WO2000012657A2

WO2000012657A2 - Controlling foam of aqueous washing liquors

Info

Publication number: WO2000012657A2
Application number: PCT/EP1999/006052
Authority: WO
Inventors: Maria Liphard; Ingrid Kraus; Ernst Innertsberger; Jakob Schmidlkofer
Original assignee: Wacker-Chemie Gmbh
Priority date: 1998-08-27
Filing date: 1999-08-18
Publication date: 2000-03-09
Also published as: DE19838938A1; WO2000012657A3

Abstract

The aim of the invention is to reduce staining of the textile surface of textiles with a no-iron finish during washing. To this end, silicone combinations consisting of essentially linear polydimethylsiloxane, essentially linear organopolysiloxane with SiC-bonded radicals R1 and additionally, similar or different SiOC-bonded radicals R2, R1 being an optionally substituted hydrocarbon radical with 1 to 18 C-atoms and R2 being a radical consisting of carbon and hydrogen atoms, carbon, hydrogen and at least 2 oxygen atoms or carbon, hydrogen, oxygen and silicon atoms, with at least 6 C-atoms, and silicone resin consisting mainly of triorganosiloxy- and SiO¿4/2? units are used for controlling foam of aqueous washing liquors during washing of textiles of this type.

Description

Foam regulation of aqueous washing liquors

The invention relates to the regulation of foams which occur when washing certain textiles, in particular machine textile washing processes.

Aqueous washing liquors containing surfactants, such as those used in household textile washing, tend to form more or less pronounced foams when exposed to mechanical energy. While a specifically set amount of foam can possibly contribute positively to the washing performance, an excessive amount of foam should be avoided, particularly in the case of machine washing processes, because of the risk of the potential loss of liquor due to overexposure. In addition to this risk of loss of active substances from the washing liquor available for washing the soiled textile, foams which occur in excessive quantities also impair the transfer of mechanical energy from the washing machine to the laundry, so that, for this reason too, washing results which are not optimal can occur . Conventional detergents therefore generally contain active substances which are intended to prevent excessive amounts of foam from forming in the wash liquor. In addition to paraffin waxes, silicone oils are primarily used as such foam regulator active ingredients. Both have in common that they are largely insoluble in water.

More recently, there are increasing numbers of articles of clothing which claim that ironing can be dispensed with after washing and drying, because they are at least largely crease-free from the washing and drying process. Such textiles also have the advantage that they do not lose their shape when worn, or at least less so. This is achieved by applying special finishing materials to the textiles or the materials or fiber materials from which they are made, for example cotton. Is common treatment with reactive siloxanes, which are drawn onto the textile or fiber surface and, if appropriate, are crosslinked with one another in a thermal aftertreatment step with the formation of resins.

In the case of such non-iron finished textiles, one can observe an increased occurrence of stains on the textile surface after washing, which can not be removed by further or repeated washing. Deeper investigations showed that these stains do not essentially go back to textile soiling that already existed before the washing process.

Surprisingly, it has now been found that the occurrence of such stains can be avoided or at least significantly reduced in extent if the non-iron textiles are washed using an aqueous washing liquor which contains certain silicone-based foam regulating agents.

The invention relates to the use of silicone combinations of (a) essentially linear polydimethylsiloxane, (b) essentially linear organopolysiloxane which, in addition to SiC-bonded radicals R ', has identical or different SiOC-bonded radicals R ² , where R ^{1 is} an optionally substituted one Hydrocarbon radical having 1 to 18 carbon atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, of carbon, hydrogen and at least 2 oxygen atoms or of carbon, hydrogen, oxygen and silicon atoms with at least 6 carbon atoms, and (c) silicone resin consisting predominantly of triorganosiloxy and SiO _4/2 units for foam regulation of aqueous washing liquors when washing textiles finished without ironing.

Another object of the invention is a method for washing non-iron finished laundry using an aqueous wash liquor containing a detergent containing a silicone combination of (a) essentially linear polydimethylsiloxane, (b) essentially linear organopolysiloxane, which in addition to SiC-bound residues R ^{1 has} identical or different SiOC-bonded radicals R ² , where R ^{1 is} a optionally substituted hydrocarbon radical having 1 to 18 carbon atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, of carbon, hydrogen and at least 2 oxygen atoms or of carbon, hydrogen, oxygen and silicon atoms with at least 6 carbon atoms Is atoms, and (c) contains predominantly silicon resin consisting of triorganosiloxy and SiO _4/2 units in addition to the usual ingredients compatible with it.

The essentially linear polydimethylsiloxane (component a), also referred to below as primary polysiloxane, can carry terminal hydroxyl groups and / or trimethylsiloxy groups in a known manner. It is preferably liquid at room temperature and, at 25 ° C., has a viscosity of in particular 35 mmV ¹ to 100,000 mmV ¹ , preferably 50 mmV to 50,000 mmV ¹ . In this context, the term “essentially linear” is to be understood to mean that there is only a very small degree of branching which cannot be avoided in terms of production technology. This means that in the primary polysiloxane normally at most 0.05 mol%, in particular at most 0.01 mol%, of CH There are ₃ SiO _3/2 units.

The silicone resins (component c) are solid at room temperature. The organosiloxy groups in the silicone resin are preferably selected from the Si-bonded methyl, ethyl and propyl groups, the use of silicone resins in which the organosiloxy groups are at least 80% methylsiloxy groups is particularly preferred. Silicone resins composed of (CH ₃ ) ₃ SiO _1/2 and SiO _4/2 units are particularly preferred, in which in particular 0.25 to 1.25 (CH ₃ ) ₃ SiO _1/2 units per 1 SiO _{4 / 2} unit are present. Due to the manufacturing process, they can contain up to about 5% by weight of Si-bonded methoxy, ethoxy or hydroxyl groups. The weight ratio of polydimethylsiloxane to silicone resin is preferably in the range from 99: 1 to 80:20, in particular from 95: 5 to 90:10.

The silicone combination contains to improve the miscibility of the silicone resin with the polydimethylsiloxane as well as because of the then generally higher foam regulator performance and low staining when used during washing in addition to the polydimethylsiloxane, an essentially linear organopolysiloxane (which is also referred to below as secondary polysiloxane; component b), which, in addition to SiC-bonded radicals R ^{1, has} identical or different SiOC-bonded radicals R ² , where R ^{1 has} an optionally substituted hydrocarbon radical 1 to 18 carbon atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, of carbon, hydrogen and at least 2 oxygen atoms or of carbon, hydrogen, oxygen and silicon atoms with at least 6 carbon atoms. R ¹ is preferably an optionally substituted hydrocarbon radical having 1 to 6 carbon atoms, in particular a methyl group. R ² (including the oxygen atom bound to Si) is preferably a C ₆ to C ₃₀ alkoxy group, in particular a C ₁₅ to C ₂₅ alkoxy group. Such secondary polysiloxanes can be prepared in a known manner, for example by condensation of organopolysiloxanes containing Si-bonded hydroxyl groups with alcohols of the general formula R ² OH, in which R ^{2 has} the abovementioned meaning, in the presence of acidic or alkaline catalysts such as acid-treated bentonite or methanolic Potassium hydroxide. The secondary polysiloxane is preferably liquid at room temperature and in particular has a viscosity in the range from 50 mmV 'to 500,000 mmV ¹ at 25 ° C. Here too, the term “essentially linear” is to be understood to mean that there is only a very small degree of branching in the secondary polysiloxane which cannot be avoided in terms of production technology. This means that in the secondary polysiloxane normally at most 0.01 mol% of CH ₃ SiO _3/2 units The weight ratio of secondary polysiloxane to silicone resin is preferably in the range from 1: 5 to 5: 1, in particular 1: 2 to 2: 1.

The silicone combination can additionally contain finely divided fillers, for example hydrophilic or hydrophobic silicon dioxide, so-called highly disperse silica. Pyrogenic or precipitated, in particular hydrophobized, silicon dioxide with a surface area of at least 50 m ² / g is particularly preferred. The weight ratio of silicone resin to silica is preferably in the range from 25:75 to 50:50. The production of silicone combinations suitable according to the invention is described in particular in European patent EP 0 301 531 B1. In addition to avoiding stains on the textile surface, their use leads to excellent foam regulation, particularly in machine washing processes.

In addition to the silicone combination essential to the invention, a foam-regulating paraffin wax can be used. This generally represents a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point. This is the temperature at which the wax changes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms are not usable according to the invention, their proportion in wax wax should therefore be as low as possible and is preferably below the limit that is significantly measurable with conventional analytical methods, for example gas chromatography. Waxes which solidify in the range from 20 ° C. to 70 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature. Preferred paraffin waxes are solid at room temperature and have a liquid content of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C. and a liquid content of at least 90% by weight at 60 ° C. on. The consequence of this is that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C., preferably down to at least 60 ° C. It is also important to ensure that the paraffins do not contain any volatile components. Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Such paraffin waxes are usually used in a mixture with bisamides which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as described in natural fats or hardened oils, such as tallow or hydrogenated palm oil, are available. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine. As described in European patent application EP 309 931, the bisamides are preferably in finely divided form and in particular have an average grain size of less than 50 μm. The maximum particle size of the particles is preferably below 20 μm, with at least 50%, in particular at least 75%, of the particles being smaller than 10 μm. This information regarding the particle size relates to the known determination method with the "Coulter Counter". The mixture of paraffin wax and bisamide can be prepared by introducing the finely divided bisamide into a melt of the paraffin wax and homogenizing it by intensive mixing. For this purpose, the melt should have a temperature of at least 90 ° C and at most 200 ° C. The temperature is preferably 100 ° to 150 ° C. The existence of a stable dispersion of the bisamide particles in the paraffin matrix is essential for a good contribution to the defoamer performance. In order to achieve this state of dispersion, a bisamide can be used and dispersed which has an appropriate fine particle size from the outset, or a more coarse starting material is used and the melt is subjected to intensive stirring treatment or grinding treatment using colloid mills, tooth mills or ball mills until the desired particle size is reached. A complete melting of the bisamides in the paraffin melt and subsequent rapid cooling to temperatures below the solidification point of the bisamides with simultaneous homogenization of the melt can lead to a correspondingly fine particle size distribution of the bisamides. The mixture of paraffin wax and bisamide preferably contains 80% by weight to 95% by weight, in particular 82% by weight to 90% by weight of paraffin wax and 5% by weight to 20% by weight, in particular 10% by weight. -% to 18% by weight bisamide. Such paraffin defoamer mixtures, that is to say paraffin waxes or paraffin wax / bis- amide mixtures are preferably used with the above-mentioned silicone combination in a weight ratio of 99: 1 to 20:80.

The use according to the invention can take place in individual form through the joint use of the components mentioned. Liquid detergents for use in textile laundry preferably contain all components in order to avoid metering problems during use; As an advantage, it should be mentioned here that the additional use of so-called deaerators, which are intended to prevent the formation of foam during production and filling, can be dispensed with in the production of such liquid agents. The use of at least some of the foam regulator components used according to the invention in solid form, in the form of a granular, free-flowing foam regulator, containing granular, water-soluble or water-dispersible, inorganic and / or organic carrier material and with which all or some of the foam counter-constituents mentioned are adsorbed, is particularly advantageous in connection with particulate detergents , preferably at least the silicone combination being made up in a solid form with the aid of granular carrier material. Such foam regulating agents preferably contain 80% by weight to 95% by weight, in particular 82% by weight to 92% by weight of carrier material and 5% by weight to 20% by weight, in particular 8% by weight to Contain 18% by weight of foam regulator components. The invention furthermore relates to the use of a particulate detergent which comprises a silicone combination of (a) essentially linear polydimethylsiloxane, (b) essentially linear organopolysiloxane which, in addition to SiC-bound radicals R ^{1, has} identical or different SiOC-bound radicals R ² , where R ^{1 is} an optionally substituted hydrocarbon radical having 1 to 18 carbon atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, of carbon, hydrogen and at least 2 oxygen atoms or of carbon, hydrogen, oxygen and silicon atoms is at least 6 carbon atoms, and (c) for the most part contains silicone resin consisting of triorganosiloxy and SiO _4/2 units in solid form with the aid of granular carrier material in addition to the usual compatible ingredients for washing non-iron finished textiles. The preferably phosphate-free carrier material has a granular structure and consists of water-soluble or water-dispersible, surfactant-free compounds, primarily of inorganic and / or organic salts, which are suitable for use in detergents and cleaning agents. The water-soluble inorganic carrier materials include, in particular, alkali carbonate, alkali borate, alkali alumosilicate and / or alkali sulfate, optionally with additions of alkali silicate, the latter being able to contribute to good grain stabilities of the agents according to the invention. The alkali silicate is preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The additional inorganic materials that can be used include, in particular, zeolites and layered silicates, for example bentonite. The zeolites which can be used in the carrier material for the foam regulating agents according to the invention include, in particular, zeolite A, zeolite P and zeolite X.

Examples of suitable organic carrier materials are the acetates, tartrates, succinates, citrates, carboxymethylsuccinates and the alkali metal salts of aminopolycarboxylic acids, such as EDTA, hydroxyalkanephosphonates and aminoalkane polyphosphonates, such as 1-hydroxyethane-1, l-diphosphonate and ethylenediaminodiamonetronamino-di-aminophonate-di-aminophosphonate-ethylenediaminodiaminotetramino-tri-aminophonate-ethylenediaminophenate. Also useful are water-soluble salts of polymeric or copolymeric carboxylic acids, for example copolymers of acrylic acid and maleic acid, and the polycarboxylic acids known, for example, from international patent application WO 93/08251, which are obtained by oxidation of polysaccharides. The preferred alkali metal in the alkali salts mentioned is sodium in all cases. Organic substances that are not in salt form, such as starch or starch hydrolysates, can also be used as carrier material components. Mixtures of inorganic and organic salts can often be used with advantage.

The carrier material can moreover be film-forming polymers, for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylates and cellulose derivatives. The cellulose derivatives which can be used include cellulose ethers, in particular alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Mixtures of sodium carboxymethyl cellulose and methyl cellulose are preferably used, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way. Such film-forming polymers are preferably not contained in the carrier material in excess of 5% by weight, in particular from 0.5% by weight to 2% by weight, based on the total carrier material.

In a preferred embodiment, the carrier material component of the foam regulating agent contains up to 99% by weight, in particular 60% by weight to 95% by weight, of alkali carbonate and / or alkali metal sulfate, in particular sodium carbonate and / or sodium sulfate, up to 35% by weight, in particular from 0.5% by weight to 30% by weight of alkali silicate, in particular sodium silicate and up to 5% by weight, in particular 0.5% by weight to 2% by weight of water-soluble or water-swellable polymer, in particular Cellulose ether.

A foam regulating agent according to the invention can be produced by applying the liquid or melt-liquefied foam regulator active ingredients to the granular carrier material, for example by successive admixing, in particular as a spray, to the carrier grain. The carrier grain, which can be produced in the customary manner by spray drying an aqueous slurry of the carrier salts, is kept in motion by mixing elements or by fluidization in order to ensure uniform loading of the carrier material. Afford. The spray mixers used for this can be operated continuously or discontinuously. One embodiment for the production consists in spinning the granular carrier material in a continuous stream through the spray zone of the at least partially melted defoamer mixture, which is also continuously generated, whereby residence times of the carrier material in the hot spray zone of usually less than 1 second can be achieved. Furthermore, it is possible immediately afterwards to cool the particles of the foam regulating agent with the aid of a gas stream, so that the thermal loads on the material can be kept extremely low. The method described above uses a type of method as is known, for example, from European patent application EP 048 312. In a further embodiment according to the invention, the foam regulating agent is prepared in such a way that the carrier material is dissolved or slurried in water, the foam regulator constituents are dispersed therein as a premix or in the form of the separate individual components, and this slurry is then spray-dried. A water-soluble, non-surfactant dispersion stabilizer in the form of a water-swellable polymer is preferably added to the dispersion since the foam regulator components are generally not sufficiently soluble in the aqueous slurry. Examples of these are the cellulose ethers mentioned, homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene. The addition of such compounds acting as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% by weight to 3% by weight, based on the composition. Depending on the type or solubility of the carrier salt, the water content of the slurry can be 30% by weight to 60% by weight. The spray drying of the dispersion can be carried out in a known manner in systems provided for this purpose, so-called spray towers, using hot drying gases conducted in cocurrent or countercurrent, as described, for example, in international patent application WO 91/12306 drying gases carried with the spray material are preferred, since the activity loss attributable to the potential hot air volatility of some constituents of the defoamer mixture to be used according to the invention Minimum can be lowered. A particularly preferred production process by means of spray drying uses the processes known from German patent application DE 40 30 688, European patent EP 0 625 922 B1 or international patent application WO 93/15815. Superheated steam is used as the drying gas, which can normally be circulated and heated outside the drying zone.

Examples

example 1

A foam regulator (B1) produced by spray drying according to WO 91/12306 and containing 10% by weight of the silicone combination according to Example 1 of EP 0 301 531, and for comparison a foam regulator (VI) containing about 0.25 mol in the primary polysiloxane % CH ₃ SiO _3/2 - units and differed from Bl in the absence of the secondary polysiloxane, was mixed in such amounts with a foam-regulator-free powder detergent that the concentration of defoamer active substance in the resulting detergent was 0.15% by weight . The non-iron finished shirts listed in Tables 1 and 2 (2.1 kg per wash load, addition of a bundle of cotton threads provided with 1.5 g of a standardized dust / skin fat stain) were in the Cottons program at 60 ° C respectively 90 ° C (Miele® W918, detergent dosage 75 g, water hardness 16 ° dH) and then dried by hanging on a hanger. This procedure was repeated two more times. The degree of staining was then assessed by a panel of 10 people, with a grading scale from 0 (stain-free) to 1 (few point stains), 2 (few larger stains), 3 (many point stains), 4 (many larger stains) , and 5 (single large-area stains) to 6 (several large-area stains) was used. The average grades are given in the table below.

Table 1: Stain marks at 60 ° C

Detergent with non-iron cotton foam regulator A B C

Bl 0.1 0.0 0.2

VI 2.8 0.0 1.2

A Etema excellent® B Yom® C Jacques Britt comfort® Table 2: Stain marks at 90 ° C

Detergent with non-iron cotton foam regulator A B

Bl 0.3 0.3 0.3

VI 2.4 0.8 1.1

A Eterna excellent® B Yom® C Jacques Britt comfort® nb: not determined

The repetition of the tests with non-iron-finished shirts or with mixtures of non-ironed and non-ironed shirts in all cases resulted in a stain-free washing result for the non-ironed shirts.

Example 2

Example 1 was repeated, except that the particulate foam regulators B1 and VI were not used, but the corresponding amount of defoamer active substances (B2 and V2) contained therein was added directly to the basic detergent. The following stain marks resulted:

Table 3: Stain marks at 60 ° C

A Eterna excellent® B Yom® C Jacques Britt comfort® nb: not determined

Table 4: Stain marks at 90 ° C

Detergent with non-iron cotton foam regulator A B C

B2 0.2 0.0 0.9

V2 3.4 0.1 2.6

A Etema excellent® B Yom® C Jacques Britt comfort®

The repetition of the tests with non-iron-finished shirts or with mixtures of non-ironed and non-ironed shirts also resulted in a stain-free washing result for the non-ironed shirts in all cases.

Claims

claims

1. Use of silicone combinations of (a) essentially linear polydimethylsiloxane (primary polysiloxane), (b) essentially linear organopolysiloxane (secondary polysiloxane) which, in addition to SiC-bound radicals R ^{1, has} identical or different SiOC-bound radicals R ² , where R ¹ an optionally substituted hydrocarbon radical with 1 to 18 C atoms and R ² a radical composed of carbon and hydrogen atoms, carbon, hydrogen and at least 2 oxygen atoms or carbon, hydrogen, oxygen and silicon atoms with at least 6 C atoms, and (c) silicone resin consisting predominantly of triorganosiloxy and SiO _4/2 units for foam regulation of aqueous washing liquors when washing textiles finished without ironing.

2. Use according to claim 1, characterized in that the weight ratio of primary porosiloxane to silicone resin is in the range from 99: 1 to 80:20, in particular 95: 5 to 90:10.

3. Use according to claim 1 or 2, characterized in that the primary polysiloxane is liquid at room temperature and in particular at 25 ° C has a viscosity in the range from 35 mmV ¹ to 100,000 mmV ¹ .

4. Use according to one of claims 1 to 3, characterized in that the weight ratio of secondary polysiloxane to silicone resin is in the range from 60:40 to 40:60.

5. Use according to one of claims 1 to 4, characterized in that the secondary polysiloxane is liquid at room temperature and in particular at 25 ° C has a viscosity in the range from 50 mm to 500 000 mmV ¹ .

6. Use according to one of claims 1 to 5, characterized in that the silicone combination additionally contains highly disperse silica.

7. Use according to claim 6, characterized in that the weight ratio of silicone resin to silica is in the range from 25:75 to 50:50.

8. Use according to one of claims 1 to 7, characterized in that the silicone combination is present in a solid form with the aid of granular carrier material.

9. Use according to claim 8, characterized in that the packaging form 80 wt .-% to 95 wt .-%, in particular 82 wt .-% to 92 wt .-% carrier material and 5 wt .-% to 20 wt .-% , In particular 8 wt .-% to 18 wt .-% silicone combination.

10. Use according to claim 8 or 9, characterized in that the carrier material up to 99 wt .-%, in particular 60 wt .-% to 95 wt .-% alkali carbonate and / or alkali sulfate, especially sodium carbonate and / or sodium sulfate, up to 35% by weight, in particular from 0.5% by weight to 30% by weight, of alkali silicate, in particular sodium silicate and up to 5% by weight, in particular 0.5% by weight to 2% by weight, of film film contains the water-soluble or water-swellable polymer, in particular cellulose ether.

11. Use according to one of claims 1 to 10, characterized in that in addition to the silicone combination, a paraffin defoamer mixture containing 70% by weight to 95% by weight of a paraffin wax and 5% by weight to 30% by weight of one of C _2-7 - diamines and saturated C ₁₂ . Contains _22- carboxylic acid derived bisamide, is present.

12. Use according to claim 11, characterized in that the weight ratio of silicone combination to paraffin defoamer mixture is in the range from 1:99 to 80:20.

13. A process for washing non-iron finished laundry using an aqueous wash liquor which contains a detergent containing a silicone combination of (a) in essentially linear polydimethylsiloxane (primary polysiloxane), (b) essentially linear organopolysiloxane (secondary polysiloxane) which, in addition to SiC-bonded radicals R ^{1, has} identical or different SiOC-bonded radicals R ² , where R ^{1 is} an optionally substituted hydrocarbon radical with 1 to 18 C - Atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, of carbon, hydrogen and at least 2 oxygen atoms or of carbon, hydrogen, oxygen and silicon atoms with at least 6 C atoms, and (c) for the most part contains silicone resin consisting of triorganosiloxy and SiO _4/2 units in addition to the usual compatible ingredients.

14. Use of a particulate detergent which comprises a silicone combination of (a) essentially linear polydimethylsiloxane (primary polysiloxane), (b) essentially linear organopolysiloxane (secondary polysiloxane) which, in addition to SiC-bonded radicals R ^{1, has} identical or different SiOC-bonded radicals R ² has, where R ^{1 is} an optionally substituted hydrocarbon radical having 1 to 18 carbon atoms and R ^{2 is} a radical composed of carbon and hydrogen atoms, carbon, hydrogen and at least 2 oxygen atoms or carbon, hydrogen, oxygen and silicon atoms with at least 6 carbon atoms, and (c) contains predominantly silicon resin consisting of triorganosiloxy and SiO _4/2 units in solid form with the aid of granular carrier material in addition to the usual compatible ingredients for washing non-iron finished textiles.