EP0250510A1 - New dirt-collecting detergent in aqueous surfactant washing and cleaning solutions - Google Patents

Abstract

Multifunctional quaternary ammonium compounds (PQAV), which are insoluble even at high wash temperatures or which are attached to insoluble carrier materials, are used as detergents to remove dirt in wash and cleaning baths . Dirt-laden cleaning detergent is separated from items to be cleaned after washing or cleaning.

Description

 "New dirt-collecting cleaning enhancers in water-based washing and cleaning solutions"

The invention relates to new agents and methods that can be used in the cleaning of items contaminated in particular with pestle dirt. This particularly affects the washing or cleaning of all articles in a water-borne fleet. The most important area of application for such cleaning processes is textile washing.

As is known, the washing process of textiles with conventional washing agents comprises breaking up and detaching the soiling on or from the fiber. Considerable parts of the soiling are components that are insoluble in the wash liquor and pass into the wash liquor in the form of small undissolved particles. A sufficient suspension of the detached dirt particles is then a prerequisite for effective washing in order to prevent their deposition and at the same time graying of the washed goods. Conventional detergents contain additives that serve this task in particular. Adequate dirt-carrying capacity is also seen as an important function of the Buϊlder components of conventional detergent mixtures, which are known to contain synthetic surfactant Components in admixture with such Buϊlder components.

It is also known that in modern laundry detergents with a reduced phosphate content, the synthetic crystalline zeolites used as phosphate substituents and in particular the correspondingly finest insoluble NaA zeolite of laundry detergent quality counteract the graying by means of the large solid surface provided.

The detergent dosage contains numerous suggestions for reducing the graying tendency and thus improving the secondary washing power. Almost exclusively, all of these suggestions aim at the improved suspension, solubilization and stabilization of the particle dirt in the wash liquor, and especially in the rinsing phases of the washing process, in which the tendency to redeposition of detached particle dirt is increased by dilution of the washing chemicals. US Pat. No. 3,694,364 describes a different approach in principle: Here it is proposed to use a so-called "trap" material to take up the undissolved particle dirt from the wash liquor, if appropriate together with the prevention of anionic dye transfer. This dirt trap material consists of a water-insoluble cellulose cloth with a modified surface. This surface is equipped with secondary and / or tertiary polyamine compounds which are to be retained on this surface by first giving the cellulose surface an anionic character. This is done by introducing acidic groups, for example by phosphorylation, carboxymethylation and the like. Polyethyleneimines which contain a degree of polymerization of 2 to 50,000, in particular 20 to 10,000, monomer units per molecule are designated as particularly suitable for the subsequent coating with polymeric amines and in which about 10 to 50% of the imϊno groups are occupied by stearyl acid residues. Cloths equipped in this way are put into the washing process together with conventional textile detergents. Dirt is to be separated from the wash liquor on the surface of the cloth. These parts of dirt can be separated from the washed goods after washing and discarded with the dirt trap cloth. The cited publication describes the production and nature of the finished flat cellulose substrate structures. However, no further statements are made regarding the wash result that can be set.

The idea of reducing the anionic dye transfer during textile oil washing - caused by insufficiently fixed anionic dyes due to bleeding on the fiber - by using polycatonic auxiliaries which bind the anionic dye components dissolved in the liquor appears in the relevant literature in a different context. For example, European Patent Specification 0 044 003 describes a liquid detergent which consists of selected non-ionic surfactants in admixture with quaternary ammonium salts, which have been added to it, and to which an ammonium group-containing starch ether has been added. In washing tests without contamination and under unspecified process conditions, increased reflectance values on washed white cotton nettle are obtained when bleeding-out, colored sections of fabric are washed with the new detergent. The loading of the washing liquor with undissolved particle dirt and the problems derived from it are not addressed. The same applies to the teaching of European Patent 0 033 815, in which, in order to prevent dye transfer to the liquor, an agent is added which is a carrier material made of cellulose with an application of, in particular, glycidyltrimethylammonium chloride or the like containing halogen-hydroxy compound. These flat washing aids are intended to control the undesired transfer of random dyes in a liquid washing liquor. It will

pointed out that multiple use of these tools is possible for the stated purpose. The problem of dirt contamination from the usual textile oil washing in tenside fleets or in other cleaning processes is not addressed.

The invention is based on the object of creating improvements in the washing and cleaning of, for example, textiles, in particular with water-based detergent liquors, which were previously not accessible in this form. The technical solution according to the invention provides for the use or the use of such components in the cleaning process - in particular in the case of textile washing - which are specifically suitable for the deposition of undissolved dirt particles and absorbed into the washing liquor and thus in particular for the collection of pigment dirt in the liquor during the washing process are suitable without negatively affecting the washing process itself. The use of this strainer should be done in such a physical form that after the cleaning or. Washing process, the manual and / or mechanical separation of the now dirty aids from the washed goods is possible. At its core, the invention thus aims to transfer the dirt from the items to be cleaned to auxiliary means used in the cleaning process, which can finally be separated from the cleaned items and discarded together with the dirt-containing oils they have collected, or - insofar as their capacity for loading dirt is not yet full is used - can be returned to a washing process. The invention accordingly relates to the use of polyfunctional quaternary ammonium compounds - hereinafter referred to simply as 'PQAV' - which are insoluble in aqueous-surfactant washing and cleaning liquors even under the temperature loads of the washing process and / or accordingly in these aqueous-surfactant liquors Insoluble solids that cannot be washed off are immobilized and present as particle cleansing cleaning agents in aqueous surfactant washing and cleaning liquors, which can be manually and / or mechanically separated from the items to be cleaned after washing or cleaning.

In further embodiments, the invention relates to textile detergents based on conventional mixtures of surfactants, associated builders and, if desired, further conventional detergents, such as bleaches, corrosion inhibitors, brighteners, foam inhibitors, graying inhibitors, enzymes, adjusting agents, fragrances and the like, these textile detergents being characterized in that they are used for Collection of particle dirt from the wash liquor additionally contain PQAV in finely divided and / or flat form, which are insoluble in aqueous-surfactant wash and cleaning liquors even under the temperature loads of the washing process and / or immobilized in these aqueous-surfactant liquors and are not washable immobilized available. These insoluble finely distributed and / or flat PQAV serve in the sense of the invention as a particle repellent cleaning amplifier which, after washing or cleaning, can be separated from the material to be cleaned manually and / or mechanically.

Finally, in a further embodiment, the invention relates to a method for strengthening the cleaning of aqueous-surfactant washing and cleaning liquors Use of flat and / or dampened oil in the fleets of undissolved solids in the washing process, which bind suspended particle dirt from the water-surfactant liquor on their surface, hold there until the washing process is complete and ϊn this form of the goods to be cleaned manually and / or mechanically can be separated. The new method is characterized in that PQAV are used as cleaning-strengthening solids which are insoluble even under the temperature loads of the washing process in the aqueous surfactant liquors and / or are immobilized in a washable manner on solids which are insoluble in these liquors.

Polyfunctional quaternary ammonium compounds (PQAV) are described and known in the most varied form in the printed state of the art and also in trade. An important area of use for such compounds is in the field of cosmetic preparations, in particular for the treatment or conditioning of hair. It is a well-known characteristic of PQAV that they are capable of being coated on solid surfaces, this capability being possible in particular in the presence of customary surfactant components. Depending on the constitution, the absorption capacity and the adhesive strength of the PQAV on the solid base are differently pronounced. The individual constitution of the PQAV plays a decisive role here. For the behavior of PQAV under the influence of aqueous surfactant baths, however, interaction with anionic surfactant components in particular can also be of crucial importance. In the case of stoichiometric or approximately stoichiometric amounts of the anionic surfactant components, the corresponding anionic salt generally forms on the quaternary ammonium group. Such PQAV anionic surfactant salts generally show a greatly reduced water solubility. Corresponding precipitation forms, compare for example German Offenlegungsschrift 22 42 914. Such anionic surfactant salts from PQAV have been proposed as antistatic agents for application to fibers. In this context, however, it is also known that excesses, in particular considerable excesses of anionic surfactant, may cause the primary PQAV / anionic surfactant salts to re-dissolve, see the publication ϊn "Seifen - Öle - Fette - Wwachs" 1985, 529 to 532 and 612 to 614. In particular in the reaction diagram on page 530 op. cit. the formation of solubilized cell systems of the anionic surfactant / -PQAV complex is shown with an excess of the anionic surfactants. Although such soluble PQAV cell complexes - particularly when diluted with water - still have a certain ability to absorb fibers, particularly those that are fibrous, no very firmly attached bonds are achieved. In practical use, hair cosmetics make use of this, which uses the interplay between soluble and insoluble forms of the PQAV reaction products with anionic surfactants and the substantivity of such components that is still preserved to produce washable hair conditionings.

In general, these previously known PQAV are oligomers and / or polymers which have a plurality or a plurality of quaternary ammonium groups on their oligomeric or polymeric matrix. Adequate water solubility of the PQAV is generally required for use in the field of cosmetics. The use of the PQAV according to the invention, on the other hand, calls for the insolubility of the PQAV-based cleaning boosters used as dirt collectors in the aqueous surfactant washing or cleaning solutions. The insolubility of the PQAV components used as dirt collectors in the sense of the invention is actually particularly for the field of textile washing indispensable requirement. If this critical precondition according to the invention is not met, the washing result is reversed. Soluble PQAV components sliding into the wash bath are absorbed onto the textile material to be washed and bind additional pigment stains in an undesirable manner there. The washing result is then almost reversed. As a result of the washing process, an at least spotty, if necessary even completely flat gray textile is obtained.

Nevertheless, in an important embodiment of the invention, all previously known, originally water-soluble PQAV components can be used for the purpose according to the invention. It is only necessary to convert the water-soluble and / or water-swellable PQAV components of the prior art to the required insoluble form or to fix and immobilize them on water-insoluble supports so that they are removed from this support during the cleaning process not be washed off. As will be described in detail, there are a variety of options available.

It is immediately understandable that this condition of indissolubility must be met both by the PQVA used as a cleaning booster and by the carrier which may also be used under the expected loads of the washing process and in particular the corresponding temperature loads. However, this also shows that polycationic starch ethers, as disclosed in the cited European patent 0 044 003, could at best be used under very specific selected conditions in the sense of the invention, which are not disclosed there. Starch and starch ethers tend to gelatinize in the aqueous phase even at moderate temperatures. Chemically, that means the transition of part of the originally crystalline starch in the dissolved phase. The result of such even a little bit of aggravation is the staining of the items to be washed.

The teaching of the invention is based on the knowledge of these facts. However, general chemical knowledge makes it possible that all of the prior art, in particular oligomeric and / or polymeric, polyfunctional quaternary ammonium compounds that are originally present in soluble form or can be used for dissolution in a particularly toxic excess under PQAV can also be used for the purposes according to the invention / Micelle formation tend.

From the extensive relevant literature, the following publications may be named by way of example, the disclosure of which is hereby expressly made the subject of the disclosure of the present invention description of the structure of the PQAV: US Pat. Nos. 3,589,978, 3,632,559, 3,910,862, 4,157,388, 4,240,450 and 4,292,212, GB-PS 1 136 842, DE-AS 27 27 255, and the US-PS 3,472,840 specified therein.

Suitable originally water-soluble or also water-insoluble PQAVs within the meaning of the invention preferably have an average molecular weight of at least about 200, preferably at least about 300 and in particular at least about 1000. The upper limit of the PQAV is basically meaningless and is, for example, 10 million or even at far higher values. This is understandable from the requirement of the PQAV's insolubility required according to the invention. If this is ensured, there are no upper limits to the molecular weight.

After suitable preparation, described below, for the purposes of the invention, all polymers are PQAVs which are initially water-soluble but then immobilized on an insoluble carrier suitable which carry either quaternary ammonium groups bonded to the polymer chain or bound to the polymer chain. Such quaternary ammonium groups can also be derived from cyclically bound nitrogen. Examples of such quaternary ammonium groups are corresponding members of 5- or 6-membered ring systems, for example. of Morpholϊn-, Pϊperϊdϊn-, Pϊperazin- or Indazol-Rϊngen. Numerous examples of such water-soluble PQAV are e.g. B. ϊn described in more detail in US Pat. No. 4,240,450.

Homopolymers or copolymers with cyclic units, as are known in detail from US Pat. No. 3,912,808, can be particularly suitable. Commercial products of this structure are e.g. B. Merquat ^(R) 100 and Marquart ^(R) 550 (Quaternϊum 41).

Further preferably suitable PQAVs are, for example, cellulose ethers whose anhydroglucose units carry substituents with quaternary ammonium groups which are bonded via ether oxygen. Such polymers are e.g. B. known from US-PS 3,472,840. A commercial product with this structure is e.g. B. the PoIymer-JR ^(R) 400.

Other particularly suitable Katϊonϊsche polymers are z. B. those known from US Pat. No. 3,910,862 and, for example. under the trade name Gafquat ^(R) 734 and 755 available quaternary polyvinylpyroIidone copolymer and the known from US Pat. No. 4,157,388 and z. B. Quaternary polymeric urea derivatives available under the trade name Mϊrapol f R) A15. Suitable copolymers with a polycatϊonic character are also the polyacrylamide copolymers described in the open European patent application 0 153 146, which in particular contain up to 50 mol% of a quaternized amino alkyl ester of acrylic acid or methacrylic acid in addition to at least 50 mol% of acrylamide units. These copolymers are water soluble. she are applied to cloths based on cellulose fibers and draw on there due to their natural pulling power. Cloths of this type can be washed out and should then be used together with anionic surfactant-free surfactant systems for cleaning hard surfaces, in particular for cleaning glass. Under these conditions, they are characterized by an increased dirt absorption capacity. However, the cleaning cloths described in the publication are unsuitable for the use according to the invention in the usual tenside washing and cleaning liquors, which can also be exposed to temperature loads of up to about 95 ° C. Not inconsiderable portions of the numerous PQAV copolymers described in the publication slide into the wash bath, pull onto the items to be cleaned and lead to increased pollution. Only the conversion of such PQAV to the physical state required according to the invention, as described below, makes them cleaning boosters in the sense of the invention.

Preferred PQAV as starting material are those compounds which, in solid form, cause difficulties in dissolving in water. Such catϊonic polymers are especially the cationic polygalactomannan derivatives known for example from GB-PS 1 136 842.

Galactomannans are polysaccharides that are found in the endosperm cells of many legume seeds, but which are produced on an industrial scale only from Johaπnesbrotkerπmeh! (locust bean gurrt), guar gum (guar gum) and tara gum (tara gum). They are made up of a linear mannan main chain consisting of beta- (1 .4) -g! Ycosidically linked mannopyranose building blocks, to which individual galactopyranose residues are fixed as branches in an alpha- (1 .6) -glycoside bond. The individual polygalactomannans differ mainly through the mannose-lactose ratio. The cationic derivatives of the polygalactomannans are prepared by reacting hydroxyl groups of the polysaccharide with reactive quaternary ammonium compounds. Suitable reactive quaternary ammonium compounds are, for. B. those of the general formula

R ²

R ¹ N ⁽⁺⁾ R ³ Z ^(-)

R ⁴

in which R ¹ , R ² and R ³ z. B. Methyl or ethyl groups and R ^{4 is} an epoxyalkyl group of the formula

CH ₂ CH R ⁵ - O

or a halohydrin group of the formula

X CH ₂ CH R ⁵

OH

mean and in which R ^{5 is} an alkyl group with 1 - 3 carbon atoms, X = chlorine or bromine and Z an Anϊon such as. B. Chloride, bromide, iodide or hydrogen sulfate. The degree of substitution should be at least 0.01 and preferably at least 0.05 and is typically between 0.05 and 0.5. A particularly suitable quaternary ammoniumdervate of a polygalactomannan is e.g. B. the guar-hydroxypropyl-trimethylammonium chloride, which is bound to the oxygen atoms of the hydroxyl groups of the polysaccharide catϊonic groups of the formula - CH ₂ - CH (OH) - CH ₂ N ^{(- +)} (CH ₃ ) ₃ CI ^(-)

wearing. Such canonical guar derivatives are e.g. B. on the market under the trade name "Cosmedia Guar C 261". The degree of substitution (DS) of Cosmedia Guar C 261 is around 0.07. The commercial products "Jaguar C-13" (DS = 0, 11 -0, 13) and "Jaguar C 13 S" (DS = 0, 13) also belong to this type.

How all of these or also of comparable other known soluble or swellable PQAV starting materials are used to form cleaning-enhancing and particle-collecting auxiliary substances in the sense of the invention is described below.

Basically, the dirt-collecting cleaning booster used according to the invention can be used in any physical configuration that allows this cleaning booster to be loaded with dirt particles and nevertheless allows the manual and / or mechanical separation of the undissolved cleaning booster from the washed items. In particular, two physical forms of state come into consideration, namely the use of the PQAV or the insoluble solid materials correspondingly impregnated with PQAV in the form of sheet-like structures, in particular as a sheet, film or cloth, and on the other hand as a finely divided solid, for example in the wash liquor during the washing process can be dispersed, but after the washing process is removed with the wash liquor and thus separated from the washed goods. The invention is described in the following in particular with reference to these two embodiments, which have as their object the use of the PQAV during the washing process in the washing liquor loaded with textile goods, for example, but it is not restricted to this. Other forms of use are also possible and fall within the scope of the invention. An example here is pumping over a washing liquor over a PQAV solid bed and recycling the washing liquor cleaned in this way, for example into the textile oil washing process.

For the field of textile washing, in particular for machine textile washing z. B. With household washing machines, two specific forms of application of the new cleaning enhancers according to the invention can be described: the incorporation of the cleaning enhancers according to the invention, preferably in the form of fine powders, into the usual textile detergents, e.g. Coarse washing powder, on the one hand, and on the other hand the separate addition of the new cleaning booster to the wash liquor, i.e. separate from the usual washing-in of the washing powder.

In the latter case, both fine and coarser-grained solids preparations are suitable as the condition for the new dirt-collecting amplifiers, but in particular the preparation of the material in the form of a flat structure, for example as a sheet, film or cloth. For example, the new cleaning booster can be made available and used as a sheet-like material in roll form, with a predetermined amount of the sheet-like material being separated from the roll for each washing process and additionally given to the washing machine with the textile goods to be washed.

After the washing process has been completed, the simple manual and / or mechanical separability of the dirt collector from the washed items must be ensured. If the material is in the form of a sheet, the fact that it is indispensable means that it can be separated when the washed textiles are removed. If the cleaning booster is used as a more or less fine-grained material, there are various forms of absorption, especially depending on the size of the grained material. given separation. If the cleaning booster is dosed into the wash liquor as an extremely fine and insoluble material, then it is removed and rinsed out together with the wash liquor together with other insoluble, finely divided components of the detergent mixture - for example with insoluble Zeolite-based Buϊlder components. However, if the cleaning or washing power booster is used in coarser-grained form, manual separation is possible, for example, by shaking out the washed textile goods.

Sheet-like or sheet-like designs of the new dirt collector can be designed according to known manufacturing processes as random fiber fleece, fiber fabric or knitted fabric, as a preferably open-cell foam sheet, as a closed film or in any other shape. The only requirement is that the surface washed by the wash liquor has the PQAV in insoluble form and in sufficient quantity.

For all configurations of the new cleaning booster according to the invention, the PQAV used are insoluble in the wash liquor under the conditions of use, so that the surface of the arbitrarily shaped washing booster can be loaded with dirt particles and holds them until the washing process is complete. There are several ways to obtain such insoluble PQAV. It is known, for example, to crosslink water-soluble PQAV by reaction with at least bifunctional crosslinking agents in such a way that sufficient water insolubility is achieved for the purposes of the invention. The selection of the appropriate crosslinking agent is determined by the structure of the compounds to be crosslinked in the individual case, taking general chemical knowledge into account. A fundamentally different route, which ultimately leads to the same result, is the subsequent application of quaternary ammonium groups to the surface of preferably already shaped, insoluble carrier compounds. Thus, for example, the surface of insoluble or insolubilized, shaped natural products and / or corresponding synthesis products can be equipped with quaternary ammonium groups by chemical reaction using methods known per se. Process steps are used for this, as are known in the Prizϊp for the production of water-soluble and / or water-swellable PQAV from the literature cited at the beginning. This is exemplified as follows: a flat building, e.g. B. a random fiber fleece or a woven or knitted cloth based on natural fibers and / or synthetic fibers can be reacted with a coupling component, for. B. Epϊchlorhydrϊn and subsequent reaction with a basic compound with subsequent quaternization to the desired dirt-collecting detergent booster. The same applies to granular or powdery material made from natural and / or synthetic water-insoluble materials. Other suitable reactive quaternizing agents are the quaternary ammonium compounds with a reactive epoxy group described in connection with the aforementioned British Pat. No. 1 136 842, or their reaction products with hydrogen halide to form the associated halohydrin group.

Natural materials of the cellulose type, insoluble cellulose derivatives and other insoluble or insolubilized poly-saccharide-like natural substances or their derivatives are particularly easily accessible and inexpensive starting materials for such reactive surface modification that are insoluble in washing or cleaning liquors of the type mentioned. The introduction of quaternary ammonium groups Tender residues run without problems here, the polyaccharide components used as carriers are either insoluble from the outset - for example in the case of cellulose - or easily converted to the insoluble state by simple chemical reactions, for example with polyfunctional crosslinking agents. It is decisive for the teaching of the invention that it is completely sufficient for the suitability of the cleaning booster if the quaternary cationic groups are on the surface of the shaped cleaning booster, even if the presence of corresponding groups in deeper material layers is not excluded. Precisely because of the accessibility and the price, such particularly simple and cost-effective cleaning amplifiers will be of particular importance.

This aspect can already influence the selection of the design. A granulate, or powdery solid material based on natural materials, is usually easier and therefore cheaper to obtain than a flat structure, for example in the sense of woven or knitted cloths. The use of such granular or powdery cleaning enhancers with an insoluble polycathonic surface can also be of particular importance for practical use in the washing process. As already shown in connection with the teaching of GB-PS 1 136 842, even very low average degrees of substitution on the surface of the natural product or natural product derivative lead to effective results in the sense of the trade according to the invention. For example, for the use of shaped quaternized polyaccharides or polyaccharide derivatives, it has proven to be entirely sufficient not to work with average degrees of substitution not above 0.5, in particular not above approximately 0.35. An average degree of substitution can be particularly suitable for cleaning reinforcement in the context of textile washing used up to about 0, 12 and preferably below 0, 1. The lower limit will generally be the average degree of substitution ϊm in the range of approximately 0.01, whereby particularly good results in the range of approximately 0.015 to 0.08 and in particular ϊm in the range of approximately 0.02 to 0.07 can be obtained. It is astonishing that fine cellulose powders of such a low degree of substitution bring about a substantial increase in washing power, in particular in textile washing. The term “washing power boost” includes the terms “primary washing power boost” as well as “secondary washing power boost”. The improvement in the secondary detergency enhancement - that is to say the reduction in the graying tendency - is still understandable from the concept of the action according to the invention. Surprisingly, however, when selecting suitable cleaning enhancers within the meaning of the invention, significant increases in the washing power of the primary washing result are obtained, which can be measured as improvements to be recorded in numerical terms den in the degrees of lightening an in the context of a textile washing process on test material contaminated with pigment. Details of this can be found in the following examples which explain the invention.

However, the embodiments which provide a water-insoluble support in flat or granular form, on whose surface PQAV, preferably a thin layer, are immobilized in such a way that they do not slide off into the wash bath during the washing process can also be of particular practical importance.

It has been shown that the suitable selection and adaptation of the structure and nature of the insoluble support and PQAV also have an influence on the fixation for the sufficient adhesive strength of the PQAV on the support surface can be . If one takes, for example, cotton materials and here in particular unfinished cotton and coats this material with water-soluble and / or at least water-swellable PQAV ϊ in the sense of the literature mentioned at the beginning for cosmetic PQAV preparations, a dirt-collecting washing power amplifier can be obtained here, which meets the usual conditions survives the washing process in a textile washing machine, fulfills its function as a dirt collector and can be separated from the cleaned textile after the washing process. However, only the PQAV fractions of higher molecular weight are apparently sufficiently fixed? additional action of surfactant. In this embodiment, disturbances due to bleeding-out PQAV components must normally be expected.

It may therefore be desirable to provide a stronger, namely reactive, connection of the PQAV coating composition to the insoluble carrier. Here, in a manner known per se, chemical bonding by means of bifunctional coupling components can again be considered. However, the following route is also important for an embodiment according to the invention: the solidification of a polymeric PQAV coating on a shaped base body can be promoted by forming or having ahϊonic groups on or on the surface of the base body. Examples of such anionic groups are carboxy groups which can be introduced into the surface of the base body, for example by carboxymethylation, or other acid groups, such as sulfonic acid residues. Further information can be found in the above-mentioned US Pat. No. 3,694,364. The catonic PQAV coating then binds salt-like to these counter-ions of the matrix, so that in this way the solidified bond between the insoluble Solid and applied PQAV layer is created. A basic body based on cellulose fibers, in which free carboxyl groups have been introduced into the cellulose molecule, is merely an example of this embodiment. This is possible, for example, in two different ways:

through physical incorporation of carboxyl-bearing compounds into viscose, i.e. into a cellulose dissolved as cellulose xanthate to form so-called incorporated cellulose fibers or

by chemical conversion (etherification) of the fiber-forming cellulose of the carboxyl group-carrying reagents to form uniform with e.g. Carboxyalkyl groups of the formula

- (CH ₂ ) _n - COOH,

der in which n can have a value from 1 to 3, modified cellulose fibers.

The physical incorporation of carboxyl-bearing compounds into the viscose is described, for. B. achieved by admixing alkali salts of acrylic acid homopolymers, acrylic acid-methacrylic acid copolymers, methyl vinyl ether-maleic anhydride copolymers, alginic acid or carboxymethyl cellulose to the viscose solution and subsequent spinning in a conventional manner in a precipitation bath. Commercial products based on such cellulose fibers as well as on the basis of fibers modified with carboxymethyl groups are available for many applications. In the embodiment described here, such fibers or carrier materials produced therefrom are coated with an insoluble PQAV layer and are therefore inextricably bonded for the intended use. A particularly simple, insoluble connection between the inert carrier and the insoluble PQAV layer applied can be achieved by implementing the so-called principle of enveloping. If, for example, a fine-grained, shaped, inert, insoluble carrier is coated with a PQAV layer - preferably covering the entire area - and this PQAV layer is then converted into the required state of insolubility under washing conditions, the inseparable union between the inert carrier core and the enveloping PQAV layer is also realized here , even if there are no special binding forces between these two materials. The conversion of the PQAV layer to the insoluble material can, for example, take place chemically again by crosslinking this enveloping material layer. The application of this coating principle is understandably not limited to granular cleaning boosters.

Not only water-insoluble organic materials are suitable as a carrier for the dirt-collecting PQAV layer. Inorganic carriers are also of particular importance. In this embodiment, in particular those water-insoluble inorganic carriers are to be considered that have already been used in the course of washing processes, in particular in the context of textile washing. Classic examples of this are natural or synthetic fine-particle alumositicates of the Bentonϊt type or synthetic crystalline zeolites, in particular the detergent-grade phosphate substitute Zeolite A, which is widely used today. Other examples of suitable materials are silica, in particular colloidal silica of the Aerosil type, finely divided, swellable or non-swellable sheet silicates, in particular the Montmorillonite group, water-insoluble metal oxides and / or hydroxides or corresponding metal salts. As examples alkaline earth metal salts such as calcium carbonate, calcium sulfate and the like or aluminum oxide and the like may be mentioned. A particular advantage can be the use of acidic or polyanionically formed inorganic carrier materials, such as are given, for example, in the case of aluminosilicates, layered silicates or silica gel. Here, too, the possibility of additional ionic influencing between the PQAV coating composition and the inorganic base body with its opposite charge ensures that the dirt-collecting PQAV layer is firmly anchored.

The quaternary ammonium group in the PQAV components used according to the invention preferably contains 1 to 3 lower alkyl radicals each having 1 to 6, in particular 1 to 3, carbon atoms. The quaternary ammonium group, which has 1 to 3 alkyl residues and contains, as counterion, residues of such acids as are usually to be expected anyway in the washing process can be of particular importance. Examples of this counterion are chloride and / or sulfate, which, however, convert to the corresponding anionic-surfactant salt group in the presence of anionic surfactants, see the designated literature references DE-OS 22 42 914 and "SFÖW" 1985, 530. As already stated, Such PQAV / anionic surfactant salt groups may have been formed in the cleaning booster according to the invention before it was introduced into the liquor.

In a modification of the invention described so far, insoluble and / or PQAV immobilized on insoluble solids are used as dirt-collecting cleaning boosters, in which the quaternary ammonium groups characteristic of this substance class are at least partly replaced by non-quaternized basic amino groups and in particular by tertiary amino groups. All other information on the description of the invention applies here analogously. Basis for this A modification is the finding on which this embodiment of the invention is based that those polycationic components and in particular those cationic polymer compounds are also suitable for the purposes of the invention which do not derive their functionality or only partially from quaternary ammonium groups but otherwise from basic amino groups. The preferred non-quaternary basic amino group is the tertiary amino group. It has been shown that polycationic compounds of this type are also capable of loading themselves with suspended dirt particles from the wash liquor. Polycationic tertiary amino compounds of the type concerned here are then either to be used either themselves as at least largely insoluble solids or as components which are soluble or swellable per se and which in turn are immobilized or insolubly fixed on sufficiently insoluble support materials. The content of quaternary ammonium groups here preferably bears at least about 5% based on the sum of quaternary and non-quaternary base groups.

A typical example of polycatϊonϊsche connections these

Type is the GAF "Copolymer 937" ^R , which is a PVP-dimethyla mino¬ethyl methacrylate copolymer with an average molecular weight of about 1,000,000.

The use of PQAV coatings in the narrower sense of true polyfunctional quaternary ammonium compounds in admixture with the polycationic compounds modified in this sense in whole or in part falls within the scope of the invention.

The respective amount of dirt-collecting PQAV used in the narrower or broader sense of the description of the invention is determined by the particular circumstances or conditions present and determinable in each case. They are done by a specialist to determine simple attempts. The amount of PQAV collecting dirt used in a wash cycle is preferably selected such that at least a substantial proportion, for example at least about 50, preferably at least about 75%, of the expected loading of the washing liquor with suspended dirt particles can be absorbed by the dirt-collecting cleaning booster. It is generally expedient to provide formulations which provide such an amount of PQAV in the washing process that excess capacity of the PQAV is available in order to be able to intercept occasionally occurring peaks in the dirt load during different washing processes. Taking into account the high catcher capacity of the cleaning enhancers according to the invention, the amounts of the cleaning enhancer to be added to the detergent formulation are nevertheless small and are, for example, below 10 g / l of washing liquor, preferably below 5 g / l of washing liquor, for. B. in the range of about 0.5 to 3 g / l of wash liquor.

The ability of the cleaning amplifier to collect dirt to collect dirt is in turn in particular determined by the amount of the functional quaternary ammonium groups or. the basic amino groups having the same effect, in particular tertiary amino groups. The respective degree of substitution of the PQAV used must be taken into account here. On the other hand, the surface of the cleaning or washing power booster, which is insoluble in the wash liquor, is another important variable which is considered in the considerations concerned here. Understandably, it may accordingly be preferred according to the invention to choose the state forms of the dirt-collecting cleaning amplifier which are distinguished by a particularly large surface area. On the one hand, highly disperse distribution states come into consideration - for example solid particles with an individual particle size up to about 1 mm and preferably below 100 μ, in particular below 40 μ and very particularly below approximately 10 μ, as are known for the known detergent builders based on zeolite A or for finely dispersed silica. On the other hand, high surfaces are also provided by fabrics made of fibers or fiber bundles. From knowledge of the characteristic parameters present here in the respective individual case for the work equipment used according to the invention and the pollution load to be expected, it is then easy to determine the minimum test requirement for dirt-collecting cleaning or washing power intensifiers for the individual case.

The cleaning or washing power intensifiers collecting dirt according to the invention can in particular be used together with conventional heavy-duty textile oil detergents or also with mild detergents. It goes without saying that both the carrier and the PQAV coating have to be selected so that the temperature loads to be expected in this application can withstand at least slightly elevated temperatures up to about 95 ° C. without damage. Anionic and / or nonionic surfactants are particularly suitable as surfactant components.

However, cationic surfactants with their special effects are not excluded. Along with this, the usual builders and co-builders as well as the other usual detergent components can be used. May be mentioned in this connection: washing alkalis, bleaching agents, corrosion inhibitors, brighteners, foam inhibitors, graying inhibitors, enzymes, adjusting agents, fragrances and the like.

A detailed description of the detergent ingredients common today can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 24, pages 81 to 107. Detailed information on textile detergent mixtures can also be found in the aforementioned US Pat. No. 3,694,364, which can also be used in the context of the present invention. In the special detergent formulations of this publication, sodium tripotyphosphate is used as an essential builder-resistant oil, which is known to be replaced at least in part today by ecologically less harmful builder components, in particular by sodium zeolite NaA.

Typical basic formulations for today's textile detergent mixtures correspond, for example, to the following information:

Frame formulation of heavy-duty detergents Western Europe (hot laundry)

Material group example proportion (%)

Anionic surfactants alkylbenzenesulfonate 5 to 10 nonionic surfactants fatty alcohol polyglycol 1 to 5 ether

Foam inhibitors soaps, silicone oils 1 to 5

Complex formers Na triphosphate 10 to 40 ion exchangers zeolite A 0 to 30 bleaching agents Na perborate 15 to 35 bleach activators tetraacetyl-ethylene 0 to 4 diamonds

Stabilizers ethylenediaminetetra0, 2 to 2, 0 acetate, Mg-Silϊkat

Graying inhibitor carboxymethyl cellulose, 0, 5 to 2, 0 or other cellulose ethers

Enzyme proteases 0, 3 to 1, 0

Optical brighteners Stϊlben-disulfonic acid, 0, 1 to 0, 3 bis (styryl) biphenyl

Derivatives

Corrosion inhibitor silicates 2 to 7 gates

Fragrances 0.05 to 0.3

Dyes 0 to 0.001

Adjusting agent Na sulfate 2 to 20 Frame formulation of US heavy duty detergents

Material group example proportion (%)

Anionic surfactants alkylbenzenesulfonate, 9 to 20

Fatty alcohol sulfate, fatty alcohol ether sulfate

Nonionic surfactants alkyl polyglycol ethers 1 to 2

Complexing agent Na triphosphate, Na- 5 to 33

Dϊphosphate

Ion exchanger zeolite A 0 to 25 alkalis Na carbonate 5 to 25

Na silicate

Graying-in carboxymethyl cellulose 0 to 1 bit

Enzyme proteases 0 to 1, 5

Optical brighteners Stϊlben-disulfonic acid, 0, 1 to 0, 3 bis (styryl) - bϊphenyl-Derϊvate

Fragrances + Dyes + Agents + General formulation of 60 ° C detergents

Active ingredient group example proportion (%)

Anionic surfactants alkylbenzenesulfonate 0 to 8

Nonionic surfactants alkyl polyglycol ethers 3 to 1 1

Foam inhibitors soaps, silicone oils 0, 1 to 3

Complexing agent Na triphosphate 20 to 40

Ion exchanger zeolite A 0 to 30

Bleaching agent Na perborate 0 to 15

Stabilizers ethylenediaminetetra0, 1 to 0, 5 acetate

Graying inhibitors carboxylmethyl cellulose 0, 2 to 2

Enzyme proteases 0, 2 to 1, 0

Optical brighteners stilbene-disulfonic acid, 0, 1 to 0, 3 bis (styryl) biphenyl derivatives

Corrosion inhibitors Na silicates 2 to 6

Fragrances +

Adjusting agent Na sulfate 5 to 20

Frame formulations of special detergents

Ingredients Delicate and WoII curtain hand wash

Colored washing detergent washing agent medium medium

Proportion of (%)

Anionsensde 5 to 15 0 to 15 0 to 10 12 to 25

(Alkylbenzenesulfonate, fatty alcohol EO suffate)

Nonionic surfactants 1 to 5 2 to 2 to 7 1 to 4

(Fatty alcohol poly25 *) glycol ether)

Soap 1 to 5 0 to 5 1 to 4 0 to 5

Cationic surfactants 0 to 5 **)

(Dialkyl-dϊmethyl-ammonium chloride)

Na triphosphate 25 to 40 25 to 35 25 to 40 25 to 35

Na perborate 0 to 12

Na silicate 2 to 7 2 to 7 3 to 7 3 to 9

Frame formulations for liquid detergents (60)

Ingredients Wool detergent Gardner detergent with without finishing agent

Proportion of (%)

Anionic surfactants - 10 to 30 0 to 8

(Alkylbenzenesulfonate,

Fatty alcohol EO sulfates)

Nonionic surfactants 20 to 30 2 to 5 15 to 30

(Fatty alcohol polyglycol ether,

Fatty acid amides)

Cationic surfactants 1 to 5 - -

Dialkyldimethylammonium chloride)

Ethanol, propylene 0 to 10 0 to 10 0 to 10 glycol

Toluene, xylene, - 0 to 3 -

Cumene sulfonate

Buϊlder - 0 to 15 2 to 5

(K-Dϊphosphate, Na-Cϊtrate)

Optical brighteners, 60 to 70 60 to 80 65 to 75

Fragrances, dyes, water and others. Frame formulations of liquid US heavy-duty detergents (60)

Ingredients Without With

Builder builder

Proportion of (%)

Anionic surfactants 7 to 25 0 to 30

(Alkylbenzenesulfonate, fatty alcohol EO sulfates) nonionic acid 10 to 35 0 to 10

(Fatty alcohol polyglycol ether, fatty acid amide)

Ethanol, propylene glycol 3 to 22

Toluene, xylene sulfonate - 0 to 7

Builder 8 through 18

(K-Dϊphosphate, Na citrate,

Na metasilicate)

Optical brighteners, fragrances, 30 to 65 50 to 60

B e i s p i e l e

The detergency of the detergent formulations used in the following examples is determined on the known artificially soiled test fabrics on the basis of different fibers and soils, which are currently used in the review and development of

Detergent formulations are common and some of them are commercially available or manufactured by the detergent industry according to their own pattern. Known manufacturers of corresponding commercially available, artificially soiled test fabrics are EMPA, Eidgenössische Materialprüfungs- und Versuchsanstalt, Unterstrasse 11, CH-9001 St. Gallen; Laundry research Krefeld, WFK-Test¬gewebe - GmbH, Adlerstrasse 44, D-4150 Krefeld; Testfabric Inc., 200 Blackford, Ave. Middlesex, N .J. UNITED STATES.

Unless expressly stated otherwise, the washing tests for determining the primary washing power have been carried out with soiled standard test cloths based on polyester / cotton wool, with pigments and skin fat soiled (H-SH-PBV). The degree of soiling of the untreated starting material and the gev / ash tissue samples is determined by measuring the degree of remission with the Elrephomat DSC 5 (Carl Zeiss, Oberkochen, FRG). The degree of soiling of the PBV test tissue used in this way is 30.0 (% remission).

The washing tests are carried out on a launderometer. The respective working conditions are given in connection with the examples. example 1

Various washing tests are carried out with the addition of 2 differently quaternized insoluble cellulose powders (average grain size 50 μm). The average degree of substitution (MS) of the first cellulose powder (C-1) is approximately 0.05, the corresponding MS of the second cellulose powder (C-2) is approximately 0.03. The quaternized cellulose powder C-1 and C-2 were prepared in a manner known per se by reacting the undissolved cellulose powder in an aqueous alkaline suspension with 3-chloro-2-hydroxypropyltrimethylammonium chloride (Qusb).

In a first series of experiments, the influence of the washing power of the aqueous washing liquor of a commercially available branded laundry detergent is examined when the test substances C-1 or C-2 are added to the washing liquor. The following details apply to the washing tests:

Launderometer: washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV test fabric, wash 30 »minutes, rinse 4 × 30 seconds.

Dosage of the commercial washing agent: 3 g / I Dosage of the test substances: 1 g / I

In each experiment, 6 test rags are used in the launderometer pot. The number of soiled test fabric flaps is gradually increased from 1 to 6 and the number of non-soiled filler fabrics used is reduced from 5 to 0 accordingly.

The washing results obtained are summarized in Table 1 below. Table 1

% Remission without addition C-1 C-2

1 H-SH-PBV / 5 filler 45.9 53.6 57.1

2 H-SH-PBV / 4 filler 41.5 51.7 53.2

3 H-SH-PBV / 3 test fabric 40.0 50.1 49.6

4 H-SH-PBV / 2 filler 38.8 47.7 46.5

5 H-SH-PBV / 1 filler 36.6 45.3 43.2

6 H-SH-PBV / 0 filler 36.1 43.3 42.4

The use of PQAV C-1 or C-2 leads to a significant increase in remission values under the process conditions used.

Example 2

In a second series of tests, the washing tests are repeated with and without the addition of the quaternized test products C-1 and C-2, at the same time a third quaternized insoluble starch with an MS of 0.1 is used in the test series.

The process conditions of the washing process correspond to those of Example 1, but now the washing process is extended to a total of 120 minutes. The following applies in detail Launderometer: washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV fabric, wash for 120 minutes, rinse 4 × 30 seconds

Dosage of the commercial detergent: 3 g / I dosage of the test substance: 1 g / I

Increasing contamination from 1 to 6 soiled test fabrics with a corresponding decrease in the amount of filler used.

The washing results are shown in Table 2 below.

T a b e l l e 2

% Remission without addition C-3 C-1 C-2

1 H-SH-PBV / 5 filler 43.4 45.5 59.7 57.3

2 H-SH-PBV / 4 filler 38.1 44.0 53.7 51.3

3 H-SH-PBV / 3 filler fabric 35.7 41.7 49.7 45.5

4 H-SH-PBV / 2 filler 34.9 40.6 47.6 42.2

5 H-SH-PBV / 1 filler 34.8 39.6 44.6 42.2

6 H-SH-PBV / 0 filler 34.8 39.1 42.9 42.0 Here, too, a significant increase in the reflectance values can be found in all cases when the quaternized test substances according to the invention are used.

Example 3

With the quaternized cellulose powders C-1 (average degree of substitution 0.05) and C-3 (average degree of substitution 0.1) of Examples 1 and 2, washing tests are carried out with increasing contamination at 30 ° C. A wash room of 30 minutes is maintained in a first test series. In a second test series, in order to test the long-term behavior of the PQAV additives according to the invention, washing is carried out with a length of time extended to 4 hours per washing process.

The individual process conditions used and the washing results obtained - determined as% remission - are summarized below.

a) Duration of the washing process 30 minutes

In the launderometer, a series of washing tests is carried out which, in the event of a gradually increasing dirt load, initially provides a commercially available full textile washing agent without the addition of PQAV compounds and then - with the same dosage of the commercially available full washing product - the addition of the chemically modified cellulose powder according to the invention.

The following individual process conditions apply to the washing tests:

Washing temperature 30 ° C, water hardness 16 ° dH, liquor ratio

1:20, 10 steel balls, H-SH-PBV fabric as soiled

Test material, wash for 30 minutes, rinse 4 × 30 seconds. Dosage: 3 g / l commercial heavy-duty detergent or 3 g / l heavy-duty textile detergent with the addition of 1 g / l PQAV component.

T a b e l l e 3

Experimental arrangement = 1) 1 H-SH-PBV / 5 filler fabric

2) 2 H-SH-PBV / 4 filling fabrics

3) 3 H-SH-PBV / 3 filler fabrics

4) 4 H-SH-PBV / 2 filling fabrics

5) 5 H-SH-PBV / 1 filling fabric

6) 6 H-SH-PBV / 0 filler fabric

% Remission without addition C-1 C-3

1) 47.5 57.9 46.3

2) 42.7 49.4 51.7

3) 41.9 46.6 48.3

4) 38.9 45.5 45.2

5) 35.3 42.4 43.6

6) 35.3 41.3 42.5

Appearance of light gray to light gray to light gray to

Brisk dark gray, dark gray, dark gray, cloudy, cloudy cloudy sediment sediment settles (staining becomes darker (staining becomes darker after approx. 1 h with increasing with a dirt buildup), shimmering gray

Sediment from. The remaining liquor is only slightly cloudy (color becomes darker with increasing contamination) b) Comparative tests with an extended washing time

Under the working conditions of the tests for a), washing tests are now carried out with a washing time of 4 hours each. The experimental setup and the results obtained are summarized below.

T a b e l l e 4

Experimental arrangement = 1) 1 H-SH-PBV / 4 filling fabric

2) 2 H-SH-PBV / 3 filling fabrics

3) 3 H-SH-PBV / 2 filling fabrics

4) 4 H-SH-PBV / 1 filling fabric

5) 5 H-SH-PBV / 0 filler fabric

% Remission without addition C-1 C-3

1) 46.5 66.2 57.3

2) 42.3 58.1 54.1

3) 40.3 53.1 52.9

4) 39.4 51.3 51.5

5) 38.7 48.8 50.7

Appearance of the fleet pale gray to gray to light gray to light gray, dark gray dark gray hardly any soil clear, strong set, strongly gray Bograuer, blue-colored. the sentence. lent schim¬

(Staining is strongly tarnishing, but hardly stains. The staining) will settle after intensive 1/2 h, from 1) after protruding 5) liquor only slightly cloudy (staining becomes more intense) Example 4

Comparative washing tests are again carried out. Here, however, finely divided minerals are used as PQAV components in the sense of the invention, which are coated with insolubilized PQAV components.

In a first test series, the swellable layered silicate from the Montmorillonite group is used as the mineral carrier, which is sold under the protected trade name "Dϊs-Thix-Extra". In a second series of tests, zeolite NaA ϊn detergent grade is used as the mineral carrier.

In comparative washing tests, washing is first carried out with a commercially available heavy-duty textile detergent alone and then with the addition of the non-coated mineral carrier materials to this aqueous washing liquor. Finally, under the same test conditions, 3 PQAV-coated minerals of the specified type are used, which can be identified as follows.

PQAV: Quaternized galactomannan type polysaccharide with an average degree of substitution of about 0.05. Weight ratio of mineral carrier to PQAV component used 10: 1 or 20: 1. Use of a surfactant of the FAES type (commercial product "Texapon N 25" / 28% active substance C 12/1 ₄ fatty acid alcohol 2EO sulfate Na salt).

In one test, a preservative (commercial product "Bronidox") is used in the coating of the mineral carrier substance. The composition of the PQAV components used in accordance with the invention is shown in Table 5 below. The PQAV additives based on swellable layered silicate are labeled DTE 1 to 3, the corresponding additives based on zeolite NaA are labeled SAS 1 to 3.

T a b e l l e 5

Weight ratio Weight ratio

Mineral / PQAV Mϊneral / PQAV: FAES (28%)

DTE - 1 10: 1 1: 5

DTE - 2 20: 1 1: 5

DTE - 3 20: 1 1: 5 + 0.2% preservative

SAS - 1 10: 1 1: 5

SAS - 2 20: 1 1: 5

SAS - 3 20: 1 1: 5 + 0.2%

Preservative

Washing tests are carried out under the following test conditions:

Launderometer, washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, wash for 30 minutes, Rinse 4 times 30 seconds.

Mixed fabric (H-SH-PBV) soiled with dust / skin fat is used again as the soiled test fabric.

Dosage:

1.) 5 g / l of a commercial heavy-duty detergent

2.) Add 0.5 or 2.5 g / l of uncoated mineral carrier base to 1. ) 3.) Add 0.5 or 2.5 g / l of the PQAV-coated mineral carrier substances DTE-1 to 3 and SAS-1 to 3.

The washing results obtained in the comparative washing tests - determined as% remission - are summarized in Table 6 below.

The commercial heavy-duty laundry detergent already delivers a high-quality cleaning result at the dosage of 5 g / l, but the addition of the PQAV components in the sense of the invention once again achieves a significant improvement in the reflectance values. The addition of the non-coated mineral carriers does not bring any corresponding improvements.

Example 5

Two fine-particle mineral masses (PQAV-1 and PQAV-2) bearing PQAV as a coating are produced as follows:

PQAV-1:

10 g of the swellable layered silicate of the Mσntmorillonit type ("Dis-Thϊx-Extra") with the PQAV compound based on galactomanan "Cosmedia Guar C-261". a quantitative ratio of mineral component to PQAV of 20: 1 in the presence of 50 g of a surfactant based on FAES (Texapon N 25) and 0.12 g of a preservative (Bronϊdox) mixed intensively and the mixture at moderately elevated temperatures ϊm Dried oven. The dry product is processed into a fine powder.

PQAV-2:

In a corresponding manner, a second PQAV-coated mineral material is produced, but a comparable synthetic layered silicate with hardly any swelling capacity is now used as the mineral base body instead of the swellable layered silicate of natural origin. Comparative studies determine the strengthening effects of an aqueous surfactant liquor, which are obtained by adding

PQAV-1 or PQAV-2

Additional amount of surfactant over PQAV-1 respectively

PQAV-2 was introduced into the system.

Common addition of these equivalent tenside amounts plus non-coated mineral base.

In two further determinations, the aqueous surfactant liquor is mixed with PQAV-1 or PQAV-2, but the FAES surfactant content in the aqueous washing liquor is reduced by the amount that is associated with the respective PQAV component. ϊn the system is entered.

The systems examined, their dosage and the ones used

Washing conditions are summarized below. The

Results of the washing tests can be found in the table below.

Test products and their dosage

1. 0.5 g / t (active substance = AS) Tensϊd based on FAES

(Texapon N 25)

2. 0.5 g / l (AS) FAES surfactant + 0.5 g / l PQAV-1

3. 0.5 g / l (AS) FAES surfactant + 0.3 g (AS) / l FAES surfactant

4. 0.5 g / l (AS) FAES surfactant + 0.3 g (AS) FAES surfactant + 0.2 g / l swellable layered silicate (Dϊs-Thix-Extra)

5. 0.2 g / l (AS) FAES-Tensϊd + 0.5 g / l PQAV-1 6. 0.5 g / l (AS) FAES surfactant + 0.5 g / l PQAV-2

7. 0.5 g / l (AS) FAES surfactant + 0.15 g / l (AS) / l FAES surfactant

8. 0.35 g / l (AS) FAES surfactant + 0.5 g / l PQAV-2

The washing conditions used are as follows:

Launderometer wash at 30 ° C, 60 ° C and 90 ° C. Water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls.

Soiled test tissue H-SH-PBV, wash for 30 minutes, spin 4 x 30 seconds.

The washing results - expressed as% remission - are summarized in Table 7 below.

T a b e l l e 7

Recipe 1 2 3 4 5 6 7 8

% Draw 30 ° C 41.3 53.3 48.0 47.3 46.0 53.1 45.5 40.8 sϊon

60 ° C 47.1 70.7 61.1 62.7 58.4 69.4 51.9 55.6

90 ° C 40.6 74.0 62.1 61.8 55.0 70.3 50.8 43.5

Example 6

Swellable layered silicate based on montmorillonite

("Dis-Thϊx-Extra") is filled with different synthetic PQAV components in a DTE: PQAV ratio of 20: 1. In the form given in Example 4, the FAES-based surfactant is added at the same time. The PQAV components obtained in this way are identified as follows: Type designation used polymer compound

PQAV-3 Merquat 100 ^(R) PQAV-4 Bϊnaquat ^(R) PQAV-5 Cellquat ^(R) PQAV-6 I R-400 ^(R) PQAV-7 Mirapot A 15 ^(R)

With these cleaning-enhancing PQAV components, washing tests are carried out in a liquor containing 0.5 g (AS) / I FAES surfactant, the washing performance of the pure surfactant liquor being determined once and then in each case with the addition of 0.5 g / l of said PQAV Components is worked.

The washing results obtained - determined as the lightening value% remission - are summarized in Table 8 below.

Ta b e l l e 8 without addition 39.0% remission

PQAV-3 43.5% remission

PQAV-4 56.8% remission

PQAV-5 44.9% remission

PQAV-6 43.4% remission

PQAV-7 44.7% remission

Example 7

Unfitted cotton rags are soaked with the following formulation and then dried by storage at room temperature for 2 days: 0.5 percent by weight "Cosmedia Guar C 261", 53.6 percent by weight "Texapon N 25" (28% AS), 0.2 percent by weight Preservative, 45.7 weight percent water.

In a washing liquor containing 3 g / l of a commercial heavy-duty detergent, washing tests are carried out under the following conditions:

Launderometer wash, wash temperature 60 ° C, water hardness

16 ° dH, liquor ratio 1: 30, 10 steel balls,

H-SH-PBV tissue, wash duration 30 minutes, rinse 4 times 30 seconds The washing result of the surfactant liquor without using the PQAV-coated cotton fabric (2 dirty rags, 2 feeding rags) is - determined as a% remoison - the numerical value of 59, 7.

If the 2 filling stages are replaced by corresponding PQAV-coated rags in the sense of the inventive action, the slightly reduced reflectance value of 57.3 is obtained under the same washing conditions.

In a further experiment, the PQAV-coated cotton flaps as such are first subjected to washing under the specified standard conditions. The coated cotton flaps separated from this wash and freed from soluble PQAV components are washed together with the test fabric in a further wash test under the specified standard conditions. The washing result now determined shows the significantly higher% remission value of 66.4. The importance of the process condition required according to the invention that the PQAV compounds as such are insoluble even under the temperature loads of the washing process and / or are immobilized in a washable manner on solids which are insoluble in these aqueous surfactant liquors is evident from these comparative washing tests.

Claims

Patent claims

1. Use of polyfunctional quaternary ammonium compounds (PQAV) which are insoluble in aqueous-surfactant washing and cleaning liquors even under the temperature loads of the washing process and / or which are immobilized in such aqueous-surfactant liquors and are not washable and immobilized as cleaning agents which collect particle dirt in aqueous surfactant washing and cleaning liquors, which can be separated from the items to be cleaned manually and / or mechanically after washing or cleaning.

2. Embodiment according to claim 1, characterized in that the PQAV cleaning enhancers are used in textile washing together with conventional tenside-containing textile detergents, in particular based on anionic and / or nonionic surfactants.

3. Embodiment according to claims 1 and 2, characterized in that the PQAV cleaning booster can be used at working temperatures in the washing or cleaning process up to about 95 ° C.

4. Embodiment according to claims 1 to 3, characterized in that the detached particle dirt from the wash liquor collecting cleaning booster in the form of a sheet, z. B. is used as a sheet, film or cloth formed from insoluble PQAV, or contains PQAV not washable immobilized on at least part of its surface.

5. Embodiment according to claims 1 to 4, characterized in that the dirt-collecting cleaning booster is used as a fine-insoluble solid which is formed from PQAV or contains another, correspondingly insoluble fine-solid as a carrier, on the surface of which PQAV are not immobilized washable.

6. Embodiment according to claims 1 to 5, characterized in that a cleaning booster is used which originally contains water-soluble and / or water-swellable PQAV reactively bound on the surface of an insoluble carrier.

7. Ausführungsfσrm according to claims 1 to 5, characterized in that the cleaning booster is used as a finely divided solid or as a sheet, on the surface of which a large number of quaternary ammonium groups has been introduced by chemical reaction.

8. Embodiment according to claims 1 to 6, characterized in that the cleaning booster is used in the form of a finely divided solid or a sheet, on the surface of which anionic groups are bound in block form at least with part of the quaternary ammonium groups of the PQAV-containing impregnation.

9. Embodiment according to claims 1 to 8, characterized in that the PQAV are present on finely divided, non-soluble in the wash liquor inorganic or organic solids, the individual particle size preferably does not exceed 1 mm and is in particular below 100 μ.

10. Embodiment according to claims 1 to 9, characterized in that the particularly finely divided cleaning enhancers are derived from insoluble or insolubilized natural products and / or insoluble synthesis products, the surface of which has been equipped with quaternary ammonium groups by chemical reaction.

11. Embodiment according to claims 1 to 10, characterized in that the cleaning enhancers are derived from fine-grain cellulose or insoluble cellulose derivatives and / or other corresponding polysaccharide-type natural substances and / or their derivatives.

12. Embodiment according to claims 1 to 11, characterized in that the dirt-collecting cleaning boosters based on optionally modified natural substances have an average PQAV degree of substitution not above 0, 5, preferably not above 0, 12, eg. B. have in the range of about 0.01 to 0.08.

13. Embodiment according to claims 1 to 12, characterized in that as a finely divided inorganic carrier for the PQAV natural and / or synthetic water-insoluble materials, e.g. Aluminum silicates, layered silicates, silica and / or insoluble salts, such as alkaline earth carbonates or sulfates, can be used.

14. Embodiment according to claim 13, characterized in that synthetic crystalline zeolites, in particular zeolite A, X and / or P - preferably ϊn detergent quality - are used as the finely divided carrier.

15. A variant of the embodiments according to claims 1 to 14, characterized in that in addition to or instead of Quaternary ammonium groups bas basic amino groups, in particular tertiary amino groups, are present in the immobilized dirt-collecting cleaning booster which is insoluble and / or cannot be washed off under washing conditions.

16. A process for strengthening the cleaning of aqueous-surfactant washing and cleaning liquors by using flat and / or finely divided undissolved solids in the liquor, which bind suspended particle dirt from the aqueous-surfactant liquor to their surface, and hold there until the washing process is complete and in this form can be separated manually and / or mechanically from the material to be cleaned, characterized in that PQAV are used as cleaning-enhancing solids which are insoluble even under the temperature loads of the washing process in the water-surfactant liquors and / or accordingly in these liquors insoluble solids are not immobilized washable bound.

17. Textile detergents based on conventional mixtures of surfactants, associated builders and, if desired, further customary washing auxiliaries such as washing alkalis, bleaching agents, corrosion inhibitors, brighteners, foam inhibitors, graying inhibitors, enzymes, bulking agents, fragrances and the like, characterized in that they are used to collect particle dirt from the washing liquor additionally contain PQAV in finely distributed / or sheet-like form, which are insoluble even under the temperature loads of the washing process in the aqueous-surfactant liquors and / or are immobilized on washable solids which are insoluble in these liquors and cannot be washed off.