DE1669412A1 - Process for the production of rubber-elastic threads - Google Patents

Description

COLOR FACTORY BAYERAG LEVERKUSEN-ierenmk June 24th, 1966

Reu / Hf

Process for the production of gnwimielastic threads

The present invention "relates to a method of manufacture Elastic threads and fibers made from easily soluble and against gel formation in polyacrylonitrile solvents "be permanent segmented polyurethane-polyurea elastomer en.

A number of methods are known to produce elastic threads and to manufacture polyurethane-based fibers for a variety of textile purposes, both as such as can also be used in wound or braided condition. The main areas of application are corsetry, sportswear fabric e, support stockings and the production of elastic bands on lingerie and stockings. The basis for manufacturing of the elastic threads and fibers are mostly high molecular weight, segmented polymers with urethane and urea groups, those containing hydroxyl groups according to the isocyanate polyaddition process Polyesters or polyethers, diisocyanates and diamines can be produced. After a Process known as "chemical spinning", the pre-adducts are extruded through spinnerets into a coagulation bath, that as a reaction component for obtaining the threads

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with high molecular weight, segmented polyurethane-polyurea structure Contains ethylenediamine and possibly also small amounts of polyamines. High reactivity the pre-adducts with free isocyanate groups and the resulting The limited shelf life of the pre-adducts made it appear desirable to have soluble, high molecular weight segmented polyurethane-polyurea adducts in solution ™ to produce means and to process these solutions into threads and fibers by the wet or dry spinning process.

It is also known, hydroxyl-containing polyesters and diisocyanates at elevated temperature to form NCO-containing preadducts implement and this then in polyacrylic · nitrile solvents at temperatures below 20 ⁰ C with ethylene diamine to implement high molecular weight polyurethane-polyurea adducts. The threads obtainable from these solutions by k spinning show good physical and elastic properties. The relatively short time in which these solutions undergo gel formation, so that spinning becomes impossible, is a particular obstacle to the production of threads on an industrial scale. This is particularly disadvantageous in the case of solutions with viscosities of 600-1000 poise at 20 ^° C. For the production of threads by the dry spinning process, however, solutions with the aforementioned viscosities are required, while

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On the other hand, storage times of over a week for the spinning solutions must be expected in normal operations.

A process has now been found for producing gummielasti shear threads if essentially linear polyesters with terminal hydroxyl groups with an average molecular weight of 1600 to 2600, optionally in the presence of small amounts of low molecular weight diols with one or more tertiary nitrogen atoms, are mixed with diphenylmethane 4,4'- diisocyanate, the ratio of OH to HCO groups used being only 1 : 1.5 to 1.95, converts to an NCO-containing pre-adduct and the reaction product in a polyacrylonitrile solvent with a mixture of ethylene diamine and a diamine of the formula

wherein R ₁ and R _{2 are} lower alkyl radicals or R ₁ and R ₂ together with the carbon atom mean a cycloaliphatic Redt, in a molar ratio of 50:50 to 85:15 to the high molecular weight polyurethane-polyurea polymer and then extending the highly viscous spinning solution the hate or dry spinning process; Examples of such Di123 - 3 -

amines are 2,2-bis (4'-aminophenyl) -propane and 1,1-bis- (4 ^f aminophenyl) cyclohexane.

To carry out the process, in a manner known per se, essentially linear polyesters containing hydroxyl groups with an average molecular weight of 1600 to 2600, preferably 1700 to 2100, are optionally used in the melt or in inert solvents such as methylene chloride, tetrahydrofuran, dioxane, benzene, chlorobenzene in a mixture with low molecular weight diols with one or more tertiary nitrogen atoms, ^{reacted with diphenylmethane-4,4'-diisocyanate below 130 °} C. The ratio of OH to NCO groups in the components used should only be 1: 1.5 to 1: 1.95, so that pre-adducts with free NCO groups are formed.

The linear polyesters with terminal hydroxyl groups and used as starting material can be prepared in a known manner by condensation of dicarboxylic acids and diols at elevated temperature. The acid numbers should generally be below 8, preferably from 0 to 3. The melting point of the polyester should be suitably less than 60 ⁰ C, otherwise the elastic properties of the end products decline, particularly at low temperatures and also to gel the polymer in solution unfa-

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stig is influenced. As dicarboxylic acids for these polyesters are, for. B. succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, thiodibutyric acid and sulfonyldibutyric acid. As diols, for. B. ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, hexahydro-p-xyIyIenglykol, 2,2-dimethyl-propanediol-1,3,2, 2-Diethyl-propanediol-1, 3, and their alkoxylation products are used. Also polyesters made from lactones, e.g. B. B- caprolactone, are advantageous starting materials to be used. Since the polyesters produced in this way are usually very reactive components, it is quite common to treat the polyesters with diphenylmethane-4,4 -'-diisocyanate before further reaction to deactivate by adding small amounts of dioxane / SC> 2 adduct, benzoyl chloride or traces of νοττ hydrogen chloride.

In the case of the low molecular weight diols, optionally used in admixture with the polyester, with one or more tertiary nitrogen atoms are bisalkoxylation products primary and disecondary amines with ethylene oxide, propylene oxide and butylene oxide with a molecular weight below 500. Examples include N-methyl-diethanolamine, N-butyl-diethanolamine, N-cyclohexyl-diethanolamine, N, N'-di- (ß-hydroxyethyl) -N, N'-diethyl-hexahydro-p-phenylene-

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diamine, N.N'-Di-Cß-hydroxyäthylJ-NjN'-dimethyl-ethylenediamine and bis-ß-hydroxyethyl-piperazih. To be favoured but N-methyl-diisopropanolamine and N, üP-di- (ß-thiydiOxypropyl) -N, N'-dimethyl-ethylenediamine used. But also low molecular weight basic polyethers with tertiary nitrogen atoms, accessible by condensation of the aforementioned compounds in the presence of phosphorous acid can be mixed with the polyester. The amount of diols with one or more tertiary nitrogen atoms should, however, always be measured so that the content of tertiary nitrogen atoms, based on the finished Elastomer substance does not exceed 200 mVal / kg, but mostly only 80 to 150 mVal are tertiary nitrogen present per kilogram of elastomer substance.

For the preparation of polyurethane-polyurea solutions are gained in the melt NGO-containing prepolymers at temperatures below 35 ⁰ C., preferably below 25 ⁰ C, slowly metered in with stirring in a solution of Äthylendiamiη and the additional diamine in a polyacrylonitrile-solvent. The amount of solvent is usually such that the desired final concentration of the polyurethane-polyurea solution is obtained after the extension reaction has ended. The extension reaction is associated with a rapid increase in viscosity, whereby

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Viscosities between 150 and 600 poise at 20 ⁰ C can be achieved. A desired higher final viscosity is then often set by adding a small amount of hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate or biuret triisocyanate, which is obtained by reacting 3 moles of hexamethylene-1,6-diisocyanate and 1 mole of water will. In most cases, however, the isocyanates are added diluted with a little solvent.

The solids content of the finished elastomer solution can be 18 to 30 percent by weight. The related PoIyacrylnitril-Lösungsaittel such as N, N-dimethylformamide, N ₁ N-dimethylacetamide and N-methylpyrrolidone must be free of such components which are capable of reacting with diisocyanates; however, these solvents can contain the small amounts of water customary in industry.

The molar ratio of the applied extender mixture Ethylenediamine and the additional diamine can be varied from 50:50 to 85:15, but is preferably 75:25 up to 80:20. The molar ratio of the extender mixture is, however, already partly determined by that during the preparation of the NCO-containing Pre-adduct used ratio of OH- to NCO-

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Groups specified. The general procedure here is that if the NCO content in the pre-adduct is relatively low, then a lower one Amount of additional diamine applied in the extender mix is, while conversely a higher NCO content in the pre-adduct also a higher proportion of additional diamine for the production of non-gel-forming polyurethane-polyurea solutions requires. The amount of diamine mixture used for the extension depends on based on the OH to NCO ratio specified in the pre-adduct and the desired final viscosity 90 to HO mol # on the free NCO groups present in the pre-adduct.

To prepare the polyurethane-polyurea solutions, however, it is not absolutely necessary to meter the melt of the NCO-containing pre-adduct into the solution of the extender mixture. In another embodiment, it is quite possible to solve the Voradduktschmelze in a part of polyacrylonitrile-solvent and rapidly to about 25 - 30 ⁰ C cool. This solution is then metered into the solution of the extender mixture as previously described. However, if the pre-adduct was prepared in one of the aforementioned inert solvents, it is generally advisable to remove the solvent by distillation before the extension reaction, but the presence of these in no way renders the process inert

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Solvent impaired, provided their proportion, related on the total amount of solvent, not 20 percent by weight exceeds. It is of course possible to use these elastomer solutions to add titanium dioxide, talc or other pigments or these pigmentation agents before further processing already to be used in the extension reaction.

The polyurethane-polyurea polymers obtainable in solution under compliance with the specified conditions are due to their good solubility and the resistance of their solutions to gel formation and degradation in the case of space or slightly increased Temperature of particular importance for technical processing. The manufacture of elastic threads or fibers takes place dry according to the known methods of spinning technology, d. H. by spinning in the elastomer solution in air or inert gases at elevated temperature or wet, d. H. by injecting the elastomer solution into coagulation baths and winding up the threads obtained, a surface treatment being applied to prevent the thread laps from sticking together done with talc or oily preparations. The spun threads show excellent physical properties Properties such as high elongation at break and strength, low permanent elongation and high modulus of elasticity.

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Example 1:

250 parts of a polyester of adipic acid, 1,6-hexanediol and 2,2-dimethylpropanediol-1,3 (weight ratio of the diols 65/35; OH number 55 _f 5; acid number 0.8) are 1 hour at 120 ⁰ C and dehydrated under a pressure of 12 Torr, and then with 50 parts of diphenylmethane-4,4'-diisocyanate at 90-95 ⁰ C for 1 hour for reaction accommodated. The melt of polyester-diisocyanate adduct is dissolved in 400 parts of Ν, ΐί-dimethylformamide, and in about 10 minutes to 20 ° - 25 ⁰ C cooled.

This solution is in ca. 5 minutes at 15 ⁰ C - 20 ⁰ C un ter stirring in a solution of 3 »8 parts ethylenediamine, 3.6 parts of 2,2-bis (4 ^l aminophenyl) propane and 432 parts of Entered N, N-dimethylformamide, the viscosity of the solution increasing rapidly.

The spinning solution ca. 27 1> containing Peststoff has / 20 ⁰ C. has a viscosity of about 390 poise It is under keeping the spinning conditions described below according to the wet spinning into filaments having the following properties Processed:

Ti-Pestig- Ultimate modulus of elasticity elongation elongation (mg / den) (den) (g / den) (*) W

700 0.40 610 19 70 Le A 10 123 - 10 -

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Example 2:

250 parts of that described in Example 1, dehydrated
Polyester are at 90 ° - 100 ⁰ C water in 130 parts of free chlorine benzene with 50 parts of diphenylmethane-4,4'-diisocyanate in the course of one hour implemented. The solution to the
Polyester diisocyanate adduct is then to about 25 ⁰ C
and cooled at 15 ° - 20 ⁰ C was added into a solution of 3.6 parts of ethylene amine, 3.4 parts of 2,2-bis (4 '-aminophenyl) -Pro oan and 702 parts Η, Ν-dimethylformamide. The / 20 ⁰ C resulting spinning solution with about 27 # Peststoff is rapid Viskosrtätsanstieg to about 300 poise after explained below wet spinning into filaments
deformed with the following properties:

Ti- Pestig- fracture- permanent modulus of elasticity
strength elongation elongation (mg / den)
(den) (g / den) (*) W

700 0.31 650 18 62

Example 1 3:

250 parts of the polyester described in Example 1 were mixed with 3 parts of a 36 $ strength SOp / dioxane solution, stirred for 4 hours at 100 ⁰ C and stirred anschürend in about 1 hour at 100 ⁰ C and then at about 1 hour

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100 ⁰ C and a pressure of 12 Torr freed from dioxane and traces of water. The mixture is stirred 5 parts of N-methyl-diisopropanolamine in the Pclyestertfchmelze and provides in 1 hour by further reaction with 63 »6 parts of diphenylmethane-4,4'-diisocyanate at 80 ° to 85 ⁰ C, an NCO preadduct containing forth in the ca . is dissolved 10 minutes in 400 parts of N, N-dimethylformamide (HgO content is 0.01 $>) and simultaneously cooled to 25 ⁰ C.

The solution of the preadduct with stirring at 16 to 22 ⁰ C in 25 minutes in a mixture of 4.95 parts of ethylene diamine, 7 _f 28 parts of 1,1-bis (4'-aminophenyl) cyclohexane, 8.3 parts of titanium dioxide and 517 parts of Ν, Ν-dimethylformamide entered. Viscosity of the solution 237 poise / 20 ⁰ C.

The solids content of the solution is 27% by weight. The elastomer substance contains 100 mVal tertiary nitrogen per kilogram.

The processing of the spinning solution into threads takes place under the conditions of the wet spinning process described below, whereby the following thread properties are achieved:

Ti- firm- fracture- permanent modulus of elasticity

strength elongation elongation (mg / den)

(den) (g / den) (*) {+)

500. 0.44 540 2.1 90

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Example 4:

250 parts of the polyester described in Example 1 are deactivated analogously to Example 3 and drained, stirred 5 parts of N-methyl-diisopropanolamine, and by reaction with 7115 parts of diphenylmethane-4,4'-diisocyanate at 80 ° to 85 ⁰ C in 1 hour, an NCO -containing pre-adduct produced. The pre-adduct is dissolved in 400 parts of Ν, Ν-dimethylformamide (HgO content 0.01 fl) in 15 minutes, at the same time ^{cooled to 25 0} C and by introducing the NCO-containing solution into a stirred mixture of 6.28 parts of ethylenedi » min, 9 _f 3 parts of 1,1-bis (4'aminophenyl) cyclohexane, 8.6 parts of titanium dioxide and 548 parts of N, N-dimethylformamide extended at 20 ° to 27 ⁰ C. Subsequently, 1 part HexMMithylen-1, 6-diisocyanate in 5 parts of N, N-dimethyl thylformaeid stirred. The viscosity is approx. 340 poise / 20 ^° C. after 4 hours.

The proportion of elastomer substance in the spinning solution is 27 jl by weight and the content of tertiary nitrogen is 97 meq / kg Feetoff. The solution is processed according to the Haflepinnr method described below, whereby threads with the following properties are obtained:

Ti breakage strength strength constant modulus ter Strength Elongation at break (mg / den) (s) (g / d) (*) (*)

COO 0.53 510 20 102

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Example 5:

250 parts of the polyester described in Example 1 are _{mixed with 2 parts of a 39 # strength SO 2} / dioxane solution, ^{stirred for 2 hours at 100 °} C. and then in about 1 hour at 100 ^° C. and a pressure of 12 torr of dioxane and freed traces of water. By reacting with 56.25 parts of diphenylmethane-4,4'-diisocyanate, ^{an NCO-containing pre-adduct is prepared in 1 hour at 85 ° 90 0} C, which is then added in 400 parts of Ν, Ν-dimethylformamide (H ₂ 0 content 0, 02 ° ß>) is dissolved and cooled ^{to 25 0} C in about 15 minutes.

a) The pre-adduct solution is added to a solution of 4.4 parts of ethylenediamine and 8.25 parts of 2,2-bis- (4'-aminophenyl) propane in 473 parts of Ν, Ν-dimethylformamide at room temperature with stirring Solution is approx. 180 poise / 20 ⁰ C. According to the following instructions for the wet spinning process, threads with the following properties are obtained from this spinning solution:

Ti- strength breaking- permanent modulus of elasticity Hin) (g / ^den ) elongation elongation (mg / den)

290 0.23 390 9 110

b) The Voradduktlösung is in 15 minutes at 18 ° - 24 ⁰ C with stirring in a solution of 5.2 parts ethylenediamine and 6.5 parts of 2,2-bis (4 ^l aminophenyl) propane in 459 TEI

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len Ν, Ν-Dlaethylformamide entered. The final viscosity of the solution is approx. 230 poise / 20 ⁰ C. According to the following instructions for the wet spinning process, this spinning solution is processed into threads with the following properties:

Ti- firm- fracture- permanent B-module

ter Strength Elongation at break (mg / den)

(the) (g / den) (*) (*)

360 0.36 UO 19 H5

Example 6:

3750 parts of the dewatered polyester described in Example 1 are added under stirring at 82 ° - 87 ⁰ C with 844 parts of diphenylmethane-i ^ '- diisocyanate, 1 hour reacted, then in 6000 parts Ν, Ν-dimethylformamide, and in 25 minutes 25 ⁰ C cooled. These NCO-containing Voradduktlösung is at 20 ° - 25 ⁰ C in a solution of 69 parts Äthylendianin and 129 parts of 2,2-bis (4 * aminophenyl) propane in 7280 parts of N, N-dimethylformamide, further, 120 parts of Contains titanium dioxide (rutile) in dispersed form. The spinning solution obtained has a solids content of 27 1 'has a viscosity of 620 poise / 20 ⁰ C. Following the procedure described below dry spinning process is then processed, the spinning solution into filaments old following properties:

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Titer
(the)

Pestig-

speed

(g / den)

Elongation at break Elongation (#) (*)

Modulus of elasticity (mg / den)

210

0.77

510

19th

126

Example 7:

3750 parts of the dewatered polyester described in Example 1 are added under stirring at 80 ° - 85 ⁰ C with 750 parts of 4,4'-diphenylmethane diisocyanate taken 1 hour for reaction, then in 6000 parts Ν, Ν-dimethylformamide, and in 20 minutes cooled to 25 ^{° C.} These NCO-containing Voradduktlösung is at 18 ° - 24 ⁰ C to a stirred mixture of 53.1 parts of ethylenediamine, 67.5 parts 2,2'Bis- (4 ^l aminophenyl) propane, 7000 parts of N, N-dimethylformamide and 185 parts of titanium dioxide (rutile) entered. 3 parts of hexamethylene-1,6-diisocyanate in 27 parts of Ν, Ν-dimethylformamide are then added dropwise. To obtain a spinning solution having a solids content of 27 i "and a viscosity of 690 poise / 20 ⁰ C. In the following given for the dry spinning method, spinning conditions could be produced from this solution filaments having the following properties:

Ti- strength (den) (g / den)

Elongation at break

permanent D E-modulus elongation (mg / den) (#)

150

0.66

490

128

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The spinning of the spinning solutions described in Examples 1-7 into endless threads

Before spinning, the solutions are well filtered through a filter press and then im Vacuum degassed.

The felt solutions can be both wet and dry to be spun.

I) FaS spinning process

The filtered and degassed solution is a spinning pump through a spinneret having nozzle diameters of 50 - 200; i in a 20 ° - heated 80 ⁰ C, especially 40 ° -70 ⁰ C _1, 2-10 m-long water bath spun as »Contains 2 - 10 Ji Η, Ν-dimethylformamide. The emerging threads are pulled off at a speed of 5-50 m / min with a delay of 0.5-5. After subsequent drying at 60 ^° C., the threads are wound up. The physical properties given in the examples are then determined by the known methods.

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II) dry spinning process

The filtered and degassed solution is fed via a spinning pump to the spinning head, depending on the viscosity at a temperature of 15 ° - 90 ⁰ C. The solution is injected into a heated shaft through a multi-hole nozzle with nozzle diameters of 80 - 250 u. The temperature of the quench air must be chosen so that the air temperature at the spinneret 130 ° - 230 ⁰ C is. The air entering the shaft from above, meanwhile loaded with the solvent, is sucked off in front of the shaft end. The threads emerging at the end of the shaft are drawn off at take-off speeds of 200-600 m / min, preferably 200-400 m / min. The Ν, Ν-dimethylformamide content of the threads is below 1 ». Before the threads are wound up, a preparation agent is applied to reduce adhesion. The Padeneigenochaften are then checked according to the known methods.

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Explanations for thread testing

1. All dynamic tests were performed with a rate of deformation of the thread of $ 400 per hour
carried out.

2. The permanent elongation is determined after three stretch distortion of the yarn by 300 i "of the original length and, after a Erholungezeit 30 seconds.

3 · The module is stretched when the thread is stretched by
300 pounds of the initial length determined.

Example 8:

21,000 parts 1,6-hexanediol / 2,2-dimethylpropanediol-1,3 /
Adipineäure mixing polyester (mole ratio of diols 65/35; OH number 63.9; acid number 1.45) are dewatered for 1 hour at 120 ⁰ C in vacuo, at 70 ⁰ C with 445 parts of N-methyldiisopropanolamine and 6300 parts of diphenylmethane-4 , 4'-diisocyanate is mixed and ^{heated to 90 °} C. for 50 minutes with stirring. 23800 parts of the above NCO-containing pre-adduct melt are poured into a cold solution of 480 parts of ethylenediamine and 600 parts of 2,2-bis-

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(4 ^f -aminophenyl) propane in 70,000 parts of Ν, Ν-dimethylformamide, which also contains 1,035 parts of titanium dioxide (rutile) in dispersed form. To obtain a spinning solution of 27 H Peststoff and a viscosity of 610 Poiee / 20 ⁰ C.

a) The solution is briefly ^{heated to 90 °} C. and immediately thereafter dry-spun from a 48-hole spinneret at a shaft ^{temperature of 200 ° C.} After leaving the spinning chute, a preparation agent that reduces adhesion is applied to the threads. The threads are wound up at a speed of 300 m / min.

Titer strength- fracture- elasticity-modulus (den) keit elongation de elongation (mg / den) (g / den) (H) (H)

450 0.68 480 20.5 134

b) The solution is briefly ^{heated to 65 °} C. and immediately thereafter dry-spun from a 12-hole spinneret at a shaft ^{temperature of 170 ° C.} The take-off speed is 450 m / min.

Titer strength- fracture- elasticity-modulus (den) keit elongation de elongation (mg / den) (g / den) (H) (H)

84 1.05 365 11.4 580

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Claims (2)

Patent claims: M. ^ Process for the production of rubber elastic threads by spinning solutions of segmented polyurethane-polyurea polymers in polar organic solvents, characterized in that solutions of polymers produced by reacting linear ones are spun Polyesters with terminal hydroxyl groups and average molecular weights from 1600 to 2600, optionally as a mixture with low molecular weight diols with one or more tertiary nitrogen atoms, with diphenylmethane-4,4 -'-diisocyanate, to an NCO-containing pre-adduct, which in a polar organic solvent with a mixture of ethylenedi «· amine and a dianine of the formula H ₂ where R ₁ and R _{2 are} lower alkyl radicals or R ₁ and R ₂ together with the carbon atom mean a cycloaliphatic radical, is further reacted. 2. The method according to claim 1, characterized in that since the molar ratio of ethylene diamine to additional diamine im The range is from 50: 50 to 85 * 15. I A 10 123 - 21 - 109809/1935 1669411 3. Process according to Claim 1, characterized in that the ratio of the hydroxyl groups to the isocyanate groups of the diphenylmethane-4,4'-diisocyanate is in the range from 1: 1.5 to 1: 1.95. 4. Process according to claim 1, characterized in that the NCO-containing pre-adduct is reacted with ethylenediamine and 2,2-bis- (4 ^f -aminophenyl) propane. L e A 10 123 - 22 - 109809/1938