EP2267216A1 - Use of aqueous wax dispersions for improving mechanical characteristics of textile fibres - Google Patents

Abstract

A method for improving the mechanical properties of textile fibres involves treating the fibres with aqueous media containing (in addition to water) at least (a) a dispersant, (b) a wax component and optionally (c) other auxiliary agents and additives.

Description

The present invention relates to a process for improving the mechanical properties of textile fibers.

Detergents and cleaners are produced in large quantities for the end user. The main application is the cleaning of textile fabrics and hard surfaces in the household and commercial area. The detergents and cleaners can be prepared both in solid, usually as a powder or granules, or in liquid form. The liquid formulations have become increasingly popular in recent years due to their ease of use with consumers. In addition, the liquid detergents and cleaners are simpler and with less energy to produce, which is an additional motivation for the manufacturers of detergents and cleaning agents. The main ingredients of liquid detergents and cleaners are water, the washing-active substances or surfactants called, the builder system, Löslichkeitsverbesserer, special additives such as grayness inhibitors or dye transfer inhibitors, the enzyme system, the perfume oils and possibly preservatives and dyes.

Furthermore, it is also known that textiles are damaged when worn, but especially during washing. In the case of washing, these can be either chemical effects, such as, for example, oxidizing bleaches, washing alkalis or also the water alone, which, for example, leads to strong swelling of the fibers in the case of cotton. In addition, there are mechanical damage to the textiles by the washing movements in the washing machine or by scrubbing and wrinkling when wearing. Both mechanisms of damage can also overlap if, for example, fibers with deposits caused by the calcium and magnesium hardness of the washing water, such as, for example, sparingly soluble alkaline earth metal phosphates, additionally rub against one another during washing. In particular, mild detergents already contain additives to protect the textiles during washing. These can be, for example, stronger or finer-pore foaming surfactant systems which surround the textiles with a foam layer during washing. Furthermore, certain cationic surfactants, which are also used in fabric softeners Find use in the liquid detergents. These cationic surfactants, such as, for example, triethanolamine-based esterquats or cetyltrimethylammonium chloride, because of their cationic charge, are substantive on cellulose-containing textiles, especially cotton, and can reduce fiber friction against one another. It is also known to use certain cationic polymers or silicone compounds for this purpose. The disadvantage of the cationic compounds is their interaction with the anionic. Surfactant systems, which are preferably used in liquid detergents due to their good price-performance ratios. This interaction often leads to a significant deterioration of the washing performance. Therefore, these cationic compounds can usually only be incorporated into nonionic surfactant systems, which, however, generally have an overall poorer wash performance than the nonionic / anionic based detergent formulations.

The object of the present invention was therefore to provide a method by which mechanically and / or chemically damaged textile fibers can be improved in their strength, or a method for preventing damage to textile fibers by detergents or washing methods.

It has been found that the application of certain aqueous wax dispersions to the textile fibers can solve the problem.

A first subject of the present application therefore relates to a process for improving the mechanical properties of textile fibers by applying to the fibers aqueous agents containing at least water (a) alkyl (oligo) glycosides together with (b) a mixture of mono- and Diesters of saturated and unsaturated fatty acids having 16 to 22 C atoms with diols and polyols, and optionally (c) other auxiliaries and additives.

Damage to the mechanical properties of fibers can be done, for example, by measuring the decrease in tear strength. For this purpose, there are various textile-technical test methods which are described in the corresponding DIN standards (strip test, maximum tensile strength DIN EN ISO 13934-1, thigh tear propagation test DIN EN ISO 13937-2, grave test, maximum tensile strength DIN EN ISO 13934-2, Elmendorf, DIN EN ISO 13937-1) are described. The fiber damage caused by chemical effects of cellulose-containing fabrics, in particular cotton, can be evaluated, for example, by measuring the degree of polymerization after dissolution in a standardized EWN solution and determining the viscosity. The use of the wax dispersions according to the invention leads to an improvement, thus to an increase in the breaking strength and a reduction in the tendency to tearing, compared in each case with untreated textile fibers. This advantageous effect preferably occurs in cellulosic fibers and / or wool fibers in appearance. In addition, the wax dispersions are suitable for generally improving the mechanical properties of textile fibers and preferably for reducing their tendency to thicken or for increasing their tensile strength.

Textile fibers are understood as meaning all fibers that can be processed textile. Compared to their cross-section, they have a great length together with sufficient strength and flexibility. The textile fibers which are treated by means of the process according to the invention may consist of or contain both natural fibers or synthetic fibers or mixed systems. Particular preference is given to those fibers which consist entirely or proportionally, but preferably more than 30%, of natural fibers, such as wool or cotton. Of course, in addition to the individual fibers, textile surface products containing these fibers, e.g. Garments accessible to the method claimed here.

The aqueous agents for use in the process according to the invention, in addition to the water, still necessarily contain the two components (a) and (b) side by side. Component (a) is preferably alkyl (oligo) glycosides, component (b) is preferably mixtures of esters based on diols or polyols with selected fatty acids. The agents themselves are wax dispersions, i. that water-insoluble wax is distributed finely distributed in the means - but the term dispersion also includes emulsions and solutions.

Component (a)

The wax dispersions necessarily contain dispersants or emulsifiers, preferably nonionic, anionic emulsifiers or mixtures, in order to keep the water-insoluble or sparingly water-soluble wax components in the solution from nonionic and anionic emulsifiers. The use of cationic emulsifiers, such as, for example, ethoxylated or propoxylated fatty amines or quaternized amine compounds, is also possible if the wax dispersions are to be used in special washing or softener formulations containing, for example, the esterquats.

The nonionic emulsifiers may be ethoxylated or propoxylated products such as ethoxylated or propoxylated fatty alcohols, fatty acids or fatty amines. In addition, ethylene oxide-free emulsifiers may also be used, such as, for example, glycerol esters, carbohydrate esters or sugar esters, methylglucoside esters or alkylpolyglucosides. The latter are particularly preferred emulsifiers for the purposes of the present invention: alkyl and / or alkenyl oligoglycosides are known nonionic surfactants which follow formula (I),

R ¹ O- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (I) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, Capric alcohol and undecyl alcohol and their technical mixtures, as obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol can be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

Furthermore, as component (a) it is also possible to use anionic emulsifiers or mixtures of anionic and nonionic emulsifiers. The anionic emulsifiers may, for example, be saturated or unsaturated fatty alcohol sulfates, it being possible for the fatty alcohols to contain 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms. Furthermore, it is also possible, for example, to use fatty alcohol ether sulfates, alkylbenzene sulfates, sulfonated fatty acids or methyl esters or sulfosuccinates.

Component (b)

The wax dispersions according to the invention contain as component (b) waxes: both waxes based on renewable raw materials may be present, as well as products based on petrochemical raw materials.
The waxes are preferably based on renewable raw materials, ie in particular waxes which can be prepared, for example, by esterification, transesterification, etherification or amidation. In these methods, for example, longer-chain fatty acids, fatty alcohols and fatty amines, preferably with C-chains of C6 - C22 can be used. Furthermore, it is also possible long-chain fatty acids, fatty acid chlorides, fatty alcohols or fatty amines, with short-chain, mono- or polyvalent Carboxylic acids, alcohols or amine compounds, aminocarboxylic acids, hydroxylamine compounds to combine, so for example, ethanol, n-butanol, ethylene glycol, diethylene glycol, glycerol, triethanolamine, aminoethylethanolamine. The melting point of these waxes is preferably between 20 ° C and 120 ° C, more preferably between 30 ° C and 80 ° C. Examples which may be mentioned, without being exhaustive, are: butyl stearate, cetyl palmitate, ethylene glycol distearate, glycerol monostearate, stearyl citrate, triethanolamine distearate, stearyl glutamate.

Furthermore, waxes based on petrochemical raw materials can also be used in principle, although not preferred. These include, for example, simple hydrocarbon compounds, such as paraffin waxes, or also prepared by polymerization homopolymers, such as polyethylenes, polyvinyl acetates, polyacrylates, oxidized homopolymers such as oxidized polyethylenes, copolymers based on ethylene-acrylic acid, ethylene-propylene-maleic anhydride, ethylene vinyl acetate or micronized polyethylene waxes. The melting point of these compounds is preferably between 40 ° C and 160 ° C, more preferably between 60 ° C and 140 ° C. Examples include a commercial product - again without being exhaustive: AC330, AC 175, AC 5120, ACumist A12 from Honeywell, Licowax PE 130, Licowax PED 521, Licowax PED 192 from Clariant, Luwax OA3 wax from Fa. BASF. Furthermore, it is also possible blends of waxes, both waxes based on renewable resources, as well as blends of petrochemical waxes and blends of waxes based on renewable raw materials and petrochemical waxes to produce.

However, the component (b) preferably consists in turn of several different components, namely esters of diols, preferably glycol or its oligo- or polymers, and also esters of polyols, preferably esters of glycerol, these glycerol esters preferably in Form of their partial esters, so as mono- and / or diesters use find. Suitable diol esters for the purposes of the present technical teaching are in particular the esters of diols, in this case preferably of glycol and its oligomers or polymers. Suitable oligomers are polyethylene glycols and as polymers the ethylene glycols having molecular weights of 100 and greater, preferably 100 to 1,000 into consideration. These are esterified in a conventional manner with fatty acids. As fatty acids, saturated fatty acids having 16 to 22 carbon atoms are used, with stearic acid being particularly preferred. A particularly preferred diester component is a glycolic stearic acid diester. Fatty acid partial glycerides, ie monoglycerides, diglycerides and their technical mixtures may still contain small amounts of di- and triglycerides as a result of the preparation. Low amounts mean that preferably only 1 to at most 10% by weight, in particular up to a maximum of 5% by weight, based on the total amount of glycerides, represent triglycerides.

in der R²CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R³ und R⁴ unabhängig voneinander für R²CO oder OH und die Summe (m+n+p) für 0 oder Zahlen von 1 bis 100, vorzugsweise 5 bis 25 steht, mit der Maßgabe, dass mindestens einer der beiden Reste R³ und R⁴ OH bedeutet. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden technische Laurinsäureglyceride, Palmitinsäureglyceride, Stearinsäureglyceride, Isostearinsäureglyceride, Ölsäureglyceride, Behensäureglyceride und/oder Erucasäureglyceride eingesetzt, welche einen Monoglyceridanteil im Bereich von 50 bis 95, vorzugsweise 60 bis 90 Gew.-% aufweisen. Insbesondere werden längerkettige Partialglyceride z.B. basierend auf Ölsäure oder Stearinsäure eingesetzt insbesondere Gemische von Glyceriden auf Basis von gesättigten und ungesättigten Fettsäuren.Preferably, such glycerides (ie, if necessary, mixtures of di- and monoglycerides) are used, which are free of triglycerides. However, the partial glycerides preferably follow the formula (II),

in the R ² CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ³ and R ⁴ independently of one another R ² CO or OH and the sum (m + n + p ) is 0 or numbers from 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R ³ and R ^{4 is} OH. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, Gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preference is given to using technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides, isostearic acid glycerides, oleic acid glycerides, behenic acid glycerides and / or erucic acid glycerides which have a monoglyceride content in the range from 50 to 95, preferably 60 to 90% by weight. In particular, longer-chain partial glycerides, for example based on oleic acid or stearic acid used in particular mixtures of glycerides based on saturated and unsaturated fatty acids.

The partial esters as described above are preferably used as a mixture of mono- and diesters of glycerol with saturated and unsaturated fatty acids having in each case 16 to 22 C atoms. As saturated fatty acid, palmitic and stearic acid are of particular importance, whereas oleic acid is to be selected as the unsaturated fatty acid. Thus, those agents are preferred which contain in the mixture of component b) glycerol partial esters based on palmitic or stearic acid and oleic acid side by side. The components a) and d) of the agents according to the invention are preferably present in a weight ratio of 1: 3 to 3: 1, preferably 1: 3 to 1: 1 and in particular from 1: 2 to 1: 1 side by side. In this case, the weight of component b) refers to all ingredients described above, ie both the diesters of the diols and the partial esters based on the polyols, preferably of glycerol. It is further preferred to use those agents in which the components a) and b) together in an amount of 0.1 to 15 wt .-% and in particular in amounts of 0.5 to 10 wt .-%, but preferably 1 to 5 wt .-% are included. The compounds according to the description of component b) are preferably water-insoluble, which means that they can be dissolved at 21 ° C. to less than 10, in particular less than 5,% by weight in water.

Furthermore, as wax compounds and esters of synthetic polyols, such as trimethylolpropane, pentaerythritol, di-pentaerythritol or neopentyl glycol can be used. Again, both completely esterified with saturated or unsaturated fatty acids products and partially esterified products for the preparation of wax dispersions can be used. In addition, wax compounds of naturally occurring polyols such as sucrose, glucose, methyl glucoside, sorbitan may also be used again as products completely esterified with saturated or unsaturated fatty acids or as partially esterified products.
In addition, for example, synthetically produced or based on renewable raw materials produced longer-chain fatty acids, fatty alcohols, hydrocarbons and fatty amines, preferably with C-chains of C6 - C22 both be used as the sole wax component as well as in admixture with the above-described possible compounds of component (b).

Component c)

In addition to water and the compulsory component (a) and (b), the compositions according to the invention may optionally contain further auxiliaries or additives. As auxiliaries or additives find thickener use.
Preferably, a thickener is used as an additive, ie a substance which increases the viscosity of the agent. Polymeric thickeners are typically selected from the groups of polyvinyl alcohols, polyacrylic acid and polymethacrylic acids and their salts, the polyacrylamides, polyvinylpyrrolidones, polyethylene glycols, styrene-maleic anhydride copolymers and salts thereof. In particular, polymers with thickening properties, in this case preferably those based on acrylate and (meth) acrylate, are preferred. Both homo- and copolymers or terpolymers can be used. In addition, it is also possible to use thickeners based on cellulose or derivatives thereof with success within the meaning of the present technical teaching. Examples of such thickeners are hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose or ethylhydroxyethylcellulose. It may furthermore be preferred to use, in addition to or as the sole component (c), polyethylene glycols, preferably those having molecular weights of 100 or greater, in particular having a molecular weight of from 100 to 500.

Furthermore, perfumes, dyes, other surfactants and / or non-aqueous solvents may be included.

Component c) is used in the wax dispersions used according to the invention in amounts of preferably from 1 to 25% by weight, preferably from 2 to 20% by weight and particularly preferably from 5 to 18% by weight. However, it should be pointed out again at this point that the component c) is optional and thus possibly completely dispensable.

The process according to the invention preferably employs agents which do not contain any additional cationic or other softening substances, it being possible in Exceptionally, it may well be possible to use such compounds with. In such cases, textile softeners of the type of quaternized ammonium compounds and in particular of the so-called ester quats are particularly preferred. As far as the use of surfactants is concerned, there is no dramatic limitation here; instead, all nonionic anionic, amphoteric or cationic surfactants known to the person skilled in the art can be used, the main emphasis being on the use of further conventional nonionic surfactants, such as, for example, fatty alcohol or fatty acid alkoxylates and / or or their derivatives may be.

Agents containing the preferred components (a) and (b) are already in the application EP 1 972 717 A1 The applicant is aware of the use of these agents to improve the sensory properties of textiles, not to improve their mechanical properties. The wax dispersions are prepared in a manner known to the person skilled in the art, that is to say for example by stirring the individual components with water, preferably at elevated temperatures.

The wax particles dispersed in the aqueous liquor during application are transferred to the washed or treated textiles during an application process in the context of the present technical teaching.
The application can be carried out, for example, by simply contacting it-preferably at temperatures of 30 to 90 ° C.-of the textile fabric with the wax dispersion or also in the course of a washing process, for example in a (household) washing machine. It is preferred to use a washing process in which in addition to the wax dispersion, a detergent, preferably a mild detergent is used. However, the present teaching also includes the configuration that the wax dispersion is applied alone to the textile.

The amounts transferred in this case depend strongly on further formulation constituents of the detergents. In particular, the presence of charged or uncharged polymers or cationic surfactants can have a noticeable effect here. In addition, the material and the weave of the washed textiles also influences the transfer of the wax particles. Related measurements in different In the case of an addition of, for example, 3% by weight of the wax dispersion, liquid detergents generally give contents of 0-100 ppm of active substance wax after 20 successive washing cycles on the treated textiles.
It may be advantageous to perform the application process several times in succession to apply an effective amount of wax to the fiber surface. Typical values are between 2 and 25 times repetition. Typical amounts of waxes applied to the fiber surfaces after application are in the range of 10 to 5000 ppm, and preferably 25 to 1500 and especially 100 to 600 ppm wax.
Furthermore, it may be advantageous if, after application of the wax dispersions to the textile, it is dried, and preferably the dried textile is subjected to a heat treatment. This heat treatment can be carried out, for example, by an ironing process, or by heating the textile with hot air, for example in a tumble dryer, or in the drying cycle of a washing machine. The temperatures should be in the range of 30 to 120 ° C for the heat treatment, but the temperature range of 30 to 80 and especially 35 to 65 ° C may be preferred.

The amount of added wax dispersion is preferably between 0.1 wt .-% - 10 wt .-% based on the amount of liquid detergent used, more preferably between 1 wt .-% - 5 wt .-%.

Furthermore, the wax dispersions in the context of the present teaching may preferably be used as constituents of detergents or cleaning agents known per se, preferably as a constituent of mild detergents and particularly preferably of liquid detergents and in particular of liquid mild detergents. For the purposes of the present teaching, mild detergents, in contrast to heavy-duty detergents, contain no brighteners and bleaching agents. If appropriate, the liquid detergents obtainable in the context of the invention may also have a non-aqueous content in the range from 5 to 50 and preferably 15 to 35% by weight. In the simplest case, however, they are aqueous solutions of said surfactant mixtures.

However, the wax dispersions according to the invention can also be incorporated into pulverulent, ie water-poor or anhydrous products. This can be done for example by adding or mixing the wax dispersion in a liquid detergent formulation, which is then sprayed subsequently. Furthermore, it is also possible to meter or spray a concentrated, aqueous wax dispersion or the molten wax itself into a detergent granulate. This can be done, for example, in a Lödige mixer and has the advantage that only the component (b), ie the actual wax, is metered and thus results in lower costs for the raw materials.
The present application also includes the teaching that wax does not apply in the form of an aqueous emulsion, but to meter in the wax as such (ie separately) into an aqueous liquor which already comprises the textile to be treated and the emulsifiers / dispersants required for dispersing or emulsifying contains.

The detergents which are used in the context of the present technical teaching together with the dispersed or emulsified waxes may contain, in addition to already mentioned surfactants, further typical ingredients, for example solvents, hydrotropes, bleaches, bleach activators, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, soil repellants, foam inhibitors, inorganic salts, polymers, and fragrances and dyes.

Suitable organic solvents are, for example, monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof. The compositions preferably contain from 2 to 20% by weight and in particular from 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or, in particular, of ethanol and glycerol. It is also possible that the preparations contain either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or polyethylene glycol alone with a molecular weight of between 200 and 2000, preferably to 600 in amounts of 2 to 17 wt .-% , As hydrotrope, for example, toluene sulfonate, xylene sulfonate, cumene sulfonate or mixtures thereof can be used.

Among the compounds serving as bleaches, which provide hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25 wt .-%. Preference is given to the use of sodium perborate monohydrate in amounts of from 10 to 20% by weight and in particular from 10 to 15% by weight. Its ability to bind free water to form tetrahydrate contributes to increasing the stability of the agent. Preferably, however, the preparations are free of such bleaching agents.

Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as the neutral reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which are present in amounts of 0.5 to 5, preferably 1 to 2 wt .-% can. As viscosity regulators, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2 wt .-%, for example, sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and especially copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably between 50,000 and 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight. The agents may additionally contain about 5 to 20% by weight of a partially esterified copolymer. These partially esterified polymers are obtained by copolymerization of (a) at least one C4-C28 olefin or mixtures of at least one C4-C28 olefin with up to 20 mol% of C1-C28 alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides having 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers having K values of 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C1-C13 alcohols, C8-C22 fatty acids, C1-C12-alkylphenols, secondary C2-C30-amines or mixtures thereof with at least one C2-C4-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, wherein the partial esterification of the copolymers is carried out to the extent that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolymers contain ethylenically unsaturated dicarboxylic anhydride maleic anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. Advantageously, the copolymers are used in the form of an aqueous solution, in particular in the form of a 40 to 50 wt .-% solution. The copolymers not only make a contribution to the primary and secondary washing performance of the liquid detergent and cleaning agent, but also cause a desired viscosity reduction of the concentrated liquid detergent. By using these partially esterified copolymers concentrated aqueous liquid detergents are obtained, which are flowable under the sole influence of gravity and without the action of other shear forces. The concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of from 5 to 15% by weight and in particular in amounts of from 8 to 12% by weight.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Their proportion can be about 0.2 to about 2 wt .-%. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are soluble in calcium salts and have a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized. However, the use of boron compounds, for example of boric acid, boron oxide, borax and other alkali metal borates is particularly advantageous.

Suitable soil repellent polymers are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, it being possible for the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate to be in the range from 50:50 to 90:10. More specifically, the molecular weight of the linking polyethylene glycol units is in the range of 750 to 5,000, that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and may have a block, but preferably a random structure. Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of from 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. For example, soaps of natural or synthetic origin, which have a high proportion of C 18-C24 fatty acids, are suitable for this purpose. Suitable non-surfactant-type foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. With advantage, mixtures of various foam inhibitors are also used, e.g. those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

In the fragrances and perfumes, which may be solid, but preferably liquid, are partially complex mixtures of different chemical compounds, the so-called fragrances. The fragrances can from the various chemical classes are selected. It is possible to distinguish between alkali-stable and less alkali-stable fragrances. The concomitant use of perfumes or fragrances in or together with the wax dispersions used according to the invention may be preferred. The content of fragrances or perfumes may vary between 0.01 and 15 wt .-%, with contents between 1.0 and 10 wt .-% and in particular 1.5 to 6 wt .-% (each based on the total weight of Wax dispersion or the detergent) are preferred.

The pH of the concentrated and particularly preferred agents according to the invention is generally from 7 to 10.5, preferably from 7 to 9.5 and in particular from 7 to 8.5. The setting of higher pH values, for example above 9, can be achieved by using small amounts of caustic soda or alkaline salts such as sodium carbonate or sodium silicate. The liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.).

However, it is of particular advantage that the agents according to the invention can be formulated or used without problems together with anionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and Dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable based wheat products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.

Examples 1.) washing tests with subsequent measurement of the tearing behavior after grave.

2500 g of cotton laundry, which in addition to the ballast laundry and a standard fabric type (wfk 10A) was twenty times in a row with 100 g of a mild detergent A, which contained a mixture of anionic and nonionic surfactants, at 40 ° C in a commercial household washing machine (Miele Softronic W 3527). Subsequently, the standardized tissue was removed and dried on a leash. The dry fabric was ironed with a commercial steam iron and cut according to DIN EN ISO 13934-2, that is, taking into account warp and weft direction. Subsequently, the excised tissue samples were clamped in each case in the direction of the chain in a Zwickmaschine and determined according to DIN EN ISO 13934-2 the maximum tensile force according to grave. The measurement was repeated five times.
For comparison, the same experiment was carried out using a mild detergent B, which contained the same mixture of anionic and nonionic surfactants as the mild detergent A, but additionally 3 wt .-% Plantatex ^® HCC from. Cognis performed.
The addition of the Plantatex ^® HCC was carried out by simple stirring of the aqueous wax dispersion in the mild detergent at room temperature.
Again, the same measurements were taken to determine the maximum tensile force according to DIN EN ISO 13934-2 (grab tensile test) and compared.

After the washing tests, the content of wax on the dry textiles was also analyzed by an extraction method with subsequent gas chromatographic determination in order to classify the effectiveness of the wax. Here, a wax content <5 ppm was found on the original (V) and the fabrics washed with mild detergent A (1A). On the fabrics washed with mild detergent B (1B), a content of 48 ppm wax was found.

In Table 1 below these values are compiled for comparison with the mean values for the maximum tensile force (+/- standard deviation). <u> Table 1 </ u> Original wfk 10A Mild detergent A Mild detergent B washing trial V 1A 1B Wax content [ppm] <5 <5 42 Maximum tensile strength [N] 556.1 471.8 519.5 +/- standard deviation +/- 51.9 +/- 19.1 +/- 39.2

A significant (T-test, 2-sided> 95%) improvement in the maximum tensile strength in the textiles washed with mild detergent B, ie using the wax dispersion, is seen here.

2.) Washing tests with subsequent measurement of the tear propagation behavior according to Elmendorf

2500 g of cotton laundry, which in addition to the ballast laundry and a standard fabric type (wfk 10A) was twenty times in a row with 100 g of mild detergent A from experiment 1, which contained a mixture of anionic and nonionic surfactants, at 40 ° C in a commercial household washing machine (Miele W Softronic ^® 3527) and dried. Subsequently, the standardized tissue was removed and dried on a leash.

The dry fabric was ironed with a commercial steam iron and cut according to DIN EN ISO 13937-1 (Elmendorf - tear resistance with the ballistic pendulum), that is, taking into account the warp and weft direction. Subsequently, the tear propagation force according to Elmendorf was determined with the cut-out tissue samples respectively in the direction of the warp or weft according to DIN EN ISO 13937-1. The measurement was repeated five times.

For comparison, the same experiment was carried out using the mild detergent B from experiment 1, which contained the same mixture of anionic and nonionic surfactants as the mild detergent A, but additionally 3 wt .-% Plantatex ^® HCC from. Cognis performed. The addition of the Plantatex ^® HCC was carried out by simple stirring of the aqueous wax dispersion in the mild detergent at room temperature.
Furthermore, the same experiment was carried out with the mild detergent C, which contained a mixture of cationic and nonionic surfactants and additionally 0.15 wt .-% of a wax consisting of a diol ester.

Furthermore, a washing test with the mild detergent D, which contained the same mixture of cationic and nonionic surfactants as the mild detergent C, but additionally 3 wt .-% Plantatex ^® HCC from. Cognis performed. The addition of the Plantatex ^® HCC was carried out by simple stirring of the aqueous wax dispersion in the mild detergent at room temperature.

Again, after analogous drying of the textiles, the same measurements were taken to determine the maximum tensile force according to DIN EN ISO 13937-1 1 and compared with each other. After the washing tests, the content of wax on the dry textiles was again analyzed to determine the effectiveness of the wax by an extraction method with subsequent gas chromatographic determination.

The following average values were determined in accordance with DIN EN ISO 13937-1 (Elmendorf - tear propagation force with the ballistic pendulum) for the tear propagation force (+/- standard deviation) in the direction of the warp and weft (Table 2): <u> Table 2 </ u> Original wfk10A Mild detergent A Mild detergent B Mild detergent C Mild detergent D washing trial V 2A 2 B 2C 2D Wax content on dried textiles [ppm] <5 <5 48 530 2400 Tear strength 10.94 9.04 9.86 17.9 20.6 - Chain [N] +/- +/- +/- +/- +/- +/- standard deviation 0.83 0.16 0.53 1.63 0.71 Tear strength 9.28 9.71 10.24 18.1 18.7 - Shot [N] +/- +/- +/- +/- +/- +/- standard deviation 0.23 0.17 0.75 0.78 1.51

It can be seen when using mild detergent B a significant (T-test, 2-sided> 95%) improvement in tear resistance, which then increases again when using mild detergent C or D with higher concentration of wax on the textiles.

Claims (13)

Process for improving the mechanical properties of textile fibers by applying to the fibers aqueous agents containing, in addition to water, at least one dispersant (a) and one wax component (b) and (c) optionally further auxiliaries and additives. A method according to claim 1, characterized in that the dispersant (a) is selected from the group of alkyl (oligo) glycosides together with waxes (b) namely a mixture of mono- and diesters of saturated and unsaturated fatty acids having 16 to 22 C Atoms with diols and polyols. A method according to any one of claims 1 to 2, characterized in that the wax component (b) is selected from the mono- and diesters of saturated and unsaturated fatty acids having 16 to 22 carbon atoms and preferably selected from palmitic or stearic acids and oleic acid with ethylene glycol or glycerin side by side. Method according to at least one of claims 1 to 3, characterized in that are selected as auxiliaries and additives (c) diols and / or polyols, preferably glycerol, glycol and / or polyethylene glycol. Method according to at least one of claims 1 to 4, characterized in that as adjuvants and additives (c) polymers, preferably those based on acrylic and / or (meth) acrylic acids are selected. A method according to any one of claims 1 to 5, characterized in that as adjuvants and additives (c) cationic compounds, preferably quaternized ammonium compounds or polymers are selected with cationic groups. A method according to any one of claims 1 to 5, characterized in that the means water in amounts of 1 to 99 wt .-%, preferably 10 to 99 wt .-% and in particular 40 to 90 wt .-% contain. Process according to at least one of Claims 1 to 7, characterized in that they contain components (a) and (b) together in an amount of from 0.1 to 15% by weight, in particular in amounts of from 1 to 10% by weight. contain. Method according to at least one of claims 1 to 8, characterized in that the components (a) and (b) in a weight ratio of 1: 3 to 3: 1, preferably 1: 3 to 1: 1 and in particular from 1: 2 to 1 : 1 next to each other. Method according to at least one of claims 1 to 9, characterized in that the wax dispersion is used together with a detergent, preferably a mild detergent. Method according to at least one of claims 1 to 10, characterized in that the wax dispersion is applied more than once to the textile fibers, preferably 2 to 25 times in succession. Use of aqueous agents as described in claim 1 for improving the mechanical properties of textile fibers, in particular a reduction of the tendency to tease. Use of aqueous agents as described in claim 1 for increasing the tensile strength of textile fibers.