EP1716580B1 - Method for producing coated electrical wires - Google Patents

Abstract

The present invention relates to a method for producing coated electrical wires for which coating is carried out using UV-curable baking enamels which comprise a) one or more oxirane-based binders, b) one or more UV crosslinking catalysts, c) if desired, reactive diluents, d) chain transfer agents, and e) further customary additives.

Description

The present invention relates to a process for producing coated electric wires.

The winding carriers used for the production of motors, solenoids, solenoids and generators are often exposed to strong mechanical loads. Especially with high-speed rotors, the resulting centrifugal and centripetal forces, which act on the windings of the moving components, quite considerable.

In order to prevent or at least reduce damage and deformations of the claimed device parts, windings are fixed at an early stage. This is done by impregnation with impregnating varnishes or impregnating resins. The impregnating varnishes or impregnating resins must be hardened. This is usually achieved by oven hardening the component at elevated temperatures over an extended period of time.

An innovation in the fixing of wires was the introduction of baked enamels, which were particularly in the field of deflection coil production in the TV technology made their entry.
The principle of the baked coatings is based on the thermoplastic property, which allows bonding of the finished painted wires after winding the coil. In this case, the baked enamel layer, which is expediently applied over an existing base insulation of the enameled wire, is first melted, wherein the interwinding spaces are partially filled with the molten thermoplastic and thus glue the individual windings over the thermoplastic. As a result of the subsequent solidification of the polymer, all the windings are fixed to one another, a deformation of the winding which would cause a change in the inductance, in particular in the case of self-supporting coils, can thus be prevented.
The melting of the baked enamel is thermally, on the one hand on the tempering of prefabricated components in the heater and the other electrically by power surge.

The advantage of the baked enamels in the production of reels of all kinds caused the designers to develop new devices for the winding technology. Today, baked enamels are used in almost all areas of enamelled wire processing for winding fixation, even with high thermal requirements.

Different classes of substances are used as a basis for baked enamels, depending on the field of application.

In EP 1 096 510 the use of polyvinyl acetals (PVA) is described. The thermal and mechanical property level of these baked coatings is modest.

In the EP 0 331 823 Polyvinyl butyrals and formal ones are described. Due to a relatively high average water absorption and a relatively low softening point of the polyvinyl butyrals, these materials are reluctantly used.

In the US 4,129,678 Phenoxy resins are described which are frequently used for moisture-sensitive and temperature-resistant applications. With the concomitant use of phenolic or melamine resins, relatively high-viscosity baked coatings are produced, which can release small quantities of formaldehyde and phenol during the caking process. This is one of the most serious disadvantages of these paint formulations.
In the EP 0 399 396 Polyamides are described for use as baked enamels. In the production of polyamides, which are suitable for use as a baked-on binder, there are far more possibilities for variation than in the other substance classes. A wide range of copolyamides of aromatic and / or aliphatic dicarboxylic acids, aromatic and / or aliphatic diamines and predominantly aromatic diisocyanates are known and are optionally used modified with blocked polyisocyanates.

In the US 4,131,714 Linear polyesters are described which are used as binders dissolved in suitable solvents as a baked enamel for wire coating.

All the above-mentioned enamel systems are applied by means of conventional wet paint application by felt wiping or nozzle application process on already insulated enamel wires and thermally dried, the expelled solvents are post-combusted in the catalysts of the conventional paint. The softening range of the remaining baked enamel layer is not infrequently regulated by the content of residual solvent in the polymer, which offers the decisive disadvantage of solvent release during the caking.

The DE 28 43 895 C3 relates to the curing of successive wire enamel layers by means of UV light. The described goal was in particular the avoidance of the solvents. Was applied a layer with good adhesion to the wire, another layer as an insulating varnish, followed by a heat and an abrasion and scratch-resistant layer, all layers are UV-curable.

In DE 29 15 011 describes the preparation and use of radiation-curable polyester imides, which are also applied as insulation material on copper wires. The preparation of UV-curable binders for use as baked enamels is not described.

The object of the present invention is to provide a baked enamel which is solvent-free and curable by UV light.

1. a) 50 - 95 % Bindemittel auf Oxiranbasis
2. b) 1 -10 % UV-Vernetzungskatalysatoren,
3. c) 0 - 80 % Reaktiwerdünner,
4. d) 0 - 40 % Kettenüberträger, sowie
5. e) 1 - 8 % Additive, Stabilisatoren usw.

This object is achieved in that UV-curable baked enamels are used for coating, which

1. a) 50-95% oxirane-based binder
2. b) 1 -10% UV crosslinking catalysts,
3. c) 0 - 80% reactive thinner,
4. d) 0 - 40% chain transfer agent, as well
5. e) 1 - 8% additives, stabilizers etc.

The baked coatings according to the invention are free from solvents of any kind, with water also counting as solvent.

1. a) 60 -93 % Bindemittel auf Oxiranbasis
2. b) 2 - 6 % UV-Vernetzungskatalysatoren,
3. c) 0 - 70 % Reaktiwerdünner,
4. d) 0 - 35 % Kettenüberträger, sowie
5. e) 1 - 3 % Additive, Stabilisatoren usw.

UV-curable baked coatings which are preferred according to the invention contain:

1. a) 60-93% oxirane-based binder
2. b) 2 - 6% UV crosslinking catalysts,
3. c) 0 - 70% reactive thinner,
4. d) 0 - 35% chain transfer, as well
5. e) 1 - 3% additives, stabilizers etc.

wobei R₁ ein Wasserstoff, ein Carboxylatrest der angegebenen Form

ein Polyetherrest

mit n = 1-50 oder ein Polyesterrest der nachfolgenden Form

sein kann, wobei R₂ ein Methyl-,Ethyl-,Propyl- oder Butylrest oder ein weiterer Oxiranring, oder eine weitere Oxiranverbingung des Typs

sein kann, wobei R₃ einen Hydroxyethylrest oder einer Oxiranverbindung folgender Form

entspricht, R₄ und R₅ eine aliphatische Kohlenwasserstoffkette von 2 - 6 Kohlenstoffeinheiten beschreibt, wobei R₅ darüber hinaus auch ein Phenylenrest sein kann und R₆ einem Hydroxyalkylrest mit 2-6 Kohlenstoffatomen oder einer Oxiranverbindung folgender Form

entspricht.The binders a) preferably contain cycloaliphatic Oxiranvebindungen the general form

where R _{1 is} a hydrogen, a carboxylate radical of the stated form

a polyether radical

with n = 1-50 or a polyester residue of the following form

wherein R _{2 is} a methyl, ethyl, propyl or butyl radical or another oxirane ring, or another Oxiranverbingung of the type

where R _{3 is} a hydroxyethyl radical or an oxirane compound of the following form

R ₄ and R _{5 is} an aliphatic hydrocarbon chain of 2 to 6 carbon units, where R ₅ can also be a phenylene radical and R _{6 is} a hydroxyalkyl radical having 2-6 carbon atoms or an oxirane compound of the following form

equivalent.

Other mono-, di- and polyoxiranes not described in detail here are also usable as binders.

Suitable for the production of baked enamels is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, which is available under the name "Cyracure UVR 6110" from Union Carbide Corporation.

The higher molecular weight mono- and dioxiranes used can be prepared by reacting the methyl 3,4-epoxycyclohexanecarboxylate with OH-functional polyethylene or polypropylene glycols having n = 1-50 ethoxy or propoxy units, preferably n = 5-25, more preferably n = 8 - 12, on the one hand to obtain the Polyether mono- and dioxiranes or with aliphatic and / or aromatic dicarboxylic acids and polyols to obtain the polyester mono- and -dioxiranen.

Suitable aromatic dicarboxylic acids and / or dicarboxylic acid dimethyl esters are, for example, isophthalic acid, terephthalic acid, terephthalic acid dimethyl ester, naphthalenedicarboxylic acid dimethyl ester. Particularly preferred are isophthalic acid and dimethyl terephthalate. Suitable aliphatic dicarboxylic acids are, for example, adipic acid, azelaic acid and decanedicarboxylic acid, with adipic acid being particularly preferred.

Suitable polyols include ethylene glycol, propylene glycol, neopentyl glycol and 1,4-butanediol. Mixtures of ethylene glycol and neopentyl glycol have proven particularly advantageous for the described application.

verwendet. Anstelle dessen oder zusätzlich kann Komponente b) auch andere übliche UV-Vernetzungskatalysatoren enthalten.Suitable UV crosslinking catalyst b) is preferably a photoinitiator suitable for cationic photopolymerization, or an initiator mixture. Preferred for the baked enamines of the present invention is the mixed arylsulfonium hexafluorophosphate salt of the following form

used. Instead or in addition, component b) may also contain other customary UV crosslinking catalysts.

As reactive diluents c), preference is given to low molecular weight oxiranes, oxetanes and the like. into consideration with the oxiranes according to the invention copolymerizable compounds.

As a chain transfer agent d) and to increase the crosslinking density, the concomitant use of optionally branched polyester polyols having molecular weights between 500 and 2000 g / mol is advantageous, preferably polyester polyols having an average molecular weight between 500 and 1000 g / mol.

As leveling agents e) it is possible to use surface-modified polydisiloxanes, for example the "Byk 306" from Byk Chemie GmbH.

The invention will be explained in more detail with reference to the following examples:

Example 1: Preparation of a dioxirane from polyethylene glycol 400 and methyl 3,4-epoxycyclohexanecarboxylate (dioxirane I)

62.4 g of methyl 3,4-epoxycyclohexanecarboxylate are mixed with 80 g of a polyethylene glycol 400, with nitrogen as a protective gas, mixed with 0.2 g of tetrabutyl titanate and transesterified with elimination of 12.8 g of methanol at 180-200 ° C. , 155.4 g of a high-viscosity polyethylene glycol dioxirane are obtained.

Example 2 Preparation of a Dioxirane from Dimethyl Terephthalate, Ethylene Glycol, Neopentyl Glycol and Methyl 3,4-epoxycyclohexanecarboxylate (Dioxirane II)

31.2 g of methyl 3,4-epoxycyclohexanecarboxylats are mixed with 97 g of dimethyl terephthalate, 15.5 g of ethylene glycol and 26.0 g of neopentyl glycol, with nitrogen as a protective gas, mixed with 0.2 g of tetrabutyl titanate and with elimination of 38, 4 g of methanol transesterified at 180-200 ° C. 131.5 g of a waxy polyester dioxirane are obtained.

Example 3 Preparation of a dioxirane from adipic acid, ethylene glycol, neopentyl glycol and methyl 3,4-epoxycyclohexanecarboxylate (dioxirane III)

31.2 g of methyl 3,4-epoxycyclohexanecarboxylate are mixed with 73 g of adipic acid, 15.5 g of ethylene glycol and 26.0 g of neopentyl glycol, with nitrogen as inert gas, mixed with 0.2 g of tetrabutyl titanate and with elimination of 6, 4 g of methanol and 18 g of water at 180 - 200 ° C esterified. 121.5 g of a waxy polyester dioxirane are obtained.

UV-curable baked enamels were formulated from the oxiranes prepared:

Example 4: Baking lacquer 1

A UV-curable lacquer is prepared from 32.5 g of Cyracure UVR 6110, 30 g of dioxirane III, 5 g of photoinitiator, 30 g of methyl 3,4-epoxy-cyclohexanecarboxylate and 2.5 g of flow additive. The components are homogeneously mixed to a colorless transparent varnish with 790 mPa s.

Example 5: Baking lacquer 2

A UV-curable lacquer is prepared from 52.5 g of Cyracure UVR 6110, 40 g of dioxirane 1, 5 g of photoinitiator and 2.5 g of flow additive. The components are mixed homogeneously to form a colorless transparent paint with 670 mPa s.

Example 6: Baking lacquer 3

A UV-curable lacquer is prepared from 67.5 g Cyracure UVR 6110, 25 g Desmophen 670 polyester polyol, 5 g photoinitiator and 2.5 g leveling additive. The components are homogeneously mixed to a colorless transparent lacquer with 2340 mPa s.

The baked enamines prepared according to the invention were by Düsenabstreifverfahren on a copper wire with 0.30 mm bare wire diameter, conventionally coated with a commercially available polyesterimide wire enamel with an overall diameter increase of 50 microns, at 10 - 80 ° C and cured by UV light. The UV source used was a microwave-excited high-pressure mercury vapor radiator. The power of the spotlight was between 25 and 100 watts per cm. Reflector and radiator form a resonator unit.

In accordance with the international standard of DIN EN 60851-3 (IEC 851-3), the caking strength tests were carried out on standard-produced coils. The minimum bonding force required for the present wire diameter was significantly exceeded with the 0.7 N determined.

• Backlack 1: Bei einer Lackschicht von 10 µm erhält man einen Lackdraht mit glatter Oberfläche und guten Verbackungseigenschaften bei 200°C und einer Verbackungskraft von 0,7 N.
• Backlack 2: Bei einer Lackschicht von 10 µm erhält man einen Lackdraht mit glatter Oberfläche und guten Verbackungseigenschaften bei 200°C.
• Backlack 3: Bei einer Lackschicht von 11 µm erhält man einen Lackdraht mit glatter Oberfläche und guten Verbackungs-eigenschaften bei 200°C und einer Verbackungskraft von 0,8 N.

The following test results were obtained:

• Backlack 1: With a lacquer layer of 10 μm, an enameled wire with a smooth surface and good caking properties at 200 ° C. and a bonding force of 0.7 N are obtained.
• Back lacquer 2: With a lacquer layer of 10 μm, an enamelled wire with a smooth surface and good caking properties at 200 ° C is obtained.
• Back varnish 3: With a varnish layer of 11 μm, a varnished wire with a smooth surface and good caking properties at 200 ° C. and a bonding force of 0.8 N are obtained.

Claims (12)

1. Use of UV-curable baking enamels containing

   a) 50%-95% by weight of oxirane-based binders,

   b) 1%-10% by weight of UV crosslinking catalysts,

   c) 0-80% by weight of reactive diluents,

   d) 0-40% by weight of chain transfer agents, and

   e) 1%-8% of further additives

   to produce coils.
2. Use according to Claim 1 or 2, characterized in that baking enamels are used containing

   a) 60%-93% by weight of oxirane-based binders,

   b) 2%-6% by weight of crosslinking catalysts,

   c) 0-70% by weight of reactive diluents,

   d) 0-30% by weight of chain transfer agents, and

   e) 1%-3% of further additives.
3. Use according to any one of the present claims, characterized in that, as baking enamel, cycloaliphatic oxirane compounds are used of the general form

   

   where R₁ can be a hydrogen, a carboxylate radical of the indicated form

   

   a polyether radical of the formula

   

   with n = 1-50 or a polyester radical of the following form

   

   where R₂ is a methyl, ethyl, propyl or butyl radical or a further oxirane compound of the following form

   

   and R₃ is a hydroxyethyl radical or an oxirane compound of the following form

   

   R₄ and R₅ describes an aliphatic hydrocarbon chain of 2-6 carbon units, it being possible in addition for R₅ to be a phenylene radical, and R₆ is a hydroxyalkyl radical having 2-6 carbons or an oxirane compound of the following form

   
4. Use according to any one of the preceding claims, characterized in that at least one photoinitiator suitable for cationic photopolymerization is added.
5. Use according to Claim 5, characterized in that, as a photoinitiator, a mixed arylsulfonium hexafluorophosphate salt of the following form

   

   is added.
6. Use according to any one of the preceding claims, characterized in that a baking enamel is used whose component a) is prepared using methyl 3,4-epoxycyclohexanecarboxylate.
7. Use according to Claim 7, characterized in that a baking enamel is used whose component a) has been prepared using polyethylene glycol.
8. Use according to any one of the preceding claims, characterized in that baking enamels are used to which low molecular weight oxiranes, oxetanes are added as reactive diluents.
9. Use according to any one of the preceding claims, characterized in that component d) comprises polyester polyols having molecular weights of between 500 and 2000 g/mol.
10. Use according to any one of the preceding claims, characterized in that component d) comprises polyester polyols having an average molecular weight of between 500 and 1000 g/mol.
11. Use according to any one of the preceding claims, characterized in that component e) comprises additives or stabilizers or mixtures thereof.
12. Use according to any one of the preceding claims,
    characterized in that after the coil has been coated with baking enamel, said enamel is cured by means of ultraviolet radiation.