DE1419403A1 - Process for conditioning and rendering molded products antistatic, in particular fibers or threads made from acrylonitrile polymers - Google Patents

Description

DR. E. WIEGAND DIPL.-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG TELEPHONE, 55547 «8000 MÖNCHEN 15, 1 & Γ63 · TELEGRAMS) KARPATENT NUSSBAUMSTRASSE

W. 10 663/61 1i / We ρ U 19 403.

Monsanto Company St. Louis, Missouri (V.St.A.)

Process for conditioning and antistatic rendering of molded products, in particular Pipes or threads made from acrylonitrile polymers

The invention relates to the treatment of molded products or articles and in particular an improved process to give products or objects made of acrylonitrile polymers antistatic properties, To give lubricity, lubricity and other desirable properties on which the Process resulting products and the compositions used.

Acrylonitrile polymers represent a class of materials that have an electrostatic charge on their surface.

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develop area or develop beeches, if Pasern or other objects made from them, during their manufacture and treatment or during processing of the pastes to fabrics or other objects as well as friction during the use of the finished objects be subjected. Before fibers made from acrylonitrile polymers are spun into yarns, the electrical To modify properties so that the pasers during carding, combing, spinning or the like Operations in which the pasers are rubbed in constant frictional contact use a minimal amount of electricity produce. The presence of static electricity on your feet creates a serious problem because it not just to stick the pasers to the machine parts leads, but also because there is a tendency that the Pasern during such operations as carding trying to repel one another, so that it becomes difficult or impossible to make a coherent one out of them to spin compact yarn.

Another problem of major importance that is to be considered with threads or fibers made from acrylonitrile polymers is to be drawn is to melt or soften the yarn so that it has the appropriate frictional properties or has the proper resistance and flexibility required for the particular purpose being imprinted.

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_OWÖ1 NAL INSPECTED

H19403

When handling continuous filament yarn, it is necessary, for example, to condition the material in order to reduce the tendency for the individual filaments to break when the yarn is subjected to mechanical stresses, such as when the yarn runs over guides, rollers or other parts of the yarn manufacturing devices and occur during twisting, winding, reeling and similar operations. In the case of yarns that are intended for use in λ technical knitting machines, it is particularly important that the yarn is soft and pliable so that it can adapt to the contour of the needles and result in a tightly knitted fabric that is free of cuts, pinholes, distortions, Ladders, mismatches, or other common mistakes.

Although molded articles made of acrylonitrile polymers are generally used to modify their properties can be treated according to the method according to the invention, the method according to the invention is of particular advantage part in the treatment of fibers in order to make them more accessible for textile processing and it is therefore in particular with reference to this use explained in more detail below.

The fibers to be conditioned according to the invention can be aue polyacrylonitrile or copolymers which at least about $ 80 acrylonitrile and up to about $ 20 others

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thus containing copolymerizable monomers, be prepared. Examples of suitable monomers which are copolymerizable with acrylonitrile to form fibers which can be processed according to the invention are acidic acid such as aoryl, haloacrylic and methacrylic acid, esters such as methyl, butyl, ootyl, methoxymethyl and chloroethyl methacrylate and the corresponding esters of acrylic and halogen aoryl acids; Methacrylonitrile, vinyl and vinylidene halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, 1-fluoro-1-chloroethylene / vinyl carboacylates such as vinyl acetate, vinyl chloro acetate, vinyl propionate and vinyl stearate; N-vinylimides _x such as N-vinylphthalimide and N-vinylsuccinimide} N-vinyllactams, such as N-vinyleaprolactam and N-vinylpyrrolidonej aryl compounds, such as styrene and vinylnaphthalene and other compounds, such as methyl vinyl ketone, methyl fumarate, methyl vinyl anhydride, pumaronitrile, maleic anhydride; the vinylpyridines, such as 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, the vinyl-P-substituted alkylpyridines, such as 4-ethyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine and 2-methyl-5-vinylpyridine; the isomeric vinylpyrazines, the various isomeric vinvichinolines, the vinylimidazoles and the vinylbenzoxazoles. The strands or threads can also be made from a mixture of two or more of the fiber or film-forming materials. For example, pastes, films, or other shaped articles that have been rendered antistatic can be used

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H19403

should be made from a mixture of a base acrylonitrile polymer with other polymeric materials be produced or contain a mixture of an acrylonitrile polymer serving as a basis, the polymeric materials the base polymer! sat in different Modified aspects, e.g. by giving it a color receptivity, its flame resistance increase or increase the hydrophilic properties of the polymer, etc. Suitable polymeric materials for Mix with the base polymer, which is made of polyacrylonitrile or a binary or ternary copolymer of acrylonitrile with the above-mentioned copolymerizable Substances can consist of those polymeric materials that are in the same solvent how the base polymer are soluble and when they are mixed with the base polymer in an amount of 2 to 50 wt the mixture are mixed, result in a mixture containing a solution of at least 5 #iger concentration in the Forms solvent, which can be processed into fibers by conventional methods. Suitable solvents are Dimethylformamide, dimethylacetamide, ^ - butyrolactone, ethylene carbonate, dimethyl sulfoxide, dimethyl sulfone, nitromethane U3W For example, the mixture can be a base polymer, such as a copolymer with at least Θ0 wt .- ^ Acrylonitrile and up to 20 wt .- ^ of another monooelfi-

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African monomers as Bind indicated above and 2 to 50 96 of a copolymer of 10 to 70 96 acrylonitrile and 30 to 90 i "contain a different monoolefinisohen monomer which is different from the Mischmonomeren in the base polymer, for example from 30 to 90 i» a vinyl-substituted heterocyclic tertiary amine, such as a vinyl pyridine, a vinyl imidazole, a vinyl lactam or) | other monomers listed above and preferably a vinyl pyridine.

According to the method according to the invention, frosted articles made of acrylonitrile polymers, copolymers and mixtures thereof are conditioned by treating them with an aqueous emulsion whose pesticide content is about 20 to 60 wt .- ^ of a niohtionogenic (nonionic), surface-active ester, 15 to 40 # * comprises a nonionic surfactant P _o ly ^ ^nera u * ^{1 1} 10 to 40 $> a cation-active (surface active kationisohen) quaternary ammonium compound. The esters which contain a substantial part of the agents according to the invention are preferably long-chain fatty acid partial esters of polyhydric alcohols or anhydrides, vie sorbitol monopalmitate and sorbitol monolaurate. The non-ionic surfactants, commonly referred to as polyethers, can be prepared by condensing a water-insoluble oxy fatty acid or an ester thereof

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Acid or mixtures of · acid and ester with 150 to 250 parts of ethylene oxide are produced.

The polyhydric alcohols or their anhydrides from which the partial esters are produced include in particular those with 2 to 8 carbon atoms, such as mannitol, sorbitol, glucose, erythritol, pentaerythritol, glycols, such as ethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, Tetraethylene glycol etc. Various saturated or unsaturated aliphatic acids can be used be reacted with the polyhydric alcohols to produce the partial esters. A preferred group of part stars are those that contain a single ester bond. However, there can also be partial esters that have more than one Containing ester bond, can be used.

The acids used to produce the partial esters can be saturated or unsaturated aliphatic acids with 10 to 20 carbon atoms. Preferred acids are those that are saturated or contain an olefinic group ^. Examples of such acids include monoolefinic unsaturated acids such as 7-hexadecenoic acid, 10-undeoenoic acid, 13-docosenoic acid and 9-octadecenoic acidj substituted olefinic Acids, e.g., oxyolefinic acids such as 16-hydroxy-7-hexadecenoic acid and 12-hydroxy-3-ootadecenoic acid, halogenated unsaturated acids, for example monochloro-9-octadecenoic acid acid, monochloro-12-hydroxy-9-ootadeoenic acid and halogenated

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ORIGINAL INSPECTED

Acids produced by dehydration of castor oil acids with the following Chlorination derived bind, saturated fatty acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, Tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, Ootadecanoic acid and nonadecanoic acid. This saturated Acids can have straight or branched or substituted chains and they can e.g. other halogen atoms, such as monochloroctadeoanoic acid or the like. Specific part esters that are suitable for use according to the invention include glyceryl monohexadecanoate, glyceryl monodeoanoate, glyceryl mono-9-hydroxyoctadeoanoate, Glyceryl mono-12-hydroxy-octadecanoate, sorbitan monododecanoate, propylene glycol octadecanoate, Ethylene glycol monooctadeaanoate, diethylene glycol monooctadecanoate, and sorbitan monooctadecanoate.

Examples of hydroxy fatty acids, as such or in Form of partial esters with the polyhydric alcohols specified above for condensation with ethylene oxide to form of the ether portion of the compositions according to the invention include both saturated and unsaturated oxyacids, such as 12-hydroxy-octadecanoic acid, 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, 10-hydroxyootadeoanoic acid, 3,12-dihydroxypalmitic acid, 9,10,16-hydroxyhexadecanoic acid, 9,10,12,13-hydroxyοοtadecanoic acid, 16-hydroxy-7-hexadecenoic acid and ^ -hydroxy-g-ootadeoene acid.

The cation-active agents according to the invention

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are used are the quaternary ammonium compounds the general sleeve

CH,.

• 2 ι

RN- C ₂ H ₅ ι

CH,

(OSO ₅ R ¹ ) __

in which R a alkyl radical with more than 10 carbon atoms and R ¹ denotes an alkyl radical with fewer than 5 carbon atoms. Examples of such quaternary ammonium compounds represented by the above formula include soyadimethylethylammonium ethosulfate in which the alkyl groups represented by R are obtained from the fats contained in soya oil, and are mainly composed of C 16 and C 18 saturated aliphatic carboxylic acids such as their esters such as lauryl dimethyl ethyl ammonium methosulfate , Myristyldimethylethylammonium ethosulfate, palmithyldimethylethylammonium propiosulfate, margaryldimethylethylammonium butyrosulfate, stearyldimethylethylammonium ethosulfate, oleyldimethylethylammonium methosulfate and idnoleyldimethylethylammonium.

If desired, the aoryl nitrile polymers to condition according to the invention in order to give them even greater lubricity and softness than

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the product which has been treated with the above equipment, the aqueous emulsion may be the Auerüstungszusammensetzung optionally include about 5 to 23 $> Geeamtfeststoffgehaltes of the aqueous emulsions substituted carbamyl derivative. The substituted carbamyl derivative is added to give the acrylonitrile fibers additional lubricity and softness when they are treated with a finishing composition containing a substituted carbamyl derivative. The substituted carbamyl derivatives which can optionally be added to the composition according to the invention are those of the general formula

0
Il H ^(CH 2> m - A e (OH ₂ ) _t - A - - (CH ₂ ) _f ? 3 ^D 1 C. -N-
D JL _ ·. - k - N
» C = I. NH ^D 2 H - (CH ₂ ) J t 0
H -N- t 0 B X -N-

In this formula, R ₁ and Rg can be the same or different and are preferably saturated aliphatic

Chains with at least 6 carbon atoms,

Rj »R * and

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1%

R ₅ can each represent hydrogen or a simple alkyl or oxyalkyl radical of less than 5 carbon atoms and, furthermore, R * and R can represent an acid amide chain which is derived from an acid and a polyamine? D- and D «denote oxygen, sulfur or an imido group, the number of such groups g being in the range from 0 to 3 and g being an integer from 0 to 3, A denoting oxygen, sulfur, an amino group or a simple alkyl - or alkyl-substituted amino groups with fewer than 5 carbon atoms (for example NC ₂ EL OH or NC ₂ H ₅ ) f and j represent integers from 1 to 6, preferably from 1 to 3; e and k represent integers from 0 to 6, preferably from 0 to 3, m and t represent integers from 1 to 6, preferably not more than 2, and a hydrogen in each dimethyl group can be substituted by a methyl group, B denotes the hydrogen of an acid or an alkyl group and X is a negative radical such as an acyl radical or a halogen.

Substances which are covered by the given formula can be obtained in that a saturated Acid, an acid ester or an acid halide is condensed with an aliphatic polyamine, the condensate with a carbamyl compound is reacted and then the substituted carbamyl derivative thus obtained into the corresponding Acid salt or alkylated product is converted

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H19A03

Acids that can be condensed with polyamines "to obtain the condensates are the saturated acids containing at least 8 carbon atoms, such as lauric, stearic, palmitic acid, etc. The acids can be mixed with any aliphatic polyamine, such as ethylenediamine, diethylenetriamine," Triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, oxyethylethylenediamine, ethylethylenediamine, 2,2-dimethyl-1,3-diaminopropane, 1,3-diaminoisopropanol,, ß-diaminodiethyl ether and d , ß-diaminodiethyl ether, which are condensed with the carbamylthioether compounds the acid-amine condensate include urea, thiourea, guanidines, biurets, guanylureas and giguanidines.

For the purposes of the invention, the substituted orbamyl derivatives must be converted into their acid salts or alkylated products. The acid salts ^ are obtained by reacting the carbamyl derivatives with an acid, for example acetic acid, lactic acid, boric acid, oxalic acid, benzoic acid, salicylic acid, puronic acid, citric acid, tartaric acid, formic acid, phthalic acid, succinic acid or alkylnaphthalenesulfonic acids. The ¹ alkylated products are obtained by post-treatment of the substituted garbamyl derivative with an alkylating agent such as ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorohydrin or dimethyl sulfate.

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H19403

. .It

13 -

The acid-amine condensates can be made is completed by heating equimolar amounts of the saturated acid selected and the polyamines at temperatures of 130 ° to 200 ⁰ C to the reaction, which is indicated by the loss of a molecule of water. The mixture is then ^{cooled to 180 °} C. and half a mol or more of urea or another carbamyl compound is added. Ammonia is released rapidly, I when the urea is substituted, wherein the! Temperature between 170 ° and 200 ⁰ C. The product so obtained is then reacted with the appropriate acid or with an alkylating agent to produce the compounds represented by the structural formula.

The compositions according to the invention are preferably used as aqueous dispersions, and it has been found that 1 to 5 provide i "Peststoffe in such dispersions, the most satisfactory results M. The compositions can be applied to the fibers in any suitable manner, for example by dipping the fibers into the medium, by spraying or dripping on using a wick or an applicator roller, etc. Manufactured to orient the molecules and to improve their tensile strength. if

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the fibers are stretched after washing to partially or completely remove the spinning solvent, the antistatic finish is applied to the pasern after washing. For certain purposes, the hot stretching or orienting can be omitted. If the Threads are not stretched danaoh, the equipment can on them after their withdrawal from the spinning zone and washing are applied to remove the spinning solvent. So it can be on continuous threads or discontinuous Fibers obtained by cutting or otherwise interrupting the threads before or after Drying or crimping of the threads or fibers are applied. However, according to a preferred embodiment of the invention, the finishing composition described above applied to a running cable or bundle of fibers, which are in the cable or bundle in continuous or discontinuous form .can be. The invention is illustrated below by way of examples explained in more detail.

example 1

Samples of 100 g staple fibers of an acrylonitrile copolymer of 93 wt .- # acrylonitrile and 7 wt .- # vinyl acetate were treated by immersion in 2000 g of the above-described aqueous dispersion for 10 minutes.

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Each sample was centrifuged, conditioned for 45 minutes dried at 110 ⁰ C in a circulating drier for 16 hours at 22.2 ⁰ C (72 ⁰ F) and a relative humidity of 30 ia. Thereafter, each sample was carded in a carding device (Davis-Furber sample card), which is equipped with a static sample, an amplifier and a display oscilloscope. The static value of each sample was evaluated by measuring a length of 25 cm of the line of the recording strip and integrating the area with the aid of a polar planimeter, the value of the area below the line changing directly with the static charge. The static amount values are expressed as the electrostatic carding charge on the sample (SCE) in square centimeters and are given in Tables A, B and C below. Each sample was then extracted with 50 parts by weight carbon tetrachloride for 45 minutes to determine the amount of equipment solids deposited on the stack. The values for the amount of equipment used are expressed as the percent equipment extracted based on the weight of a 100 g sample.

a) There were prepared three aqueous dispersions containing 2 i> solids, of which 60 # of sorbitan monopalmitate and 40 i "from the condensation product of castor oil with 200 molar equivalents of ethylene oxide passed (equipment 1 - Control) 2 i" solids _y of welohen 42 i » made of sorbitol

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monopalmitate, 23 # from the condensation product of rioinue oil with 200 molar equivalents of ethylene oxide and 30 # from N-octyl-, N-ethylmorpholine ethosulfate, an already known antistatic agent (equipment 2) and 2 $> pesticides, of which 4-2 # consisted of sorbitol monopalmitate, 28 $> from the condensation product of castor oil with 200 molar equivalents of ethylene oxide and 30 passed i "Soyadimethyläthylammoniumäthosulfat wherein the alkyl group obtained from the fats in the soybean oil and consisting essentially of saturated aliphatic C 16 and G 18 carboxylic acids in the form of their esters passed (equipment 3 ). The static amount, expressed as SCE, and the amount of finish solids applied, expressed as the percentage extracted from 100 g samples of the acrylonitrile polymer staple fibers described above, were determined as noted above and are listed in Table A below.

Tabel A. SCE ( cm ) ψ extracted 28 61 , 3 0, 27 10 ,1 0, 28 <1 , 0 ο,

Equipment 1 (control)
Equipment 2
Equipment 3

From the above Table A is eraiohtlioh that The finish 3 antistatic agent for aoryl nitrile

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polymer staple fibers produce considerably superior antistatic effects.

It is sometimes desirable to treat aoryl nitrile polymer staple fibers to make them softer, more open and to make them more lubricious than those fibers which have been finished for general textile purposes, regardless of the absence of static charges. This is most conveniently done by adding a plasticizer chers to the textile finishing and application achieved with it. The plasticizer, however, must go with the other ingredients be compatible with the equipment and must not reduce the antistatic effect of the equipment. It is shown by the results of the following experiments that these effects are exerted by the antistatic agents and plasticizers according to the invention can be obtained.

b) Ea three aqueous dispersions were prepared which contained 2 <f » pesticides, of which 52 $> from sorbitol monopalmitate, 34 # from the condensation product of ricinus oil with 200 molar equivalents of ethylene oxide and H # from ^, β-dioxyethyl- ^ 'ß ^f di (/ 3-stearamidoäthyl) -harnstoffacetat passed (equipment 4 - control), 2 # Peststoffe, wherein $ 36> from sorbitan monopalmitate, 24 $> from the condensation product of castor oil with 200 mole equivalent Ithylenoxyd, 10 i> from C / ,, / 3 -Dioxyäthyl- ^<J%, # '- di (/ S-stearamidoäthyl) -hams tof face did and i 30' of N-Oetyl-, N-Äthylmorpholinäthosulfat passed (Auerüstung 5) and 2 # Pest -

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Substances, of which 36 # aua sorbitol monopalmitate, 24 ° h from the condensation product of castor oil with 200 molar equivalents of ethylene oxide, 10 $ oL, ß- dioxyethyl- *. », Fc '- di ( β- stearamidoethyl) urea acetate and $ 30> soyadimethylethylammonium ethosulfate passed (Equipment 6). The static amount and amount of equipment solids applied, expressed as a percentage, extracted from 100 g samples of the acrylonitrile polymer staple fibers as described above were determined as noted above and reported in Table B below.

Table B. SCE (cm) # extracted

Equipment 4 (control) 79.8 0.35

Equipment 5 16.5 0.25

Equipment 6 ^ 1.0 0.30

Again from Table B above, it can be seen that the antistatic agent of the kit 6 is considerable superior antistatic effects for acrylonitrile polymer staple fibers when applied in the presence of one of the plasticizers according to the invention got.

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- 39 -

• Example 2

Samples of 100 g of washed staple fibers having a Acrylnitrilpolymerisatmischung from about 88 wt .- # of a copolymer of 93 wt .- # acrylonitrile and 7 wt .- # vinyl acetate and about 12 i "of a copolymer of about 50? 6 2-methyl-5-vinylpyridine listed and 50 # acrylonitrile, in a ratio such that the total content of 2-methyl-5-vinylpyridine of the polymer mixture 6 i "sawn g wore, in the same, given in example 1 as above, with 2000 g samples of the following Treated aqueous dispersions. Bs were prepared aqueous dispersions containing 2 $> solid contained, of which 36 i "from sorbitan monopalmitate, '24 i" from the condensation product of castor oil with 200 mole equivalent Äthylenöxyd, 10 # of Ui / 3 Dioxyäthyl aC ¹ /?' - di ( β- stearamidoethyl) urea acetate and in one case 30 # N-getyl, N-ethylmorpholine ethosulfate (equipment 7) and, in the other case, 30 <fo soyadimethylethylammonium ethosulfate (equipment 8) passed / an aqueous control was used Dispersion of 2 $> solids from 52 $> sorbitol monopalmitate, 34 i> of the condensation product of Rioinus oil with 200 molar equivalents of ethylene oxide and 14 $> U , β- dioxyethylot ¹ , / 3 '-di (/ 3 -stearamidoethylj-urea acetate (equipment 4) The static amount of the samples and the amount of equipment solids applied were

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- 20 -

as indicated in Example 1 above, and are listed in Table C below.

4th Table C. example om ² ) $> extracted , 44 7th SCE ( ,1 0 , 23 equipment 8th (Control) 57 , 5 O , 30 equipment VJl , 3 0 equipment 2 3 '

There was prepared an aqueous dispersion containing 2 io Peststoffe contained, of which 36 # of sorbitan monopalmitate, 24 $> from the condensation product of castor oil with 200 molar equivalents of ethylene oxide, 10 # from O £, $ - Dioxyäthyl- <£ '/ 3 ♦ -di ( β- stearamidoethyl) urea acetate, and 30 io of Soyadimethy'läthylammoniumätholsulfat consisted ». This composition was applied to a cable which has been obtained by spinning a mixture of a copolymer of 93 wt .- ^ acrylonitrile and 7 $> acetate _ta it a copolymer of methyl-5-vinylpyridine-2 from about 50 $> and a 50 $> acrylonitrile so that the mixture contained 6 io of the 2-methyl-5-vinylpyridine units * The application was carried out by immersing the cable in the dispersion.

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Extraction analyzes of the treated cable showed 0.6 to 0.9 $> finish solids present based on the weight of the cable. The resulting chopped staple fiber was found to be open, soft, and of good lubricity, and exhibited very little tendency to develop static electricity charges during textile processing such as carding, spinning, and drawing of the staple fibers and the yarns made therefrom.

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Claims (4)

Claims 1. A method for conditioning and antistatic rendering of shaped products, in particular fibers or threads made of an acrylonitrile polymer which preferably contains at least 80 wt .- ^ acrylonitrile in the molecule, characterized in that the product is treated with an aqueous dispersion which is 1 to 5 $ > Contains pesticides of the following composition: a) 20 to 60 wt .- # of a nonionic surface-active Partial ester of an aliphatic carboxylic acid and a polyhydric alcohol with 2 to 8 carbon atoms, b) 15 to 40 fd of a nonionic surface-active polyether obtained by condensing 150 to 250 parts of ethylene oxide with a component selected from the group consisting of water-insoluble oxyfatty acids, esters of such acids or mixtures of such acids and esters, and c) 10 to 40 # of a cationic quaternary ammonium compound the general formula CH, t s RN- C ₂ H ₅ (OSO ₃ R ¹ ) - in which R is an alkyl radical with more than 10 carbon 9098 ^ 2/1140 atoms and R ¹ denotes an alkylreat with fewer than 5 carbon atoms. 2. The method according to claim 1, characterized in that an aqueous dispersion with a content of 1 to 5 i ° pesticides is used, which 20 to 60 wt. - <fi sorbitol monopalmitate, 15 to 40 $ Rioinus oil which is condensed with ethylene oxide and 10 to 40 wt. # soy dimethyl ethyl ammonium ethosulfate. 3. The method according to claim 1, characterized in that an aqueous dispersion with a content of 1 to 5 $ solids is used, which is also 5 to 25 $> a substituted carbamyl compound of the general formula R ₉ I * C-N-H X 0 Rc Il I C-N-H X (OH - A «3H ₂ ) _t - A C = D : oh ₂ ) contains, in which R ₁ and Rg are saturated alkyl radicals having at least 6 carbon atoms, R ₂ , R ,, R. and 9008 ^ 2/1 UO R ₅ denotes hydrogen, alkyl or oxyalkyl radicals with fewer than 5 carbon atoms, where R, and R- furthermore. can represent an acid amide chain which is derived from an acid and a polyamine, D ^ and D _{2 represent} oxygen, sulfur or imido groups, where g denotes the number of groups and 0 to 3 denotes, A is oxygen, sulfur, amino groups, alkyl or alkylol-substituted amino groups with fewer than 5 carbon atoms, f and j represent integers from 1 to 6, e and k represent integers from 0 to 6, m and t represent integers from 1 to 6 and X represents a negative radical such as acyl or halogen means. 4. The method according to claim 3, characterized in that an aqueous dispersion is used with a content of 1 to $ 5> solids containing 30 to 60 wt .- # sorbitan monopalmitate, 15 to 40 i »Rieinusöl, the 150 to \ 250 Parts of ethylene oxide is condensed, 10 to 40 & soy dimethylethylammonium ethosulfate and 5 to 25? £, d , β- dioxyethyl-ot »/ 3'-di (ß-stearamidoethyl) urea acetate. 909822/1 UO