EP0235686A1 - Process for the laundering and/or cleaning of dirty textiles - Google Patents

Abstract

Dirty textiles are treated in a washing bath that contains surfactants and if desired other usual components of washing baths under the influence of ultra-sound. The washing bath further contains insoluble pigment and/or fat stain captors which can be manually or mechanically separated from the textile after cleaning. The captors are polyquaternary ammonium compounds, preferably immobilised on the surface of insoluble carriers. In a multistage process, after pigments and fats have been removed, bleachable and/or enzymatically affected stains are removed with the help or bleaching or enzymatically active adjuvants.

Description

The invention relates to a new method for washing and / or cleaning soiled textile goods by treatment in a detergent-containing washing liquor. The method according to the invention is suitable for the improved removal of pigment and / or grease stains, which may also be present together with so-called problem stains, for the removal of which washing and / or cleaning auxiliaries of a special type are usually required. The best-known examples of this are the use of bleaching agents for, in particular, oxidative bleaching of particularly resistant color stains, and the use of enzymatically active washing aids, in particular the known detergent proteases, for removing, for example, protein-based stains, the method according to the invention also making use of such additional cleaning aids can.

The new method can be carried out in one or more stages, the invention particularly relating to the improved multi-stage treatment of a soiled textile material which, in addition to pigment and / or grease stains, also has problem stains, for example of the type mentioned above, at least in part.

The essence of the teaching according to the invention is to facilitate the washing or cleaning process on the textile by the action of ultrasound on the washing liquor loaded with the soiled textile. The cleaning of hard surfaces in aqueous and / or organic washing baths under the influence of ultrasound has been known for decades and has been implemented on an industrial scale. The application of this measure to the washing or cleaning of textiles has also long been known as a wish. However, proposals that can be used in practice have so far not become known. Probably the most recent proposal provides for the treatment of the textile goods to be cleaned with ultrasound in pure water at room temperature, the water being gassed with finely divided air. However, checking this working methodology on textile samples with the standard soiling that is common today does not reveal any significant cleaning effects even after several hours of exposure to the ultrasound treatment.

The invention is based on the task of realizing the possibility of easier cleaning or washing under the influence of ultrasound now also for soiled textile goods. The invention has in particular the task of elaborating laws that are suitable for such an ultrasonic washing process on the one hand from the special nature of the textile goods and on the other hand the varied nature of possible soiling of textiles in daily life in connection with the effect of ultrasound on the Wash bath result.

The teaching of the invention relates on the one hand to elements which have to be taken into account in the ultrasonic washing stage. On the other hand, the teaching of the invention relates to the sensible combination of such an ultrasonic wash with known further measures of textile washing or cleaning, in particular for Removal of residual parts from the area of so-called problem soiling.

The invention accordingly relates in its most general form to a process for washing and / or cleaning contaminated textile goods by treatment in a detergent-containing washing liquor, if desired with the addition of further washing and / or cleaning aids, the new process being characterized in that the detachment of pigment and / or grease soiling at least partially under the influence of ultrasound and working with a liquor which contains at least largely insoluble catchers in this liquor for the absorption of at least part of the detached pigment and / or grease soiling, these catchers being such are designed so that they can be separated manually and / or mechanically from the cleaned goods - and if desired also from the washing liquor.

The undissolved catchers used in the surfactant-containing washing liquor in the process according to the invention and present as solids for the pigment and / or grease dirt detached under the action of ultrasound are designed in such a way that they prevent a substantial retransfer of the dirt particles absorbed onto the textile material to be cleaned under the washing conditions . Details of this are explained in detail below.

In a further embodiment, the invention relates in particular to measures which are expedient in the context of a combination treatment in which ultrasound washing is preferably used to remove pigment and / or grease stains, while treating problem stains which have not been removed or have not been adequately eliminated in separate process steps of the washing process will. In particular, in this Embodiment of the method according to the invention describes a combination treatment that works with the use of enzymatic and / or bleaching washing or cleaning aids. In a particularly preferred embodiment described in detail below, the bleaching and / or the enzymatic cleaning of the soiled textiles is carried out at least in part following a previous ultrasound treatment to remove at least the substantial proportion of the pigment and / or fat soiling. Such prior ultrasonic washing exposes the areas of problem soiling for the separate and targeted treatment of these contaminants. It is clear that a particularly effective and simplified removal of residual problem soiling is possible in a corresponding multi-stage process.

The ultrasound wash

From the numerous problems of using ultrasonic washing on soiled textiles, the most important parameters are described below which have a decisive influence on the washing result, are not described in the relevant and comparable prior art for cleaning processes using ultrasound on hard surfaces and are not described there or occur only to a less serious extent.

The investigations of the applicant on ultrasound washing on textiles have shown that the process-facilitating and improving effects of the use of ultrasound are directed, in particular, at the removal of pigment and / or grease stains. The detachment of these types of dirt from the textiles to be cleaned is promoted by the use of ultrasound under suitable process conditions in such a way that often the practically complete detachment of these dirt components is possible at best at moderately elevated temperatures within a few minutes, possibly even within a period of less than one minute. Accordingly, in a preferred embodiment, the method according to the invention provides the use of ultrasound as a washing aid, in particular in a method step which is aimed at removing pigment and / or grease stains, subsequent method steps with or without the use of ultrasound being able to be provided, in which the more stubborn residues are removed.

The easier removal of pigment and / or grease dirt in the context of technical processes in the treatment of hard surfaces under the influence of ultrasound is not readily transferable to the field of textile washing. This is due to incomparable starting conditions, of which - without claiming to be complete - the following are listed: Loading a washing liquor with layers of textile material not only creates the shading problems known per se for ultrasonic textile washing, but also the known problems in particular Ability and willingness of the textile material to take up dispersed dirt from the wash liquor again. This problem known from conventional textile washing occurs under the conditions of ultrasound washing in the washing bath, which is usually not uniformly sonicated or sonicated, and is much more common. The possible advantage of facilitating dirt detachment under the influence of sound is so overcompensated by this disadvantage that the use of ultrasound washing has hitherto been prohibited.

Further difficulties can arise from air inclusions, to which textiles based on or with the use of fibers of natural origin in particular tend. To be mentioned here in particular the cotton, which both in the unrefined but also in the so-called refined state - and here also in the context of the widespread blended fabrics - provides stubborn resistance to ultrasonic cleaning when pigment and / or grease stains are detached. Compared to cleaning the hard surface, the following aggravating condition also applies to textile washing: The inherent considerable forces or vibrations from the collapse of the cavities created by ultrasound due to cavitation, which in any case only work in the close range, are probably due to the elastic structure of the Fiber bundles in the textile material are also caught in such a way that their transmission into lower-lying areas of the multi-part thread structure is inhibited. Even for the process of dirt removal, there are completely different starting conditions here than with the known and technically used cleaning of hard surfaces under the influence of ultrasound.

For the process step of cleaning under the influence of ultrasound on textile materials, the invention provides as an essential element the co-use of so-called catchers for the absorption of at least part of the detached pigment and / or grease dirt. As such, these catchers are insoluble in the wash liquor and are present in such a form that they can be separated manually and / or mechanically from the cleaned goods and, if desired, from the wash liquor used.

Such insoluble capture substances are in particular the corresponding components which are considered in the earlier applications P 35 45 990.5 (D 7478/7495), P 36 05 716.9 (D 7538) and in particular in patent application P 36 06 729.6 (D 7554) are described.

A first class of such capture substances, which is particularly important according to the invention, is insoluble and / or polyfunctional quaternary ammonium compounds (PQAV) which are immobilized on correspondingly insoluble solid supports and which are used in particular in the form of their insoluble or immobilized PQAV / surfactant complexes and in particular in the earlier applications and here again in particular are described in the application P 36 06 729.6 (D 7554). The disclosure of the older applications mentioned and in particular the last-mentioned application is hereby expressly made the subject of the present description of the invention.

The earlier application P 35 45 990.5 (D 7478/7495) relates to the use of polyfunctional quaternary ammonium compounds (PQAV) which are insoluble in aqueous-surfactant washing or cleaning solutions, even under the temperature loads of the washing process, and / or on aqueous ones Solutions corresponding to insoluble solids are not washable, immobilized, as a particle-dirt-collecting cleaning booster in aqueous surfactant washing or cleaning solutions, which can be manually and / or mechanically separated from the goods to be cleaned after washing or cleaning. This older application describes in particular the strengthening of the washing power of conventional aqueous-alkaline textile detergent solutions by using such PQAV dirt collectors. At least a considerable proportion of the dirt, in particular pigment dirt, that is solubilized in textile washing is absorbed by the PQAV present in the solid phase and thus ultimately transferred from the textile material that was originally soiled and to be cleaned to the dirt collector. In the washing result, an increase in the reflectance values of the washed items can be set in this way under selected conditions.

The teaching of the earlier application P 36 05 716.9 (D 7538) changes the use of those PQAVs which are insoluble in aqueous washing and cleaning solutions and / or are immobilized on solids which are correspondingly insoluble in these aqueous solutions in such a way that the new auxiliaries containing PQAV are present for the at least partial regeneration of dirt-laden cleaning liquors, in particular for their subsequent reuse. According to the teaching of this property right, in particular aqueous alkaline cleaning liquors, if desired containing surfactants, in particular washing solutions from textile washing, can be subjected to regeneration in such a way that either during the washing of the textile and / or subsequently, the soiled cleaning liquor with the insoluble or immobilized PQAV treated and thereby at least partially freed from solubilized dirt, in particular pigment dirt. The washing solution treated in this way can be reused - for example in the context of textile washing.

The use of appropriate PQAV or PQAV / surfactant complex compounds as from the reaction of PQAV with surfactant components, in particular anionic, amphoteric and / or nonionic surface-active agents, as dirt-absorbing weight-loss agents for reducing the need for conventional chemicals in washing and / or cleaning agents is the subject of said patent application P 36 06 729.6 (D 7554). If such catchers which are insoluble in the wash liquor are also used, the use of conventional phosphate-containing and / or phosphate-free builder components, for example, can be completely or partially dispensed with. The amount of surfactant components can also be reduced compared to the usual amount used. It is also possible, for example, to dispense with the use of conventional dirt-carrying agents, for example of the carboxymethyl cellulose type. Also on the Mitver The use of common washing alkalis can be dispensed with in whole or in part, since it has been shown that such PQAV-based dirt traps are particularly effective in the neutral to weakly alkaline range, ie, for example, from about pH 6 to 9, preferably in the range from about 7 to 8 , 5 can be used.

The following general information, to be understood in particular by way of example, of the older applications cited relating to the PQAV to be used or the PQAV / surfactant complexes derived therefrom also apply to the teaching of the present invention:

Polyfunctional quaternary ammonium compounds (PQAV) are described and known in the most varied form in the printed prior art and also in commerce. 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 known characteristic of the 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 absorbency and the adhesive strength of the PQAV on the solid base are different. The individual constitution of the PQAV plays a crucial 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. With stoichiometric or approximately stoichiometric amounts of the anionic surfactant components, the corresponding anionic surfactant salt generally forms on the quaternary ammonium group. Such PQAV anionic surfactant salts generally show a greatly reduced water solubility. Corresponding precipitates form, see for example the German laid-open specification 22 42 914. Such anionic surfactant PQAV salts have been proposed as antistatic agents for application to fibers. However, it is also known in this connection that excesses, in particular considerable excesses, of the anionic surfactant can lead to a redissolution of the primarily precipitated PQAV / anionic surfactant salts, compare the publication in "Seifen - Öle - Fette - Wachsen" 1985, 529 to 532 and 612 to 614. In particular in the reaction diagram on page 530 op. cit. the formation of solubilized micelle systems of the anionic surfactant / PQAV complex is shown with an excess of the anionic surfactants.

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 PQAV according to the invention, on the other hand, calls for the insolubility of the PQAV-based auxiliaries 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 in fact an indispensable prerequisite, particularly for the field of textile washing. If this critical precondition according to the invention is not met, the washing result is reversed to the contrary. Soluble PQAV components sliding into the wash bath are absorbed onto the textile goods to be washed and there bind undesirably additional amounts of pigment dirt.

Nevertheless, in an important embodiment of the invention, all previously known, originally water-soluble PQAV components can be used for the application according to the invention. It is only necessary to do this, the water-soluble and / or water-swellable PQAV compo to convert the prior art into the required insoluble form or to fix it on appropriately water-insoluble supports and thus immobilize them so that they are not washed off by this support during the cleaning process.

From the extensive relevant literature, the following publications may be named by way of example, the disclosure of which is hereby expressly also made the subject of the disclosure of the present description of the invention on 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 water-insoluble PQAV in the sense 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, 50 million, e.g. 10 million. This is understandable from the requirement of the insolubility of the PQAV 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 which carry quaternary ammonium groups either in the polymer chain or bound to the polymer chain are suitable as PQAV which are initially water-soluble but then immobilized on an insoluble carrier. 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 morpholine, piperidine, piperazine or indazole rings. Numerous examples of such water soluble Lichen PQAV are described in more detail, for example, 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. Merquat®100 and Marquart®550 (Quaternium 41).

Further preferably suitable PQAV are, for example, cellulose ethers, the anhydroglucose units of which bear substituents with quaternary ammonium groups bonded to ether oxygen. Such polymers are e.g. known from US-PS 3,472,840. A commercial product with this structure is e.g. the Polymer-JR®400.

Further particularly suitable cationic polymers are, for example, the quaternary polyvinylpyrolidone copolymers known from US Pat. No. 3,910,862 and available, for example, under the trade name Gafquat® 734 and 755, and those known from US Pat. No. 4,157,388 and, for example, under the trade name Mirapol® A15 quaternary polymeric urea derivatives available. Suitable copolymers with a polycationic character are also the polyacrylamide copolymers described in published European patent application 0 153 146, which in particular contain up to 50 mol% of a quaternized aminoalkyl ester of acrylic acid or methacrylic acid in addition to at least 50 mol% of acrylamide units. These copolymers are water soluble. There they are applied to cloths based on cellulose fibers and are drawn up there due to their natural drawing 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. For the invention Intended use in conventional surfactant washing and cleaning liquors, which can also be exposed to temperatures up to about 95 ° C, the cleaning cloths described in the publication are unsuitable. Not inconsiderable proportions of the numerous PQAV copolymers described in the publication slip into the wash bath, pull onto the items to be cleaned and lead to increased pigment contamination. Only the conversion of such PQAVs to the physical state required according to the invention, as described below, makes them tools 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 cationic polymers are especially the cationic polygalactomannan derivatives known for example from GB-PS 1 136 842.

in der R¹, R² und R³ z. B. Methyl- oder Ethylgruppen und R⁴ eine Epoxyalkylgruppe der Formel

oder eine Halohydringruppe der Formel

bedeuten und in welchen R⁵ eine Alkylengruppe mit 1 - 3 C-Ato­men, X = Chlor oder Brom und Z ein Anion wie z. B. Chlorid, Bromid, Jodid oder Hydrogensulfat ist. Der Substitutionsgrad sollte wenigstens 0,01 und bevorzugt wenigstens 0,05 sein und liegt typischerweise zwischen 0,05 und 0,5. Ein besonders geeignetes quartäres Ammoniumderivat eines Polygalactomannans ist z. B. das Guar-hydroxypropyl-trimethylammoniumchlorid, welches an die Sauerstoffatome der Hydroxylgruppen des Poly­saccharids gebundene kationische Gruppen der Formel

- CH₂- CH(OH) - CH₂ - N⁽⁺⁾- (CH₃)₃]Cl^(-)

trägt. Solche kationischen Guar-Derivate sind z. B. unter der Handelsbezeichnung "Cosmedia Guar C 261" auf dem Markt. Der Substitutionsgrad (DS) von Cosmedia Guar C 261 liegt bei etwa 0,07. Auch die Handelsprodukte "Jaguar C-13" (DS = 0,11 - ­0,13) und "Jaguar C 13 S" (DS = 0,13) gehören diesem Typ an.Galactomannans are polysaccharides that occur in the endosperm cells of many legume seeds, but which are obtained on an industrial scale only from locust bean gum, guar gum and tara gum. They are made up of a linear Mannan main chain, consisting of beta- (1.4) -glycosidically linked mannopyranose building blocks, to which individual galactopyranose residues are fixed as branches in an alpha- (1.6) -glycosidic bond. The main difference between the individual polygalactomannans is the mannose-lactose ratio. The cationic derivatives of the polygalactomannans are produced 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

in the R¹, R² and R³ z. B. methyl or ethyl groups and R⁴ an epoxyalkyl group of the formula

or a halohydrin group of the formula

mean and in which R⁵ an alkylene group with 1 - 3 C atoms, X = chlorine or bromine and Z an anion such. B. is 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 ammonium derivative 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 cationic groups of the formula

- CH₂- CH (OH) - CH₂ - N ⁽⁺⁾ - (CH₃) ₃] Cl ^(-)

wearing. Such cationic guar derivatives are e.g. B. under the trade name "Cosmedia Guar C 261" on the market. The degree of substitution (DS) of Cosmedia Guar C 261 is about 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.

For all configurations of the new cleaning agent according to the invention it applies that the PQAV used are insoluble in the wash liquor under the conditions of use, so that the surface of the arbitrarily shaped agent can be loaded with dirt particles and hold it until the 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 water-insolubility which is sufficient for the purposes of the invention is achieved. 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 expertise into account.

A fundamentally different way, 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 processes known per se. Process steps are used for this, as are known in principle 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 structure, for example a non-woven fabric or a woven or knitted cloth based on natural fibers and / or synthetic fibers can by reaction with a coupling component z. B. epichlorohydrin and subsequent reaction with a basic nitrogen compound with subsequent quaternization to the desired dirt-collecting liquor cleaner. The same applies to granular or powdered material made from natural and / or synthetic water-insoluble feedstocks. 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.

Particularly easily accessible and inexpensive starting materials for such a reactive surface modification which are insoluble in washing or cleaning liquors of the type mentioned are natural substances of the cellulose type, insoluble cellulose derivatives and other insoluble or insolubilized poly-saccharide-like natural substances or their derivatives. The introduction of quaternary residues containing ammonia proceeds 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 crucial for the teaching of the invention that it is completely sufficient for the suitability of the dirt collector if the quaternary cationic groups are on their surface, 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 aids are 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 auxiliaries with an insoluble polycationic 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, very low average degrees of substitution in 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 to work with average degrees of substitution not above 0.5, in particular not above about 0.35. An average degree of substitution of up to about 0.12 and preferably below 0.1 can be used particularly well for cleaning reinforcement in the context of textile washing. The lower limit will generally be the average degree of substitution in the range of approximately 0.01, with particularly good results being able to be obtained in the range from approximately 0.015 to 0.08 and in particular in the range from approximately 0.02 to 0.07.

However, the embodiments which provide a water-insoluble carrier in flat or granular form, on the surface of which PQAV are applied by sufficient fixation in a preferably thin layer 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.

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 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 salt group in the presence of anionic surfactants, see the references DE-OS 22 42 914 and "SFÖW" 1985, 530.

Any insoluble materials of an inorganic and / or organic type are suitable as insoluble carrier materials for fixing PQAV and thus for the immobilization of these dirt-collecting active components, provided that they are otherwise inert in the washing solutions. Suitable organic materials can be of vegetable origin. Preferred inorganic carriers are mineral substances of natural and / or synthetic origin, which are in the form of finely divided solids. PQAV-coated carrier substances having a specific surface area of at least about 0.5 m² / g are preferably used according to the invention, this specific surface area in particular preferably being at least 1 m² / g. The specific surface is understood to be the area that can be covered with PQAV. Certain minerals, which are particularly suitable here, have additional surface areas inside the solid phase - be it due to their pore structure or their ability to swell - which, however, are not or only to a limited extent accessible with PQAV. The verifiable outer surface can, however, reach considerable values, which lead to the range of 100 m² / g or even up to, for example, 300 m² / g. As examples of such extreme occupancy with Surfaces accessible to PQAV are called colloidal silicas.

The maximum particle sizes of the PQAV-loaded fine particles here are preferably not above about 100 μ, preferably not above about 40 μ - these numerical values are based on the absolute particle diameter and mean that all or at least the vast majority of the fine particles present Framework conditions correspond. Particles which have an average particle size (volume average) of at most about 10 .mu.m can be particularly useful for textile washing, the absolute particle size also being below this value, at least for the majority of all solid particles.

Suitable inorganic carriers are in particular insoluble and finely divided salts, oxides, silicates and the like. For example, aluminosilicates of the type of zeolites or zeolite-like compounds are particularly suitable, in particular sodium zeolite A which is widely used in detergents today. Instead of this, zeolite A can also be used in an exchanged form e.g. find use as calcium salt.

A particularly suitable mineral carrier class are swellable, finely divided substances of the type of clays and / or swellable layered silicates, in particular from the smectite class. Swellable inorganic minerals of this type are characterized by a particularly large surface when swollen. This can be used within the scope of the invention. The known smectite clays montmorillonite, hectorite and / or saponite are particularly suitable here. However, comparable synthetic materials with only limited swellability are also suitable, as are described, for example, in the earlier application P 35 26 405.5 (D 7031).

In a preferred embodiment, insoluble and / or PQAVs immobilized on insoluble carriers are used as dirt-absorbing emollients, the counteranions of which - originally present from the quaternization reaction - are at least partially replaced by surface-active agents before use in the washing or cleaning liquor. It may be preferred to use corresponding reaction products between the original PQAV and the surface-active agents, in which at least 50 equivalent percent and in particular at least about 80 equivalent percent of the quaternary ammonium groups are activated with regard to their counteranions by exchange with the surface-active agents. In the preferred embodiment of the invention, the activation of the quaternary ammonium groupings is carried out by using at least equivalent amounts of PQAV on the one hand and surface-active agent on the other hand in the preparation stage of the dirt-absorbing emollient. Excess surfactants do no harm and may even be preferred. In particular, surfactant components which are capable of such an exchange of the counter anion originally present are used as surface-active agents. For example, the counter anion can be replaced by known anionic surfactants with a surfactant character.

Suitable agents for pretreating PQAV are, however, amphoteric surfactants, for example of the amphoteric surface-active agent type of the aminocarboxylic acid type. However, the pretreatment of the insoluble PQAV with surfactants which are not to be addressed as anionic surfactants or amphoteric surfactants is also of particular importance according to the invention. Non-ionic surfactants are particularly suitable here as activation components. Details on this known class of substance can be found in the already cited reference "Ullmann" loc. Cit. Within this group, in addition to those customary in today's textile detergents Nonionics - in particular from the class of condensation products of longer-chain alcohols, for example fatty alcohols, with x mol of ethylene oxide (x preferably equal to or greater than 3, for example 3 to 10) - washing-active alkyl glycosides are also of particular importance. Even if the mechanism for such activation has not yet been clarified, it is true that a pretreatment of the PQAV scavenger with Nonionics can achieve a noticeable increase in effectiveness.

The insoluble catchers based on PQAV can - as described in detail in the older applications - be used in sheet or film form or in the form of a wipe that is also used. In particular, however, it is preferred according to the invention to use these essential auxiliaries in the form of finely divided solids, which enable their disperse fine distribution in the washing or cleaning liquors, and thus ensure that, with the most homogeneous possible distribution of the dirt-adsorbing PQAV, every contaminated area of the items to be cleaned is of the PQAV is ready for adsorption. In this way, the transport route of a detached dirt particle from its original location to the desired landfill location on the catcher surface is kept as short as possible. The movement and mixing of the goods to be cleaned, which are preferably also used under the conditions of exposure to ultrasound in accordance with the invention, also make it possible in this way to continuously provide new adsorption-ready PQAV surfaces of the surface of the goods to be unloaded from pigment dirt. From this, the limitation of the surfactant performance now required and the resulting considerations for the selection and / or reduction of the surfactants or amount of surfactant can be understood.

The PQAV-based scavengers present as heterogeneous solid phase according to the invention absorb from the dirt-laden one Fleet, in particular negatively charged parts, for example corresponding particle dirt. In addition, the PQAV solid material can have a cleaning or cleaning-enhancing effect due to other surface forces. In the important further embodiments described below, it is consciously assumed that not only negatively charged dirt can be removed from soiled washing liquors.

In the context of conventional washing processes, for example, existing greasy or oily soiling is hydrophilized to such an extent that it is dissolved in the wash liquor. In an important embodiment of the invention, together with the dirt-collecting PQAV, an auxiliary is also used in the heterogeneous solid phase, which excels due to its high absorption capacity for oleophilic soiling. It is known that selected plastics, for example polyethylene or polypropylene or polyurethane or surface-insoluble solids of any origin which have a highly hydrophobic finish, have the ability to pull the oleophilic dirt content, which has been hydrophilized under the action of surfactants, from a wash liquor and to hold it on its surface. This working principle is also used in this embodiment for the effective cleaning of soiled washing liquors. The collectors for such oleophilic dirt can be used, for example, in the form of flakes, fibers or fiber structures such as cloths, random fiber fleeces, poromer skins and the like. What is essential for this component is only the condition previously stated for the PQAV cleaners that a manual and / or mechanical separation between the liquid phase and the dirt collector present in the solid phase is ensured. A particularly important embodiment will be discussed below.

The oleophilic dirt-collecting auxiliaries can be used simultaneously with the treatment of the wash liquor by PQAV and / or separately therefrom. The working conditions in detail are determined by the nature of the pollution in the wash liquor and the expected load of the dirt-collecting auxiliary substances in the solid phase.

In a further embodiment of the invention, in addition to the PQAV-based catchers and the oleophilic dirt-collecting solids, polyanionic cleaning aids present in a separate solid phase are also used. Polyanionic components in dissolved and / or undissolved form play a considerable role in today's washing and cleaning agents. They are used, for example, as builders or cobuilders for the surfactants. They have a wide range of tasks, the binding of calcium and / or magnesium ions from the present water hardness being mentioned as an example. The following is important for the embodiment of the invention concerned here: by using insoluble polyanionic components according to the invention - which, like the previously discussed dirt-collecting auxiliaries, are also used in manually and / or mechanically separable form - it is possible to undesirably influence one another Avoid PQAV-based additives and the polyanionic additives discussed here. Both collectors are so spatially separated from each other as a solid phase that each of these auxiliaries can develop its cleaning effect without being affected by the other undissolved auxiliaries.

The teaching of the invention covers the joint use of the PQAV auxiliaries and the polyanionic insoluble auxiliaries in the presence or in the absence of the previously discussed third collector component, which is particularly suitable for the absorption of oleophilic dirt from the washing solution.

Natural and / or synthetic solids with a plurality of anionic acid residues are particularly suitable as the insoluble polyanionic solid phase. Examples include insoluble components containing carboxyl groups, sulfonic acid residues, phosphonic acid groups and the like.

If catchers are used which contain the insoluble active component - for example the PQAV / surfactant complex and / or the strongly oleophilic coating - as a surface finish for intrinsically insoluble solids, it may be preferred according to the invention to use these active surface finishes in as thin a layer as possible Provide layer on the insoluble solid supports. This ensures optimal use of the dirt-collecting active materials. In this context, it can be preferred, for example, to work with layer thicknesses of PQAV or PQAV / surfactant complexes on insoluble supports which do not, or do not significantly, exceed the range of approximately 100 μ. In a preferred embodiment of the invention, however, much smaller layer thicknesses of such immobilized PQAV collectors are provided. If one works with finely divided coated carriers, for example on a mineral basis, with a high specific surface, the thickness of the coating containing PQAV can reach into the range of monomolecular layers. Accordingly, layer thicknesses of the active substance on the carrier materials in the range up to about 1 μ and below can preferably be used.

The invention in particular creates new, previously unknown possibilities for effective washing or cleaning supply. Even if it is assumed that based on the previous knowledge of cleaning solid surfaces using ultrasound, the easier detachment of pigment and / or grease stains was generally known, it was not to be expected that the ultrasound would succeed under the same conditions to anchor pigment detached and / or greasy dirt particles detached and conditioned by the use of surfactants so securely on the surface of the catcher substrates used in accordance with the invention that the textile cleaning takes place without substantial retransfer of the detached dirt portions to the textile material to be cleaned. Dirt loads in the fleet can be coped with without reducing the washing result, as they are unknown with conventional textile washing. High degrees of whiteness or high reflectance values of the washed textile material are obtained under the conditions according to the invention even if the wash liquor is already deeply dark colored due to the absorption of large amounts of dirt, provided that the adsorption capacity of the trapping surfaces has not yet been exhausted.

The amount of PQAV or PQAV / surfactant complex to be used in the detergent is matched to the expected dirt load. If it is intended to use these dirt absorbers only once, even the smallest amounts of these absorbers are sufficient to bind the pigment dirt that is usually obtained, for example, in textile washing. PQAV components of the type affected here are able to bind the same to pigment dirt up to a multiple of their weight - in particular due to the spreading of the PQAV-based catchers on the carrier substrate in the thinnest layer.

In the context of the invention, dirt-absorbing catchers are used which are impregnated with PQAV or an organic and / or inorganic insoluble carrier. PQAV / surfactant complex, then it may be preferred to use the amount of this impregnation - based on the total weight of the impregnated solid - in the range from about 0.01 to 20% by weight and in particular in the range from about 0.1 to 10 % By weight.

In the preferred embodiment, the stage of textile cleaning using ultrasound, in particular for removing pigment and / or grease stains, is carried out in such a way that the material to be cleaned is at least partially - preferably completely - immersed in the sonicated liquor, whereby it can be important to take measures to ensure that the immersed material is largely free of adhering gaseous components - in particular of air pockets.

In the method according to the invention using ultrasound, it can be advantageous to additionally stimulate the tendency of the wash liquor to form cavitation and to act on ultrasound by virtue of the fact that a sufficient amount of finely divided solids can to a certain extent act as cavitation cores. In the method according to the invention, this principle, which promotes cleaning, is already implemented by the use of very finely divided, insoluble catcher substrates which are preferably homogeneously distributed in the wash liquor. It is of particular importance that these very finely divided solids are also present in the immediate vicinity of the textile material to be cleaned and can thus promote cavitation in the vicinity of the contamination.

The temperature of the wash liquor in the ultrasound treatment can be up to about 95 ° C., but is preferably considerably lower and usually does not exceed temperatures of about 80 ° C. Effective cleaning is possible at room temperature Lich. Lowering the process temperature toward room temperature is even preferred from the standpoint of promoting desired cavitation formation. On the other hand, it should be borne in mind that in the process according to the invention there is a certain interplay of conventional effects of textile cleaning by means of surfactants and the known effect of ultrasonic cleaning. It has often proven to be expedient to carry out the washing step of the ultrasound treatment in the temperature range from approximately 30 to approximately 70 ° C. and here in particular in the temperature range from approximately 35 to approximately 50 ° C.

The frequency range for carrying out the method according to the invention in the stage of ultrasound treatment concerned here is the entire range known today and also partially used in cleaning methods. Particularly preferred frequencies of the sonication are in the range up to approximately 100 kHz, the lower limit for the ultrasound usually being specified as approximately 16 kHz. Accordingly, a range of approximately 20 to 60 kHz for the sound frequency used can be particularly suitable.

It has proven to be expedient to move the textile material to be cleaned continuously and / or discontinuously during the sonication step in the washing bath, in particular to circulate, compress and / or stretch it. This not only compensates for the disadvantages of any shadow areas, it can also significantly accelerate the removal of pigmented dirt.

The design of the sound reinforcement stage in the method according to the invention or of the devices suitable for carrying out this method stage is generally influenced by a plurality of parameters. His example is: Together Setting and selection of the detergent system, size and degree of loading of the cleaning bath, operating conditions of the cleaning bath, accessibility, durability and energy consumption of the sound reinforcement elements as well as the expected degree of loading of the device in use, for example in the sense of a practically continuous use in the field of commercial cleaning or only periodic use in the area of personal household linen.

Such considerations ultimately also determine in the design of the cleaning devices that the cleaning step under ultrasound is carried out with a uniform frequency or with mixed frequencies and / or with sliding frequencies in the case of continuous or pulsating sonication. Values of up to approximately 10 W / cm² and in particular values in the range of approximately 0.5 to 5 W / cm² have also proven to be quite useful and effective as power density, with the power input into a bath depending on its Size, for example in the range of at least about 20 W to a few hundred W. Larger amounts are also suitable for larger bathrooms. Based on 1 liter bath volume, values up to about 25 W / l, in particular in the range up to about 15 W / l, e.g. 5 to 10 W / l may be particularly preferred.

Satisfactory washing results in the ultrasound stage are often obtained in the period from 0.5 to 60 minutes, in particular in 0.5 to 15 minutes, a period of about 1 to 15 minutes, in particular about 1 to 10 minutes, generally providing the desired cleaning action.

The further stages of the cleaning process according to the invention

In the preferred embodiment, the invention provides a multi-stage cleaning process which, in addition to the ultrasound treatment with removal of pigment and / or grease stains, also provides for the treatment of the textile goods to be cleaned in order to remove problem stains which are still remaining. It is preferred to carry out these additional work stages at least in part following the ultrasound treatment. The advantage of this work is obvious: The problematic soiling is now free of pigment and grease so that it is accessible to the direct and targeted attack of the cleaning aid used.

The two most important additional cleaning aids are dye-killing, in particular bleaching additives and enzymatically active washing aids, in particular detergent proteases.

In such a multi-stage procedure, the enzymatic and / or bleaching work stages following a first ultrasound treatment can likewise be carried out using ultrasound, but they are preferably carried out at least in part over time without the use of ultrasound. This applies in particular to a subsequent work step with enzymatic action. As is well known, ferments can be sensitive to the effects of ultrasound and even ineffectiveness.

These considerations are less important for the use of bleaching agents to remove resistant stains from paint. However, it has been found that bleaching is generally not promoted to such an extent by using ultrasound that the additional energy expenditure is worthwhile for this work step. It can make more sense following the removal of the pigment and / or grease soiling, it is very easy to provide work stages in which the partially cleaned textile material is now subjected to the bleaching and / or enzymatic treatment - possibly with the setting of optimal working temperatures for these process steps. The textile material to be treated can be moved batchwise or continuously in the fleet if desired, although not even this auxiliary measure is necessary. In general, the known knowledge of conventional cleaning processes applies here.

The bleaching and / or enzymatic treatment can be carried out in the original liquor which contains the loaded strainer. In a particular embodiment of the invention, however, it is provided that the liquor for carrying out these process stages is at least partially freed from the dirt-laden catcher. This can be done in detail as described in the context of the older applications mentioned. The liquor can therefore be pumped through separation stages, for example, in which the contaminated undissolved catcher is retained.

The bleaching and / or enzymatically acting washing aids can be added to the liquor right from the start and / or separately after the end of the ultrasound treatment stage. In particular, ultrasound-sensitive washing aids are preferably added to the cleaning bath after completion of the first sonication step.

An intermittent, preferably short ultrasound treatment can be provided in connection with these subsequent work stages. Here, in particular, there is a corresponding final sound level, which is expediently also present in the presence of undissolved catcher portions free capacity for dirt particles is carried out. In this way it can be ensured that in such a final sonication phase, the last portions of conditioned dirt particles are also removed from the textile and from the wash bath.

An important, known tool, which can now be used much more effectively than before in the process according to the invention, is the bleaching treatment of stubborn stains of paint by using UV radiation. If such a work step is placed at the end of the multi-stage washing process, for example, and if the washing liquor from the dirt-laden catcher particles is also clarified for this purpose, the bleaching effect of such UV radiation can be used here in a previously unknown effectiveness. Overall, such a measure once again serves the goal of reducing the chemical requirement and thus overall reducing the environmental impact of the wash liquor that is ultimately to be drained into the sewage system.

example

Washing tests were carried out with different tissue samples, which were provided with standard soiling. The tests were carried out in a stainless steel tub, which was equipped with ultrasonic vibrating elements on the bottom.

• 1. Fassungsvermögen des Waschbottichs: 4 l; auf die Wasch­flotte übertragene Ultraschallfrequenz: 35 kHz.
• 2. Zusammensetzung der Waschflotte:
      0,6 g/l Talgalkoholsulfat (Sulfopon T55)
      1 g/l alpha-Sulfo-C_16/18-Fettsäure-di-Natriumsalz
      0,4 g/l Ölsäurediethanolamid (Comperlan VOD)
      0,5 g/l Cosmedia Guar C261 (PQAV)-beschichteter Schichtsilikat im Sinne der P 35 45 990.5 (D 7478/7495)
        pH 9, eingestellt mit NaOH
• 3. Mit Standardschmutz angeschmutzte eingesetzte Testgewebe:
      Baumwolle, nicht augerüstet
      Polyester-Baumwoll-Mischgewebe, veredelt
      Polyester
  Als Schmutz diente eine Mischung aus synthetischem Stra­ßenstaub und synthetischem Hautfett.
• 4. Waschbedingungen in der ersten Verfahrensstufe zur Ent­fernung der Pigment- und/oder Fettanschmutzung:
      Temperatur der Waschflotte: 41 °C;
      Dauer der Beschallung: 5 Minuten;
      kontinuierliche Beschallung während der ersten Wasch­stufe;

Specifically, the following information was used to carry out these washing tests:

• 1. Washing tub capacity: 4 l; Ultrasound frequency transmitted to the wash liquor: 35 kHz.
• 2. Composition of the wash liquor:
  0.6 g / l tallow alcohol sulfate (Sulfopon T55)
  1 g / l alpha-sulfo-C _16/18 fatty acid disodium salt
  0.4 g / l oleic acid diethanolamide (Comperlan VOD)
  0.5 g / l Cosmedia Guar C261 (PQAV) -coated sheet silicate in the sense of P 35 45 990.5 (D 7478/7495)
  pH 9, adjusted with NaOH
• 3. Test fabrics soiled with standard dirt:
  Cotton, not upgraded
  Polyester-cotton blend, refined
  polyester
  A mixture of synthetic street dust and synthetic skin fat served as dirt.
• 4. Washing conditions in the first stage of the process for removing pigment and / or grease soiling:
  Wash liquor temperature: 41 ° C .;
  Duration of the sonication: 5 minutes;
  continuous sonication during the first washing stage;

The table below summarizes the standard test fabrics examined, the associated reflectance values of the soiled material used and the reflectance values of the cleaned material after the old-sound treatment.

To remove enzyme-specific soiling such as EMPA blood-milk ink on unfinished cotton was subsequently added to the liquor with 70 mg / l of a protease (Maxatase) and allowed to act in the manner of a soaking process. To remove bleachable stains (tea, red wine), 0.2 to 0.5 g / l of a dipercarboxylic acid (diperdodecanedioic acid) was added to the wash bath in a further step. The action of the bleaching agent was supported by the ultrasound mechanics and delivered results that corresponded to those achievable in the launderometer.

Claims (17)

1. A method for washing and / or cleaning soiled textile goods by treatment in a surfactant-containing washing liquor, if desired with the addition of further washing and / or cleaning aids using ultrasound, characterized in that the detachment of pigment and / or greasy soils at least partially under Exposure to ultrasound is carried out and a fleet is used which contains at least largely insoluble catchers in this fleet for the absorption of at least part of the detached pigment and / or grease soils, which catchers can be separated from the cleaned material manually and / or mechanically. 2. The method according to claim 1, characterized in that work is carried out with undissolved, solids catchers for pigment and / or grease soiling which prevent a substantial retransfer of the dirt particles taken up under the washing conditions. 3. The method according to claims 1 and 2, characterized in that in the context of a combination treatment using enzymatic and / or bleaching washing or cleaning aids is used, preferably the bleaching and / or the enzymatic cleaning at least partially following the Ultrasound treatment to remove pigment and / or grease dirt is carried out. 4. The method according to claims 1-3, characterized in that the ultrasound treatment on one in the fleet immersed textile material takes place, which is at least largely freed from adhering gaseous components, in particular air pockets. 5. The method according to claims 1-4, characterized in that in the case of a multi-stage procedure, the enzymatic and / or bleaching work stages following a first ultrasound treatment are likewise carried out using ultrasound, but preferably over time, at least in part, without using ultrasound. 6. The method according to claims 1-5, characterized in that insoluble catchers for pigment and / or grease dirt in sheet form, for. B. as a cloth, sheet and / or film, as a fiber or fiber bundle, but in particular in the form of finely divided solids, which are preferably largely homogeneously distributed in the wash liquor. 7. The method according to claims 1-6, characterized in that insoluble, finely divided dirt traps are used which have active surfaces of at least about 0.5 m² / g, in particular at least about 1 m² / g. 8. The method according to claims 1-7, characterized in that dirt traps are used, the organic and / or inorganic - in particular mineral - origin and have at least on their surface a pigment and / or grease dirt binding equipment immobilized. 9. The method according to claims 1-8, characterized in that in particular for the detachment and binding of pigment dirt in the wash liquor with anionic surfactants and / or nonionic surfactants is used together with a catcher which contains polycationic elements which are insoluble in the wash liquor. 10. The method according to claims 1-9, characterized in that one works with insoluble dirt traps which have at least on their surface immobilized polyquaternary ammonium compounds (PQAV) or PQAV / surfactant complexes. 11. The method according to claims 1-10, characterized in that as insoluble scavenger finely divided organic solids with PQAV or PQAV / surfactant complexes modified surface and / or finely divided mineral solids, for. B. insoluble metal oxides, carbonates, silicates and / or aluminosilicates are used, on the surface of which PQAV or PQAV / surfactant complexes are immobilized. 12. The method according to claims 1-11, characterized in that the scavengers used to bind dirt have the equipment immobilized on the surface in a thin layer, preferably at layer thicknesses of not more than about 100 µ, in particular in the range of 1 u and below. 13. The method according to claims 1-12, characterized in that the ultrasonic treatment is carried out at temperatures up to about 80 ° C, preferably in the range from about room temperature to 70 ° C. 14. The method according to claims 1-13, characterized in that the ultrasound treatment with frequencies in the range up to about 100 kHz, preferably in the range of about 20-60 kHz. 15. The method according to claims 1-14, characterized in that the process is carried out in several stages such that the addition of enzymatic and / or bleaching auxiliaries to the washing bath before and / or preferably at least partly also after the initial removal of pigment and / or grease soiling is provided . 16. The method according to claims 1- 15, characterized in that the catchers loaded with pigment and / or grease soiling are at least partially separated from the partially cleaned textile material before the subsequent cleaning stages in multi-stage work. 17. The method according to claims 1 to 16, characterized in that the textile material in the wash liquor, in particular also just during the sonication stage to remove the pigment and / or grease soiling, e.g. is circulated.