DE1690163B2 - DOUBLE LACQUERED ELECTRIC CONDUCTOR - Google Patents

Description

69Otl63

is characterized in that the polyesterimide rope method, such as, for example, B, according to the in the USA, -

optionally after the addition of alkyl titanates, poly-patent specification 3 201276 described immersion process

isocyanates or phenol-formaldehyde resins in customary or the form lacquer also described there

solvents as the first continuous coating process on a dielectric conductor, such as

layer on a bare conductor 5 wise copper, silver or stainless steel wire, aaf-

and that the conductor coated in this way is brought with a top coat

layer of polyalkylene terephthalate is provided. between 4.5 and 11 m / min and the temperatures in

The tower according to the process of the main patent application is between 120 and 430 ^° C., with polyesterimides usually produced being able to achieve a final temperature above 260 ^° C. by incorporation. The 1 to 25% polyisocyanate, based on the total lacquer absorption, ie the total increase in the through weight of polyisocyanate and polyesterimide, and / or knife compared to the unpainted wire, can be achieved by incorporating 0.01 to 10% of an alkyl between 0 , 00127 and 0.0254 cm and is titanates, based on the total dry substance - preferably 0.00508 to 0.0102 cm when using the wire enamel content. of a No. 18 wire. The wire is once or

As polyisocyanates, 2,4-tolylene diisocyanate, 15 more times through the coating until the desired

2,6 - tolylene diisocyanate, m - phenylene diisocyanate, lacquer absorption is achieved.

1.ö-Hexamethylene diisocyanate, the cyclic trimer. The outer lacquer made from linear polyethylene terephthalate

of 2,6-tolylene diisocyanate, the trimer of 4,4'-di- can be prepared from any suitable solvent-

phenylmethane diisocyanate, 1,3,5-triisocyanatobenzene system are applied. Preference is given to

or blocked isocyanates such as 7. B. the reaction solvent systems, as described in the USA patent

product of 3 moles of a mixed 2,4- and 2,6-To-3 141 859 are described. As a result, dis-

lylene diisocyanate with trimethylolpropane, in which persions of polyethylene terephthalate in a solution

the isocyanate groups by esterification with phenol sungsmiUel from chlorophenol, z. B. o-chlorophenol,

are blocked (Mondur S), and Mondur SH, in which m-chlorophenol or p-chlorophenol or an alky-

the three free isocyanate groups of the mixed cyclic »5 Herten C hlorphenol, z. B. p-chloro-m-cresol, 4-chloro-

between trimers of 2,4- and 2,6-tolylene diisocyanate sec-butylphenol or chlorothymol, or a Mi-

blocked by esterification with m-cresol, these chlorophenols and a cresol, z. B.

be turned. Further examples of suitable poly-o-cresol, m-cresol, p-cresol or cresolic acid

isocyanates including blocked isocyanates, a mixture of m- and p-cresol, can be used

US Pat. No. 2,982,754, column 1, 30. The cresol can also be partially replaced by phenol

Row 41 through column 3, row 7th will be.

Usable alkyl titanates are, for example, Tetra- Preferred solvent systems for the poly-

Isopropyl titanate, tetraniethyl titanate, tetrabutyl titanate, ethylene terephthalate are those which have at least one

Tetrahexyl titanate. and tetrapropyl titanate. Chlorophenol, at least one cresol and phenol are

The polyesterimides will generally hold in the 35 e.g. B. a mixture of p-chlorophenol,

Solvents applied as wire enamel, in which p-cresol and phenol. Another preferred solution

The polycondensation of these polymers also consists of p-chlorophenol and m- and

will lead. So can be used as a solvent z. B. p-cresol.

N-methylpyrrolidone, dimethylacetamide, dimethylcresolic acid is in Bennett's Concise Chemical and

formamide, dimethyl sulfoxide, N-methylcaprolactam, 40 Technical Dictionary "(1947) as a mixture of o-, m-

Xylene, cresylic, p-cresol, mixtures of m- and p-cresol and having a boiling range 185-230 ⁰ C.

p-cresol, dimethyl sulfone and the like can be used. Are defined.

Furthermore, solvent mixtures such as. B. I _n the preferred solvent mixtures for

Mixtures of N-methylpyrrolidone with dimethyl dissolving the linear polyethylene terephthalate can

acetamide and / or dimethylformamide, a mixture 45 the chlorophenol in amounts of 30 to 50%, the

of N-methylpyrrolidone, dimethylacetamide and to-phenol in amounts of 25 to 50% and the cresol in

luene in a ratio of 6: 3: 4 or mixtures of amounts of 10 to 35%, each based on the

N-methylpyrrolidone can be used with xylene. Total solvent, be present. When replacing the

Both aliphatic phenol and cresol can be used as diluents, the total content of cresol

as well as aromatic hydrocarbons such as. B. 50 to 70%.

Solvesso No. 100, toluene, xylene, octane, decane, as already mentioned, the first lacquer is dodecane and tetradecane can be used. Due to the coating of polyester imides up to a varnish application of higher-boiling aliphatic cohorts from 0.00127 to 0.0254 and preferably from Hydrogen as a solvent component is applied the 0.00508 to 0.102 cm. The second varnish smoothness of the wire enamel improved. 55 polyethylene terephthalate coating is up to one

In some cases, 0.2 to 1.0% paint uptake is still between 0.00127 and 0.00762 cm

Metal siccatives calculated on the metal content and preferably not more than 0.00508 cm

based on the solids content of the wire enamel, as applied. The entire paint fixture made of polyester

z. B. zinc octoate, cadmium linoleate, zinc resinate, calcium imides and polyethylene terephthalate is between

cium octoate, cadmium naphthenate and zinc naphtnenate, 60 0.00508 and 0.033 cm and preferably between

added. The wire enamel is preferably still 0.00762 and 0.0152 cm.

1 to 5%. On a total solids basis, the invention is illustrated by the following examples

Melamine-formaldehyde resin or preferably phenol- explained in more detail,

resin such as B. Phenol-formaldehyde-, cresol-form- Example 1

aldehyde or xylenol formaldehyde resin added. 6g ^p

The polyesterimide is used as a wire enamel in a volume of 192 g (1 mol) of trimellitic anhydride in 300 ml

Solvents such as B. one of the above N-methylpyrrolidone, 100 g (0.5 mol) of oxy-

Solvent systems used and added to 300 ml of N-methylpyrrolidone according to conventional dianiline. It

an exothermic reaction took place and a clear solution formed. Then 99 g of tris (2-hydroxyethyl) isocyanurate, 165 g of ethylene glycol, 388 g of dimethyl terephthalate and 0.0345 g of lead (II) oxide were added as a catalyst. The mixture was on 227 ° C heated, a suspension of an orange precipitate was obtained. It turned out like that heated for a long time until the solution became clear again (48 to 72 hours). This wire enamel solution is for that Painting of z. B. copper wire suitable. The finished wire enamel solution was made with a thinner of 40% p-chlorophenol, 40% phenol and 20% o-cresol added to the total solids content Reduce 25% and set a suitable viscosity (viscosity W according to Gardtner - Holdt). The product can be applied to copper wire no. 18, for example by the form painting process and then the coated wire through a tower at a temperature at a speed of 8.2 m / min of 400 ° C.

Example 2

A solution of 100 g of oxydianiline in 150 g of N-methylpyrrolidone was slowly added ^{at 93 °} C. to 192 g of trimellitic anhydride in 150 g of N-methylpyrrolidone. A mixture of 254 g of dimethyl terephthalate, 103 g of ethylene glycol, 120 g of tris (2-hydroxyethyl) isocyanurate, 50 g of xylene and 0.15 g of lead (II) oxide was then added. The temperature of the mixture was increased to 227 ° C. over the course of 24 hours, while methanol and xylene were distilled off. After the batch had reached a viscosity of M (Gardtner-Holdt) at 21% solids in cresolic acid, 1800 g of cresolic acid were added in order to set a viscosity of U 3/4.

The following mixture was made with this polyesterimide solution:

840 g polyesterimide with 24% solids, 8 g tetraisopropyl titanate,
56 g of a 40% solution of Mondur SH in cresolic acid,

25 g phenol-formaldehyde resin solution in cresolic acid with 40% solids.

This mixture was heated to 121 ⁰ C, cooled and then used in a conventional manner for coating a copper wire with use of a temperature of 400 ° C in the wire tower. The enamelled wire thus obtained had excellent electrical properties.

Examples 3 to 8

In the following Examples 3 to 8, the same procedure as in Example 2 was followed. The half of the N-methylpyrrolidone was with the trimellitic anhydride and the remainder is added with the methylenedianiline or oxydianiline. All polyesterimides of Examples 3 to 8 were mixed with tetraisopropyl titanate, Mondur SH and phenyl formaldehyde resin, so that wire enamels with the same proportions of these components as in Example 2 were obtained. These lacquers were then used in the same manner as in Example 2 to coat copper wire. Polyethylene terephthalate was used as the second layer of lacquer in those cases where this was applied used.

example

Trimellitic anhydride

N-methylpyrrolidone

Methylenedianiline

Oxydianiline

Dimethyl terephthalate

Ethylene glycol

Tris (2-hydroxyethyl) isocyanurate

Xylene

Lead (II) oxide

768 800 396

1016

416

480

200

0.9

384 600 199

766 260 396 200 t), 6 288
400

148.5

1020

282

540

300

0.9

Properties without a second coat of paint

Cone after honing

Heat shock, 15% elongation, 200 ⁰ C breakdown temperature in ° C .... Heat Daner test at 260 ⁰ C

(AffiE test No. 57)

Heat test at 24O ⁰ C

(AIEE test No. 57)

2x IX 300

122 461

4x 2x

> 5x

310

465
816

192
300

100

254

103

120

0.15

2x
3x
312

170

properties Cone after honing ... 2x ' with second Lackschich t 2X Heat shock, 15% elongation, 200 ° C i Ix _ Ix ffiteeschock, 15% Dehntmg, 250 ⁰ C. - - - 4x Breakdown temperature in ⁰ C 270 i - 308 Ifite endurance test at 26O ⁰ C - (AffiE test No. 57) 170 zn Heat test at 24O ⁰ C < » - (AIEE test number 57) > 1579 -

192 300

100 388 130 198 100 0.3

2X 5x 300

170

96 200

50 340

94 180 100 0.3

2X Sx

303

108> 2141

2X Ix

310 320

Examples 9-11

The procedure was the same as in Example 2 to 8, except that in Example 11 the The order of mixing changed so that the methylenedianiline was added as the last component was, d. that is, the polyimide was not prepared prior to the addition of the polyester forming components.

example

Trimellitic anhydride

Cresolic acid

N-methylpyrrolidone ..

Methylenedianiline

Dimethyl terephthalate ..

Ethylene glycol

Tris - (2 - hydroxyethyl) -

isocyanurate

Xylene

Lead (II) oxide

10

768 192 192 160 800 160 - 396 99 99 1016 254 254 416 60 60 480 240 240 200 - 0.9 0.15 0.15

11th

The polyester imides according to Examples 1 to 11 can be used to coat electrical conductors and then provided with a second outer lacquer coating made of polyethylene terephthalate. As can be seen from example 3, 6 and 8, a substantial improvement of the aging resistance is obtained at high temperatures through the second lacquer coating, such as the heat endurance test at 260 ⁰ C show. Jem except the heat shock resistance at 15 ° / ₀ stretch and 200 ⁰ C is improved.

Example 12 approach:

Cresolic acid (solvent) ... 943.467 kg

Ethylene glycol 291.889 kg

Tris (2-hydroxyethyl) isocyanate

rat 1168.213 kg

Trimellitic anhydride 756.326 kg

Methylenedianiline 387.673 kg

Terephthalic acid 854.334 kg

ρ-toluenesulfonic acid

(Catalyst) 1.503 kg

These components were placed in a stainless steel reaction vessel with a capacity of 75701, equipped with a stirrer, heat source and fractionating column. The reaction was heated in the course of 15 hours at 227 ⁰ C and as long as kept at this temperature until a sample of 42 ° / o solids in cresylic exhibited a viscosity of Z4 ^+. Then the approach with a mixture of 2371.437 kg of cresolic acid and 1770.815 kg

to Solvesso 100 diluted. The polyesterimide solution then had a viscosity of Z 2%, a solids content of 40.5% and a specific weight of 1.115.
4638.865 kg of this polyesterimide solution were mixed with 1272.320 kg of cresolic acid and 676.303 kg of Solvesso 100. The mixture was heated to 49 to 54 ° C. and then 82.551 kg of tetraisopropyl titanate were added over the course of 15 minutes. Subsequently, 510.289 kg MondurSH (40 ° / ₀ solution in

so cresolic acid) and 218.630 kg of phenolic resin 709 (40% m '/ p-cresol-formaldehyde resin solution in cresolic acid) were added and the batch was heated to 118 to 121 ° C. over the course of 75 minutes. The temperature was kept at 121 ^° C. for 2 hours and the mixture

»5 then cooled down. The approach was with a mixture diluted from 324.317 kg of cresolic acid and 174.632 kg of Solvesso 100. The wire enamel thus obtained had a Viscosity of R, a solids content of 29.6% and a specific weight of 1.055.

With this wire enamel copper wire No. 18 was. After Formlackierverfahren with a wire speed of 9 m / min and a temperature of 400 ⁰ C wire tower painted. The wire was passed through the solution and through the tower six times, whereupon the paint pick-up was 0.00762 cm. A second conductor was covered in the same way, but the wire was only passed five times through the solution and through the tower. Thereafter, the conductor by a single passage through a solution of 1496.847 kg p-chlorophenol, 7O ° / oiges phenol from Koppers 2366.379 kg (70 ° / ₀ phenol, cresol 30%) and 662.695 kilograms Dacronfasern (linear polyethylene terephthalate) with provided a second coat of paint.

The properties of the two conductors obtained in this way are shown in the following table with one another compared.

ladder {AJBl test
(AÜäE test No. 57) I.
No. 57) Without a second coating 40% happened
10% happened
100% happened
22nd With a second coating Heat shock, 15%
Elongation, 200 ^° C. IX
2x
3X 564 hours
131 hours Ix 100% happened
2X 100% happened
3 χ 100% happened
30th Heat endurance test at
Heat endurance test at 1000 stands
168 hours 260 ⁰ C
28O ⁰ C

In the table, Ix means the simple diameter.

Example 13

The Polyesteriraid was produced from the following components in the same way as in Example 3:

Trimellitic Acid Arihydride 768g

Methylenedianiline 396 g

N-methylpyrrolidone SOCi g

Dimethyl terephthalate 1016 g

«5 ethylene glycol 416g

Ttis-CZ-hydroxyääiylJ-isocyanurate ... 480g

Lead (iII) Oxide Λ $ 0.90

Xylene 200ml

309507/1

ίο

To 1992 g of the polyesterimide solution thus obtained, 507 g of Solvesso, 100.94 g of a 40% solution of m-Zp-cresol-formaldehyde resin in cresolic acid, 207 g of a 40% solution of Mondur SH in a solvent of 65% cresolic acid and 35 % Solvesso 100 and 30 grams of tetraisopropyl titanate added, the mixture heated to 121 ⁰ C and then cooled. The wire enamel obtained in this way had a viscosity of HI and a solids content of 30%. It was applied to No. 18 copper wire in the same manner as in Example 12 at wire speeds of 9 and 10 m / min. For each wire speed, one test with no and one test with a second coating was carried out using the same polyethylene terephthalate solution as in Example 12. The coated wires showed the following resistance in the heat endurance test (AIEE test No. 57):

Wire!
swiftly
speed 220 ³ C 240 'C Oh, the second
Coating ... 9 m / min
10 m / min 2838
1056 Hours.
Hours. 461
264 Hours.
Hours. With the second
Coating ... 9 m / min
10 m / min 4260
5500 Hours.
Hours. 1435
1805 Hours.
Hours.

Example 14
Approach:

Trimellitic anhydride 288 g

Oxydianiline 150 g

N-methylpyrrolidone 600 g

Dimethyl terephthalate 1020 g

Ethylene glycol 282 g

Tris (2-hydroxyethyl) isocyanurate ... 540 g

Lead (II) oxide 0.9 g

™ xylene 300 g

The polyesterimide was produced in the same manner as in Example 3. 360 g of cresolic acid, 840 g of Solvesso 100, 124 g of a 40% solution of m- / p-cresol-formaldehyde resin in cresolic acid, 280 g of a 40% solution of Mondur SH in a solvent were added to 2144 g of the polyesterimide solution thus obtained 65% cresylic and 35% Solvesso 100 added and 40 g of tetraisopropyl titanate, the mixture to 121 ⁰ C. and then cooled. The wire enamel produced in this way had a viscosity of W and a solids content of 28.4%. It was drawn up in the same way as in Example 12 at wire speeds of 9 and 10 m / min

The copper wire No. 18 applied for each wire speed one test with no and one test with a second coating was used the same polyethylene terephthalate solution as in Example 12 carried out. The painted wires showed the following resistance in the heat endurance test (AIEE test No. 57):

wire
speed 220 C 240 C 260C Without a second coating
With a second coating 9 m / min
10 m / min
9 m / min
10 m / min 5380 h
3077 h
6012 h
5672 h 2141 h
1349 h
2201 h
1459 h 118 hours
98 hours
295 h
343 h

Example 15 approach:

N-methylpyrrolidone 28 800 g

Trimellitic anhydride 34,600 g

Methylenedianiline 17 800 g

Xylene 9000g

Ethylene glycol 10 800 g

Dimethyl terephthalate 45 800 g

Tris (2-hydroxyethyl) isocyanurate 43 200 g Lead (II) oxide 41 g

The polyesterimide was produced in the same manner as in Example 12 in a pilot plant having a capacity of about 300 liters. The mixture was diluted with 8,100 g of cresolic acid and 59,000 g of Solvesso 100 to form an ice-free product with a viscosity of Z 3+ and a solids content of 41.6%

60 g of cresolic acid, 500 g of Solvesso 100, 24 g of tetraisopropyl titanate, 75 g of a 40% solution of m- / p-cresol-formaldehyde resin in cresoic acid and 165 g of a 40% solution of Mondur SH in were added to 1440 g of the polyesterimide solution thus obtained optionally a solvent of 65% cresylic and 35% Solvesso 100, the mixture at 121 ⁰ C. and then cooled. The wire enamel produced in this way had a viscosity of DE and a solids content of 31%. It was applied to copper wire No. 18 in the same way as in Example 12 at wire speeds of 9 and 10 m / min: for each wire speed, an experiment without and an experiment with a second coating was carried out using the same polyethylene terepnealate solution carried out as in example 12. The painted ones

Wires showed the following resistance in the hip endurance test (AIEE test No. 57):

i. jV ' ¹ ' Wire-
speed ; 220 ° C 24O ⁰ C 260 ° C ΌΜ | wide cover .....
Far too shy 9 m / min i
lOm / inin ■
9 m / min \
10 m / min : 1254 h
2547 h
7482 h
5957 h 329 hours
545 h
1648 h
1838 h 131 h
127SId.
353 h
233 h

1 sheet of drawings

Claims (6)

ι 3 ² another di- or polycarboxylic acid or their claims: anhydride are replaced, and with cV one or more polyhydric alcohols, 1 Use of according to patent application _where bci the components under b) and c) in solcnen P16 45 435 6-44 produced polyesterimides are used as 5 proportions that aur Wire enamel for double-coated electrical conductors,! Equivalent of di- and polycarboxylic acids characterized in that the j _b £ i, ₆ equivalents of the polyhydric alcohols Polyesterimides, if necessary after the addition of, are omitted, Alkyl titanates, polyisocyanates or phenol form "" indicates that one is more- Aldehydbarzen _m common solvents as » ^ J ^^ g ^^ lyL ^ & y ^^ cyan ^ t first continuous lacquer layer on a bare 'JJSe ^ see nrit polyhydric alcohols, conductor and that the so ^worth ^ βΓ ^^. ^ 20 Equivalent percentage of Trisschichtete ladder with a DecUackschicht aas f ^^ SSSjÄeiÄ consist, used polyalkylene terephthalate is provided. ⁽ according to the procedure according to the main patent 2. Use of polyester amides according to Aais Those according to the ver * «J» ^ are characterized by claim 1, characterized in that em poly- ^^^ S ^ i ^^ ^from *** "*** ekerimide from oxydianiline or Methylendiamlm, ^ f ^^ TSJ ^ eai carboxylic acids by trimellitic anhydride, terephthalic acid and an alcohol »" ^ güS; wtart hardness and at least 30% tris- (2-hydrox _y äthyl -iso- increased J ^ J ^ _en particularly advantageous to cyanurate and otherwise from low molecular * o flexibility a * and where _lek ^ _{scher ladder) such as z} . _B. Alkanediols existing alcohol component ak ^. ^^^, SwwSrt For this use first continuous layer of varnish is applied. Copper ^ hte £ ™ _{n way by adding} 3. Use of polyester imides after arrival purpose, "in D ^eKa Metallsiccativen, entitlement 1 or 2, characterized in that a ^^^^^^^ omälaAsdia ^ alkyl titanates with modified polyesterimide as" 5 ^Phenolhar ^ _L; "° ^a '°°! Len first continuous layer of lacquer is applied. weUer ^^ _& ^ hSng _the polyesterimide a!> 4. Use of polyester imides after arrival in front of the _Lich aer _{a tsa} J _for heat-resistant claim 1. or 2, characterized in that E Ekue em ^ ^ra ° f ™ ^e _fZ 5 ^P _vcrwe "Deten polyester coating wamit organic polyisocyanates Ψ ** ™? * Sn Sv? * ^ En ^ phthalate paints. This polyester from polyesterimide as the first conformal lacquer layer 30 ™ ^ ™ ^% * £ l _amTl derivatives and glycols.! is applied. thanks to an excellent thermoforming 5. Use of polyester imides after arrival distinguished durcn ei ^ _n zageuung. Claim 4, characterized in that a poly- ^ e tand'gke.tbs ™ ^ resistance of polyesterimide, which by small amounts of an alkyl ^^ 'IJäUen not excessively large, since the titanates, organic polyisocyanates and a 35 athyJj ^ gÄ ^^ 'higher temperatures after phenol / formaldehyde resin is modified than Τ ^^^ ρ ^^ π, volatilized and thus the first continuous layer of paint is applied. ^ ^^^^ G ^ ttrf ^ duneWnitu ^ 6. The use of polyesterimides leads to ^a ^, ^! T "Yack films. However, since polyethylene 1 to 5 is characterized by the ^ an ^ ruchter JjJ ™ ™ _Eltiität J ^ _n ' _at 6. Use of Polyeste ^, ^! TYackfilme leads. But there is polyethylene Claim 1 to 5, characterized in that the ^ an ^ ruchter JjJ ™ ™ _elasticity J ^ _n ' _with polyesterimide as the first continuous lacquer layer 40 teiephthdateL _D ^Ü _e ^ _ur e _n have already been pre-set 000127 to 00254 nd preferred higher TOTperaturw ^ venuge ^ Polyesterimide is the first to have continuous l _De ^ _ur e _n in a strength of 0.00127 to 0.0254 and preferably higher TOTperaturw ^ venuge ^ ^ ^ wise, 0.00508 to 0.0102 cm. on the bare _bones . electrical conductor applied and covered with a ^ J ^^^^^ o ^^ zu ^^ rigitr top coat of polyethylene terephthalate with ^s P ' ^elswe . ^lse . . ^m . ° j ^h J n to be added a thickness of 0.00127 to 0.00762 and preferred 45 ^ £ ^^^ _now found that one w.rd w.rd. _d J ^ SSÄS £ head niil a reason paint layer from according to the in the main patent application described process produced polyester 50 imides and one above this base coat Top coat made of linear polyesters, preferably polyethylene terephthalate, with insulation The subject of patent application F> 16 451435 ^ -44 a - _r ^ _e S £ S _g is a process for the production of polyesterimides high Temp ^ tur un ^^,. ^ _Impairment through the implementation of 55 B ^ J ^ _{themical or} electrical Eigena) 5 to 50 percent by weight, based on the final _sc can produce. Since the thermal _{loadable product, a reaction product of 1.92 speed of the} polyesterimide, is in itself better than that of up to 2 08 mol of a cyclic anhydride of a known polyester, the fact that aromatic tri- or tetracarboxylic acid with _{such an} outer coating of linear Polyathyleno-pendant carboxyl groups and from 1 mol of terephthalate to significantly improve the Old one diamines or its components in the presence gsbeständigkeit _run at high temperature to achieve the given molar ratio, with can, particularly surprising. mimi