DE3802633A1 - Modified polyurethanes containing perfluoroaliphatic groups, and the use thereof - Google Patents

Abstract

The present invention relates to modified polyurethanes containing perfluoroaliphatic groups, obtained by reacting oligo(poly)urethanes containing free hydroxyl or isocyanate groups and perfluoroaliphatic groups with difunctional or polyfunctional polysiloxanes at elevated temperature with reaction of all the reactive groups of the urethane. These compounds are employed to render fibre materials oil-repellent and water-repellent, the treated materials not only being provided with washing- and dry cleaning-resistant effects, but also being provided, in particular, with a very soft, full hand (handle) with very good surface smoothness. These excellent hand effects are further optimised by the addition of a polyethylene dispersion.

Description

The present invention relates to modified perfluoroaliphatic groups R _f containing polyurethanes and their use for the oil and water-repellent finishing of fiber materials.

Polyurethanes containing perfluoroaliphatic groups are already known from the prior art (US-PSS 39 68 066 and 40 54 592). It is also known this Connections to oil and water deviating equipment of fiber materials. These equipments have the disadvantage, however, that water repellency as a whole seen unsatisfactory. It was therefore in the PCT application WO 86/02115 already proposed by Use of selected extenders, namely NCO groups containing compounds with a molecular weight of at least 450 in blocked form, these Eliminate disadvantage. In fact, through this Addition washable and cleaning resistant water repellency received, but the handle is given today Requirements do not always meet, because of the  state of the art handle often too dry is and also the desired soft-hand effect with inner Softness and pleasant fullness and surface smoothness not nearly reached.

There have now been modified perfluoroaliphatic groups Containing polyurethanes found that the posed To fit in requirements.

The present invention thus relates to the modified polyurethanes described in claim 1 and containing perfluoroaliphatic groups R _f . In subclaims 2 to 10, preferred compounds according to the invention are protected and in subclaims 11 to 14 the use thereof is claimed.

The free hydroxyl used as starting compounds or isocyanate groups and perfluoroaliphatic groups containing oligo- and / or polyurethanes (compounds 1) are generally from the recorded state of the Technology (US-PSS 39 68 066 and 40 54 592) known. they are made by implementing perfluoroaliphatic groups containing diols with 1 to 18, in particular 6 to 16 carbon atoms in the perfluoroalkyl radical with polyvalent isocyanates (Di / polyisocyanates) obtained. Details can can be found in the two US patents mentioned. As particularly suitable perfluoroaliphatic groups Diols containing have those of the formula

So 2,3-bis (1,1,2,2-tetrahydroperfluoroalkylthio) butane-1,4-diols, (R _f = -C₁₆F₃₃ to -C₆F₁₃) proved. Particularly good di / polyisocyanates are aliphatic diisocyanates, e.g. B. 1,6-Hexamethalendiisocyanat or trimethyl hexamethylene diisocyanate and isophorone diisocyanate and a diisocyanate derived from a dimer acid (DDJ® 1410 from Henkel Corp.), also in a mixture with each other, suitable. The preparations made from them are free of their own color.

What is decisive for the subject matter of the invention is now that the equivalence ratio in the manufacture of the Oligo (poly) urethane is chosen so that after the reaction either free OH groups (compound 1a) or free NCO groups (compound 1b) remain. To the reaction can be controlled within wide limits. This makes usable starting materials for production the modified perfluoroaliphatic according to the invention Group-containing polyurethanes in the range of OH to isocyanate groups from 3: 2 to 15:14 as well obtained in the range from 2: 3 to 14:15 and accordingly Polyurethanes containing perfluoroaliphatic groups with free OH or NCO groups with block formation formed, the latter used particularly advantageously as the end of the reaction with the polysiloxanes in a simple manner, e.g. B. IR spectographically, can be determined.

The further starting compound are di- or multifunctional polysiloxanes (compounds 2). Depending on whether compound (1) now has free OH groups (compound 1a) or free NCO groups (compound 1b), different compounds (2) will be used. For the reaction with the free OH groups, in particular with epoxy and carboxy groups are suitable and it is therefore used as compounds (2) those polysiloxanes with at least 2 functional groups which have such groups (compound 2a), preferably in α , ω position. Free NCO groups, on the other hand, react primarily with OH and amine or amide groups, so that for the reaction of the compounds (1b), especially those compounds (2) are to be considered which are OH-, in particular carbine-functional (OH-group) bonded to silicon via C chain) or amine / amide-functional (compound 2b). Of the compounds (2b), preference is again given to those which are difunctional and which have the functionality in the α , ω position. For the rest, no special conditions are attached to the structure of the polysiloxanes, other reactive groups being largely excluded and otherwise the usual substituents, such as ethyl, phenyl and in particular methyl radicals, are present.

Examples of such compounds are without Completeness of the following:

α , ω- carbinol functional dimethylpolysiloxane with a molecular weight of 600 to 10,000,
α , ω- epoxy-functional dimethylpolysiloxane with a molecular weight of 600 to 10,000,
α , ω -dihydroxy-functional dimethylpolysiloxane with a molecular weight of 1200 to 15,000,

Silicones of the formula

with a viscosity at 20 ° C of approx. 30 to 100 mPa · s.  

The compounds (1a) and (1b) are with the compounds (2a) or (2b) preferably in such amounts implemented that a small excess of di / multifunctional Groups of the polysiloxane is present. It is but easily possible, the two reaction parameters to react in approximately equivalent amounts. Generally the reaction takes place in an organic Solvents, especially in esters, such as in butyl acetate or in fluorinated hydrocarbons such as xylene hexafluoride performed to systems in this way received that can be easily processed. The The reaction itself can take place under normal air pressure be carried out with the exclusion of air humidity, but is preferably under inert gas, in particular Nitrogen, worked. The temperature at the implementation is 30 to 160 ° C, especially 80 to 120 ° C. Without the use of a catalyst reduces the reaction very long times for the production of the invention, modified, containing perfluoroaliphatic groups Polyurethane claim. It is therefore preferred this reaction in the presence of known from the literature Catalysts carried out. As examples Dialkyltin dicarboxylates, e.g. B. dibutyltin dilaurate and tertiary amines such as triethylamine and N-benzyldimethylamine called. The duration of the reaction depends on the chosen conditions, but takes even under optimal Requirements still take 2 to 8 hours, whereby the end point of the reaction is reached when none free groups of those used as starting compounds Connections (1) are more available. Now that free NCO groups can be easily determined the compounds (1b) with the compounds are particularly preferred (2b) implemented.

The reaction products according to the invention thus produced  can be used as such directly in the form of organic solutions for oil and water repellent finish for Fiber materials, especially textiles, are used will. Working with organic solvents, especially halogenated hydrocarbons but exposed to increasing criticism and therefore it will preferably the products according to the invention in solvent-free, transferred aqueous dispersion and in this Form applied.

The dispersions are prepared in a known manner Way and the professional will have no difficulty here the right emulsifiers and the right procedure to choose. For the sake of completeness but some emulsifiers and also a standard method listed for the preparation of the dispersions. As elulsifiers come - due to the further use of the dispersions - particularly weakly cationic and non-ionic emulsifiers are considered in quantities from 3 to 50%, in particular 8 to 40%, based on Solid, can be used.

Examples of emulsifiers are ethylene oxide adducts of fatty alcohols, especially those of primary ones and / or secondary, linear or branched alcohols with 8 to 16 carbon atoms and ethoxylated C₆ to C₁₂ alkylphenols, the number of ethylene oxide units between 5 and 30 is suitable. In addition are in the same Also nitrogenous emulsifiers, such as those by Ethoxylation of fatty amines or fatty acid amides arise suitable, these compounds by adding of acids can also be in salt form. Examples are 2,6,8-trimethyl-4-nonyloxihexaethylenoxiethanol, Isotridecyl ethoxylate with an average of 8 ethylene oxide  units and hexadecylamine ethoxylated with average 15 moles of ethylene oxide in the form of the acetate.

In general, the preparation of the aqueous dispersions the water and the emulsifier mixed to approx. 60 to 80 ° C warmed to about the same temperature heated reaction product according to the invention, if appropriate in the form of a solution, engineered. Then the resulting predispersion on a high pressure homogenizer homogenized at elevated pressure and 40 to 60 ° C. Finally may still exist from the manufacture Stripped solvent under reduced pressure. The dispersions obtained have about 10 to 40 wt .-% of active substance.

The aqueous dispersions thus obtained are also like the organic solutions of the reaction products according to the invention excellent for oil and water repellent Equipment of fiber materials, in particular Suitable for textiles. The quantities used are taking into account a usual fleet admission chosen so that the finishing baths about 1.5 to 4.5 g / l Contain fluorine, which is usually an amount used from 15 to 100 g / l of those prepared as described Corresponds to dispersions. The equipment itself is done in a known manner, primarily by padding, Drying and condensing, but also spraying is particularly suitable.

According to the invention, it is surprisingly possible very good, easy to clean with just one component and washable oil and water repellency and at the same time a surface-smooth handle with a special inner softness on all common fiber materials  to obtain. By combining perfluoroalkyl polyurethane blocks different size with different silicone Molecular weight it is possible to get the effects and vary the grip as you like.

It is also possible to use the invention Product again clearly in terms of handle improve when the dispersions prepared as described itself or the aqueous prepared from it Liquors, based on the dispersion of the invention Implementation product, 15 to 100 wt .-%, in particular 30 to 50 wt .-% of a 20 to 35% dispersion of a emulsifiable polyethylene (polyethylene wax) with a Density (at 20 ° C) of at least 0.92 g / cm³ and one Acid number of at least 5 can be added.

This emulsifiable polyethylene (polyethylene wax) that can be used here is known and in the prior art (DE-PS 23 59 966, DE-A 28 24 716 and DE-A 19 25 993) in detail described. As a rule, it is emulsifiable polyethylene around those with functional Groups, especially COOH groups, that are partially esterified could be. These functional groups will be introduced by oxidation of the polyethylene. It is but also possible by copolymerization of ethylene with z. B. acrylic acid to maintain functionality. Those that can be used in the present invention emulsifiable polyethylenes have a density at 20 ° of at least 0.92 g / cm³ and an acid number of at least 5 on. Such emulsifiable ones are particularly preferred Polyethylene in the form of dispersions in the frame of the present invention uses a density at 20 ° from 0.95 to 1.05 g / cm³, an acid number of Have 10 to 60 and a saponification number of 15 to 80. This material is generally commercially available  To have the form of scales, lozenges and the like. The preparation of the dispersions from this material is described in detail in the prior art.

It goes without saying that the equipment bath within the scope of the present invention, in which Textile industry usual aids are added can. In this context, it should be particularly emphasized Wrinkle-free agent, since not only the desired one Crease resistance, but also also a certain stabilization of the effects is achieved. In addition, there are also filling resins, flame retardants, Anti-slip agents and similar products as well as given if the also necessary catalysts, all in usual amounts, to be mentioned as additional products.

With the products according to the invention as well according to the known methods fiber materials of all Be equipped. As fiber materials are included especially textiles, again those Textiles are preferred that come from Cellulose fibers consist or at least partially cellulose fibers contain. As additional fibers in addition to the Cellulose comes with both synthetic fibers Polyester, polyamide or polyacrylonitrile fibers, as also wool. Of course they can modified perfluoroaliphatic according to the invention Groups containing polyurethanes are also used for finishing of pure synthetic fiber and wool fiber materials be used. The oil and water-repellent finishing of cotton / polyester blends. And here, too, have the invention Proven products in an excellent way.

Already according to the state of the art  get very good oil and water repellent properties, which is also a perfectly adequate washing and Have cleaning resistance. Towards this State of the art are the subject of the invention no discernible effects in terms of effects, but the effect level of the known equipment processes is achieved without restrictions. The clear superiority of the object of registration lies in a decisive improvement of the Handle of the finished textile materials. While according to the prior art only a relatively hard one and above all dry grip results when using the invention according to the invention Products of the treated materials a soft, full grip with very good surface smoothness, a typical soft hand effect achieved. This a very high grip level can still be used increase if the products themselves or the fleets emulsified polyethylenes can be added. To this This is because the inner softness can be added improve and the fullness and surface smoothness is in specially optimized way without any deterioration the wash and cleaning resistant oil and water repellency is observable, rather these values slightly raised. It must be particularly surprising can be viewed that solely by the described Contain silicone modification of the perfluoroalkyl groups the polyurethanes (compounds 1), i.e. in the absence of a commonly used extender, the entirety the effects could be brought to a high level, after the person skilled in the art knows that in use of silicone extenders the oil repellency as part of the  combined equipment is largely lost.

The present invention is described in the following Examples described in more detail, where parts = parts by weight and percentages = percent by weight.

Preparation of the perfluoroalkyl diol

In a heatable and coolable vessel with stirrer, thermometer, reflux condenser and funnel, 1012.4 parts of 2- (perfluoroalkyl) ethanethiol (average C₁₀F₂₁- in the R _f residue and 75.2 parts of butyne-2-diol-1.4) mixed under nitrogen, then 278 parts of m-xylene hexafluoride are also added under nitrogen and heated to 60 ° C. After dissolving, a catalyst solution (solution of 39.2 parts of azobis (2,4-dimethylvaleronitrile in 50 parts of methylene chloride) added in portions (1.6 ml per 5 minutes) within 4 hours, after 1 hour a significant rise in temperature being discernible above 76 ° C. After the addition of the catalyst is complete, the mixture is stirred for a further 4 hours at 60 ° C. The product obtained is approx. 75% bisperfluoroalkyl diol and has a fluorine content of approx. 45%.

Example 1

In an appropriately dimensioned 4-necked flask with Reflux condenser (with drying tube), nitrogen supply, Thermometers and stirrers become the following starting substances mixed together:

33.4 parts of the perfluoroalkyl diol solution prepared above,
3.2 parts of trimethyl hexamethylene diisocyanate (mixture of isomers),
9.2 parts of DDI®-1410 diisocyanate,
28.8 parts of butyl acetate as well
0.15% based on the above mixture, of catalyst solution (dibutyltin dilaurate and triethylamine in a ratio of 4: 1, 10% in butyl acetate). This mixture is stirred for 4 hours at 90 ° C under nitrogen (block formation in the equivalence ratio OH to isocyanate groups of 2: 3) and then 10 parts of polysiloxane ( α , ω- carbinol-functional dimethylpolysiloxane with a molecular weight of approx. 1000 and

Viscosity about 45 mPa · s, refractive index n about 1.415 and OH number 110) and 10 parts of butyl acetate and again the same amount of the above-mentioned catalyst solution and stirred at 90 ° C for a further 4 hours. The product no longer has any NCO groups.

80 parts of the above solution are used for emulsification at 70 ° C in a mixture heated to 70 ° C 250 g water, 4 g emulsifier (dodecyloxypropylamine ethoxylated with an average of 12 moles of ethylene oxide in the form of the acetate) and 24 g of ethyl glycol and at 300 bar on a high pressure homogenizer homogenized at 50 to 60 ° C.  Finally, the solvent in a rotary evaporator deducted and a dispersion with a Solids content of 17.8% (fluorine content 5.25%) receive.

Example 2

In the same device as described in example 1, will

66.8 parts of the above perfluoroalkyl diols,
10.7 parts of trimethyl hexamethylene diisocyanate (mixture of isomers),
43.8 parts of butyl acetate, as well
0.18%, based on the above mixture, of the catalyst solution mentioned in Example 1 was reacted for 4 hours at 90 ° C. under nitrogen (end product determined by checking for freedom from NCO groups), then 80 parts of polysiloxane (chemical structure as in Example 1 polysiloxane described with a molecular weight of about 8000) and 80 parts of butyl acetate and again the same amount of catalyst solution and reacted at 100 ° C for 6 hours. In the same way as described in Example 1, a 20% dispersion is prepared, if necessary by filling with water.

Example 3

Example 1 is repeated with the following amounts of compounds for the first reaction step:

116.7 parts of said perfluoroalkyl diol, 8.4 parts of said diisocyanate, 24.5 parts of DDI® 1410 diisocyanate and 90.7 parts of butyl acetate.

All procedural measures and other initial connections correspond to example 1 (block formation in Equivalence ratio OH to NCO groups of 7: 8).  The solids content is adjusted to 20% and one Obtained dispersion with 7.17% fluorine.

Example 4

In the apparatus described in Example 1

83.5 parts of the perfluoroalkyl diol prepared above,
24.5 parts of DDI®-1410 diisocyanate,
65.8 parts of butyl acetate,
0.23 part of a 10% solution of dibutyltin dilaurate in butyl acetate and 0.06 part of a 10% solution of triethylamine in butyl acetate are combined and heated to 80 ° C. with stirring under nitrogen. After 3 hours no more free NCO groups were detectable (equivalence ratio in the block polymer OH: isocyanate groups of 5: 4).

Now 10 parts of polysiloxane ( α , ω- epoxy-functional dimethylpolysiloxane with a molecular weight of approx. 1000), 10 parts of butyl acetate and 0.5 part of a 10% strength solution of triethylamine in butyl acetate are added and also with stirring and under nitrogen to 80 ° C heated up. After a total reaction time of 9 hours, the mixture reacted completely and no change in the epoxy number can be determined. To produce an aqueous dispersion, 80 parts of the product prepared as described at 70 ° C in the mixture described in Example 1 (also at a temperature of 70 °, but as an emulsifier, 4 g of an ethoxylated C _16-18 fatty alcohol with 25 moles of ethylene oxide each Mole of fatty alcohol) and a finished, bluish dispersion obtained on a high-pressure homogenizing machine at 50 to 60 ° C. and 300 bar. Finally, the solvent is drawn off in a rotary evaporator and adjusted to a solids content of 20% (fluorine content 5.9%) by filling with water.

Example 5

0.04 mol of a perfluoroalkyl diol (see Example 40 US Pat. No. 4,054,592) are described in Example 1 Way with 0.025 mol isophorone diisocyanate and 0.025 mole of 1,6-hexamethylene diisocyanate under nitrogen implemented (block formation in equivalence ratio OH: NCO groups such as 4: 5).

25 g of polysiloxane ( α , ω -epoxifunctional dimethylpolysiloxane with a molecular weight of approx. 2500 and a refractive index n of approx. 1.4090), 25 g of butyl acetate and 0.12% are added to this mixture at 90 ° C. with stirring to the entire mixture, the catalyst solution mentioned in Example 1. After 3 hours at 90 to 110 ° C, NCO groups can no longer be detected by IR spectroscopy. According to the information in Example 1, an approximately 18% dispersion is prepared using nonylphenol polyglycol ether (5 moles of ethylene oxide per mole of nonylphenol) as an emulsifier.

Example 6

Example 1 is repeated using 6.4 parts of trimethylhexamethylene diisocyanate and 23 parts of butyl acetate (1 reaction step); Block formation in the equivalence ratio of OH to isocyanate groups 2: 3) and 43.4 parts of a 2: 1 mixture ( α , ω- carbinol-functional dimethylpolysiloxane with a molecular weight of 2500 (2 parts) or 8000 (1 part) both with

and 43.4 parts of butyl acetate (2nd reaction step). The Emulsification takes place as described in Example 1 a 30% dispersion (5.51% fluorine).

Equipment example 1

A dark blue cotton body (approx. 170 g / m²) and a blue polyester / cotton-coated poplin 67/33 (approx. 210 g / m²) are with the following fleets A to C padded (fleet absorption approx. 69% or 63%), dried at 110 ° C for 10 minutes and at 150 ° C condensed for 5 minutes.

Fleet A 1
20 g / l of an approximately 70% aqueous aminoplast resin solution
(Contains dimethylol dihydroxy etherified with urea and about 5% neutral salt),
20 g / l of an approximately 50% aqueous solution of pentamethylolmelamine methyl ether,
6 g / l of a 30% zinc nitrate solution (pH approx. 1.0),
1 g / l 60% acetic acid and
51 g / l dispersion according to Example 3.

Fleet A 2
Like liquor A 1 with 50 g / l dispersion according to Example 6 (fluorine identical to liquor A 1).

Fleet B
Like fleet A with 61 g / l of emulsion B according to Example 1 of PCT application WO 86/02115
(same fluorine content as fleet A).

Fleet C
Like fleet A with 30 g / l of a commercially available polymer dispersion based on perfluoroalkyl acrylate (® SCOTCHGARD FC 251 from 3M Company) used in the same fluorine.

The results of the equipments are in the following Tables compiled, with the washes around usual 60 ° C or 40 ° C household machine washes and in the chemical cleaning (CRM) to such in Presence of 2 g / l of a conventional cleaning booster and 2 g / l water (liquor ratio 1:10). The measurements were taken after 5 days of exposure Normal climate made. The oil repellency was there according to AATCC 118-1972, water repellency according to DIN 53 888 (a = water absorption in%; b = water repellency) or the Spray test carried out according to AATCC 22-1974. The The soft grip effect is determined according to the specified Key:

Grip by rating levels:
1 = dry, hard grip
2 = dry, somewhat hard grip
3 = moderate, somewhat full soft handle
4 = good, somewhat smooth surface soft handle
5 = good to very good, voluminous, smooth surface soft handle
6 = very good to excellent soft feel with a pleasant fullness and smooth surface

Equipment example 2

The polyester / cotton jacket poplin mentioned in equipment example 1 is matched with a fleet Equipment example 1 equipped, but instead the dispersion of Example 3, the same amount of Dispersion according to Example 1 (fleet A) and additionally 20 g / l of a commercially available, non-ionogenic, finely divided, aqueous 20% polyethylene wax dispersion (50% nonylphenol ethoxylated with 15 moles of ethylene dioxide, based on polyethylene wax, as an emulsifier; Polyethylene wax with a density of approx. 1 g / cm³ at 20 ° C, acid number 13, saponification number approx. 22; Fleet B) also used will.

The results of this equipment are as follows Table summarized:

By using polyethylene wax dispersions the hydrophobic / oleophobic effects are stabilized and especially a noticeable improvement in the grip effects reached.

Claims (14)

1. Modified polyurethanes containing perfluoroaliphatic groups, obtained by reacting free hydroxyl or isocyanate groups and perfluoroaliphatic groups (R _f ) containing oligo- and / or polyurethanes (compounds 1) with polysiloxanes with at least 2 functional groups (compounds 2) at elevated temperature if appropriate in an inert gas atmosphere and if appropriate in the presence of a catalyst and if appropriate in a carrier medium, the equivalence ratio of the free hydroxyl or isocyanate groups of the oligo (poly) urethanes to the di- / multifunctional groups of the polysiloxanes reacting therewith being chosen such that all reactive Groups of compounds (1) have been implemented. 2. Modified polyurethanes according to claim 1, characterized in that as connections (1) free hydroxyl groups and perfluoroaliphatic groups containing oligo- and / or polyurethanes (compounds 1a) with polysiloxanes (compounds 2a) have been implemented in which the di / multifunctional Groups were epoxy or carboxy groups. 3. Modified polyurethanes according to claim 2, characterized in that the compounds (1a) with α , ω -functional polysiloxanes have been implemented. 4. Modified polyurethanes according to claim 1, characterized in that as connections (1)  free isocyanate groups and perfluoroaliphatic groups containing oligo- and / or polyurethanes (compounds 1b) with polysiloxanes (compounds 2b) have been implemented in which the di / multifunctional Groups OH, especially carbinol and amine / Were amide groups. 5. Modified polyurethanes according to patent claim 4, characterized in that the compounds (1b) with a , ω -functional polysiloxanes have been implemented. 6. Modified polyurethanes according to claims 4 and 5, characterized in that compounds (1) have been reacted, which in turn by reaction of R _f -alkyl group-containing diols having 1 to 18, in particular 6 to 16 carbon atoms in the perfluoroalkyl radical and di / Polyisocyanates or their mixtures in the equivalence ratio (OH to isocyanate groups) of 2: 3 to 14:15 have been obtained with block formation (compound 1b). 7. Modified polyurethanes according to the claims 1 to 6, characterized in that the implementation at 30 to 180 ° C, in particular 80 to 120 ° C. is. 8. Modified polyurethanes according to the claims 1 to 7, characterized in that the equivalence ratio in the implementation of the compounds (1) with the compounds (2) is chosen so that a small excess of di / multifunctional groups of the polysiloxane was present.   9. Modified polyurethanes according to the claims 1 to 8, characterized in that in an inert gas atmosphere has been implemented. 10. Modified polyurethanes according to the claims 1 to 9, characterized in that in the presence implemented a catalyst / catalyst mixture has been. 11. Use of the modified, perfluoroaliphatic Groups containing polyurethanes according to the claims 1 to 10 in the form of organic solutions or aqueous dispersions for oil and water repellent Equipment of fiber materials, in particular Textiles. 12. Use according to claim 11, characterized in that that the aqueous dispersions up to 100 % By weight, in particular 30 to 50% by weight, based on the dispersion of the modified polyurethane, one 20 to 35% dispersion of an emulsifiable polyethylene (Polyethylene wax) with a density (at 20 ° C) of at least 0.92 g / cm³ and an acid number of at least 5 can be used. 13. Use according to claim 12, characterized in that that the emulsifiable polyethylene is a Density from 0.95 to 1.05 g / cm³, an acid number of 10 to 60 and a saponification number from 15 to 80 having. 14. Use according to claims 11 to 13, characterized in that the usual Textile auxiliaries used in a known manner will.