen. In der DE-OS 26 05 790 werden wasserverdünnbare PEI-Elektroisolierlacke beschrieben, die mit Hilfe von beträchtlichen Ls/PIn addition to coating electrical conductors with solvent-free resins from the melt, aqueous systems have also been proposed as environmentally friendly and economical alternatives. For example, DE-OS 23 51 077 and 23 51 078 describe aqueous PEI secondary dispersions. However, these secondary dispersions have too low a solids content and also require special application devices. In DE-OS 26 05 790, water-thinnable PEI electrical insulating lacquers are described, which can be obtained with the help of considerable Ls / P

'Mengen (5 bis 30 Gew.%, vorzugsweise 20 bis 30 %) tertiären Amins und unter Mitverwendung von 5 bis 20 Gew.% Hilfslösungsmittel in eine wäßrige Form überführt werden.Amounts (5 to 30% by weight, preferably 20 to 30%) of tertiary amine and with the use of 5 to 20% by weight of auxiliary solvent are converted into an aqueous form.

In der DE-OS 17 20 321 wird ein Verfahren zur Herstellung wasserverdünnbarer Polyesterimidharze mit Hilfe von Ammoniak beschrieben. Gemäß dieser DE-OS werden aromatische Tricarbonsäureanhydride zunächst mit bis zu 80 % der stöchiometrischen Menge an primären Diaminen, die zur Imidbildung notwendig sind, umgesetzt und mit einem Überschuß an Di- und/oder Trialkoholen kondensiert. Anschlies- send wird der überschüssige Alkohol abdestilliert und das Kondensationsprodukt mit einer geringen Menge an wäßrigem Ammoniak, ggf. unter Zusatz von Dialkoholen auf eine Temperatur von über 80°C erwärmt und anschließend das Kondensationsprodukt mit Wasser verdünnt.DE-OS 17 20 321 describes a process for the preparation of water-dilutable polyesterimide resins with the aid of ammonia. According to this DE-OS, aromatic tricarboxylic anhydrides are first reacted with up to 80% of the stoichiometric amount of primary diamines which are necessary for imide formation and condensed with an excess of di- and / or trial alcohols. Anschlies- se nd the excess alcohol is distilled off and the condensation product with a small amount of aqueous ammonia, optionally with the addition of dialcohols heated to a temperature of about 80 ° C and then diluted the condensation product with water.

Die so hergestellten Lacke genügen jedoch nicht dem heute geforderten Eigenschaftsbild konventionell zu verarbeitender Polyesterimid-Drahtlacke.However, the lacquers produced in this way do not meet the properties required today for conventional polyesterimide wire lacquers.

Auch der DE-OS 27 24 913 sind wasserlösliche Polyesterimidharze und Verfahren zu ihrer Herstellung zu entnehmen. Die hierin beschriebenen Produkte und Herstellverfahren führen jedoch zu Produkten, die man auf einen pH >7 mit Aminen einstellen muß, d.h. diese Produkte riechen stark nach Aminen, was sich hinsichtlich der Arbeitsplatzhygiene nachteilig auswirkt. Außerdem werden auch hier, wie in DE-OS 26 05 790 größere Mengen Hilfslösungsmittel benutzt (>10 %, wie sich aus den Beispielen ergibt).DE-OS 27 24 913 also shows water-soluble polyesterimide resins and processes for their preparation. However, the products and manufacturing processes described herein result in products that must be adjusted to pH> 7 with amines, i.e. these products smell strongly of amines, which has an adverse effect on workplace hygiene. In addition, as in DE-OS 26 05 790, larger amounts of auxiliary solvents are used (> 10%, as can be seen from the examples).

Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Herstellung wäßriger hitzehärtbarer Elektroisolierlacke auf Basis von Polyesterimiden aufzuzeigen, das es erlaubt, auf einfache Weise zu wäßrigen Elektroisolier- lacken zu kommen, die die oben geschilderten Nachteile ' nicht aufweisen.It is an object of the present invention to provide a process for the preparation of aqueous thermosetting electrical insulating lacquers based on polyesterimides which makes it possible to convert aqueous electrical insulation to come paints that do not have the disadvantages described above.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung wäßriger hitzehärtbarer Elektroisolierlacke auf Basis von Polyesterimiden, die durch Kondensation von aromatischen Tricarbonsäuremonoanhydriden, aromatischen Dicarbonsäuren oder deren veresterbaren Derivaten, Diaminen, Diolen und einen Isocyanuratring enthaltenden Triolen erhalten worden sind, das dadurch gekennzeichnet ist, daß hydroxylgruppenhaltige Polyesterimide mit kinematischen Viskositäten von 16 bis 30 mm2 . s-1 (gemessen in einer Lösung von 1 Teil Polyesterimid in 2 Teilen N-methylpyrrolidon bei 30°C) und Säurezahlen <10 bei Temperaturen zwischen 80 und 130°C, gegebenenfalls unter Mitverwendung von bis zu 5 Gew.%, bezogen auf Polyesterimid, eines organischen Lösungsmittels, mit 5 bis 15 Gew.%, bezogen auf Polyesterimid, Ammoniak in Form einer wäßrigen Ammoniaklösung unter Aminolyse und Hydrolyse behandelt, so daß eine neutrale bis schwach saure Lösung resultiert, und durch Zusatz von vollentsalztem Wasser auf eine Viskosität zwischen 100 und 10 000 mPa.s verdünnt werden, wobei gegebenenfalls nach der Behandlung mit Ammoniak noch 0,1 bis 5 Gew.%, bezogen auf Polyesterimid, eines wasserlöslichen Härtungskatalysators zugegeben werden.The present invention relates to a process for the preparation of aqueous thermosetting electrical insulating lacquers based on polyesterimides which have been obtained by condensation of aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their esterifiable derivatives, diamines, diols and a triols containing an isocyanurate ring, which is characterized in that hydroxyl group-containing Polyesterimides with kinematic viscosities from 16 to 30 mm 2 . s - 1 (measured in a solution of 1 part polyesterimide in 2 parts N-methylpyrrolidone at 30 ° C) and acid numbers <10 at temperatures between 80 and 130 ° C, optionally with the use of up to 5% by weight, based on polyesterimide , an organic solvent, treated with 5 to 15% by weight, based on polyesterimide, ammonia in the form of an aqueous ammonia solution with aminolysis and hydrolysis, so that a neutral to weakly acidic solution results, and by adding demineralized water to a viscosity between 100 and 10,000 mPa.s are diluted, with 0.1 to 5% by weight, based on polyesterimide, of a water-soluble curing catalyst optionally being added after the treatment with ammonia.

Gegenstand der vorliegenden Erfindung ist außerdem die Verwendung dieser wäßrigen Elektroisolierlacke als Drahtlacke oder Tränklacke.The present invention also relates to the use of these aqueous electrical insulating lacquers as wire lacquers or impregnating lacquers.

Überraschenderweise erhält man nach dem erfindungsgemäßen Verfahren völlig klare, mit Wasser verdünnbare Lacke, die im Wärmeniveau gegenüber den mit tertiären Aminen erhaltenen wasserverdünnbaren Lacken verbesserte Werte zeigen. Außerdem sind die erfindungsgemäßen Elektroisolierlacke minfolge der Verwendung von billigem Ammoniak an Stelle von Ethanolaminen wirtschaftlicher und wesentlich umweltfreundlicher. Sie können unter Verwendung üblicher Applikationssysteme auf die zu beschichtenden Substrate aufgebracht werden und zeigen sich nach dem Einbrennen den konventionellen in den oben erwähnten organischen Lösungsmitteln gelösten und damit hinsichtlich ihrer Umweltbelastung problematischen Polyesterimidlacken in ihren technischen Eigenschaften als zumindest gleichwertig.Surprisingly, the process according to the invention gives completely clear, water-dilutable lacquers which have improved heat levels compared to the water-dilutable lacquers obtained with tertiary amines. In addition, the electrical insulating varnishes according to the invention m more economical and much more environmentally friendly due to the use of cheap ammonia instead of ethanol amines. They can be applied to the substrates to be coated using customary application systems and, after baking, show that the technical properties of the conventional polyesterimide lacquers dissolved in the above-mentioned organic solvents and thus problematic with regard to their environmental impact are at least equivalent.

Hinsichtlich der für das erfindungsgemäße Verfahren zu verwendenden Polyesterimide und ihrer Aufbaukomponenten ist auszuführen, daß der prinzipielle Aufbau geeigneter Polyesterimide den DE-AS 14 45 263 und DE-AS 14 55 100 zu entnehmen ist. Das erfindungsgemäß zu verwendende hydroxylgruppenhaltige Polyesterimid kann vorzugsweise nach dem in der DE-OS 14 55 182 beschriebenen Verfahren hergestellt werden.With regard to the polyesterimides to be used for the process according to the invention and their structural components, it should be stated that the basic structure of suitable polyesterimides can be found in DE-AS 14 45 263 and DE-AS 14 55 100. The hydroxyl-containing polyester imide to be used according to the invention can preferably be prepared by the process described in DE-OS 14 55 182.

Die PEI sind Kondensationsprodukte aus aromatischen Tricarbonsäuremonoanhydriden, aromatischen Dicarbonsäuren oder deren Derivaten, Diaminen, Diolen und Triolen mit Isocyanuratring.The PEI are condensation products from aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their derivatives, diamines, diols and triols with an isocyanurate ring.

Als aromatische Tricarbonsäuremonoanhydride kommen z.B. in Betracht Trimellithsäureanhydrid, 3, 4, 3'-Benzophenontricarbonsäureanhydrid und Hemimellithsäureanhydrid, wobei Trimellithsäureanhydrid bevorzugt wird.Examples of aromatic tricarboxylic acid monoanhydrides are consider trimellitic anhydride, 3, 4, 3'-benzophenone tricarboxylic acid anhydride and hemimellitic acid anhydride, with trimellitic acid anhydride being preferred.

Geeignete aromatische Dicarbonsäuren und deren veresterbare Derivate sind z.B. Terephthalsäure, Isophthalsäure, Benzophenon-4,4'-dicarbonsäure, Ester aromatischer Dicarbonsäuren, wie z.B. die Ester der Terephthalsäure mit niederen 1 bis 3 Kohlenstoffatome enthaltenden Alkoholen, z.B. Dimethylterephthalat, Dinethylisophthalat, Diethyl- terephthalat.Suitable aromatic dicarboxylic acids and their esterifiable derivatives are, for example, terephthalic acid, isophthalic acid, benzophenone-4,4'-dicarboxylic acid, esters of aromatic dicarboxylic acids, such as, for example, the esters of terephthalic acid with alcohols containing 1 to 3 carbon atoms, for example dimethyl terephthalate, dinethyl isophthalate, diethyl terephthalate.

Als Diamine eignen sich vorzugsweise solche mit primären Aminogruppen, die an aromatische Gruppen gebunden sind, z.B. solche der allgemeinen Formel

Figure imgb0001
wobei X für einen zweiwertigen Rest, z.B. -CH2-, -0-, -CO-, -S- oder -SO2- steht. Beispiele für derartige Diamine sind Diaminodiphenylmethan, Diaminodiphenyloxid und Benzophenondiamin.Suitable diamines are preferably those with primary amino groups which are bonded to aromatic groups, for example those of the general formula
Figure imgb0001
 where X stands for a divalent radical, for example -CH 2 -, -0-, -CO-, -S- or -SO 2 -. Examples of such diamines are diaminodiphenylmethane, diaminodiphenyloxide and benzophenonediamine.

Als Diole kommen übliche zweiwertige aliphatische Alkohole in Frage, wie: Butandiol-1,4, Trimethylenglykol, vorzugsweise Ethylenglykol.Suitable diols are customary dihydric aliphatic alcohols, such as: 1,4-butanediol, trimethylene glycol, preferably ethylene glycol.

Als Triole mit Isocyanuratring eignen sich Trishydroxyethylisocyanyrat, Trishydroxypropylisocyanurat, insbesondere Trishydroxiethylisocyanurat (=THEIC). Gegebenenfalls können in untergeordneten Mengen von bis zu 10 Mol%, bezogen auf die Gesamtheit der Triole, auch andere Triole, wie z.B. Glycerin mitverwendet werden.Suitable triols with an isocyanurate ring are trishydroxyethyl isocyanate, trishydroxypropyl isocyanurate, in particular trishydroxy ethyl isocyanurate (= THEIC). If necessary, other triols, such as, for example, can also be used in minor amounts of up to 10 mol%, based on the total of the triols. Glycerin can also be used.

Tricarbonsäuremonoanhydrid, Dicarbonsäure(derivat), Diamin, Diol und Triol werden im allgemeinen im Molverhältnis von 1,7-2,8/0,5-1,2/0,7-1,4/0,4-1,2/0,8-1,4, vorzugsweise 1,9-2,1/0,7-1,0/0,9-1,1/0,5-0,8/1,0-1,3 eingesetzt.Tricarboxylic acid monoanhydride, dicarboxylic acid (derivative), diamine, diol and triol are generally in a molar ratio of 1.7-2.8 / 0.5-1.2 / 0.7-1.4 / 0.4-1.2 / 0.8-1.4, preferably 1.9-2.1 / 0.7-1.0 / 0.9-1.1 / 0.5-0.8 / 1.0-1.3.

Wie bereits oben erwähnt, können die hydroxylgruppenhaltigen Polyesterimide beispielsweise nach dem in der DE-OS 14 55 182 beschriebenen Verfahren hergestellt werden. Die Kondensation wird hier in Ethylenglykol durchgeführt, wobei Polyesterimide erhalten werden, die keineAs mentioned above, the hydroxyl-containing polyester imides can procedures described 14 55 182 are produced for example by the in the D E-OS. The condensation is carried out here in ethylene glycol, polyesterimides which do not

Carboxylgruppen mehr enthalten and damit keine Säurezahl aufweisen.Contain more carboxyl groups and therefore have no acid number.

Die für das erfindungsgemäße Verfahren zu verwendenden hydroxylgruppenhaltigen Polyesterimide weisen Säurezahlen <10, vorzugsweise <5 und kinematische Viskositäten von 16 bis 30, vorzugsweise 18 bis 28 mm2.s-1 (gemessen in einer Lösung von 1 Gew.-Teil Polyesterimid in 2 Gew.-Teilen N--methylpyrrolidon bei 30°C) auf.The hydroxyl group-containing polyesterimides to be used for the process according to the invention have acid numbers <10, preferably <5 and kinematic viscosities of 16 to 30, preferably 18 to 28 mm 2 .s -1 (measured in a solution of 1 part by weight of polyesterimide in 2 parts by weight . Parts N - methylpyrrolidone at 30 ° C).

Das übliche Prinzip der Herstellung wasserlöslicher Harze durch Neutralisation von freien Carboxylgruppen mit Aminen unter Bildung der Salze kann bei diesen PEI somit nicht angewendet werden.The usual principle of producing water-soluble resins by neutralizing free carboxyl groups with amines to form the salts cannot therefore be used with these PEIs.

Erfindungsgemäß werden die hydroxylgruppenhaltigen Poly- esterimide bei Temperaturen zwischen 80 und 130o C, vorzugsweise 90 und 110°C, gegebenenfalls unter Mitverwendung von bis zu 5 Gew.%, bezogen auf PEI, eines organischen Lösungsmittels, mit 5 bis 15, vorzugsweise 7,5 bis 10 Gew.%, bezogen auf PEI, Ammoniak in Form einer wäßrigen Ammoniaklösung, die beispielsweise 5 bis 25 Gew.% Ammoniak enthalten kann, unter Aminolyse und Hydrolyse behandelt. Dabei resultiert eine neutrale bis schwach saure wäßrige Lösung mit pH-Werten zwischen 6 und 7, vorzugsweise 6,5 und 6,9.According to the invention the poly-hydroxyl-be it terimide at temperatures between 80 and 130 o C, preferably 90 and 110 ° C, optionally with the addition of up to 5 wt.%, Based on PEI, an organic solvent, with from 5 to 15, preferably 7 , 5 to 10% by weight, based on PEI, of ammonia in the form of an aqueous ammonia solution, which may contain, for example, 5 to 25% by weight of ammonia, treated with aminolysis and hydrolysis. This results in a neutral to weakly acidic aqueous solution with pH values between 6 and 7, preferably 6.5 and 6.9.

Als gegebenenfalls in Mengen von bis zu 5 Gew.%, bezogen auf PEI, mitzuverwendende organische Lösungsmittel kommen wassermischbare Lösungsmittel, wie z.B. N-methylpyrrolidon, Glykole, wie Ethylenglykol, Glykoläther, wie Butylglykol, Methyldiglykol, Ethyldiglykol, Butyldiglykol oder andere polare Lösungsmittel, wie Dimethylformamid oder Dimethylacetamid in Betracht.Water-miscible solvents, such as, for example, organic solvents to be used, optionally in amounts of up to 5% by weight, based on PEI. N-methylpyrrolidone, glycols, such as ethylene glycol, glycol ethers, such as butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol or other polar solvents, such as dimethylformamide or dimethylacetamide.

Nach der Behandlung des PEI mit wäßrigem Ammoniak kann die PEI-Lösung, die zweckmäßigerweise auf 20 bis 50°C abgekühlt wird, noch mit 0,1 bis 5, vorzugsweise 2 bis 4 Gew.%, bezogen auf PEI, eines wasserlöslichen Härtungskatalysators vermischt werden. Als solche wasserlösliche Härtungskatalysatoren eignen sich vorzugsweise wasserlösliche Titanate, wie z.B. Titantetralactat.After the PEI has been treated with aqueous ammonia, the PEI solution, which is expediently cooled to 20 to 50 ° C., can also be mixed with 0.1 to 5, preferably 2 to 4,% by weight, based on PEI, of a water-soluble curing catalyst . As such water-soluble curing catalysts, water-soluble titanates such as e.g. Titanium tetralactate.

Die Verdünnung der Polyesterimidlösungen auf Viskositäten zwischen 100 und 10 000 mPa.s erfolgt durch Zusatz von vollentsalztem Wasser.The polyesterimide solutions are diluted to viscosities between 100 and 10,000 mPa.s by adding deionized water.

In dieser Form können die erfindungsgemäß hergestellten Polyesterimidlösungen direkt zur Lackierung von Drähten, z.B. von Kupferdrähten oder als Tränklacke zur Imprägnierung von Lackdrahtwicklungen verwendet werden. Als Applikationsverfahren und -vorrichtungen kommen die für diese Zwecke üblichen in Frage.In this form, the polyesterimide solutions produced according to the invention can be used directly for coating wires, e.g. copper wires or as an impregnating varnish for impregnating enamelled wire windings. Application methods and devices which are customary for this purpose are suitable.

Das Einbrennen der Lackierungen erfolgt im allgemeinen bei Temperaturen von 200 bis 550, vorzugsweise 400 bis 520°C.The paintwork is generally baked at temperatures of 200 to 550, preferably 400 to 520 ° C.

Die erfindungsgemäß hergestellten wäßrigen hitzehärtbaren Polyesterimidlacke sind gut lagerstabil, sind völlig klar und weisen keinen Geruch nach Ammoniak auf. Die damit erhaltenen Lackierungen zeigen hervorragende Eigenschaften auch bezüglich der Erweichungstemperatur, des Wärmeschocks und des Wärmealterungsverhaltens.The aqueous thermosetting polyesterimide lacquers produced according to the invention have good storage stability, are completely clear and have no ammonia odor. The paintwork thus obtained also shows excellent properties with regard to the softening temperature, the thermal shock and the thermal aging behavior.

Die in den folgenden Beispielen genannten Teile und Prozente sind, soweit nicht anders angegeben, Gew.-Teile und Gew.-%e.Unless stated otherwise, the parts and percentages given in the following examples are parts by weight and% by weight.

Beispiel 1example 1

960 Teile Trimellithsäureanhydrid (entspr. 5,0 Mol) 485 Teile Diaminodiphenylmethan (entspr. 2,5 Mol) 815,5 Teile Trishydroxyethylisocyanurat (ent. 3,12 Mol) 339,5 Teile Dimethylterephthalat (entspr. 1,75 Mol) 1375 Teile Ethylenglykol 9 60 parts of trimellitic anhydride (equivalent to 5.0 mol) 485 parts of diaminodiphenylmethane (equivalent to 2.5 mol) 815.5 parts of trishydroxyethyl isocyanurate (equivalent to 3.12 mol) 339.5 parts of dimethyl terephthalate (equivalent to 1.75 mol) 1375 Parts of ethylene glycol

werden nach Zugabe von 2,6 Teilen Bleiacetat bei Temperaturen bis 220°C bis zum Klarpunkt verestert. Dann wird bei 150 bis 200°C das überschüssige Ethylenglykol in Vakuum (40 Torr) abdestilliert, bis das Harz, im Verhältnis 1:2 in N-Methylpyrrolidon gelöst, eine Viskosität von 19 mm2·s-1 (Ubelohde 3) bei 300C aufweist. Bei 95°C werden dann 87,8 Teile N-Methylpyrrolidon zugefügt und 851,4 Teile Ammoniak (25 %ig) langsam hinzugegeben. Nach 1 Stunde bei dieser Temperatur werden 991 Teile vollentsalztes Wasser zugegeben und erneut 3 Stunden bei 100°C gehalten. Nach dem Abkühlen werden 95 Teile Titantetralactat hinzugegeben. Der so erhaltene wäßrige Drahtlack hat einen Feststoffgehalt von 52,3 % mit einer Durch- laufviskosität im Ford-Becher (4 mm) nach DIN 53 211 von 41 sek.are esterified after the addition of 2.6 parts of lead acetate at temperatures up to 220 ° C to the clear point. The excess ethylene glycol is then distilled off in vacuo (40 torr) at 150 to 200 ° C. until the resin, dissolved in a ratio of 1: 2 in N-methylpyrrolidone, has a viscosity of 19 mm 2 · s -1 (Ubelohde 3) at 30 0 C. 87.8 parts of N-methylpyrrolidone are then added at 95 ° C., and 851.4 parts of ammonia (25% strength) are added slowly. After 1 hour at this temperature, 991 parts of demineralized water are added and the mixture is again held at 100 ° C. for 3 hours. After cooling, 95 parts of titanium tetralactate are added. The aqueous wire enamel thus obtained has a solids content of 52.3% with a transit l aufviskosität Ford cup (4 mm) according to DIN 53 211 of 41 sec.

Der Lack wird unter Verwendung eines üblichen Drahtlackierofens von 2,50 m Länge auf einen Kupferdraht von 0,5 mm 0 in 8 Durchzügen aufgetragen und bei 460°C eingebrannt. Die Abzugsgeschwindigkeit betrug 22 m/min.The varnish is applied to a copper wire of 0.5 mm 0 in 8 passes using a conventional wire varnishing furnace 2.50 m long and baked at 460 ° C. The take-off speed was 22 m / min.

Der Lackdraht hatte bei der Prüfung nach DIN 46 453 folgende Eigenschaften:

Figure imgb0002
Figure imgb0003
 The enamelled wire had the following properties when tested according to DIN 46 453:
Figure imgb0002
Figure imgb0003

Vergleichsbeispiel (nach DE-AS 17 20 321)Comparative example (according to DE-AS 17 20 321)

Beispiel 1 der DE-AS 17 20 321 wurde nachgearbeitet. Mit der so erhaltenen Lösung wurde beschichtet (Einbrenntemp. 460°C, Abzugsgeschwindigkeit 22 m/min).

Figure imgb0004
Example 1 of DE-AS 17 20 321 was reworked. The solution thus obtained was coated (baking temperature 460 ° C., take-off speed 22 m / min).
Figure imgb0004

Claims (4)

1. Verfahren zur Herstellung wäßriger hitzehärtbarer Elektroisolierlacke auf Basis von Polyesterimiden, die durch Kondensation von aromatischen Tricarbonsäuremonoanhydriden, aromatischen Dicarbonsäuren oder deren veresterbaren Derivaten, Diaminen, Diolen und einen Isocyanuratring enthaltenden Triolen erhalten worden sind, dadurch gekennzeichnet, daß hydroxylgruppenhaltige Polyesterimide mit kinematischen Viskositäten von 16 bis 30 mm2 . s-1 (gemessen in einer Lösung von 1 Teil Polyesterimid in 2 Teilen N-methylpyrrolidon bei 30°C) und Säurezahlen <10 bei Temperaturen zwischen 80 und 130°C, gegebenenfalls unter Mitverwendung von bis zu 5 Gew.%, bezogen auf Polyesterimid, eines organischen Lösungsmittels, mit 5 bis 15 Gew.%, bezogen auf Polyesterimid, Ammoniak in Form einer wäßrigen Ammoniaklösung unter Aminolyse und Hydrolyse behandelt, so daß eine neutrale bis schwach saure Lösung resultiert, und durch Zusatz von vollentsalztem Wasser auf eine Viskosität zwischen 100 und 10 000 mPa.s verdünnt werden, wobei gegebenenfalls nach der Behandlung mit Ammoniak noch 0,1 bis 5 Gew.%, bezogen auf Polyesterimid, eines wasserlöslichen Härtungskatalysators zugegeben werden.1. A process for the preparation of aqueous thermosetting electrical insulation coatings based on polyesterimides which have been obtained by condensation of aromatic tricarboxylic acid monoanhydrides, aromatic dicarboxylic acids or their esterifiable derivatives, diamines, diols and a triols containing an isocyanurate ring, characterized in that hydroxyl-containing polyesterimides 16 have kinematic viscosities up to 30 mm 2 . s -1 (measured in a solution of 1 part of polyesterimide in 2 parts of N-methylpyrrolidone at 30 ° C.) and acid numbers <10 at temperatures between 80 and 130 ° C., optionally with the use of up to 5% by weight, based on polyesterimide , an organic solvent, treated with 5 to 15% by weight, based on polyesterimide, ammonia in the form of an aqueous ammonia solution with aminolysis and hydrolysis, so that a neutral to weakly acidic solution results, and by adding demineralized water to a viscosity between 100 and 10,000 mPa.s are diluted, with 0.1 to 5% by weight, based on polyesterimide, of a water-soluble curing catalyst optionally being added after the treatment with ammonia. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Isocyanuratring enthaltendes Triol Tris- hydroxiethylisocyanurat verwendet wird. 2nd A method according to claim 1, characterized in that is used as the isocyanurate triol containing tris ydroxiethylisocyanurat h. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als veresterbares Derivat einer aromatischen Dicarbonsäure Terephthalsäuredimethylester verwendet wird.3. The method according to claim 1 or 2, characterized in that is used as the esterifiable derivative of an aromatic dicarboxylic acid dimethyl terephthalate. 4. Verwendung der nach einem Verfahren gemäß einem der vorhergehenden Ansprüche hergestellten wäßrigen Elektroisolierlacke als Drahtlacke oder Tränklacke.4. Use of the aqueous electrical insulating lacquers produced by a process according to one of the preceding claims as wire lacquers or impregnating lacquers.
EP82104390A 1981-05-29 1982-05-19 Process for preparing an electrically insulating aqueous and thermosetting enamel, and its use Expired EP0066194B1 (en)

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