EP0258816A2 - Process for washing and cleaning textiles - Google Patents

Abstract

Soiled textiles are wetted and washed by treatment with aqueous washing liquors, these liquors having such high wettability during the wetting operation that the textile material is thoroughly wetted and deaerated, ultrasound acting simultaneously and/or subsequently on the textile material located in the washing liquor.

Description

The invention relates to a new method for washing and cleaning soiled textile goods by treating them in aqueous washing liquors which contain dissolved, emulsified and / or suspended washing auxiliaries under the action of ultrasound on the washing bath to intensify and / or accelerate the washing process.

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 dream. In the years around 1950, the development of washing processes using ultrasound was considered to be of greater importance for the future. Ludwig Bergmann "Ultrasound and its application in science and technology" 6th edition, S. Hirzel Verlag Stuttgart 1954, p. 788 and the literature cited there, in particular Schilling et al., J. acoust Amer., Volume 21 (1949) Page 39 - Sonic Laundering. According to this last cited literature reference, for example, a white cotton fabric heavily soiled with oil soot was washed acoustically just as clean in soapy water with five changes of water in one hour, as in the laundry with fifty changes of water in 1 to 6 hours, without the loss of strength observed in the usual washing process would have occurred.

While the technical application for cleaning hard surfaces under the influence of ultrasound has been used intensively since then, ultrasound textile washing has become quiet. Based on the experience gained in the meantime, it is unanimously considered to be impracticable. The textile material in the washing liquor so rapidly dampens the entry of ultrasonic energy into the bath that it has so far not been possible in practice to increase the effectiveness of the washing performance by the effects of ultrasound. The problems caused by shading and / or by dirt-redeposition are still unsolved. The supple, soft nature of textile materials is largely responsible for this, which cannot be compared with the rigid surfaces of the solid, soiled materials or material parts used in technical cleaning. Corresponding to this is the experience of technical ultrasonic cleaning that elastic materials - for example the rubber parts of gas masks - are not accessible to the cleaning reinforcement by the action of ultrasound on the washing bath.

The most recent proposal from this field that has become known 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 elements of the invention described below relate in particular to proposals for solving the shading problem. The teaching of the invention is based on the surprising finding that in reality there are no fundamental differences between rigid cleaning Surfaces of solid molded parts on the one hand and softer pliable textile pieces on the other hand. For the cleaning-enhancing effect of ultrasound, the softest textile material, for example pure unfinished wool, can also be regarded as a "hard surface", provided that the elements of the invention described below are observed. The invention is based on the knowledge that a decisive factor for the inhibition or limitation of the ultrasound effect in textile washing is caused by microdispersed residual air which is also present in the fiber microstructure of the soaked textile material and is stubbornly retained here.

As is known, a sound wave advancing in the liquid or solid medium breaks off at the phase boundaries liquid / gaseous or solid / gaseous. The immersed textile material covered with microdisperse residual air is accordingly a strong insulator against the effects of ultrasound. Not only is the passage of the ultrasound wave through sufficient areas of the loaded wash bath impeded, the cleaning of the ultrasound influence cannot have an effect on the microstructure of the soiled area of the textile material either. The result is that not even a 1-layer layer of the textile material can be washed effectively by the action of ultrasound. Fundamental remedies are created here by the measures of the invention described below.

The invention accordingly relates to a process for washing and cleaning contaminated textile goods by treating them in an aqueous washing liquor containing dissolved, emulsified and / or suspended washing aids, under the action of ultrasound on the washing bath. The new process is characterized in that the soiled textile material is treated with an aqueous liquor which, under the conditions this treatment has such a high wetting ability that the fiber microstructure of the textile goods, including its soiled areas, is thoroughly wetted and ventilated, while displacing microdispersed residual air, and simultaneously and / or subsequently the textile goods immersed in the aqueous washing liquor are exposed to the action of ultrasound and thereby ensured, that the soiled areas of the textile goods remain at least in the state of their sufficient wetting and ventilation for at least a few seconds in the ultrasonic range.

Accordingly, the displacement of the residual air held in the fiber microstructure is of crucial importance in the method according to the invention. To make matters worse, a large number of fibers are usually bundled tightly together to form a thread and this bundling severely hinders the escape of residual air, in particular from the inside of the thread. Despite this difficulty, the liquid phase should also network the fiber as completely as possible in its microstructure, so that the concentration of gas-filled microvoids in the textile material is at least substantially reduced.

To solve this subtask, textile or detergent chemistry has a large number of effective washing-active wetting aids that can be classified as appropriate surfactants, emulsifiers and / or detergent boosters. From the wide range of relevant wetting aids given to the person skilled in the art, the latter can easily be determined by simple preliminary tests, in coordination with the other conditions of the washing or cleaning process. In this context, the following further findings on which the teaching according to the invention is based are important:

The action of ultrasound of the technical frequencies customary today does not have to mean any or no significant relief in the removal of microdisperse residual air from the textile goods. Although it is known that dissolved or very finely divided gas components in aqueous baths combine under the influence of ultrasound to form larger gas bubbles, it is known that these gas bubbles are - depending on their size - stabilized in the antinodes or nodes of the sound wave. Only in special cases do they come together under the influence of sound to form larger gas bubbles, which then emerge from the sonicated bath due to the difference in density. This stabilizing effect of the ultrasonic wave on the distribution of fine gas bubbles in the wash bath is evidently reinforced by the presence of the dipped textile material. In the visual inspection, the formation of microfine gas bubbles in the network of the textile, which cannot detach from the textile as long as the ultrasound exposure persists, can often be determined on the immersed textile piece in the sonication phase, unless further measures are taken that lead to the desired phase separation. A long-lasting and, in particular, continuous exposure to ultrasound on the dipped textile piece to be cleaned can therefore not have a cleaning-enhancing effect, but rather has a self-inhibiting effect. One of the causes is likely to be found here, which has prevented an improved textile washing under the influence of ultrasound.

The displacement of the microdispersed residual air required according to the invention takes place through the suitably selected play of forces in the wetting process known per se, which can thus become the time-determining step of the washing process under the influence of ultrasound. The action of ultrasound may influence this process, but not necessarily accelerate it. Trapped dirt particles are evidently detached from the fiber almost immediately under the influence of sound. Then, however, further penetration of the wetting liquid phase into the deep structure of the fiber bundle and the displacement of the air held here microdispersed before further cleaning effects can be made visible by the effect of sound. A possible fixation of detached air components by exposure to sound can possibly hinder the desired degassing. The means of the method according to the invention to be used against this are described below.

The technical solution to the problem on which the invention is based lies in the correct combination of the forces or force constellations, which can be subsumed on the one hand by the concept of wetting in the conventional sense and on the other hand by the concept of surface cleaning by the action of ultrasound, in particular using the cavitation forces caused thereby. Different combinations of networks and ultrasound treatment can lead to the desired success. The following are four characteristic patterns that illustrate the action according to the invention:

In a first embodiment, the textile material to be cleaned can first be thoroughly penetrated in a conventional manner, taking care to ensure that the microdisperse residual air is displaced as far as possible from the fiber microstructure and is replaced by liquid phase which preferably contains surfactant detergents. Only when this condition has been achieved to the desired extent is the textile material immersed in the wash liquor exposed to the action of ultrasound on the wash bath.

In a next embodiment of the method according to the invention, the wetting process can be facilitated in that the soiled textile material immediately after it is immersed in the washing liquid or after only a short period of wetting of a rough cleaning by the action of ultrasound is exposed. This removes the dirt particles captured in the volatile pre-wet. This can facilitate the subsequent intensive wetting of the problem areas in the inner thread structure. After this intensive wetting while displacing at least substantial portions of the microdisperse residual air, also in the inner core of the textile material, the final cleaning takes place under the influence of ultrasound on the washing bath.

In a variation of the last-described embodiment, the repeated repetition of the successive steps of wetting and sonication can be provided as part of a washing process, which, if desired, can also be modified to give impulsive sonication to the washing bath filled with textile.

Finally, the principle of changing wetting and sonication can also be realized in that sonicated and non-sonicated areas are provided in the washing bath, so that even with continuous sonication of the washing bath by simultaneously ensuring continuous or discontinuous movement of the items to be cleaned through the washing bath and alternating process sections of wetting in the absence of ultrasound and knocking off the wetted dirt components by the action of cavitation are connected with one another through its various zones.

In a preferred embodiment of the method according to the invention, it is provided, regardless of what has been said so far, that adequate ventilation of the washing liquor is ensured, here again various elements have to be taken into account: The liquor freshly introduced into the washing process contains dissolved air which, under the action of ultrasound In a manner known per se, it first meets to detectable blisters with the naked eye, but then in the Ultrasound field can be stabilized and held. The same is done with the air portions that are released from the textile fiber by the wetting process, but then macrodispersely stubbornly adhere to the textile under the influence of ultrasound.

For the technical solution to these multiple ventilation problems, the preferred embodiments of the invention provide that the unstable equilibrium conditions are sufficiently disturbed by sufficient textile mechanics in the wash bath so that the unification of air bubbles takes place to form larger air bubbles and ultimately the phase separation takes place due to the difference in density. In addition to adequate textile mechanics in the wash bath, the at least intermediate, possibly repeated use of sound-free treatment phases is an important tool of the invention. The fact that the desired wetting process is supported in a manner known per se by a textile mechanism in the wash liquor is an advantage for this preferred mode of operation of the invention.

Obviously, the mechanical movement of the textile loading in the wash liquor is of important importance in the process according to the invention. In a preferred embodiment, such a degree of textile loading and such a form of movement mechanics of the textile goods in the wash liquor are used that the continuous contact and deformation contact of adjacent textiles or textile areas is ensured by the upheaval of the textile liquor loading. It is sufficient if the textile material is immersed substantially in the liquid phase in a calm movement, and is circulated in the washing liquor in a breaking manner, with comparatively low average movement speeds of the individual textile sections not being exceeded. If an intensive rapid circulation of the textile goods in the liquor in the process according to the invention is not ruled out, this can, however, exacerbate the additional problem of undesirable air entry into the wash liquor and thus counteract the aim according to the invention of venting the fleet as completely as possible. Accordingly, it is preferred to provide a slow, smooth movement of the material in the wash bath, which can be continuous or alternate sections of movement and rest. A usable maximum value for the average movement speed of the textile in the wash liquor is, for example, about 0.5 m / sec, but preferably considerably lower, for example at most 0.4 m / sec or even less, for example not more than 0, 2 m / sec.

The movement of the textile goods in the wash liquor can be effected in a manner known per se by means of mechanically moving inserts or by pumping around the wash liquor. In a preferred embodiment of the invention, a combination of these measures is used in order to ensure that the textile liquor loading breaks open while continuous contact and deformation contact between adjacent textile areas.

In this way, influence can be exerted on the expression of air from the inside of the thread and on the stripping and unification of the air bubbles which form during the wetting process at the boundary phase of the textile solid / liquid phase, so that in this way the direct wetting of the textile with liquid phase and so that the access of ultrasound to these textile areas is promoted. On the other hand, this measure promotes another important element of the teaching according to the invention, which is described below.

The shading effect of the microdisperse on the textile phase is on the textile material that is not or only fleetingly wetted adhering residual air so strongly that the range of action of an ultrasonic transmitter - for example through the wall of the wash bath - is only very limited. Even if you work with washing baths - and this is preferred according to the invention - which have a plurality of sound transducers, which can preferably be arranged distributed over as large an area of the bath walls as possible, when working with a ball immersed in the bath and largely filling the bath volume Textile pieces - as is the case, for example, with conventional household washing machines - when exposed to ultrasound, only a comparatively limited area of the bathroom volume can be regarded as penetrated by ultrasound. The situation is different in the cleaning of textile web products, which will be discussed below.

In the method according to the invention it can therefore be important to design the movement mechanics of the textile goods to be cleaned in the washing bath in such a way that there is a sufficient probability for all soiled areas of the textile to get into the vicinity of at least one ultrasound transmitter and to linger here for so long that the desired performance is achieved by the ultrasound effect. This requirement can be met within the scope of the method according to the invention.

The determination on which the invention is based, inter alia, is crucially helpful here that after sufficient wetting of the textile material, in particular also in its dirt areas, the detachment of the dirt takes place almost spontaneously under the action of the cavitation forces. If a dirty fabric is placed in a sonicated wash bath, the spontaneous removal of the pigment dirt can be visually perceived, depending on the state of its wetting. The pigment dirt falls off directly from the textile and is taken up by the washing bath. That on the dirty piece of textile The cleaning result to be set depends on the state of wetting, which in turn can be determined by the nature of the fiber. Closed synthetic fibers, for example polyester fibers or textile sample pieces made therefrom, can be cleaned in strongly tending baths under the influence of ultrasound even without sufficient pre-wetting within seconds - for example in a period of 10 to 30 seconds - into the textile interior structure. The situation is quite different when using textiles which have a more complicated microstructure of the fiber, which is characterized in particular by the formation of cavities or capillaries. Fibers of natural origin, in particular fibers of vegetable origin in the refined or unrefined state, are characteristic of this. In particular, cotton or linen come into consideration here, whereby in the practice of textile washing predominantly mixed fabrics are used which contain a not inconsiderable proportion of fibers of natural, in particular vegetable, origin. The microscopic examination of such a fiber material shows the problems that underlie textile washing under the influence of ultrasound. Each fiber in itself, but especially the fiber bundles present in the thread, have a myriad of micro-cavities that are normally filled with air. The sufficient wetting that is absolutely necessary for the effect of ultrasound requires the selection of particularly effective wetting agents even on the non-soiled textile. This wetting problem is particularly aggravated in the soiled textile areas when oleophilic soiling, for example fats and / or oils, envelop substantial areas of the fiber.

Accordingly, a textile material soiled with standard pigment and / or greasy dirt based on such fibers of natural origin is subjected to the ultrasonic washing - for example unfinished or refined cotton or Appropriate blended fabric based on cotton / polyester as a textile carrier - then, when the soiled textile piece is introduced into a sonicated washing bath without sufficient pre-wetting, no or only a limited cleaning effect can be determined. The conditions change in the extent of the wetting of the soiled sample. Provided there is sufficient wetting and thus displacement of the microdispersed residual air, the almost spontaneous removal of the pigment dirt in the sonicated wash bath is visible within a few seconds, so that, for example, it is also full in the period between 10 and 60 seconds - but also in even shorter intervals Cleaning result can be obtained. Whiteness levels must be set on the textile that cannot be achieved in conventional laundry or only in special cases.

On the basis of these requirements, the teaching according to the invention in its most general form demands that the soiled areas of the textile goods remain in the ultrasound effective area for at least a few seconds, at least in the state of their sufficient wetting and ventilation. The average residence time of the soiling areas of the textile goods in the vicinity of the ultrasound transmitters can be less than 10 minutes and preferably a maximum of about 5 minutes for setting high-quality cleaning results. It has proven to be completely sufficient that the fully wetted and thus deeply vented textile material fulfills an average residence time of the soiling areas in the vicinity of the ultrasound transmitter of approximately 2 to 200 seconds and preferably of approximately 3 to 120 seconds. For the purposes of the definition according to the invention, the terms of the near range and the effective range of a respective ultrasound transmitter are to be seen separately. The close range of an ultrasound transmitter is understood as the distance up to approximately 40 cm, preferably up to approximately 25 cm and in particular up to about 15 cm each calculated from the sound source or sound-emitting wall piece.

Particularly preferred values for this close range are up to about 10 cm and in particular up to about 7 cm, calculated from the sound source. In contrast, the area of action of the sound generator in the washing process is a variable and depends on the shading effect of the textile goods contaminated with residual air. If there is not sufficient pre-wetting to suppress at least substantial portions of this residual air, there is a very small effective range, again calculated as the distance from the sound source. The absolute values for the effective range can be significantly below the numerical values of the close range mentioned above. To the extent of the increasing ventilation of the textile in its microstructure, the effective area expands and - provided there is sufficient wetting and ventilation of the bath - can reach the size of the near area.

Taking into account the overall parameters influencing the washing result, effective washing processes can be performed in a variety of ways in accordance with the teaching of the inventive action. So you can work with continuous sonication of the washing bath, but preferably with alternating phases of sonication and non-sonicated washing phases, with the mechanical movement of the textile loading in the washing liquor preferably also being continued during the non-sonicated phases. Sufficient pre-wetting without the action of ultrasound or even short-term ultrasound pretreatment, which only covers the dirty outer areas of the textile, can be carried out. One can work with a multiple treatment, preferably short-term sonication phases, which are separated from one another by non-sonicated washing phases, the duration of these non-sonicated washing phases being equal to, shorter or longer than that which can be sonicated wash phases. In a preferred embodiment, the non-sonicated wash phases are at least approximately of the same duration as the sonicated wash phases. The duration of the respective sonication phases can be in the range up to about 15 minutes, preferably in the range from about 0.25 to 10 minutes and in particular in the range from about 0.5 to 5 minutes. However, it is also possible - preferably with continuously continued textile mechanics in the washing bath - to work with selective sonication phases, the duration of which does not exceed 1 to 2 minutes and is, for example, in the range from 10 to 60 seconds. The required residence time of the soiled area in the area of action of a sounder is measured in seconds, even fractions of a second result in a clear cleaning-enhancing effect - provided sufficient wetting is required.

To promote degassing, it may be desirable to work with wetting or surfactant washing liquors which are kept at least largely free of foam or free of foam. Since, in comparison with conventional textile mechanics, ultrasound-free washing processes can also be used in accordance with the invention, practically non-foaming working conditions can nevertheless be used in the washing liquor with surfactants, emuglators and / or detergent boosters, which in themselves should lead to excessive foaming in the conventional washing process . Here is an important freedom for the selection of particularly effective wetting agents from the large range of washing aids mentioned. If desired, foam formation can be prevented or eliminated by foam brakes known per se from textile washing.

It is preferred to use wash liquors which contain at least about 0.2 g / l and preferably at least about 0.5 g / l of wetting additives, in particular from the class Corresponding detergent surfactants, emulsifiers and / or detergent boosters. The content of these wetting auxiliaries in the washing bath will usually be in the range from about 0.3 to 5 g / l, preferably in the range from about 0.3 to 2 g / l. If desired, the wetting fleets additionally contain reinforcing auxiliaries, in particular detergent builders and / or soluble electrolyte salts, as are extensively known from the field of conventional textile washing and are described in the relevant literature.

Different treatment solutions can be used in the stages of wetting and washing under the influence of ultrasound, although wetting and ultrasound washing are carried out in the same washing bath in the preferred embodiment of the invention discussed here. If particularly intensive pre-wetting is desired, the process parameters - for example the type and amount of wetting aids, process temperature and the like - can be adjusted. Like. - This need be taken into account. Highly effective detergent wetting agents can be found in the well-known large classes of ionic, especially anionic, nonionic or zwitterionic detergent raw materials of the type mentioned, the person skilled in the art using standard wetting tests, as are customary in detergent chemistry, to determine and determine the highly wetting, highly detergent systems distinguish weaker wetting or washing systems with less usability. Detailed factual information on this area of wetting textile materials of various chemical properties and origins based on natural and / or synthetic fibers can be found, for example, in Ullmann "Encyclopedia of Industrial Chemistry" 4th edition, volume 24, detergents, in particular subchapter 2, "Theory of the washing process" , loc. cit. page 68 ff., as well as subchapters 3.1 "Tenside" and 3.2 "Builder", loc. cit. pages 81 - 96.

The process according to the invention is preferably carried out with aqueous liquors in the pH range from approximately neutral to waschalkalic. For example, the pH range from about 6.5 to 12 and in particular from about 7.5 to 11 is particularly suitable. The conditions of the suitable washing alkalinity can be set by customary alkalizing additives. Soluble sodium silicates, in particular water glass, basic detergent salts, in particular sodium tripolyphosphate, but also phosphate-free alkaline additives such as soda, sodium hydroxide solution, ammonia or organic water-soluble bases such as triethanolamine may be mentioned here. Auxiliaries known from conventional textile washing, in particular builder substances, for example those based on finely divided, water-insoluble crystalline zeolites, in particular zeolite NaA and / or soluble builder salts which form soluble alkaline earth metal complexes, can be used. It has been shown that the desired rapid wetting of the fiber microstructure, while displacing the microdispersed residual air, can be significantly promoted by the use of such aids to remove the water hardness or by using deionized water. The use of soluble electrolyte salts, for example sodium sulfate, can also work in this direction. The wetting effect of a given wash liquor can be significantly increased by adding considerable amounts of such soluble electrolyte salts to the wash bath. For example, 2 to 20 g / l, in particular 3 to 10 g / l sodium sulfate, based on the washing liquor used, are suitable.

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 75 ° C. The temperature range from approximately 15 to 75 ° C. has proven to be particularly suitable, expediently in the range from approximately 20 to 50 ° C. and in particular in the Temperature range of about 25 to 40 ° C is washed. It is interesting that when adapting the wetting systems and wetting conditions, excellent washing results under the influence of ultrasound, even at temperatures below room temperature, e.g. B. can be obtained in an ice bath at 0 ° C, and only with brief exposure to ultrasound. There are clearly conditions here which are not directly comparable to those of conventional textile washing, even if the knowledge from conventional textile washing is an essential part of the inventive action, in particular regarding the wetting process.

From this possibility of the rapid removal of dirt on a sufficiently wetted textile, even at low temperatures, by the action of ultrasound, important embodiments for carrying out the washing and cleaning process according to the invention are derived, even if the invention is in no way restricted to this. Here, the invention makes use of the possibility, by selecting suitable wetting agents or wetting agent systems and / or the conditions of the wetting treatment, to set a comparatively short-term penetrating wetting in the sense of the inventive action, while displacing the microdispersed residual air. At a low temperature, for example in the region of room temperature or only moderately elevated temperatures, the ultrasonic treatment and thus the cleaning of the textile is then carried out or completed. All in all, this opens up possibilities for effective washing and cleaning of textile materials that have not previously been available. Highly effective washing results are also obtained at low temperatures on materials for which the use of elevated washing temperatures has previously been considered indispensable. An example of this is textiles based on cotton. At the same time or alternatively, the period of time required for effective washing or cleaning can occur such short periods of time can be shortened as were previously not considered possible with the same input material.

In preferred embodiments of the invention, an effective textile wash is carried out, for example, in the temperature range up to about 30 ° C., 35 ° C. or also 40 ° C. even on materials for which a cook wash has previously been considered essential. Depending on the selection and wetting effect of the wash bath used, the duration of the washing and cleaning process can be in the usual range, for example up to about 90 minutes, preferably not more than about 60 minutes. However, it is particularly preferred to shorten the duration of the washing process overall - that is, based on the sum of phases of the wetting and the ultrasound treatment.

Washing and cleaning processes can be carried out effectively for a total of at most 45 minutes and particularly preferably of at most about 30 minutes in the sense of the inventive action. Depending on the type of textile to be cleaned and the washing or cleaning liquor used, effective washing results can be obtained for a total of 3 to 30 minutes, in particular 5 to 25 minutes and preferably 5 to 20 minutes. The ultrasound treatment of the textile goods can only make up a small fraction of the time periods specified here; the predominant part of the washing process is used for the penetrating wetting required according to the invention. As previously stated, this abbreviation of the washing process is largely independent of the temperature and can therefore be achieved with washing or cleaning results even at low temperatures from, for example, room temperature to about 40 ° C. and in particular in the temperature range from about 20 to 35 ° C. until now they could only be achieved by using higher temperatures and longer washing cycles.

The process according to the invention, carried out in the sense of a batch process, for example a household washing machine, is usually carried out with liquor ratios of dry fabric weight / weight of the aqueous wash liquor in the range from about 1: 4 to about 1:50, preferably in the range from about 1: 5 to about 1 : 30 and in particular in the range from about 1: 8 to 1:15. For the practical implementation of the process, it is important that the process of displacing the microdispersed residual air is not quickly reversed even if the wetted piece of textile is completely or partially removed from the closed liquor without drying . Accordingly, it is possible to work effectively with relatively limited amounts of closed aqueous bath phase, as long as sufficiently fully wetted textile goods are repeatedly or continuously introduced into this bath.

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 sound are in the range up to about 100 kHz, the lower limit for the ultrasound usually being specified at about 16 kHz. Accordingly, a range of approximately 20 to 60 kHz can be particularly suitable for the sound frequency used, it being true that the tendency toward cleaning-enhancing cavitation formation becomes greater the lower the sonication frequency is selected in the range mentioned here.

The power input or the power density in the sonicated wash bath volume is preferably values up to about 25 W / l and in particular in the range up to about 15 W / l, the range from about 5 to 10 W / l being particularly preferred. The in the Ultrasonic cleaning technology available technical elements correspond to this data, so that a direct transfer of ultrasonic cleaning to the field of textile washing can be realized. In principle, however, there are no concerns about working with higher power inputs and / or shifting the above-mentioned frequencies into much higher ranges, such as were used extensively in research work decades ago, see the literature cited at the beginning, Dr. L. Bergmann loc

It can also be provided in the method according to the invention to work in the context of a combination treatment using enzymatic and / or bleaching washing or cleaning aids, as is known from conventional textile washing. It has been shown that exposure to ultrasound does not cause at least no bleaching of typical standard color stains under the working conditions according to the invention in comparison to conventional working in the absence of ultrasound.

Accordingly, the teaching of the present invention encompasses washing and cleaning processes on textile materials which, by adding bleaching aids, combat undesirable color stains. The field of oxidative bleaching is particularly affected, preferably peroxide bleaching, which generally provides for the use of so-called bleach activators in accordance with the processes dominating in Europe. These are generally acylating agents incorporated in detergents which, in the wash liquor, preferably form intermediate organic peracids with hydrogen peroxide between pH 9 and pH 12 and which, owing to their comparatively high oxidation potential in the range of low temperatures, have a good bleaching effect. It is common in conventional laundry of this type, the concomitant use of a peroxide-providing compound, inorganic peroxides and peroxyhydrates being suitable. The most important representative is sodium perborate. For details on bleaching textile laundry, peroxide bleaching and the bleach activators used, reference is made to Ullmann "Encyclopedia of Industrial Chemistry", 4th edition, volume 24, detergents, under chapter 3.3 "Bleaching Agents", in particular 3.3.1. "Bleach-active compounds" and 3.3.2. "Bleach activators" AAO, pages 97 to 99.

In a preferred embodiment of the invention, the addition of peroxide compounds, which are known per se as effective bleaching agents from conventional textile washing, is accordingly provided in the bleaching wash bath. In addition to the peroxide salts which supply hydrogen peroxide, such as sodium perborate in its various hydrated forms, percarboxylic acids or percarboxylic acid salts should be mentioned here. In a further particularly preferred embodiment of the invention, use can be made of the peroxide activation known per se by simultaneously using the bleach activators mentioned, so that in this embodiment of the process according to the invention - as is known in principle from conventional textile washing - Components that supply peroxide, such as sodium perborate, are used together with bleach activators, for example of the TAED and / or TAGU type.

The bleaching per compounds, in particular peroxide-providing salts of the sodium perborate type, can be used, for example, in amounts of up to 5 g / l, preferably in amounts of 0.1 to 4 g / l and in particular in amounts in the range from about 0.2 to 2.5 g / l can be used.

Bleach activators can be used in the washing liquor, for example, in amounts of 0.05 to 2 g / l or in amounts beyond that can be added, the use of about 0.1 to 1 g / l of these bleach activators being preferred. This opens up the embodiment which is particularly important according to the invention for the new washing and cleaning process, the removal of pigment and / or fat stains on the one hand, on the other hand, to carry out impurities required by bleaching in one step and in one process step. Understandably, the teaching of the invention is not limited to this joint treatment of the different types of soiling, so that bleaching at different times under the conditions according to the invention also falls within the teaching of the invention. The bleaching textile treatment is then preferably carried out subsequently to free the soiled textile from pigment and / or fat stains.

Surprisingly, it has also been shown that another aid for eliminating certain problem soils can be enhanced by the action of ultrasound. These are the detergent enzymes used on a large scale today, which are used in minor quantities to remove protein soiling in conventional detergent mixtures. For example, it has been shown that the detergent enzymes that are customary today for an optimum effect in the temperature range around 60 ° C under the action of ultrasound even at substantially lower temperatures, for example in the temperature range of about 25 to 40 ° C, within comparatively short exposure times result in substantial cleaning effects.

In particular, the method of the present invention thus also relates to the variant of textile washing which at least partially eliminates undesirable problem soiling, for example stubborn protein soiling of various origins, by using detergent enzymes. This enzymatic cleaning step can be done simultaneously with the removal of pigment / oil stains or afterwards. In one embodiment of the invention, the enzymatic cleaning involved here is associated with the removal of undesirable paint stains by using bleaching agents.

Known sources of such problem soiling are, for example, milk, cocoa, blood, egg yolk, but also dirt stains of vegetable origin, for example grass stains. Such problematic soiling can be eliminated by using enzymatic washing aids. In particular, proteolytic enzymes are used in suitable formulations, for example in the form of granules, prills and / or pellets, to a large extent in household and commercial laundry detergents. The effect of the enzymes is based on the enzymatic hydrolysis of peptide or ester bonds. In order to be effective during the washing process, the enzymes must meet a number of requirements, in particular high effectiveness against heterogeneous soiling, stability at elevated temperatures and in the alkaline range, and stability towards other detergent components, in particular surfactants, the frequently used oxidizing agent of the type Have perborates, complexing agents and the like. Serine-active, alkali-stable proteolytic enzymes, especially those based on bacillopeptidases, are used to a great extent in modern detergents. They are characterized by high temperature and pH stability. Regarding the area of detergent enzymes, reference is made to Ullmann "Encyklopedia of technical chemistry", volume 24, 4th edition, detergent, under chapter 3.4.1 "Enzymes" loc. Cit., Pages 100 to 102 and "detergent chemistry", current topics from research and development (HENKEL & Cie GmbH), Dr. A. Hüthing Verlag, Heidelberg 1976, pages 155 to 178.

It has been found that under the influence of ultrasound on a textile washing bath containing detergent enzymes unexpectedly high effectiveness-enhanced cleaning effects can be obtained. With comparatively low temperatures in the wash bath and short treatment times, excellent cleaning results can be obtained on test textiles that contain standardized enzyme-specific soiling. It is evident that there is an interaction of the cleaning-active auxiliary substances in the sonicated wash liquor, which is not to be observed in this intensity under the conditions of conventional textile washing.

Suitable wash-active microbial enzymes are, in particular, alkali-stable proteolytic enzymes and, above all, corresponding serine-active components. Typical examples of this are the most widely used bacillopeptidases today, for example the Bacillopeptidase P 300 described by the applicant in the literature and used in practice. But also other microbial enzymes, for example the amylases, lipases, pectinases proposed for use in detergents, Nucleases and / or oxidoreductases can also be used. In particular, in addition to proteases in textile detergents, amylases have recently been used, which are effective, for example, against soils containing carbohydrates. The use of lipases is said to facilitate the washing out of fatty stains. Commercial lipases show sufficient stability under washing conditions.

In one embodiment of the method according to the invention, the two areas of the large problem soils - the soils to be cleaned enzymatically and the soils to be removed by bleaching processes - are connected to one another in such a way that laundry and bleaching laundry which are enzymatically promoted and / or subsequently carried out are carried out simultaneously in one wash cycle. In a particularly important embodiment of the invention, the removal of pigment and / or oil or Grease stains integrated. In this embodiment too, work can be carried out in one or more stages. Common to all these embodiments is that at least the enzymatic cleaning takes place under the influence of ultrasound, but preferably also the removal of pigment and / or grease stains or the action of the detergent bleaching agents is carried out under at least partial exposure to ultrasound.

The amount of detergent enzymes used in the process according to the invention can be in the usual range. Amounts of at least about 0.005 g / l are preferably used in the wash liquor. The concentration of such enzymes used is usually not above 1 g / l and in particular not above about 0.5 g / l. Amounts in the range of about 0.01 to 0.1 g / l and in particular in the range of about 0.01 to 0.07 g / l can be particularly suitable for the field of proteolytic enzymes used in detergent chemistry today. These details relate to the enzymes currently used in practice with protease activities of at least about 50,000 PE / g, preferably of at least about 100,000 PE / g and in particular in the range of about 100,000 to 200,000 PE / g.

Another important embodiment of the invention relates to a novel special embodiment of the aspect of the method of working according to the invention, which deals with the penetrating wetting of the textile material to be cleaned, while displacing the microdispersed residual air from the fiber microstructure of the textile material, including its soiled areas. It has been found that this complete and rapid deaeration of the textile fibers or fiber bundles can be accelerated by means of a method of operation which has been proposed per se in the context of textile washing processes, but has not found any practical application to date. This is the measure that the washing liquid with the laundry in to displace mechanical vibrations which lie below the frequency range of ultrasound and in particular can be assigned to the frequency range of the audible sound or the frequencies below it of the so-called infrasound range.

DE-AS 26 01 549 describes, for example, a process for washing wool-containing textiles, in which the heated washing liquid is set into vibration with the laundry, this process being characterized in that the washing liquid with the laundry oscillates between 10 and 1000 Hz is added, the washing liquid being heated to at least 80 ° C. Further relevant literature is referenced in this prior art publication. For example, reference is made to DT-PS 596 868, in which a method for washing laundry is described, in which the washing liquid is mixed with the laundry in vibrations of 3 to 4 Hz. This process is said to be unsuitable for washing woolen textiles because the laundry is moved so much that the resulting friction leads to matting. This is particularly the case when working at elevated temperatures of the washing liquid. In DT-PS 973 083 it is pointed out that vibrations in the sound area significantly promote the washing process. The frequency range perceivable by the ear of an adult human is approximately in the range from 16 to 16,000 Hz and is referred to as "sound". From a physical point of view, this area of the audible sound as well as the infrasound area underneath and the ultrasound area above it are characterized by the longitudinal character of the excited mechanical vibration state.

The well-known cleaning effect of the ultrasonic area on soiled hard surfaces is known to be due to cavitation, a phenomenon that occurs for the Ultrasonic range is characteristic. Under the influence of the high-frequency mechanical vibration, vacuoles are formed in the liquid bath, the implosion of which releases extremely high energies in the immediate vicinity of the cavitation bubbles. Because of the high-frequency longitudinal vibration, tremendous acceleration forces also occur in the ultrasound-impinged liquid, but tests have shown that this material acceleration cannot be held responsible for the cleaning effect in the ultrasound field, but that it is the phenomenon of cavitation, which is of crucial importance here, compare for example J. Olaf, "Surface cleaning with ultrasound", Acustica 7 (1957), Issue 5, 253 to 263.

The lower-frequency areas of longitudinal mechanical vibration in liquid baths, for example in a washing liquor, do not know this phenomenon of cavitation formation. This applies in particular to lower ranges of the audible sound and the infrasound range already mentioned. However, this area has always been proposed for cleaning textiles in the course of washing processes, compare in addition to the literature already mentioned, for example US Pat. No. 3,134,990, in which sound frequencies in the range of 2000 Hz are to be used or DE-PS 29 07 562, in which low-frequency vibrations, in particular in the frequency range between 30 and 100 Hz, are used.

In the particularly preferred embodiment of the invention discussed here, specific use is also made of the action of mechanical vibration regions which lie below the ultrasound region and thus cover the region of the audible sound and / or the infrasound. This tool can be used in the context of the inventive action to the necessary network operation while expelling the to accelerate microdisperse residual air distributed on the fiber structure and / or to expel the air bubbles from the fiber, the fiber bundle and / or the piece of textile, which stubbornly cling to the textile or the fiber or the fiber bundle under normal conditions and / or under the influence of ultrasound and here substantially impede the passage or impact of ultrasound. The effectiveness of this method must be immediately apparent: the adhesion of the air bubbles in the fiber microstructure or on the textile is much lower than the adhesion of the dirt to be removed. Accelerating forces as they occur in the longitudinal vibration of the infrasound area or the audible sound area in the microstructure of the liquid phase are generally sufficient to bring about the desired detachment of the air bubbles from the fiber or the textile structure. Associated with this can be the simultaneous facilitation of dirt removal under washing conditions that has been repeatedly observed in the prior art. In terms of the intensity of the cleaning action, however, this treatment cannot be compared with cleaning by cavitation in an ultrasonic field, which is used as an essential cleaning aid in the method according to the invention. The simultaneous use of comparatively low-frequency vibration discussed here thus serves in particular as a wetting aid or for conditioning the textile goods in the liquid phase in the sense of accelerated ventilation.

This process aid according to the invention can take place during the wetting of the textile material to be cleaned and / or together with its treatment in the ultrasound field. In an important embodiment, the action of comparatively low-frequency sound or infrasound and ultrasound is used in separate process periods. The wetting accelerated by low-frequency vibration can take place in the washing bath and / or in separately used wetting liquids. In another, also important embodiment The invention uses low-frequency vibration and ultrasonic vibration at least partially together.

If the entire frequency range up to the ultrasound limit - d. That is, up to an oscillation number of 15 kHz - is suitable for low-frequency treatment, but lower values can again be particularly preferred within this range. Vibrations of approximately 10 Hz to 10,000 Hz and in particular the range of approximately 10 to 5,000 Hz are particularly suitable. Low-frequency ranges of approximately 10 to 2,000 Hz are technically particularly easily accessible, which can also have the advantage that here there are no additional problems due to annoying noise pollution. Working with devices of this vibration range is common practice today, for example in the range of electric toothbrush frequency about 30 to 100 Hz - or vibrating knife, for example for cutting meat - frequency usually in the range of about 1,000 to 2,000 Hz.Technical tools This type can be put into practical use in a simple adaptation to the conditions of textile washing and / or the pre-wetting of a textile material in a wetting or washing liquid, without the use of the ultrasound field being impaired in the sense of the main idea of the action according to the invention.

The washing method according to the invention is suitable for cleaning textiles based on all types of fibers used in practice. It is suitable for washing and cleaning fiber structures of natural origin such as cotton, linen and wool in the untreated or chemically refined state. It is also suitable for cleaning textile fiber structures based on synthetic fibers, for example based on polyester, polyamide and / or polyacrylonitrile, and their mixtures with the aforementioned types of fibers of natural origin in the refined and / or unfinished state.

The principles of the process according to the invention are applicable to washing or cleaning processes of textile fiber structures with aqueous washing liquors in batches and / or in continuous operation. A typical example of batch-wise cleaning of soiled textiles is batch-wise textile washing in the home or business, the commercial processes often having continuously operated car washes, but which are then characterized in detail by batches of batches. However, the applicability of the invention is not limited to this. It also applies to the cleaning treatment of textile fabrics in continuously carried out processes, as are known in the context of textile technology. As is well known, web-like goods are usually guided at high speed through successive process stages of, for example, wetting, washing and rinsing. The application of the principles according to the invention can be of particular importance here, it being particularly important to ensure that in the wetting stage the fiber microstructure of the textile material, including its soiled areas, is adequately vented while displacing the microdispersed residual air. The gradual treatment of repeated wetting and subsequent ultrasound treatment can be of particular importance for the treatment of such web-like material.

Another area of application for the principles according to the invention is the cleaning or rinsing of strand-like textile materials, for example in connection with the rinsing out of color residues after the dyeing of corresponding materials.

The suitability of the respective washing liquor under the intended process conditions, in particular the specified washing temperature, can be determined from case to case in a very simple test: the artificially soiled test fabrics or fibers based on serve as an indicator different fibers and soiling, which are common today in the practice of checking and developing detergent formulations and some of which are commercially available or manufactured by the detergent industry according to their own design. Well-known manufacturers of corresponding commercially available, artificially soiled fibers or test fabrics are EMPA, Eidgenössische Materialprüfungs- und Versuchsanstalt, Unterstrasse 11, CH-9001 St. Gallen; Laundry research Krefeld, WFK-Testgewebe-GmbH, Adlerstrasse 44, D-4150 Krefeld; Testfabrics Inc., 200 Blackford Ave. Middlesex, NJ USA.

Soiled standard test cloths and / or test fibers - e.g. based on wool, cotton finished and unfinished, mixed fabrics (e.g. polyester / cotton finished) are inserted in the non-pre-wetted state in the ultrasound-exposed washing bath at the intended washing temperature and here in the effective range of one Sound generator held for a period of 1 minute and once turned over so that the test fabric piece immersed in the wash liquor is sonicated for 30 seconds from the bottom and 30 seconds from the top. Test soils present in the form of strands, for example corresponding wool strands, are easily moved by hand in the effective range of the sounder for the test period of 1 minute. After 1 minute of treatment in the ultrasound field, the test material is removed from the bath, rinsed and dried. The degree of soiling of the test material treated in this way is determined by measuring the degree of remission with the Elrephomat DFC 5 (manufacturer Carl Zeiss, Oberkochen, Baden-Württemberg, FRG) and compared with the correspondingly measured degree of soiling of the untreated test fabric used. An increase in the reflectance value on the 100% scale by 10% (Delta R = + 10%) already shows the suitability of the wash bath for the purposes of the method according to the invention. Wetting and cleaning are achieved more quickly if the one determined in a corresponding manner Delta R value is at least + 20% or even + 25% or + 30%. In highly effective wash baths, the Delta R value is + 40% or more.

The method according to the invention thus makes it possible to set highly effective cleaning results both with regard to the removal of pigment and / or grease stains and with regard to the removal of problem stains, in particular the removal of enzyme-specific paint stains, in a short time at low temperatures which were previously not considered possible. Washing cycles of a total duration of about 10 to 30 minutes in the temperature range of about 20 to 40 ° C can deliver washing results that are only achieved in conventional laundry at significantly higher temperatures - for example at 60 ° C - and over a much longer washing period - for example 50 to 60 minutes - can be set. It is also striking that by adapting the wetting characteristics of the washing liquors used in accordance with the invention to the fiber types to be cleaned in each case, the washing result can be set to be equivalent to the most varied types of textiles, as was previously not possible or only with difficulty with conventional detergents from just one washing liquor is accessible.

Examples

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 two ultrasound-generating vibrating elements on the bottom.

• 1. Fassungsvermögen des Waschbottiches:      4 Liter
  Flottenvolumen im Waschbottich :       3 Liter
  Auf die Waschflotte übertragene Ultraschallfrequenz:      35 kHz
• 2. Mit Standardschmutz (Staub/Hautfett) angeschmutzte Test­gewebe aus der Eigenfertigung der Anmelderin:
  
  Baumwolle, nicht ausgerüstet (B)
  Baumwolle, veredelt (BV)
  Polyester-Baumwoll-Mischgewebe, veredelt (PBV)
  Polyester (P)
  
  Darüber hinaus werden käuflich erwerbliche mit Standard­schmutz angeschmutzte Woltestgewebe der folgenden Hersteller eingesetzt:
  
  WFK (Wäschereiforschung Krefeld)
  EMPA (Eidgenössische Materialprüfungsanstalt St. Gallen)
  T (Testfabrics Inc. Middlesex).
  
  Die durch Messung des Remissionsgrades mit dem Elrephomat DFC 5 (Carl Zeiss, Oberkochen, Baden-Württemberg, BRD) bestimmten Verschmutzungs-Ausgangswerte der eingesetzten verschmutzten Testgewebe sind wie folgt (sofern nicht aus­drücklich etwas anderes angegeben ist):
  
  Baumwolle, nicht ausgerüstet      39,5 (% Remission)
  Baumwolle, veredelt      29,0 (% Remission)
  Polyester-Baumwoll-Mischgewebe, veredelt      30,0 (% Remission)
  Polyester      28,0 (% Remission)
  
  Die Anschmutzungswerte der käuflich erworbenen Woll-Test­gewebe sind wie folgt:
  
  WFK      34,4 (% Remission)
  EMPA      14,1 (% Remission)
  T      39,5 (% Remission)
• 3. Angeschmutzte Testlappen werden unter den in den nachfol­genden Beispielen im einzelnen angegebenen Verfahrensbe­dingungen gewaschen, nachfolgend mehrfach gespült und ge­trocknet. Anschließend wird das Wasch- bzw. Reinigungser­gebnis durch Bestimmung des jetzt vorliegenden Remissions­grades ermittelt. Die Wasch- bzw. Reinigungsleistung ermittelt sich als der Differenzbetrag Delta R zwischen dem Remissions­wert der gewaschenen Materialprobe abzüglich des Anschmut­zungswertes des eingesetzten Testgewebes.
• 4. Die Waschflotten aus den nachfolgenden Beispielen wurden durchweg mit Benrather Leitungswasser einer durchschnitt­lichen Härte von 16 °dH angesetzt, sofern nicht ausdrücklich anderes angegeben ist. Die Mehrfachspülung der gewaschenen Materialproben erfolgte durchweg mit Benrather Leitungs­wasser des angegebenen Härtegrades.

Unless otherwise stated, the following general conditions apply to the performance of these washing tests:

• 1. Washing tub capacity: 4 liters
  Fleet volume in the wash tub: 3 liters
  Ultrasound frequency transmitted to the wash liquor: 35 kHz
• 2. Test fabric soiled with standard dirt (dust / skin fat) from the applicant's own production:
  
  Cotton, not equipped (B)
  Cotton, refined (BV)
  Polyester-cotton blend, finished (PBV)
  Polyester (P)
  
  In addition, commercially available Woltest fabrics from the following manufacturers, soiled with standard dirt, are used:
  
  WFK (laundry research Krefeld)
  EMPA (Federal Material Testing Institute St. Gallen)
  T (Testfabrics Inc. Middlesex).
  
  By measuring the degree of remission with the Elrephomat DFC 5 (Carl Zeiss, Oberkochen, Baden-Württemberg, FRG) Certain initial contamination values of the soiled test fabric used are as follows (unless expressly stated otherwise):
  
  Cotton, not equipped 39.5 (% remission)
  Cotton, refined 29.0 (% remission)
  Polyester-cotton blend, refined 30.0 (% remission)
  Polyester 28.0 (% remission)
  
  The soiling values of the wool test fabric purchased commercially are as follows:
  
  WFK 34.4 (% remission)
  EMPA 14.1 (% remission)
  T 39.5 (% remission)
• 3. Soiled test rags are washed under the process conditions detailed in the examples below, subsequently rinsed and dried several times. The washing or cleaning result is then determined by determining the degree of remission now present. The washing or cleaning performance is determined as the difference Delta R between the reflectance value of the washed material sample minus the soiling value of the test fabric used.
• 4. The wash liquors from the examples below were all made up with Benrather tap water with an average hardness of 16 ° dH, unless expressly stated otherwise. The washed material samples were rinsed several times with Benrather tap water of the specified degree of hardness.

Examples 1 to 7

Standardized, soiled test rags based on polyester / cotton blended fabrics (PBV) are refined (PBV) in a wash bath, which is mixed with active components in the manner described below, each time without prewetting for a period of 1 minute with gentle movement in the wash bath in the effective area washed by an ultrasound generator.

The temperature of the wash bath is 42 - 43 ° C. After 1 minute of washing in the ultrasonic field, the respective samples are removed from the wash bath, rinsed several times and dried. The reflectance values (double determination) are determined on the dried specimen.

The washing bath is built up in stages as follows:

Example 1:

0.5 g / l of an etheramine C _12/14 -3.6 EO-NH- (CH₂) ₂OH (C _12/14 fatty alcohol with an average of 3.6 ethylene oxide groups, end-capped with the rest of the monoethanolamine)

pH of the bath: 7 to 7.5

Example 2:

Add 0.5 g / l water glass (active substance) to the bath of example 1

pH of the bath: 8.5 to 9

Example 3:

Add 2 g / l sodium tripolyphosphate (STP) to the bath of Example 2

Bath pH: 9 to 9.5

Example 4:

Add 0.5 g / l alkylbenzenesulfonate (ABS) to the bath of Example 3

Example 5:

Addition of 0.5 g / l coconut fatty acid diethanolamide (Comperlan KD)

Example 6:

It is washed with the bath of Example 5. The contaminated PBV standard material is, however, wetted in an aqueous water glass solution before immersion in the bath solution until the piece of textile appears visually penetrated and wet. Duration of impregnation approx. 10 to 15 seconds.

Example 7:

It is washed again in the bath of Example 5, but the PBV textile material to be cleaned is first wetted in dilute aqueous water glass to which a small amount of palm kernel fatty acid diethanolamide had been added. Here too, the pre-wetting time is less than 15 seconds.

The reflectance values of the PBV samples washed and dried in this way are summarized in Table 1 below; the comparison value of the soiled standard material used is known to be 30.

Examples 8-10:

As in the previous examples, a wash bath is gradually built up as follows:

Example 8:

0.5 g / l coconut fatty acid (C _12-18 ) diethanolamide (Comperlan KD)

Example 9:

Addition of 1.1 g / l STP

Example 10:

Add 1.1 g / l STP again

The temperature of the wash bath is consistently 42 ° C. Standardized, soiled PBV test rags are washed without prewetting for 1 minute with gentle movement in the area of action of a sounder in the respective bathroom.

The reflectance values (double determination) determined on the washed and dried material samples are summarized in Table 2 below.

Examples 11-13:

As in the previous examples, active components are gradually added to a washing bath. Standard test rags based on PBV are washed without prewetting for a period of 1 minute in the area of action of a sounder with gentle movement, temperature of the wash liquor consistently 42 ° C. The following applies in particular:

Example 11:

0.7 g / l Comperlan KD

Example 12:

Add 3 g / l sodium sulfate to the bath of Example 11

Example 13:

Add 1 g / l soda to the bath of Example 12

The reflectance values determined on the washed and dried material samples are summarized in Table 3 below.

Example 14:

Contaminated PBV fabric of the type used in Examples 1-13 is treated in a washing liquor which contains 1.7 g / l Comperlan KD and 2 g / l STP. The temperature of the wash liquor is 42 ° C.

In contrast to the light movement mechanics according to Examples 1-13, however, the soiled test cloths are fixed on the bottom of the container immediately above the two sounders in that these cloths are covered in the wash bath by cotton terry cloths. In this arrangement, the soiled test rags are exposed to the direct action of the ultrasound transducers without movement for a period of 3 minutes. The test pieces are then removed from the bath, rinsed and dried.

In spite of the use of a bath with considerable washing power - compare the similarly constructed but even less surfactant bath of Example 10 - and the tripled duration of the ultrasound exposure, a comparatively poor washing result is obtained. The following series of numbers shows the individual determinations of remission values on 5 test cloths:
56.5 / 59.6 / 52.6 / 48.4 / 56.0.

The unevenness of the washing result is also evident from this series of numbers. When averaging this result by determining the reflectance value on 3 superimposed cloths, the following reflectance values (double determinations) are obtained:
54.6 / 54.4.

The cleaning action on these non-moving samples, which are nevertheless fixed in the range of optimal ultrasound exposure, is evidently much worse than the cleaning action in the comparatively low-tensile bath of example 10 under textile movement under otherwise comparable conditions.

Examples 15 and 16:

A wash bath of the following composition is put together:

2 g / l Comperlan KD
1 g / l (active substance) of a fatty alcohol ether sulfate (FAES ,
C _12/14 fatty alcohol 2.0 EO sulfate sodium salt)
2 g / l STP

The bath temperature is 42 ° C.

The bath is loaded with cotton terry cloths with a liquor ratio (textile dry weight: bath weight) of 1:10. A large number of larger and smaller PBV test fabric cloths soiled with standard dirt are placed evenly between these cotton terry towels.

In two successive experiments under these same initial conditions, the bath contents are slowly circulated by hand with 2 wooden sticks for a period of 12 minutes and the dense packing of the textile goods is also broken open in the bath.

In the first experiment (example 15), the filled washing liquor is under the continuous action of the two ultrasound transmitters at the bottom of the trough. In the second identical experiment (Example 16), the procedure of Example 15 is repeated with a fresh, identical bath filling, and here, too, the textile material is circulated intensively with the wooden sticks. In this case, however, ultrasound is not used.

The washed and dried PBV material from Example 15 obtained under the action of ultrasound shows a consistently high degree of whiteness with largely uniform decolorization of the PBV test material used overall.

Even the PBV test material washed without the influence of ultrasound shows uniformity in the washing result, but the achieved reflectance values are significantly lower. The following applies in particular (averaged values, double determination):

Example 15: 81.1 / 81.7

Example 16: 51.0 / 52.2

Examples 17-20:

Standard soiled PBV test rags are washed without pre-wetting for 1 minute in a sonicated wash bath with gentle agitation, the content of which was gradually increased in the manner described below. The washing temperature is 42 ° C in all cases.

Example 17:

1 g / l of a commercially available dishwashing detergent containing approximately equal parts by weight of alkanesulfonate, FAES and ABS (bath pH: 7)

Example 18:

Add 0.5 g / l (active substance) of water glass

Example 19:

Add 1 g / l Comperlan KD to the bath of example 18

Example 20:

Add 0.5 g / l of a wash-active alkylglycoside compound based on a fatty alcohol with 12 to 14 carbon atoms and an average degree of glycoside oligomerization of 1.5 to the bath of example 19.

The reflectance values (duplicate determination) of the washed and dried PBV test materials are summarized in Table 4 below.

Examples 21-31:

A number of wash baths are used, all of which have the following combination of active ingredients:

1 g / l C _x E _y
2 g / l STP

C _x E _y stands for fatty alcohol ethoxylates of chain length x = 12 or 14, while the degree of ethoxylation y is varied in the range from 2 to 10. Examples 21 to 23 and 27 to 31 work at a bath temperature of 50 ° C, Examples 24 to 26 work at a bath temperature of 28 ° C.

In addition to standard-soiled PBV, corresponding textile samples based on polyester (P) and based on cotton, not finished (B), are washed with standard soiling.

In Example 30, the surfactant component used here is increased by using 0.6 g / l FAES. For comparison, Example 31 uses a liquor which contains only 0.6 g / l of this FAES in admixture with 2 g / l STP as the surfactant component.

The baths used in each case - characterized only by the particular surfactant used - the selected temperature Conditions and the washing results on the soiled standard textile samples (double determination) are summarized in Table 5 below. The same applies that in all cases, without pre-wetting the textile samples, the test cloth was kept in the effective range of the ultrasound generator for a period of 1 minute.

Examples 32 to 52

It is washed with a bath of the following composition:

2 g / l Comperlan KD
1 g / l FAES
2 g / l STP

Test fabrics provided with standard soiling based on PBV, B and P and also based on cotton, refined (BV), are first at bath temperatures of 40 ° C (Examples 32 to 37), then at bath temperatures of 30 ° C (Examples 38 to 41), then at a bath temperature of 20 ° C (Examples 42 to 44), then at bath temperatures of 10 ° C (Examples 45 and 46) or 8 ° C (Examples 47 and 48) and finally at a bath temperature of 0 ° C (Examples 49 to 52) washed.

The following working conditions apply:
The test sample to be washed is pre-wetted in the bath without the action of ultrasound at the intended process temperature for the ultrasound washing. In the majority of cases, a double test is used in such a way that this stage of pre-wetting is carried out once without moving the textile goods - ie by simply immersing and leaving the immersed textile piece - and in a parallel test with light hand mechanics during the period of pre-wetting.

The pre-wetting time is 3 minutes at the bath temperature of 40 ° C and 5 minutes at the bath temperatures of 30 ° C, 20 ° C, 10 ° C and 8 ° C.

The wash bath temperature of 0 ° C is ensured by a floating layer of pieces of ice. The treatment of the textile goods in this washing bath is explained in more detail in the relevant examples (Examples 49 to 52).

The duration of treatment in the sonicated area of action of the bath is generally 1 minute, in the case of Examples 45 and 46 two minutes, the process instructions for washing at a liquor temperature of 0 ° C. (Examples 49 to 52) are following Table 6 below specified, in which the reflectance values obtained in each case (double determination) are assigned to the individual test examples.

The sonication time in Example 49 is 1 minute. It was worked here without pre-wetting.

Examples 51 and 52 work with a bath of the stated composition, to which a limited amount of a quaternized water-insoluble hydroxyethyl cellulose had been added in fine-grained form. The textile samples used are held for 5 minutes without pre-wetting in the effective range of the ultrasound generator with light textile mechanics.

In the case of example 50, the procedure was as follows:

The non-pre-wetted test material is moved for 30 seconds in the area of action of an ultrasound transmitter immediately after being introduced into the wash bath kept at 0 ° C. Then the movement of the textile is continued for 3 minutes without the action of ultrasound. Then sonicate again for 30 seconds, then move again in the bathroom for 2 minutes without sonication. Subsequently, sonication (respective sonication duration 30 seconds) and subsequent movement in the non-sonicated bath (movement duration 1 minute each) continue until a total treatment time of 11 minutes is reached. The textile material is removed from the bath, rinsed, dried and measured as usual.

Examples 53 to 59

A wash bath of the following composition is used:

2 g / l Comperlan KD
2 g / l STP
1 g / l FAES (C _12/14 fatty alcohol-2.0 EO sulfate sodium salt)

Variously soiled standard test materials are prewetted at a bath temperature of approx. 35 ° C for a period of 10 to 20 minutes without the influence of ultrasound, then the material pretreated in this way is brought into the range of action of an ultrasound generator in the washing bath and moved there with light textile mechanics . The temperature of the sonicated bath is consistently 32 ° C.

The following treatment conditions apply:

Example 53:

PBV, 10 minutes forward, then 1 minute ultrasound treatment

Example 54:

BV, 15 minutes forward, then 1 minute ultrasound treatment

Example 55:

BV, 2 times in a row for 10 minutes each without ultrasound treatment and both times 1 minute ultrasound treatment

Example 56:

P, 20 minutes forward without ultrasound exposure, then ultrasound treatment for 0.25 minutes

Example 57:

B, 10 minutes forward without ultrasound exposure, then 1 minute ultrasound treatment

Example 58:

B, 20 minutes pretreatment without ultrasound exposure, then 1 minute ultrasound treatment f

Example 59:

PBV, 30 seconds of ultrasound exposure to the non-pre-wetted textile material in the sonicated bath, then 10 minutes of wetting in the bath solution without ultrasound exposure to light textile mechanics, followed by 30 seconds of ultrasound treatment, another 10 minutes of wetting in the bathroom without ultrasound exposure to light textile mechanics, finally 1 minute of ultrasound exposure.

The reflectance values obtained on the washed and dried material samples are summarized in Table 7 below.

Examples 60 to 63:

A bath solution with the following composition is used:
1 g / l Comperlan KD
1 g / l STP
0.5 g / l FAES as before

The working temperature of the bath in experiments 60 and 61 is 25 ° C, in experiments 62 and 63 the temperature rises to a final temperature of 30 ° C. The individual work is as follows:

Examples 60 and 61

Standard-soiled PBV (Example 60) and P (Example 61) are brought into the field of action of an ultrasound transmitter without immersion in the washing bath immediately after immersion in the washing bath and held here for 1 minute under light textile mechanics. It is then rinsed, dried and measured as usual.

Examples 62 and 63:

In the same bath, a fresh, standard-soiled PBV sample (example 62) is first introduced into the washing bath without pre-wetting and is agitated here for a total of 30 minutes using light textile mechanics. During this period, the textile material is sonicated at regular intervals, a total of 10 times, for a period of about 1/2 minute.

The treatment according to Example 63 corresponds to that of Example 62, except that instead of PBV, a standard soiled polyester material is used.

The measured reflectance values from the washed material are given in Table 8 below. It is particularly clear here that the suitable combination of nets and sonication can be used to obtain good washing effects even with such baths and under such conditions, which only give completely unsatisfactory washing results in the 1 minute test.

Examples 64 to 68:

STP is added in an amount of 2 g / l to the used and contaminated bath of experiments 60 to 63.

At a bath temperature of 30 ° C, tests 64 (PBV) and 65 (P) are first carried out in analogy to the previous tests 60 and 61, i.e. treatment of the respective soiled textile material in the bath in the effective range of the ultrasound generator without pre-wetting for the period of 1 minute.

In trials 66 to 68, standard-soiled textiles based on PBV (example 66), P (example 67) and BV (example 68) were each treated for 10 minutes with light textile mechanics, evenly distributed over this period, 5 times 0 each , 5 minutes of ultrasound is applied to the items to be washed.

In all cases, the washed material samples are rinsed, dried and measured. The values obtained are summarized in Table 9 below.

Example 69:

A wash bath of the following composition is used:
0.7 g / l FAES (according to Example 53 ff.)
0.2 g / l ethoxylated decyl alcohol (C₁₀ 2.9 EO)
2 g / l STP Contaminated standard tissue based on PBV is moved slightly in the wash bath for 20 minutes and brought 8 times into the range of action of an ultrasound generator for a period of about 0.5 to 1 minute each and held there under light textile mechanics. The temperature of the wash bath increases from 30 to 35 ° C during this treatment.

The rinsed and dried PBV tissue shows the following remission values:
87.9 / 88.2

Examples 70 to 72

It is working again with a wash liquor, which is gradually increased in its active substance. The following information applies:

Example 70:

A wash liquor with a content of 1 g / l Comperlan KD and 1 g / l FAES (as before) is used to pre-wet soiled PBV at 27 ° C for 20 minutes. Then the pre-wetted textile is treated in this wash liquor for 1 minute under the influence of ultrasound.

Example 71:

1 g / l water glass (active substance) is added to the bath from example 70. A soiled PBV material is pre-wetted in this bath at 27 ° C for 5 minutes, while maintaining a slight movement mechanism. Afterwards, the pre-wetted textile is sonicated in the bathroom for a period of 1 minute.

Example 72:

2 g / l sodium perborate and 1 g / l water glass (active substance) are mixed into the bath from example 71, then a fresh, soiled standard material based on PBV is prewetted for 25 minutes without the action of ultrasound, but with light textile mechanics at 27 ° C. then the material so wetted is treated with ultrasound in the stocked bath for 1 minute.

The reflectance values of the material samples processed in the usual way are summarized in Table 10 below.

Examples 73 to 75

A bath of the following composition is used:
0.2 g / l fatty alcohol ethoxylate C₁₀ 2.9 EO
0.5 g / l disodium salt of a C _16/18 -alpha-sulfofatty acid (disalt)
0.3 g / l alkyl glycoside according to Example 20

The bath temperature is 30 ° C in all cases. Here too, a step-by-step bathroom is used as follows.

Example 73:

Bath of the above composition, pH 7

Example 74:

Bath from example 73 with the addition of 1 g / l water glass (active substance), pH 9

Example 75:

Add 2 g / l dry zeolite NaA powder to the bath from example 74

In all 3 examples, soiled PBV standard fabric is used. In this case, according to Example 73, the wetting solution is first prewetted for 5 minutes, then treated in the ultrasound field for 30 seconds, then wetting again without the action of ultrasound, and this rhythm of sonication and wetting is repeated until a total of 15 minutes of treatment time are fulfilled.

The same alternating treatment of networks without the action of ultrasound for 2 minutes each and subsequent sonication in the bath for a period of 1/2 minute each is carried out in Example 74, but only up to a total duration of 10 minutes. The same treatment rhythm is followed in Example 75, but here again for a total period of 15 minutes. The reflectance values of the rinsed and dried material samples are summarized in Table 11 below.

Examples 76-79

While simple tap water (16 ° dH) had been used in each of Examples 1 to 75 to prepare the washing liquors, in the following Examples 76 to 79 the liquor was prepared with deionized water. The following active ingredient components are first introduced into the wash liquor (examples 76 and 77):
0.5 g / l Comperlan KD
0.5 g / l of a water-containing mixture of ABS (55% solids content) and C₁₀ 2.9 EO (anhydrous) in a ratio of 3: 1
1.0 g / l water glass (active substance)

In the rhythm of Examples 73 to 75 - 2 minutes of wetting without the action of ultrasound, but light textile mechanics in the bathroom, then 0.5 minutes of exposure to ultrasound - PBV textile goods soiled in Example 76 and BV textile goods soiled in Example 77 are treated. The bath temperature is 25 ° C in Example 76 and 29 ° C in Example 77.

Subsequently, sodium sulfate is added in an amount of 4 g / l to the bath used. Then soiled PBV textile goods (example 78) and soiled cotton, unfinished, are subjected to wetting and sonication for a total period of 10 minutes at the same time rhythm. The end temperature of the bath is 79 32 ° C after the end of the test.

The reflectance values measured on the material samples processed in the customary manner are summarized in Table 12.

Examples 80-85

To investigate the washing behavior of wool fabrics, the following test soils available on the market are washed on wool fabrics:
EMPA Indian ink / olive oil wool
WSK dust / wool fat wool
T (testfabric) mineral oil / vegetable fat / lampblack wool

A wetting and washing bath is put together as follows:
deionized water
2 g / l Comperlan KD
2 g / l STP
0.3 g / l FAES

In Examples 80 to 83 below, the particularly stubborn dirt of the EMPA material is washed in the temperature range from 25 to 28 ° C (Examples 80 to 82) or 28 to 32 ° C (Example 83). The following conditions apply:

Example 80:

The soiled test fabric is pre-wetted in the wash liquor at 25 ° C. using light mechanics and then washed for 1 minute at the specified temperature in the range of action of the ultrasound generator.

Example 81:

Fresh, soiled EMPA material is first subjected to the following treatment rhythm for 3 minutes: 20 Seconds of ultrasound treatment, then 40 seconds of wetting under textile mechanics without ultrasound in the wash bath. The rhythm is then modified for a further 3 minutes as follows: 15 seconds of ultrasound, 15 seconds of non-ultrasound. Total duration of treatment 6 minutes as in Example 80, bath temperature 26 ° C.

Example 82:

Fresh, soiled EMPA wool fabric is pre-wetted for 10 minutes in the washing bath at 28 ° C, then exposed to ultrasound for 1 minute

Example 83:

Fresh, soiled EMPA wool fabric is treated as follows:
5 minutes pre-wetting in a wash bath at 25 ° C
1 minute treatment with ultrasound in the washing bath
3 minutes more meshing under textile mechanics without the influence of ultrasound
1 minute ultrasound treatment at 32 ° C
3 minutes of wetting in a 32 ° C wash bath without ultrasound
finally 1 minute exposure to ultrasound

In Examples 84 and 85 below, the test soils WFK wool and T wool are treated as follows:
5 minutes in the wash bath of the specified composition at 27 ° C, under light textile mechanics, then finally 1 minute ultrasound treatment in the bath at the specified temperature.

The reflectance values of the soiled standard materials used were previously determined as follows:
EMPA 14.1 / 14.1
WSK 34.4 / 34.3
T 39.4 / 39.6

The reflectance values of the washed-up material samples from Examples 80 to 85 worked up in the usual way are summarized in Table 13 below.

Example 86:

The behavior of characteristic samples soiled with test dirt is examined in a comparative series examination. The following specific conditions apply:
Test materials examined:
Material samples soiled with dusty skin fat
Polyester (P)
Polyester-cotton blend fabric finished (PBV)
Unfinished cotton (B)
Cotton refined (BV)
Mineral oil refined on cotton (M-BV)
as well as cosmetic soiling (lipstick) on PBV (LS-PBV)

Treatment conditions:

After determining the respective initial values of the test materials used, the material is treated in tap water (16 ° dH) at 30 ° C under the influence of ultrasound for a period of 3 minutes each. In a second series of experiments, fresh material samples are moved for 8 minutes at 30 ° C in an aqueous bath containing the following combination of active washing components:
1 g / l fatty alcohol ethoxylate (Dehydol LT 5)
1 g / l alkyl glycoside
1 g / l water glass
2 g / l sodium zeolite NaA (detergent quality)
4 g / l sodium sulfate

In a final series of tests, fresh material samples are again moved at 30 ° C in a bath of the previously specified composition, but now under the double exposure to ultrasound in accordance with the following working rule:
3 minutes of wetting without ultrasound
1 minute exposure to ultrasound
3 minutes of rewetting without ultrasound
1 minute treatment with ultrasound

The reflectance values determined in each case on the rinsed and dried textile material are summarized in Table 14 below.

Example 87:

In a further series examination, a wash liquor of the following composition is used:
0.75 g / l ABS
0.75 g / l Comperlan KD
0.5 g / l dehydol LT 5
1 g / l water glass
2 g / l sodium zeolite NaA (detergent quality)

Tap water (16 ° dH)
pH of the liquor 9.9
Bath temperature 28 ° C

Standard test textiles soiled with dusty skin oil BV, P, PBV and B are wet in four stages (each stage) for 3 minutes and immediately afterwards exposed to 30 seconds of ultrasound. The remission values of the washed and dried material are determined after each treatment stage. These values are summarized in Table 15 below.

Example 89:

It is wetted and washed with an aqueous liquor (16 ° dH) at approx. 28 to 30 ° C in the following process rhythm:
3 minutes of netting
30 seconds exposure to ultrasound
3 minutes of netting
60 seconds exposure to ultrasound

Different combinations of surfactants and builders are used, whereby the cleaning effect is determined on the standard soiled textile samples H-SH-B and H-SH-P. The washing result is recorded on the washed and dried pieces of material by determining the reflectance value.

• a) 1 g/l ABS + 1 g/l Dehydol LT 5 + 2 g/l Natriumzeolith NaA + 1 g/l Wasserglas
  
  B: 57; P: 75
• b) 1,25 g/l ABS + 0,75 g/l Comperlan KD + 2 g/l Zeolith NaA
  
  B: 69; P: 65
• c) Dem Bad zu b) werden 1 g/l Wasserglas zugesetzt
  
  B: 70; P: 74
• d) 0,75 g/l ABS + 1,25 g/l Comperlan KD + 2 g/l Zeolith NaA
  
  B: 67; P: 67
• e) Dem Bad zu d) werden 1 g/l Wasserglas zugesetzt
  
  B: 72; P: 76
• f) 2,0 g/l Comperlan KD + 2 g/l Zeolith NaA + 1 g/l Wasserglas
  
  B: 67; P: 77
• g) 2 g/l Dehydol LT 5 + 2 g/l Zeolith NaA + 1 g/l Wasserglas
  
  B: 70; P: 79
• h) 1 g/l Talgalkoholsulfat + 1 g/l Dehydol LT 5 + 2 g/l Zeolith NaA + 1 g/l Wasserglas
  
  B: 68; P: 72
• i) 1 g/l Alkylgycosid + 1 g/l Dehydol LT 5 + 2 g/l Zeolith NaA + 1 g/l Wasserglas
  
  B: 71; P: 78

The washing liquors used in each case and the washing results determined therein (% remission) are summarized below.

• a) 1 g / l ABS + 1 g / l dehydol LT 5 + 2 g / l sodium zeolite NaA + 1 g / l water glass
  
  B: 57; P: 75
• b) 1.25 g / l ABS + 0.75 g / l Comperlan KD + 2 g / l zeolite NaA
  
  B: 69; P: 65
• c) 1 g / l water glass are added to the bath to b)
  
  B: 70; P: 74
• d) 0.75 g / l ABS + 1.25 g / l Comperlan KD + 2 g / l zeolite NaA
  
  B: 67; P: 67
• e) 1 g / l water glass is added to the bath to d)
  
  B: 72; P: 76
• f) 2.0 g / l Comperlan KD + 2 g / l zeolite NaA + 1 g / l water glass
  
  B: 67; P: 77
• g) 2 g / l dehydol LT 5 + 2 g / l zeolite NaA + 1 g / l water glass
  
  B: 70; P: 79
• h) 1 g / l tallow alcohol sulfate + 1 g / l dehydol LT 5 + 2 g / l zeolite NaA + 1 g / l water glass
  
  B: 68; P: 72
• i) 1 g / l alkylgycoside + 1 g / l dehydol LT 5 + 2 g / l zeolite NaA + 1 g / l water glass
  
  B: 71; P: 78

Example 90:

After the treatment cycle of example 89, enzyme-specific test soils are washed under the conditions specified below:

Enzyme-specific soiling

Milk / Cocoa (H-MK-B)
Blood (H-BL-B)
Blood / milk / soot (H-BMR-B)
Composition of the wash bath:

1 g / l ABS
1 g / l dehydol LT 5
1 g / l water glass
2 g / l zeolite NaA
4 g / l sodium sulfate
Tap water 16 ° dH
Bath temperature 28 to 29 ° C

In parallel experiments, the washing results are first repeated with simultaneous treatment in the bath specified above without the use of ultrasound and secondly with the use of ultrasound (3 minutes of wetting, 30 seconds of ultrasound) 3 minutes of wetting, finally 60 seconds of ultrasound).

The same washing tests are repeated in the following test series, but now 0.1 g / l of a detergent protease (Maxatase CX) are added to the baths used.

The reflectance values determined in each case on the washed and dried specimens are summarized in Table 16 below.

Claims (28)

1. A process for washing and cleaning soiled textile goods by treating them in an aqueous washing liquor containing dissolved, emulsified and / or suspended washing auxiliaries under the action of ultrasound on the washing bath, characterized in that the soiled textile goods are treated with an aqueous liquor which, under the conditions of this treatment have such a high wetting ability that the fiber microstructure of the textile goods, including its soiled areas, is thoroughly wetted and ventilated, while displacing microdisperse residual air, and simultaneously and / or subsequently exposing the textile goods immersed in the aqueous washing liquor to the action of ultrasound and thereby ensuring them will that the soiled areas of the textile goods remain in the ultrasonic effective area for at least a few seconds, at least in the state of their sufficient wetting and ventilation. 2. The method according to claim 1, characterized in that one also ensures the adequate ventilation of the wash liquor. 3. Process according to claims 1 and 2, characterized in that the air bubbles which form in particular during the sonication phases and which are macrodispersedly adhering to the textile are removed from the textile material and preferably also at least partly from the washing liquor. 4. The method according to claims 1 to 3, characterized in that the textile material is moved at least during the wetting in the washing bath and is preferably circulated. 5. The method according to claims 1 to 4, characterized in that the textile material is at least partially moved and circulated in the washing bath during sonication in such a way that at least the areas contaminated with pigment and / or grease are brought into the vicinity of an ultrasound transmitter and here - on average over the sonication period of the washing process - at least a few seconds remain. 6. The method according to claims 1 to 5, characterized in that one works with continuous sonication of the washing bath, but preferably with alternating phases of sonication and non-sonicated washing phases, and preferably the movement mechanics of the textile load in the washing liquor also continues precisely during the non-sonicated phases. 7. The method according to claims 1 to 6, characterized in that one works with a plurality of preferably short-term sonication phases, which are separated from one another by non-sonicated washing phases, preferably of at least approximately the same duration. 8. Process according to Claims 1 to 7, characterized in that the duration of the respective sonication phases is from 0.25 to 10 minutes, preferably from 0.5 to 5 minutes. 9. The method according to claims 1 to 8, characterized in that one works with a washing bath which has sonic and non-sonic areas of action, the textile material preferably being guided continuously through these alternating regions. 10. The method according to claims 1 to 9, characterized in that work is carried out with such a degree of textile loading and a form of movement mechanics in the washing liquor that by continuously breaking up the textile liquor loading the continuous contact and deformation contact of adjacent textiles or textile areas is guaranteed. 11. The method according to claims 1 to 10, characterized in that the textile load is immersed in the wash liquor in a calm movement substantially immersed in the liquid phase and preferably mean moving speeds of the textile of 40 cm / sec are not exceeded. 12. The method according to claims 1 to 11, characterized in that one works with baths which have a plurality of sound transducers, which are preferably arranged distributed over the largest possible area of the bath walls. 13. The method according to claims 1 to 12, characterized in that one works with surfactant washing liquors, which are kept at least largely low-foam or foam-free. 14. The method according to claims 1 to 13, characterized in that the movement of the textile material in the wash liquor is effected by means of mechanically moving inserts and / or by pumping around the wash liquor. 15. The method according to claims 1 to 14, characterized in that the average residence time of the soiling areas of the textile material in the vicinity of the ultrasonic transmitter is about 2 to 200 seconds, preferably about 3 to 120 seconds. 16. The method according to claims 1 to 15, characterized in that the near range of the respective ultrasound transmitter results as the distance up to about 25 cm, preferably up to about 15 cm and in particular up to about 10 cm - in each case calculated from the sound source. 17. The method according to claims 1 to 16, characterized in that washing liquors are used which have at least about 0.2 g / l, preferably at least 0.5 g / l wetting additives, in particular corresponding surfactants, emulsifiers and / or detergency boosters, and, if desired, reinforcing auxiliaries, in particular detergent builders and / or soluble electrolyte salts. 18. The method according to claims 1 to 17, characterized in that the content of surfactants, emulsifiers and / or detergency boosters in the range from about 0.3 to 4.5 g / l, preferably in the range from about 0.3 to 2 g / l lies. 19. The method according to claims 1 to 18, characterized in that is carried out with aqueous liquors of the pH range from about neutral to waschalkalic, preferably from about 6.5 to 12. 20. The method according to claims 1 to 19, characterized in that washing in the temperature range from about 15 to 75 ° C, preferably in the range from about 20 to 50 ° C. 21. The method according to claims 1 to 20, characterized in that soiled, in particular pigment and / or fat-soiled textile material is washed, which at least partially contains fiber material of natural origin in the unfinished and / or refined state. 22. The method according to claims 1 to 21, characterized in that the ultrasonic treatment is carried out at frequencies in the range up to about 100 kHz, preferably in the range from about 20 to 60 kHz. 23. The method according to claims 1 to 22, characterized in that the sonication is carried out with a power input in the bath up to about 15 W / l and preferably with a power input in the range of about 6 to 10 W / l. 24. The method according to claims 1 to 23, characterized in that in the context of a combination treatment with the use of bleaching and / or enzymatically acting washing or cleaning aids. 25. Process according to Claims 1 to 3, characterized in that surfactant washing liquors are used which contain additional bleach activators, in particular bleach activators which form intermediate organic peracids. 26. The method according to claims 1 to 25, characterized in that one works with liquors, the bleach activators, in particular intermediate peracid-forming bleach activators in amounts of 0.05 to 2 g / l, preferably in the range of 0.1 to 1 g / l , contain. 27. The method according to claims 1 to 26, characterized in that washing liquors are used, the persalts, in particular sodium perborate, in amounts of 0.1 to 4 g / l, preferably in amounts of 0.2 to 2.5 g / l , contain. 28. The method according to claims 1 to 27, characterized in that work is carried out with surfactant washing liquors which contain alkali-stable proteolytic enzymes, in particular serine-active bacillopeptidases, which are preferably in ready-made form, for example as granules, prills and / or pellets.