EP0823120A1

EP0823120A1 - Wire enamel formulation with internal lubricant

Info

Publication number: EP0823120A1
Application number: EP96914118A
Authority: EP
Inventors: Klaus-Wilhelm Lienert; Irmgart Gebert; Helmut Lehmann; Michael W. MÜLLER
Original assignee: Dr Beck & Co AG; Beck & Co AG Dr
Current assignee: Altana Electrical Insulation GmbH
Priority date: 1995-04-26
Filing date: 1996-04-25
Publication date: 1998-02-11
Anticipated expiration: 2016-04-25
Also published as: ATE204093T1; WO1996034399A1; JPH11504156A; TW315387B; ES2163626T3; KR100382621B1; EP0823120B1; US6022918A; DE19515263A1; KR19990008063A; BR9608294A; DE59607451D1

Abstract

PCT No. PCT/EP96/01723 Sec. 371 Date Jan. 13, 1998 Sec. 102(e) Date Jan. 13, 1998 PCT Filed Apr. 25, 1996 PCT Pub. No. WO96/34399 PCT Pub. Date Oct. 31, 1996The present invention relates to a wire enamel formulation comprising components which are known per se and an internal lubricant consisting of a polyethylene wax, preferably having a molecular mass of from 3000 to 6000 g/mol, and a wetting agent, preferably fatty alcohol ethoxylate.

Description

Wire enamel formulation with internal lubricant

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.

These and other disadvantages are eliminated when internal lubricants are used. Such lubricants are added to the paint. After the wire enamel has hardened, they are incompatible with the wire enamel. They migrate to the surface and form a layer that has improved lubricity.

The problem is that many of these internal lubricants are incompatible with the liquid paint and lead to phase separation or precipitation. 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.

Comparisons between paraffinic and polymeric lubricants are described in EP 0 267 736. The polymeric lubricants perform considerably better in the reliability test of relays. No Information is given about the stability of the processed polymer-wire enamel mixtures.

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.

The examples listed show that an optimal lubricant must be an internal lubricant. In addition, the additive that improves lubricity should be a polymeric material and the formulation should be stable on storage.

It was accordingly an object of the present invention to provide a wire enamel formulation comprising components known per se and an internal lubricant which meets the requirements mentioned.

This object is surprisingly achieved in that 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.

According to the invention, the lubricant can also consist exclusively of the polyethylene wax and the wetting agent. According to the invention, wire enamels with a polyesterimide can be used as a binder. Such 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. 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.

Examples of compounds with a cyclic

Carboxylic anhydride grouping with a further functional group are, above all, pyromellitic dianhydride and trimellitic anhydride. However, other 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. Aromatic diprimary diamines, such as benzidine, are also suitable.

Diaminodiphenylmethane, diaminodiphenyl ketone, sulfone, sulfoxide, ether and thioether, phenylenediamines, toluenediamines, xylylenediamines and also diamines with three benzene nuclei in the molecule, such as bis- (4-aminophenyl) - α, α'-p-xylene or bis ( 4-aminophenoxy) -1, 4-benzene, and finally cycloaliphatic diamines such as the 4,4'-dicyclohexylmethane diamine. Amino alcohol-containing compounds with a further functional group are also amino alcohols, z. As monoethanolamine or monopropanolamines, furthermore amino carboxylic acids such as glycine, aminopropionic acids, aminocaproic acids or aminobenzoic acids.

Known transesterification catalysts are used to prepare the 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. As

Crosslinking catalysts in the curing of the polyesterimides, the same transesterification catalysts can be used - advantageously in a proportion of up to 3% by weight, based on the binder. 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,

Ethyl glycol acetate, butyl glycol acetate and 3-methoxy-n-butyl acetate; cyclic carbonates, such as B. propylene carbonate; cyclic esters such as B. γ-butyrolactone and, for example, dimethylformamide and N-methylpyrrolidone. 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®.

According to the invention, wire enamels with a polyamideimide can also be used as a binder. Such 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. Furthermore, it is also possible to prepare the polyamideimides from diisocyanates or diamines and dicarboxylic acids if one of the components already contains the imide group. In particular, 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, in which 2 carboxyl groups are in the vicinal position, 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-aminoρhenyl) -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, ω, ω'-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-aliphatic and aromatic-hydroaromatic diisocyanates, such as 4-

Phenyl isocyanate methyl isocyanate, tetrahydronaphthylene-1, 5-, hexahydrobenzidine-4,4'-diisocyanate. 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.

The following 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, such as, for example, 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.

According to the invention, 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.

The 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.

If a polyethylene wax dispersion, e.g. B. Luwax® in xylene to an N-methylpyrrolidone-containing solution of the binders described above, a phase separation takes place. However, if wetting agent is added, the phase separation can be suppressed to different extents.

According to the invention, wetting agents are accordingly added to the wire enamel formulation. In particular, 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. Here, a polyethylene wax, preferably with a molecular mass of 3000 to 6000 [g / mol], is first mixed with 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.

In a further step, 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.

Finally, a wire enamel containing components known per se is mixed with the dispersion thus obtained. Here, wire enamels are particularly suitable which contain polyesterimides or polyesteramideimides described above as binders.

The wire enamels according to the invention thus produced are used in particular in the coating of electrical conductors.

The invention is described in more detail below with the aid of examples:

Examples

Example 1: Production of a Polvesterimid wire enamel

By reacting 3.9 parts of ethylene glycol, 8.7 parts of dimethyl terephthalate, 10.2 parts of tris (2-hydroxyethyl) isocyanurate, 11.5 parts of trimellitic anhydride and 5.9 parts of 4,4'-diaminodiphenylmethane in the presence of 0.04 part of tetra-n-butyl titanate, a polyester imide manufactured. This polyester imide is dissolved in 56 parts of a mixture of Kresol / Solventnaphtha® in a ratio of 2: 1 and 0.7% of the total recipe, a commercially available titanium catalyst, is added. The wire enamel obtained in this way has a solids content of 39% (1 g / 1 h / 180 ° C) at a viscosity of 800 mPas (23 ° C).

Example 2: Preparation of a polvamidimide wire enamel

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 3: Preparation of a Luwax® AH6 dispersion in xylene

900 g xylene and 100 g Luwax® AH6 are heated to 80 ° C. After the wax has dissolved, it is cooled. 20 g Emulan® AF are added to the cooled dispersion. Example 4: Preparation of a Luwax® A dispersion in xylene

900 g xylene and 100 g Luwax® A are heated to 80 ° C. After the wax has dissolved, it is cooled. 20 g Emulan AF are added to the cooled dispersion.

Example 5: Production of a Polvesterimid wire enamel with internal lubricant

1000 g of wire enamel from Example 1 are mixed with 50 g of dispersion from Example 3. The varnish thus produced is varnished.

Painting conditions - single-layer painting

Oven: MAG AW / 1A

Temperature: 520 ° C

Application system: nozzles wire diameter: 0.71 mm take-off speed: 30 m / min number of passes: 10

Increase rate: 2L

Example 6: Production of a polvamidimide wire enamel with internal lubricant

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.

Painting conditions - two-layer painting Oven: MAG AW / 1A

Temperature: 520 ° C

Application system: nozzles

Wire diameter: 0.71 mm

Take-off speed: 30 m / min

Number of swipes:

Base coat 8

Top coat 2

Increase rate: 2L

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.

Five twists were produced and tested for each varnish. At the same time, five twists of a wire that was coated with a conventional paraffinic lubricant were tested.

An average force of 2.5 Newtons was measured for a standard wire. 1.5 Newtons were found for the wire from Example 5 and 1.9 Newtons were found for the wire from Example 6.

Claims

claims

1. Wire enamel formulation containing known components and at least one internal lubricant, characterized in that the lubricant

Polyethylene wax, preferably with a molecular mass of 3000 to 6000 [g / mol], and a wetting agent, preferably fatty alcohol ethoxylate, contains.

2. Wire enamel formulation according to claim 1, characterized in that the lubricant from 0.1 to 4.5, preferably 1.0 to 2.2 wt .-% polyethylene wax and 0.1 to 2.0, preferably 0.2 to 1 . 2% by weight of wetting agent, the% by weight being based on the proportion of binder in the wire enamel.

3. Wire enamel formulation according to one of claims 1 or 2, characterized in that it contains polyesterimide or polyesteramideimide as a binder.

4. A process for the preparation of a wire enamel formulation according to one of claims 1 to 3, characterized in that a) a polyethylene wax, preferably with a molecular weight of 3000 to 6000 [g / mol], with a solvent, preferably in an amount of 5 to 25 % By weight based on the polyethylene wax, mixed, b) heated, preferably to 70 to 100 ° C., c) after the polyethylene wax has completely dissolved, cooled, d) a wetting agent, preferably fatty alcohol ethoxyate, is added and e) the wire enamel containing components known per se is mixed with the dispersion thus obtained.

5. The method according to claim 4, characterized in that the proportion of the solvent added to the polyethylene wax is 8 to 11, preferably 10 wt.%.

6. The method according to any one of claims 4 or 5, characterized in that xylene or toluene are used as solvents.

7. The method according to any one of claims 4 to 6, characterized in that in step b) is heated to about 80 ° C.

8. The method according to any one of claims 4 to 7, characterized in that a lubricant consisting _of 0.1 to 4.5, preferably 1, 0 to 2.2 wt .-% polyethylene wax and 0.1 to 2.0, preferably 0 , 2 to 1.2 wt .-% wetting agent, each based on the binder content in the wire enamel, is used.

9. The method according to any one of claims 4 to 8, characterized in that a wire enamel containing polyesterimide or polyesteramide imide is used as a binder.

10. Use of the wire enamel according to claim 6 or 7 for coating electrical conductors.