FI70917C - LACK BASERAT PAO POLYESTER- ELLER POLYESTERIMIDHARTSER LOESLIGA I ICKE-FOERORENANDE SPECIELLT VATTENHALTIGA LOESNINGSMEDEL - Google Patents

Description

[· - + »- · I ADVERTISEMENT 7nQ17 igä® lBJ <11 * UTLÄGGNINGSSKRIFT 'V' I / C (45) Pzte-itti.; '. YU.4.:;ctty

P “tent no-Idolat 27 10 100C

(51) Kv.ik.vint.ci. · C 09 D 3/64 // C 09 D 5/25, C 08 L 79/08 FINLAND —FINLAND (21) Patent application Patentansökning 701625 (22) Application date Ansökningsdag 23-05.78 (23) Starting date — Giltighetstlag 23-05-78 (41) Made public— Graters offentlig 01 -12-78

National Board of Patents and Registration Date of publication and hearing. - | g Qη gg

Patent- och registerstyrelsen '} Ansnkan utlagrf <> ch ud.skriiten publicerad' '(86) Kv. application Int. trap (32) (33) (31) Privilege claimed — Begärd priority 31 -05-77

France-France (FR) 7716565 (71) AI sthom-At1 antique, 38, Avenue Kleber, 75784 Paris Cedex 16,

France-Frankr i ke (FR) (72) Richard Wagner, Meyzieu, France-Frankrike (FR) (74) Oy Jalo Ant-Wuorinen Ab (54) For non-polluting polyester or polyester-imide solids, especially those soluble in aqueous solvents The present invention relates to varnishes containing a polyester resin obtained by polyesterifying at least one polycarboxylic acid with at least one pentacid acid having at least one pentacid. capable of forming such an acid, with at least one polyalcohol.

Varnishes of this type are known with which electrical wires can be easily coated. However, they are dissolved in organic solvents based on cresols and phenols, possibly diluted with a hydrocarbon solvent. However, cresols and phenols are the most polluting solvents and belong to Class I of the Federal Pollution Regulations of the Federal Republic of Germany, which stipulate that their residual concentration must not exceed 20 mg / m3 in the exhaust gases from varnishing furnaces. In addition, cresols are expensive solvents and require handling such as gloves, goggles, etc. due to their irritant properties.

Thus, it would be advantageous if similar varnishes could be prepared in solvents that have little or no contamination, such as water or aqueous solvents.

Water-soluble polyester or polyesterimide resins have already been prepared by polycondensing polycarboxylic acids with polyalcohols such as diols or triols, leaving excess carboxyl groups, which are then salted with ammonia or amine at the end of the reaction in the reaction mixture, or adding such excess to the reaction mixture. or partially soluble therein. However, these resins have high acid numbers in the order of about 40-100. Carboxyl residues adversely affect adhesion to a metallic substrate when coating wires or metal sheets. In addition, the amount of amine required for salt formation of carboxyl groups is relatively large; commonly used amines, especially for the preparation of polyester imide resins, are expensive products.

The invention makes it possible to eliminate the above-mentioned disadvantages and to prepare varnishes based on polyester or polyesterimide resins which are soluble in low-polluting or non-polluting solvents and preferably in partially aqueous solvents, which, however, have a low acid number and require only a small amount of amine for salt formation, and which can provide very highly adhesive coatings on metal substrates, and which in addition have physical and electrical properties at least as good as the corresponding properties of water-insoluble polyester or polyesterimide resins.

The present invention relates to a lacquer comprising polyester or polyesterimide resins obtained by polyesterifying at least one polycarboxylic acid containing at least one pentagonal lactam ring or a compound forming such an acid with at least one polyalcohol, the polycarboxylic acid being prepared by condensing any of its acids an imported derivative or ester, with a primary amine which also contains another primary amino group or carboxyl group at the chain end, and which is characterized in that the lacquer contains 3,70917 low-polluting or non-polluting, water-miscible organic solvents in a mixture with water.

It has been found that, in contrast to polyester and polyester imide resins in which the polycarboxylic acid is at least partially terephthalic or isophthalic acid, polyester and polyester imide resins in which the polycarboxylic acid is more soluble in water-soluble at least one pentagonal lactam ring are more soluble in water.

The lacquers according to the invention have at least one or more of the following properties: - the solvent is a mixture of water and another organic solvent consisting at least in part of dimethylaminoethanol, - the solvent also contains dimethylformamide, - the solvent also contains methyl glycol, - the solvent also contains N-methylpyrrolidone, is an anhydrous solvent from the group consisting of at least one alkyl ester and one glycol ester or ether, - a polycarboxylic acid containing at least one pentagonal lactam ring is lactamic acid obtained by condensing about 2 moles of itaconic acid or one of its substituted derivatives or derivatives thereof; an ester with a mole of a diamine containing a primary amino group at each end of the chain, the ratio of lactic acid in the polyesterification reagent mixture being 30-90% by weight and preferably about 70% by weight, - the polycarboxylic acid containing at least one pentagonal lactam ring is a diacid substantially equimolar amounts of itaconic acid or one of its substituted derivatives or its ester with an amino acid, preferably glycine, - it also contains a polyester imide resin obtained by polyesterifying diimide diacid obtained by condensing at least about two moles of aromatic polyacid, three carboxyl groups, two of which are in the ortho position, or a compound capable of forming such an acid, with one mole of a diamine containing a primary amino group at each end of the chain 4 7091 7, - the proportion of lactamic acid in the polyesterification reaction mixture is 10 to 40% by weight, and is preferably about 30% by weight and the proportion of diimide diacid is 20-80% by weight and preferably about 40% by weight, - the polyesterification is carried out with a mixture of at least one diol and at least one triol, the amount of diol in the reaction mixture being 5-20% by weight -% and is preferably about 10% by weight and wherein the amount of triol is 10-40% by weight and is preferably about 20% by weight. the polyalcohol consists at least in part of trihydroxyethyl isocyanurate.

The following are examples of methods for preparing polyester or polyester-imide resins and varnishes according to the invention, as well as their use for electrical wires and the physical, mechanical, chemical, thermal and electrical properties of the varnishes on the resulting wires.

Example 1; 220.6 parts by weight of N-methylpyrrolidone (hereinafter abbreviated as NMP) are placed in a flask equipped with a stirrer, a Vigreux column and a thermometer under a nitrogen atmosphere. The following substances are then added with stirring: 138.8 parts by weight of methylene dianiline (hereinafter abbreviated as MDA), 48.85 parts by weight of monoethylene glycol and 205.6 parts by weight of trihydroxyethyl isocyanurate (hereinafter abbreviated as THEIC). ). All parts mentioned below also mean parts by weight. The mixture is heated at 100 ° C until dissolved. Then 182.15 parts of itaconic acid, 138 parts of MDA, 269 parts of trimellitic anhydride (hereinafter abbreviated as TMA) and 21 parts of tetrabutyl titanate (which acts as a crosslinking agent and subsequently abbreviated as TBT) are added in 20 parts of xylene. Heating is continued, raising the temperature by 20 ° C per hour to 220 ° C. The distillation of water begins at about 130 ° C. A total of 100.8 parts of water is removed.

Itaconic acid condenses in methylene-dianiline according to the following reaction scheme: 5 7091 7 CHg ------- COgH yy «^ 2 +1 Η2Ν-γ '\ -CH2- ^' VnH2 c - co2h v = s / W / ch2 CH2 - C/O. / -, -v / CO - CH? -> I X> <X 1

CH - CH 2 '-' '-' CH 0 - CH - CO 2 H

/ H02C (lactamic acid) + 2H2O The resin thus obtained can be cast to form a hard and brittle solid at a concentration of 80% by weight in NMP. The resin has an acid number of 12 and an Ubbelohde Drip Point of 120 ° C. This resin can be formed into a solution as follows: 250 parts of the above resin, 45 parts of dimethylformamide (DMF), 30 parts of 2-dimethylaminoethanol (DMAE), 45 parts of methyl glycol (MG), 130 parts of water; 2 parts of ammonium lactate-titanate crosslinker (sold by DuPont Nemours, trade name TyzorLa) and 10 parts of a surfactant known under the trade name Noramox CV15 (intended to give suitable surface properties to the varnish) to give 512 parts of a varnish with 40% active ingredient .

It has a viscosity of 550 centipoise at 20 ° C.

Corresponding resins can be obtained by using a diamine condensable with itaconic acid other than methylenedianiline and preferably an aromatic diamine such as diaminodiphenyl ketone, diaminodiphenylsulfone, glycol or propylene, diaminodiphenyl ether, benzidine and the like. taerythritol, etc., other polycarboxylic acids such as pyromel lithium anhydride.

6 7091 7

Example 2: 20 parts of NMP and 48.85 parts of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vig-reux column and a thermometer. The mixture is heated to 100 [deg.] C. while stirring, the following substances are added: 138.8 parts of MDA, 182.5 parts of itaconic acid, 205.6 parts of THEIC and 17.65 parts of TBT in 20 parts of xylene. The temperature is gradually raised from 20 ° C per hour to 210 ° C. The water begins to distill off at about 130 ° C. The amount of water removed is 50.4 parts. The mixture is cooled to 180 ° C and 86.9 parts of monoethylene glycol are added. The temperature is lowered to 115 ° C and 289 parts of TMA and 20 parts of xylene are added. The mixture is reheated at a rate of 20 ° C / hour to 185 ° C. The amount of water removed is about 17 parts. The mixture is cooled to 130 ° C and 138.2 parts of MDA and 20 parts of xylene are added, after which the mixture is reheated, the temperature rising to 20-220 ° C per hour at 20 ° C. The amount of water removed is 33.6 parts.

The resin thus obtained can be cast into a hard and brittle solid at a concentration of 89%. The resin has an acid number of 10 and an Ubbelohde Drip Point of 145 ° C.

A solution of the resin can be prepared as follows: 134.5 parts of the resin described above, 25.1 parts of DMF, 12 parts of DMAE and 68.4 parts of water to give 240 parts of a lacquer containing 50% of active ingredient. It has a viscosity of 800 centipoise at 20 ° C.

Example 3: 116.3 parts of NMP are placed under a nitrogen atmosphere in a flask equipped with a stirrer, a Vigreux column and a thermometer. While stirring, 43.95 parts of monoethylene glycol are then added. The mixture is heated to 100 ° C and 138.80 parts of MDA, 182.15 parts of itaconic acid, 205.60 parts of THEIC and 8 parts of TBT in 20 parts of xylene are added. The temperature is raised to 195 ° C at a rate of 20 ° C per hour. Water begins to distill off at about 130 7 7091 at 7 ° C. The total amount of water removed is 50.4 parts. The mixture is cooled to 180 ° C and 4.90 parts of monoethylene glycol and 104.3 parts of NMP are added. After the temperature has dropped to 110 ° C, 138.80 parts of MDA and 269 parts of TMA are added to the mixture. The mixture is reheated at 20 ° C per hour to 220 ° C. Distillation begins at about 140 ° C. The total amount of water removed is 50.4 parts.

The resin thus obtained can be cast into a hard and brittle solid at a concentration of 80%. The resin has an acid number of 12 and an Ubbelohde Drip Point of 117 ° C.

A solution of this resin can be prepared as follows: 112.5 parts of the resin described above, 31.5 parts of DMAE and 156 parts of water to give 300 parts of a lacquer containing 30% of active ingredient. It has a viscosity of 150 centipoise at 20 ° C.

Example 4; 220.6 parts of NMP and 48.85 parts of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The mixture is heated to 100 ° C with stirring and 138.8 parts of MDA, 182.15 parts of itaconic acid, 205.60 parts of THEIC, 3 parts of TBT in 20 parts of xylene, 3 parts of cerium octoate, 0.15 parts are added zinc acetate, 138.8 parts MDA and 269 parts TMA. The temperature is raised to 220 ° C at a rate of 20 ° C per hour. Distillation begins at about 130 ° C. The total amount of water removed is 100.8 parts.

The resin thus obtained can be cast into a hard and brittle solid at a concentration of 80%. The resin has an acid number of 16 and an Ubbelohde Drip Point of 111 ° C.

A solution of this resin can be prepared as follows: A. 180 parts of the resin described above, 32.25 parts of DMP, 54 parts of DMAE, 21.60 parts of monoethylene glycol, 72.15 parts of water, 8 7091 7 7.20 parts of Disperbyk surfactant BYK Mallinckrodt to give 367.2 parts of a lacquer containing 40% of active ingredient. It has a viscosity of 800 centipoise at 20 ° C.

B. 180 parts of the resin of Example 4, 32.40 parts of DMF, 21.60 parts of DMAE, 32.40 parts of methyl glycol, 93.60 parts of water, 1.44 parts of TyzorLA crosslinker and 7.20 parts of Noramox CV15 surfactant, giving 386.84 parts of lacquer, is 40% of active ingredient. It has a viscosity of 550 centipoise at 20 ° C.

Example 5; 220.6 parts of NMP and 48.85 parts (0.787 moles) of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The mixture is heated to 100 ° C with stirring and 138.8 parts (0.7 moles) of MDA, 182.15 parts (1.4 moles) of itaconic acid, 205.60 parts (0.787 moles) of THEIC are added, 3 parts of TBT in 20 parts of xylene, 3 parts of cerium octoate, 0.15 parts of zinc acetate, 138.8 parts (0.7 moles) of MDA and 269 parts (1.4 moles) of TMA. The temperature is raised to 220 ° C at a rate of 20 ° C / hour. Distillation begins at about 130 ° C. A total of 100.8 parts of water is removed. The reaction ends when the Ubbelohde Drip Point is 120 ° C. The mixture is cooled and 195.85 parts of DMF are added at 170 ° C, 195.85 parts of methyl glycol at 150 ° C, 130.55 parts of DMAE at 130 ° C, 565.75 parts of water at 115 ° C and 8, 7 parts ammonium lactate titanate and 43.5 parts Noramox CV15 at 60 ° C.

A solution is obtained containing 40% of active ingredient with a viscosity of 530 centipoise at 20 ° C.

Example 6: 212.75 parts of NMP and 58.60 parts (0.944 moles) of monoethylene niglycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The mixture is stirred at 100 DEG C. with stirring and 138.8 parts (0.7 mol) of MDA, 182.15 parts (1.4 mol) of itaconic acid, 164.50 parts (0.63 mol) of MDA are added. ) THEIC, 3 parts TBT in 20 parts xylene, 3 parts cerium octoate, 0.15 parts zinc acetate, 138.8 parts (0.7 moles) MDA and 269 parts (1.4 moles) TMA. The temperature is raised to 220 ° C at a rate of 20 ° C per hour. Distillation begins at about 130 ° C. A total of 100.8 parts of water is removed.

The resulting resin can be cast into a hard and brittle solid at a concentration of 80%. The resin has an acid number of 15 and an Ubbelohde Drip Point of 110 ° C.

The same resin can also be prepared as a solution as in Example 1 to prepare a varnish in solution containing 40% of active ingredient and having a viscosity of 530 centipoise at 20 ° C. Example 7: 225.7 parts of NMP and 52.75 parts (0.85 moles) of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The mixture is heated with stirring and 138.8 parts (0.7 moles) of MDA, 182.15 parts (1.4 moles) of itaconic acid, 222.05 parts (0.85 moles) of THEIC, 3 parts of TBT are added. 20 parts of xylene, 3 parts of cerium octoate, 0.15 parts of zinc acetate, 138.8 parts (0.7 moles) of MDA and 269 parts (1.4 moles) of TMA. The temperature is raised to 220 ° C at a rate of 20 ° C per hour. Distillation begins at about 130 ° C. The total amount of water removed is 100.8 parts.

The resulting resin can be cast into a hard and brittle solid at a concentration of 80%. The resin has an acid number of 12 and an Ubbelohde Drip Point of 118 ° C.

This same resin can also be prepared as in Example 1 into a solution containing 40% of active ingredient having a viscosity of 560 centipoise at 20 ° C.

Example 8; 80 parts of NMP and 48.8 parts (0.787 moles) of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The mixture is heated to 90 ° C with stirring and then 91 parts of 10 7091 7 (0.7 moles) of itaconic acid and 52.5 parts (0.7 moles) of glycine are added. Heating is then continued to 110 ° C and 205.60 parts (0.787 moles) of THEIC are added. The mixture is heated to about 140 ° C until 15 parts of water have been removed. 3 parts of a complex of lead phenoxide and hexamethylenediamine are added as a catalyst and then in small portions a mixture of 138.8 parts (0.7 mol) of MDA and 269 parts (1.4 mol) of TMA is added. These substances are added within about 1.5 hours. Towards the end of the MDA and TMA addition period, the mixture is heated to 160 ° C to promote stirring. The mixture is then gradually heated at a rate of 20 ° C per hour to 220 ° C. The amount of water removed is 88.2 parts. The reaction is stopped when the Ubbelohde Drip Point of the resin is 139 ° C; the acid number is then 29. The resin thus prepared is a hard and brittle solid at a concentration of 90% in NMP.

Itaconic acid and glycine are then condensed as follows:

COOH COOH

1 I

CH2 - C «\ CH2 _CH

I "\ Il o = c CH2 -> CO ch2 J N ^ [öh V h '] nhch2 ch2-cooh

The resin can be diluted as follows: 42.1 parts of the resin described above, 20 parts of NMP, 10 parts of DMF, 6 parts of DMAE and 45 parts of water to give 135.1 parts of a resin having 30% of active ingredient.

Corresponding resins can be prepared by using another amino acid instead of the amino acid condensable with glycine; the second amino acid is preferably aliphatic, such as aminopropionic acid, aminocaproic acid, etc.

11 7091 7

Example 9: 241.13 parts of NMP, 78.21 parts (1.26 moles) of monoethylene glycol and 92.09 parts (1 mole) of glycerol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The following substances are then added with stirring and at 60 [deg.] C.: 407.42 parts (2.055 mol) of MDA, 534.71 parts (4.11 mol) of itaconic acid and 1.1 parts of TBT in 20 parts of xylene. The mixture is heated to 220 ° C at a rate of 20 ° C per hour. Distillation begins at about 120 ° C. The total amount of water removed is 147.96 parts.

The concentration of the resin thus obtained is 80% in NMPr. Its Ubbe Point Drip Point is 78 ° C.

A solution of this resin can be prepared as described in Example 1.

Example 10: 283.4 parts of NMP and 78.21 parts (1.26 moles) of monoethylene glycol are added under a nitrogen atmosphere to a flask equipped with a stirrer, a Vigreux column and a thermometer. The following substances are then added with stirring and at 60 ° C: 284.24 parts (1 mol) of THEIC, 407.42 parts (2.055 mol) of MDA, 534.71 parts (4.11 mol) of itaconic acid and 1.3 parts TBT in 20 parts xylene. The mixture is heated to 220 ° C at a rate of 20 ° C per hour. Distillation begins at about 120 ° C. The total amount of water removed is 147.96 parts.

The resin thus obtained has a concentration of 80% at NMP and an Ubbelohde Drip Point of 91 ° C.

A solution of this resin can be prepared as described in Example 1.

Example 11: 27.9 parts (0.45 moles) of monoethylene glycol and 20 parts of xylene are placed in a flask equipped with a stirrer, a Vigreux column and a thermometer under a nitrogen atmosphere. The following substances are then added with stirring and at a temperature of 80 [deg.] C.: 183 parts (0.7 mol) of THEIC, 75 parts (1 mol) of glycine, 130 parts (1 mol) of itaconic acid and 1 part of catalyst (lead). 7091 7 phenoxide and hexamethylenediamine complex with a concentration of 25% in cresol), the mixture is heated to 200 ° C at a rate of 20 ° C per hour. Distillation begins at about 130 ° C. The total amount of water removed is 54 parts.

The Ubbelohde drop point of the resin thus obtained is 129 ° C.

A solution of this resin can be prepared as follows: 40 parts of the resin described above, 9 parts of DMF, 9 parts of methyl glycol, 6 parts of DMAE, 36 parts of water, 1 part of TyzolLA and 5 parts of Noramox CV15 to give 106 parts of lacquer, containing 40% of active ingredient.

The 0.8 mm diameter copper wire is varnished with the solutions described in Examples 1-11 in a vertical furnace capable of varnishing 3.6 m long metal wires and having 4 heating zones at 210, 330, 460 and 350 ° C for six consecutive treatments.

Varnished wires are examined as follows:

Koe No. 1: Measurement of excessive thickness (IEC standard, Article 4).

This experiment is performed on five samples using a precision micrometer. The diameter of the insulated wire is measured first, then the diameter of the wire after the varnish has been removed. The average of the five results is calculated.

Koe No. 2: Deflection of varnished wire (IEC standard, act 8-1).

The wire is wound on spindles whose diameter is an integer times the normal diameter of the wire before and after it is stretched by 10, 20 and 30%. In the latter case, winding to one diameter means excellent flexibility.

Koe No. 3: Adhesion (IEC standard, act 8-2).

In this experiment, the lacquered wire is suddenly stretched until it breaks. No cracks should occur.

13 7091 7

Experiment No ♦ 4: Tensile adhesion (VSM Standard 23713, November 1956).

This test is performed according to VSM Standard 23713, November 1956. It involves twisting a 1 meter long lacquered wire after being scratched along the base line. Calculate the torsional revolutions required to remove the varnish.

Koe No. 5; Abrasion resistance.

There are two measurement methods whose results are not comparable.

1) Back-and-forth method (IEC standard 251-1, Article 11).

Abrasion resistance is defined as the number of back-and-forth rotations performed by a small polished 0.4 mm diameter cylinder pressed against a lacquered wire under load, which is a function of the wire diameter, until the lacquer layer wears out.

2) One-way method (NEMA NW 1000 standard, part 3, paragraphs 3-2 and 22-4-2).

Abrasion resistance is described by the amount of grams of lead required to wear the varnish when scraping with a steel needle 0.23 mm in diameter, which is pressed against the wire with increasing force during this movement. Take the average of the six experiments carried out on each of the two samples scratched along the three mother lines at 120 ° C.

Koe No. 6: Resistance to solvents (IEC standard 251-1, Article 12).

The pen hardness of the varnish is measured after the 30 mm wire is immersed in a mixture of 30% xylene, 10% butanol and 60% naphtha.

Koe No. 7; Thermoplasticity test (IEC standard 251-1, Article 10).

The two lines are placed crosswise and placed in a heating device heated to a certain temperature and adjusted to an accuracy of 2 ° C.

One minute after heating, the cross section of the wires is loaded.

14 7091 7

The softening point of the varnish is greater than or equal to the temperature of the heater unless the insulation is damaged after two minutes. Short circuits are detected at a voltage of 100 V, which is permanently connected between both wires.

The heater temperature is varied until the line lasts less than 2 minutes under load.

Koe No. 8; The thermal shock resistance.

The windings made of the lacquered wire on the spindles, the diameter of which increases from one to six times the nominal diameter of the wire, are exposed to the selected temperature for half an hour or an hour, depending on the type of lacquer. In some cases, the cord has been stretched in advance. Determine the smallest diameter at which no cracks are observed when examined with a magnifying glass at eight times magnification.

Koe No. 9; Dielectric strength (IEC standard 251-1, Article 13).

The tests are performed on threads manufactured in accordance with the IEC standard. The reported values are obtained by averaging the average of five experiments. For diameters of 0.135 and 0.800 mm, the threads are 125 mm long and comprise 23 turns at 1.70 N and 8 turns at 13, 50 N, respectively.

Koe No. 10: Tangent of loss angle (IEC Standard 251-1, Article 19).

Measure the tangent S using the method described in the IEC standard at a frequency of 1 MHz with a U-shaped lacquered wire in a mercury-silver tank. Some measurements have been made at 50 Hz.

The following table shows the varnishing results.

15 7091 7

CO (C

; m (O q5. _

e <D i? rl O: (0 4-1 O

• n <—I Ui (0 00 p Ö CP

m, -! -h -H m - cd o o S in o ro DC

W rl W Λ! > O VO rl (N .C lOrl'S * CO id E '<$ J «?> -I o: (0 -P o

ω o * oo s s> iS o cn DG

M rl (0 λ;> O VO rl (N £ C 'ί' "Ί · rl ^

: id id (D S

e a) -n h o = (0 4-1 o

-3 i — I Ui (0 oo p O O I

m -h -hm - oo s ό> ico o (N rc W o inii> o vo hn sz m ri ro in m 6 S ^ rl o: jö + jo -3 ri ui m oo> O om -h-hio - of OPS S in o in ΓΕ

Woo m .y> o vo h in xg n · m. — I n * in S id 6 'S .3 rl ^ o = (0 4-1 ° • 3 ri Ui id in co> o o __

in -h -h top - oo o d S n o m DC

W r- ~ ω ϋ> C o vo h in xc n1 mri ^ r tn i§ id

g 'S i H ϋ o = £ 0 4-) O

• h ri ui id in oo> o o

(0 -H -H 10 3 - 00 O TS> i (N O CN DC

W VO 01 j) 1> c O VO rl CV] XG Ν 'N rl N

ε 1 5 I I o = td 4_> o 3 ri u ie tn oo> o o

m -h -h id 9 - σ o o S n o m DC

W in in M t> U o vo rt cn xg n in ri n tn m id

e ’S JS rl M O = (0 UJ O

• 3 rl u m en oo> o o

m -h -h (d 9 - σ o is »S cm o ro DG

W M J (> S o VO rl 04 XG N U "l rl N

. S S k

E-ciio = id -P 2 T

ή v-i in oo> in o i

in Id 9 - 00 O O> i O O CN DC

W CO i2 Ui O VO CN ro XG N vf H M

. S S cc E £ M o: <d -U o • 3 ui in oo pool

in id 9 - oo oo £> i o o cn DC

w CM, £ tl o vo CV) m _C N N rl CO

•: id S

E <D M o: jd +) o • h ri tn oo> o ir>

in -ri 9 - σ oo. S ro tn cn DC

W ri 4-> in Ui o vo H n xc n n rl n Φ Ό 4-) g m 9 rl Γ & tn 30

• rl O 3 «N

S in -h O § I r m H 3 Φ id Z -P: 0 is g s -1 «» jssäc

id „.2 E O US: rtC <U

-u> c E ^ -ous c tmqj-ric <uo -h Euu: id *> # «(Did> Q (i) -ri ö5jZ ui mi oi ii v incT-i- ^ w-Hidin ri H = fd idininiuinoog-ri nj -u> 3

rl 3> -Γ1 -rl -H K 3 rl CN 3 .V C N v -¾ S P

Λ -h ri a) -h 3 i> 3 a3 in id 3> id c c c in e c>: 13 3: idC09-P90

ii O O O -h C 0 Ϊ3 3 6 -P - -h Z id I to .V

• p ^ 'Ό -σ id S m id a> i jj-ue m --i S

m £ j £ £ i J3 S ii -hq MxciSgjgcuinc> o O o 1 (3 -h 3 id δ «Ριωοδ'ΟΛίΡι W co» gb £ iJ 6 S EH> eh - .3 .y dc φ>. uc 7091 7 1 6 g ·> '5 «k, ρ ooo CQfH SS m ia (N in W Ή mm sz mm, _i ^ •> B: (po

• H> O O ID

(QO SS ^ <amm W> H mm xz mm r-ι, -ng> '3 r ° o in Ά ^ SS ^ o <s * mm W o mm _C mm, -h, -h J _> §: ! 5 o • h> mmo tQ _ KK> i iDxSi m r- ~ - W oo mm xz mm, —i, —ι g *> '3 ^ ρ oo in tn KM> im si ή * r- W r- m sz mm rH ri B: 3 p

Ή> O O O

W SS p »m <a m <x>

W KO m t * xz mm rH rH

• ^> B M o

Ή p O o O

SS m o m m

Wm m m * jc mm m rH

g = (0 o • 4 p o o o ω SS> i m o m r—

W ^ m ή · mm, -h rH

g *> • H p O O 00 UJ KK> i <—I si m id

W m mm X mm, h rH

•. . > E: rt o • H p O in Γ 'tn KK> i m o m i £> W m mm xz mm, -h, η E -ti>

H p O O O

tn KW tnrHisimr ^

W> -h m-crtx; mm rH rH

-P -H

j) O H

Ό m Q C -H

3 «3 O -H <1) -P

3 tn tn r-j i id c -p tngtn <υ tn 2 -h c o

§ · Η 3. · Ö rH (C Q (0 H 0) O

p u to c m u h jCtn-U-P — CT '11; ie I if ft s I a1i io F vo _ S ro 3 § OE ° 3Q) om >>, <o -h A -P i /): So: ^ otn-Hoccn -PA q tn -pp, m -h »H γΗο-ηΌγη® ·· 0) S t» u S r, * · * η m <egn tn vfl) .H0tnTmc - jj - d *.-T tH κ o

-h id A —t 3 3-Hm-HmjJoo (tf -h cr, - 3 rH

Ή rHO-H4-> P E Q) -HP ΛίΟ ^ s s s ΐ s s | s s s ΐ I s s s s s • H P CJ -P rH OJ & -H 3a 3 Vi

Sq) C3Wwi4HPEQ) tnm4j2m-m-H> m 0) O · Η i3 m (0 -H K: S O -h O: t0 O 3: <0 O

AA El I> Ό- | ϋ) Α4) λ | Η.ιϊΐΑΗΚ-Α 17 7 0 91 7

Lacquer-coated wires have excellent slipperiness.

Due to the high solubility of these resins, they can be dissolved without the use of amines, non-polluting, ester-type solvents and / or glycol ethers.

This type of composition has the advantage that it also does not contaminate the atmosphere when the solvents are incinerated.

As solvents, there may also be mentioned: methyl benzoate, methyl adipate, 2-nitropropane, propylene carbonate and ethylene carbonate, DMF, NMP, etc.

A non-limiting example of dilution is: 250 parts of the resin described in Example 1 and 113 parts of methyl benzoate and 37 parts of xylene to give 400 parts of a lacquer containing 50% of active ingredient and having a Baume viscosity of 1100 centipoise at 20 ° C.

The varnish has two advantages: - very low pollutant (solvents classified as non-polluting), - highly concentrated varnish which can be used as such (with an economic advantage).

Although the preparation instructions described above are preferred, it will be appreciated that various modifications may be made without departing from the scope of the invention, and it is possible to replace certain procedures, reagents or solvents or additives with other substances giving the same technical result. In particular, itaconic acid can be replaced by an ester thereof.

The resins described above are particularly suitable for the production of varnishes for insulating electrical conductors, but they are also suitable for the production of insulating films, mold sheets and molding compounds, in particular for electrotechnical use.

Claims (3)

18 Claims: 7 0 91 7 A varnish comprising a polyester or polyesterimide resin obtained by polyesterifying at least one polycarboxylic acid containing at least one pentagonal lactam ring or a compound forming such an acid with at least one polyalcohol, the polycarboxylic acid being prepared by condensing an itaconic acid or a substituted derivative or ester thereof, with a primary amine which also contains a second primary amino group or carboxyl group at the chain end, characterized in that the lacquer contains, as solvent, a low-polluting or non-polluting, water-miscible organic solvent in admixture with water. Varnish according to Claim 1, characterized in that the organic solvent consists at least in part of dimethylaminoethanol. Varnish according to Claim 2, characterized in that the solvent also contains dimethylformamide and / or methylglycol and / or N-methylpyrrolidone.