EP1716056B1 - Dispenser bottle for liquid detergents that are comprised of at least two partial compositions - Google Patents

Abstract

The invention relates to a dispenser bottle for a liquid aqueous washing composition which consists of at least two, preferably exactly two, part-compositions kept separate from one another. The dispenser bottle has a first receiving vessel ( 1 ) and at least one, preferably exactly one, second receiving vessel ( 2 ) and the first receiving vessel ( 1 ) contains a first part-composition and the second receiving vessel ( 2 ) a second part-composition. The two receiving vessels ( 1, 2 ) are either designed separately or connected to one another or designed together in one piece, The receiving vessels ( 1, 2 ) each have an outlet ( 3, 4 ) for the part-composition. The outlets ( 3, 4 ) are arranged adjacently to one another such that the two part-compositions can be applied in a common application field ( 5 ) of an application region. The first part-composition comprises water, hydrogen peroxide and surfactant and has an acidic pH and the second part-composition has an alkaline pH. In this dispenser bottle, the outlets ( 3; 4 ) are each equipped with at least one, preferably with exactly one, expulsion nozzle ( 6, 7 ), so that the part-compositions are not mixed with one another until after they leave the expulsion nozzles ( 6, 7 ).

Description

The invention relates to a dispenser bottle for a liquid water-containing detergent composition, which consists of at least two subcomponents held separately from one another, with at least two receptacles for partial compositions which can be stored separately from one another.

From some fields of application, in particular in the field of cleaning of surfaces, the use of drug fluids is known, which are to be stored separately or must. These drug fluids should meet shortly before or during application to the application area, such as a floor, the surface of a toilet bowl, etc., meet. Examples include chlorine-containing bleaching, cleaning, descaling and disinfecting agents (for example WO 98/21308 A2 ). Active fluids of the type in question are also applied, for example, to surfaces in the bathroom or in other hygienically sensitive areas.

Active fluids are stored in different receptacles, in particular when they are not together stable in storage. But other reasons for a separate storage of active fluids, which are to be applied together, are known, for example, different colors that should communicate different functions of the active fluids, different light sensitivities etc ..

A known dispenser bottle for at least two different non-storage-stable active fluids, WO 98/21308 A2 and US 5,398,846 A ), has a two separate chambers, which form the receptacles, having bottle, which is provided at the upper end with immediately adjacent outlets for the active fluids in the two receptacles. In a receptacle is a first aqueous solution and in the second receptacle, a second aqueous solution. The concentration of the components in the two aqueous solutions is chosen so that, if a certain Amount of the first aqueous solution is mixed with a certain amount of the second aqueous solution, the desired in this prior art acidic bleaching solution is the result.

The dispenser bottle of the prior art explained above has a pump device which can be placed on the outlets of the two receptacles of the dispenser bottle. In the pumping device, the active fluids are brought together and ejected from a discharge nozzle in a common spray. the drug fluids are thus mixed together before they leave the ejection nozzle.

A similar dispenser bottle, in which a cross contamination between the two receptacles can be largely safely avoided, is also known ( WO 91/04923 A1 ). In this dispenser bottle pump spray device is not provided, but the outlets are simply open and provided with spouts and can be closed by means of a cap. For a spray application, however, this dispenser bottle is not agreed.

Especially for cleaning toilet bowls, a dispenser bottle for a drug fluid with a receptacle made of flexible plastic and an ejection nozzle is known ( EP 0 911 616 B1 ), wherein for optimal application of the active substance fluid in the toilet bowl, in particular under its inner edge, the ejection nozzle is designed as an angled dosing tube.

In detergents in liquid form, especially if they contain water, it may due to chemical incompatibility of the individual ingredients to negative interactions of these ingredients with each other and to decrease their activity and thus decrease the washing performance of the agent altogether, even if it is stored only relatively short becomes. This decrease in activity relates in principle to all detergent ingredients which carry out chemical reactions in the washing process in order to contribute to the washing result, especially bleaches, although enzymes, surfactant or sequestering ingredients responsible for solubilization or complexing steps, especially in the presence of said chemically reactive ingredients in aqueous systems are not unlimited shelf life. A possible way out, for example, is that the reactivity of the chemically active ingredients is not the same at all pH values, so that by adjusting the pH of the agent, the harmful effect of an ingredient or its decomposition reaction can be minimized. However, a difficulty arises in that the minimum of the reactivity of the chemically active ingredients is usually not at the same pH, and therefore stabilization via the pH is not normally possible for all ingredients at the same time. A further difficulty arises from the fact that the lowest possible minimum in the minimum of reactivity during storage must change under conditions of use of the agent, so that the reactivity of the chemically active ingredients under the washing conditions can be higher and they are thus able to contribute to the washing result.

To solve this problem, it has been variously proposed in the prior art not to incorporate all detergent ingredients desirable for a good washing result simultaneously into a liquid detergent, but to provide the user of the detergent with several components which he will compound shortly before or during the washing process should and contain only mutually compatible ingredients that are used together under the conditions of use.

So is from the international patent application WO 00/61713 A1 a liquid detergent known which consists of at least two liquid partial compositions, wherein the active fluids are stored separately in a container having at least two chambers (receptacles) and at least one of which has an imine or oxaziridine bleach activator and at least one alkalizing agent, at least one of the partial compositions containing a peroxygen bleach and any part composition has a pH leading to stability. When the partial compositions are mixed, the alkalizing agent increases the pH of the final composition so that bleach and bleach activator effectively react with each other.

From the European Patent EP 0 807 156 B1 For example, there is known a dispenser with two chambers, the first chamber of which contains an aqueous composition of hydrogen peroxide or an organic peracid having a pH greater than 2 and less than 7 and the second compartment containing an acidic component and from which the contents together or successively so on a surface is output that the resulting mixture has a pH of at most 2.

The international patent application WO 94/15465 A1 describes a two-pack system comprising on the one hand an aqueous aliphatic peracid and the second of an aqueous hydrogen peroxide solution containing corrosion inhibitor, peracid and / or hydrogen peroxide stabilizer. The two solutions are combined to produce a disinfectant.

In the German patent application DE 100 24 251 A1 It is proposed to store a bleaching agent which consists in a first component of an aqueous 1 to 40 weight percent aqueous imidoperoxycarboxylic acid dispersion and in a second component of a first component activating substance mixture separately in a double-chamber bottle and the two components only at the Application to mix. The second component, also referred to as pH-regulating buffer solution in this document, consists of an aqueous solution of sodium bicarbonate and sodium carbonate which has been thickened with the aid of methylcellulose.

• eine erste Kammer für eine erste fließfähige Zusammensetzung, wobei die erste Kammer einen unteren Abschnitt und einen oberen Abschnitt hat, der untere Abschnitt der ersten Kammer eine innere Gegenwand und eine Außenwand hat, der obere Abschnitt der ersten Kammer eine Innenwand und eine Außenwand hat, der obere Abschnitt der ersten Kammer eine erste Ausgangsöffnung umfasst; und
• eine zweite Kammer für eine zweite fließfähige Zusammensetzung, wobei die zweite Kammer einen unteren Abschnitt und einen oberen Abschnitt hat, der untere Abschnitt der zweiten Kammer eine innere Gegenwand und eine Außenwand hat, der obere Abschnitt der zweiten Kammer eine Innenwand und eine Außenwand hat, der obere Abschnitt der zweiten Kammer eine zweite Ausgangsöffnung umfasst,

wobei die innere Gegenwand der ersten Kammer an die innere Gegenwand der zweiten Kammer grenzt, und dadurch eine Vorderwand, Seitenwände und eine Rückwand für die Flasche definiert;
wobei die Vorderwand der Flasche mindestens einen Teil der Innenwand des oberen Abschnitts der ersten Kammer, die Rückwand der Flasche mindestens einen Teil der Innenwand des oberen Abschnitts der zweiten Kammer umfasst und sich mindestens ein Teil der inneren Gegenwand der ersten Kammer und mindestens ein Teil der inneren Gegenwand der zweiten Kammer zwischen den Seitenwänden der Flasche erstrecken.From the US patent application US 2004/0026535 A1 a bottle is known for dispensing two flowable compositions according to the preamble of claim 1, the bottle comprising:

• a first chamber for a first flowable composition, the first chamber having a lower portion and an upper portion, the lower portion of the first chamber having an inner mating wall and an outer wall, the upper portion of the first chamber having an inner wall and an outer wall upper portion of the first chamber comprises a first exit opening; and
• a second chamber for a second flowable composition, the second chamber having a lower portion and an upper portion, the lower portion of the second chamber having an inner mating wall and an outer wall, the upper portion of the second chamber having an inner wall and an outer wall upper portion of the second chamber comprises a second exit opening,

the inner opposing wall of the first chamber being adjacent to the inner opposing wall of the second chamber, thereby defining a front wall, side walls and a rear wall for the bottle;
wherein the front wall of the bottle comprises at least a portion of the inner wall of the upper portion of the first chamber, the rear wall of the bottle comprises at least a portion of the inner wall of the upper portion of the second chamber and at least a portion of the inner wall of the first chamber and at least a portion of the inner Extending opposite wall of the second chamber between the side walls of the bottle.

1. (I) Der pH-Wert des Wirkstoffs A liegt im Bereich von 1 bis 6,5 bei 20 °C und das Volumen an wäßriger 0,1 N Natriumhydroxidlösung, die nötig ist, um den pH-Wert von 1 000 ml des Wirkstoffs A auf 7 bei 20 °C zu bringen, liegt bei 50 bis 1000 ml; und
2. (II) der pH-Wert des Wirkstoffs B liegt im Bereich von 9 bis 12 bei 20 °C und das Volumen an wäßriger 1 N Schwefelsäurelösung, die nötig ist, um den pH-Wert von 1 000 ml des Wirkstoffs B auf 7 bei 20 °C zu bringen, liegt bei 450 bis 2 000 ml.

The US patent application US 2003/0119697 A1 relates to two-drug type liquid bleach compositions prepared from Active Agents A and B which have been filled into and located in separate compartments of a container, the two-drug type liquid bleach compositions containing: active ingredient A composed of hydrogen peroxide; the 0.1 to 10 wt .-% of a acidic substance and water, the active substance B, composed of an alkaline active substance and water,
wherein the active compounds A and B respectively satisfy the following conditions (I) and (II):

1. (I) The pH of the active substance A is in the range of 1 to 6.5 at 20 ° C and the volume of aqueous 0.1 N sodium hydroxide solution necessary to maintain the pH of 1 000 ml of the active ingredient A. to bring to 7 at 20 ° C, is 50 to 1000 ml; and
2. (II) the pH of drug B ranges from 9 to 12 at 20 ° C and the volume of aqueous 1 N sulfuric acid solution required to bring the pH of 1000 ml of drug B to 7 at 20 ° C is 450 to 2 000 ml.

The teaching is based on the problem, a dispenser bottle for a liquid detergent composition, which consists of at least two separately held subcomponents (active fluids) to provide at least two receptacles for the at least two subcomponents, which is inexpensive to manufacture and easy to handle by an operator and it allows to apply the at least two partial compositions separated from each other, but in an application field to meet.

The above-indicated problem is solved by a dispenser bottle according to claim 1.

Another object of the invention is the use of such a dispenser bottle for the application of detergents, according to claim 45.

The receptacles are preferably designed as compressible containers. By squeezing the receptacle by hand of an operator so the necessary internal pressure in the receptacles generated to expel the drug fluids from the separately provided ejection nozzles. The required pressure can also be generated by gravity, if the product delivery is not horizontally or not up against gravity, but down discharged, such as the application of textile treatment agents on contaminated fabrics for stain removal or when entering detergents in the washing machine or their bleach dispenser. The active fluids thus mix only after leaving the ejection nozzles in the application field. This results in the application of the two drug fluids, the desired product to be applied, especially the detergent, which unfolds the desired effect in the application field.

The claimed dispenser bottle achieved the result described above with a structurally very simple and easy to handle solution, especially waiving a Pumpsprühvorrichtung. Thus, the claimed dispenser bottle is ideal for use as a mass product.

For the purposes of the teaching of the present patent application, active fluids are to be understood as meaning all liquid and other flowable media, from low-viscosity to viscous to gelatinous to pasty substances. It is also possible to apply powdery and particulate active ingredients, such as granules, with the dispenser bottle according to the invention. On the one hand, the viscosity of the active substance fluids or flowability of the active ingredients for the particular application of interest, on the other hand, and in a special way, the thixotropy of the active fluids is important (for explaining the concept of thixotropy, the phenomenon that certain drug fluids are exposed to mechanical Liquefy forces, after the end of the mechanical stress, but if necessary with a considerable time delay but again solidify, so have a dependent on the action of mechanical forces viscosity, see RÖMPP LEXIKON Chemie, 10th Edition, Georg Thieme Verlag, Stuttgart, 1999, Volume 6, page 4533 ).

Preferred embodiments and further developments of the teaching are the subject of the dependent claims.

Special and independent significance is assigned to an embodiment for which the design and the dimensions of the ejection nozzles and the properties, in particular the viscosities and / or the thixotropy, of the active fluids are coordinated so that - with average pressure of the hand an operator or gravitational pressure - the fluid streams overlap at a predetermined pre-calculated distance. A particular embodiment consists in the fact that the nozzle channels of the ejection nozzles are indeed aligned substantially parallel to each other, but in each case have an asymmetrical to the total flow cross section arranged cross-sectional constriction. The cross-sectional constrictions are arranged on the mutually facing sides of the nozzle channels in such a way that the emerging under pressure drug fluids have a mutually directed swirl. This means that due to the clever design of the ejection nozzles, the streams of the active substance fluids emerging from the ejection nozzles flow toward one another in an arcuate manner and hit one another in a dependent on the outflowing pressure slightly varying distance from the ejection nozzles. Here then the application field of the application area can be located. This embodiment with the cross-sectional constrictions is of particular importance, in particular when the active substance fluids are essentially the same type of thixotropic active substance fluids.

The swirl effect is also caused when the openings of the nozzle channels of the Austoßdüsen are chamfered against each other, that is, the opening planes of the nozzle channels are at an angle to each other, wherein the longitudinal axis of the nozzle channel inner portion of the wall of the ejection nozzle is longer than the outside to the longitudinal axis of the nozzle channel lying section of the wall.

Other embodiments and further developments are apparent from the rest of the dependent claims.

Fig. 1a

in einer perspektivischen Ansicht ein erstes Ausführungsbeispiel einer erfindungsgemäßen Spenderflasche,

Fig. 1b

in einer perspektivischen Ansicht ein zweites Ausführungsbeispiel einer erfindungsgemäßen Spenderflasche,

Fig. 2a

die Spenderflasche aus Fig. 1a von der Seite gesehen,

Fig. 2b

die Spenderflasche aus Fig. 1b von der Seite gesehen,

Fig. 3

die Spenderflasche aus Fig. 1a in einer Fig. 2a entsprechenden Darstellung, jedoch ohne Düsenkopf,

Fig. 4

in einer Fig. 3 entsprechenden Darstellung die Spenderflasche in einer Ansicht von der Schmalseite her,

Fig.5a

die Spenderflasche in einer Seitenansicht gemäß Fig. 2a, die Verschlußkappe für die Ausstoßdüsen entfernt,

Fig. 5b

die Spenderflasche in einer Seitenansicht gemäß Fig. 2b, die Verschlußkappe für die Ausstoßdüsen entfernt,

Fig. 6a

die Spenderflasche in einer Ansicht von der Rückseite her, wie in Fig. 5a ohne Verschlußkappe,

Fig. 6b

die Spenderflasche in einer Ansicht von der Rückseite her, wie in Fig. 5b ohne Verschlußkappe,

Fig. 7

den Dosierkopf der Spenderflasche aus Fig. 6 in einer Seitenansicht,

Fig. 8

den Dosierkopf aus Fig. 7 im Schnitt,

Fig. 9

den Dosierkopf aus Fig. 7 im Schnitt senkrecht zum Schnitt aus Fig. 8,

Fig. 10

in einer Fig. 9 entsprechenden Darstellung den Dosierkopf, jetzt mit aufgesetzter Verschlusskappe,

Fig. 11a

das Strahlbild der Wirkstofffluide bei einem ersten Ausführungsbeispiel einer erfindungsgemäßen Spenderflasche,

Fig. 11b

das Strahlbild der Wirkstofffluide bei einem zweiten Ausführungsbeispiel einer erfindungsgemäßen Spenderflasche,

Fig. 12

das Strahlbild der Wirkstofffluide bei einem weiteren Ausführungsbeispiel einer erfindungsgemäßen Spenderflasche mit Auslassdüsen mit schrägendenden Dosierkanälen,

Fig. 12a

den Dosierkanal im Schnitt in Höhe der Querschnittsverengung bei einem weiteren Ausführungsbeispiel und

Fig. 12b

entsprechend den Dosierkanal bei einem dritten Ausführungsbeispiel,

Fig. 13

eine Verschlusskappe mit Positionierungshilfe, sowie

Fig. 14

eine Spenderflasche mit einer Verschlusskappe gemäß Fig. 13.

In the following, the invention will now be explained in more detail with reference to a drawing showing merely exemplary embodiments. In the drawing shows

Fig. 1a

in a perspective view of a first embodiment of a dispenser bottle according to the invention,

Fig. 1b

in a perspective view of a second embodiment of a dispenser bottle according to the invention,

Fig. 2a

the donor bottle out Fig. 1a seen from the side,

Fig. 2b

the donor bottle out Fig. 1b seen from the side,

Fig. 3

the donor bottle out Fig. 1a in a Fig. 2a corresponding representation, but without nozzle head,

Fig. 4

in a Fig. 3 corresponding representation of the dispenser bottle in a view from the narrow side,

5a

the donor bottle in a side view according to Fig. 2a removing the cap for the ejection nozzles,

Fig. 5b

the donor bottle in a side view according to Fig. 2b removing the cap for the ejection nozzles,

Fig. 6a

the donor bottle in a view from the back, as in Fig. 5a without cap,

Fig. 6b

the donor bottle in a view from the back, as in Fig. 5b without cap,

Fig. 7

dispense the dosing head of the dispenser bottle Fig. 6 in a side view,

Fig. 8

off the dosing head Fig. 7 on average,

Fig. 9

off the dosing head Fig. 7 in section perpendicular to the section Fig. 8 .

Fig. 10

in a Fig. 9 corresponding representation of the dosing head, now with attached cap,

Fig. 11a

the jet image of the active substance fluids in a first embodiment of a dispenser bottle according to the invention,

Fig. 11b

the jet image of the active substance fluids in a second embodiment of a dispenser bottle according to the invention,

Fig. 12

the jet image of the active substance fluids in a further embodiment of a dispenser bottle according to the invention with outlet nozzles with oblique dosing channels,

Fig. 12a

the metering in section at the level of the cross-sectional constriction in a further embodiment and

Fig. 12b

corresponding to the metering channel in a third embodiment,

Fig. 13

a cap with positioning aid, as well

Fig. 14

a dispenser bottle with a cap according to Fig. 13 ,

The invention relates to a dispenser bottle as in Fig. 1a or 1b perspective and in the Fig. 2a and 2 B is shown laterally. On the left, a first receptacle 1 for a first partial composition (a first active substance fluid) can be seen, and on the right, a second receptacle 2 for a second partial composition (a second active substance fluid). Basically, for the teaching of the invention that more than two receptacles 1,2 may be provided, for example, three receptacles for three partial compositions (active fluids) or even four receptacles for four partial compositions (active fluids), which should meet in the application area.

The drug fluids will often be non-shelf stable drug fluids; but this is not a mandatory requirement for the teaching of the invention. Reference may be made to the statements above. Likewise, reference may be made to the above statements with regard to the definition of the term of the active substance fluid in the sense of this patent application and the particular, preferred properties of such active substance fluids.

The two receptacles 1,2 are either carried out separately and connected to each other, for example by gluing or latching or other connection element or, as in the illustrated embodiment, integral with each other. In that regard, reference may be made to the prior art explained for the different variants that can be chosen here. In fact, a dispenser bottle in which the two receptacles 1, 2 are made in one piece with one another is preferred.

Fig. 3 and 4 show the receptacle 1,2 for the first embodiment of the dispenser bottle Fig. 1a and 2a separately. It can be seen that the receptacles each have an outlet 3,4 for the respective active substance fluid. The outlets 3, 4 are arranged adjacent to one another in such a way that the two active substance fluids are in a common application field 5, indicated in FIG Fig. 11 , Applicable to a larger application area. The special significance of this external mixing of the active substance fluids from the two receptacles 1, 2 has been pointed out in detail in the general part of the description; reference may be made to this. For the embodiment of the dispenser bottle after Fig. 1b and 2 B the receptacles were not dargstellt separately, would be different only that it has no holding area, since the application is carried out by pivoting and the liquid outlet due to gravity.

In the following, the dispenser bottle according to the invention is always explained as if there were only two receptacles 1,2 for two active fluids. The above-explained statement that also several receptacles can be used, it must be remembered, because the explanations should also apply to such multi-container dispenser bottles. Likewise, that contained in the dispenser bottle Liquid laundry detergent is explained as consisting of only two component compositions, although it must be remembered that it may also contain several component compositions. It is advantageous if the number of receptacles 1.2 corresponds to the number of subcompositions, so that in each receptacle 1.2 another subcomposition is included. If desired, however, the number of receiving containers 1, 2 may also exceed the number of partial compositions, so that more than one receiving container 1, 2 has an equally composed partial composition.

It is essential for the dispenser bottle according to the invention that the receiving containers 1, 2 are each provided with at least one outlet 3.4, in each case at least one, preferably with exactly one ejection nozzle 6, 7 so that the active substance fluids do not intercommunicate with one another until they have left the ejection nozzles 6, 7 be mixed. For the dispenser bottle according to the first embodiment ( Fig. 1a ) is further essential that the receptacles 1,2 are designed as compressible container, since it is preferably used for a product delivery against gravity. The ejection nozzles 6, 7 are preferably inclined with respect to the longitudinal axis of the receptacles 1, 2. For the dispenser bottle according to the second embodiment ( Fig. 2 ) is further essential that the ejection nozzles 6, 7 are parallel in the direction of the longitudinal axis of the receptacle 1,2 extend because with this dispenser preferably detergent in the dispensing compartment of a washing machine or a dosing aid for the drum of a washing machine or directly on the textile to be cleaned be applied by gravitational force. The receptacles 1,2 can be designed as a compressible container. One recognizes the ejection nozzles 6,7 first in Fig. 6a and 6b , by the way then also in Fig. 8 and shown schematically in FIG Fig. 11 a . b ,

As a result of the claimed embodiment of the dispenser bottle, the pressure for pushing out the active substance fluids from the receiving containers 1, 2 is applied by the hand of an operator or by gravity after pivoting by more than 90 °. The active fluids leave under pressure the ejection nozzles 6, 7, to which they flow from the outlets 3, 4 of the two receptacles 1, 2. Only after leaving the ejection nozzles 6,7 results, depending on the pressure exerted by the operator, at a certain distance the clash the flows of the active fluids and their mixing to the applied product in the application area.

The illustrated and preferred embodiment according to Fig. 1a . 2a now further shows that the receptacle 1.2 consist of a material with a return characteristic and / or have a provision in the original shape supporting shaping. In particular, it is recommended to produce the receptacle 1,2 made of a resiliently elastic plastic material. Such a material for the receiving containers 1, 2 can be, for example, a polyolefin, in particular a polypropylene (PP), a polyethylene (PE), a polyvinyl chloride (PVC) or a polyethylene terephthalate (PET), in particular a glycol-modified polyethylene. Terephthalate (PETG), act. In that regard, may again on the above-mentioned plastic spray bottle of EP 0 911 616 B1 to get expelled. Such materials are also suitable for the present application.

It is interesting in the above-described embodiment of the receptacle 1,2 that can be connected by the special geometry of the receptacle 1,2 in conjunction with the material used optimal compressibility with a uniform Rücksaugeffekt for the drug fluids. A consistent, effective back suction effect for the active fluids from the ejection nozzles 6, 7 back into the receptacles 1, 2 is important for clean product separation at the outer ends of the ejection nozzles 6, 7 upon completion of the feedstock fluid dosage.

Overall, the use of plastic containers with a corresponding return characteristic is cost-effective and allows regardless of an effective dosage of drug fluids in the desired manner described above without premixing.

The illustrated in the drawings embodiments of a dispenser bottle according to the invention shows for the receptacle 1.2 concretely equal volumes and mirror image same shape. In principle, it is also possible to provide different volumes, if it is achieved by the shape, wall thickness and choice of material of the receptacle 1.2 that the desired dosage of drug fluids, then different, is reached from the receptacles 1.2. Typical volumes of receptacles 1, 2 within the scope of the budget are between 50 ml and 1500 ml, with a preferred range between 300 ml and 500 ml for each of the receptacles 1, 2. Of course, this is application-specific and depends on the drug fluids.

The illustrated and preferred embodiments according to Fig. 1a and 1b let in particular Fig. 4 , but also in Fig. 6a and 6b recognize that the receptacle 1,2 are each designed as complete containers and connected to each other only via at least one, preferably exactly one formed between the receptacles 1.2 connecting web 8. The connecting web 8 is preferably integrally formed on the mutually facing inner sides of the receptacle 1.2, in particular formed, for example, in the blow molding process with the receptacles 1.2 at the same time. It is particularly useful if the connecting web 8 is arranged approximately centrally and extends substantially - optionally with interruptions - over the full length of the receptacle 1.2. The connecting web 8 thus forms a stiffening element for the mutually facing walls of the receptacles 1,2, stabilizes them and at the same time leads to the design of an abutment for the pressure forces exerted by the hand of the operator. Overall, the receptacles should have 1.2 together in such a cross-section that they can be covered by the hand of an operator in any case for the most part.

Previously, the blow molding process has already been addressed as a convenient method of manufacturing the receptacles 1,2. With a corresponding modification, in particular of the blow-molding process, it is possible that the receptacles 1, 2, which are embodied in one piece with one another, have a different translucency and / or a different coloration. In particular, it may be advisable, despite a one-piece design opaque a receptacle, the other receptacle transparent or run in several receptacles, the receptacle in different colors. It has been shown that some drug fluids are photosensitive. Other drug fluids to be administered with the respective drug fluid are less sensitive to light. An opaque coloring of the receptacle provided for the more photosensitive active substance fluid eliminates problems here.

With regard to the handling by an operator, the dispenser bottle shown in the drawings is characterized according to Fig. 1a . 2a further characterized in that at the receptacles 1.2 a to be comprehensive by the hand of an operator holding area 9 formed by special edge formations 10,11 and / or surface designs and / or is characterized. One recognizes this particularly well in Fig. 1 and 2 , The recessed grip tempts you to cover the dispenser bottle with your hand from here. The dispenser bottle has a certain position relative to the hand of the operator, which is determined by the edge formations 10,11. For example, corrugations, other colorations, etc. are also suitable as surface designs.

With regard to the dimensions, it has proved to be expedient not to let the receiving containers 1, 2 be too large in order not to obstruct the handling. Preferred dimensions result in such a way that the receptacles 1, 2 in cross-section in the holding area 9 to be encompassed by the hand of an operator have an outer circumference of approximately 18 to approximately 30 cm, preferably approximately 20 to approximately 28 cm, in particular ca 22 to about 26 cm, in particular of about 24 cm.

The volume of the receptacle (1,2) depends, for example, on the weight or volume fraction of the active substances in the overall formulation of the detergent contained therein or the nature of the preparation of these active substances, for example in the form of the pure substance, as a solution or dispersion. In a preferred embodiment, all receiving containers (1, 2) have the same size, their volume preferably being between 10 and 2000 ml, preferably between 20 and 1500 ml, particularly preferably between 50 and 1000 m and in particular between 100 and 800 ml. Dispenser bottles according to the invention are suitable for the repeated dosing of mechanical detergents, they therefore preferably contain for this purpose at least two, but in particular at least 6, more preferably at least 12, 24 or 36 metering units.

It has already been explained above what is done by the dispenser bottle with the receptacles 1, 2 designed according to the invention. With particular reference to Fig. 6a and 6b . Fig. 8 . Fig. 11a and 11b . Fig. 12 may be explained so far that the design and dimensions of the ejection nozzles 6,7 and the properties of the drug fluids are coordinated so that-at average pressure from the hand of an operator or caused by Gravitaion pressure the fluid flows at a certain distance in overlap come. In particular, this means that in the illustrated embodiment of a dispenser bottle, the fluid flows at a distance about 50 mm to about 300 mm, preferably from about 100 mm to about 250 mm, in particular of about 150 mm, come in overlap. So that's about the distance between the ejection nozzles 6,7 and the application field. This corresponds to the usual distances in the dimensions, as they are to be observed in the household during cleaning measures, such as the cleaning of carpets.

With regard to the viscosity of the active substance fluids, it is recommended to use active substance fluids having viscosities in the range from 1 to 100,000 mPas, preferably up to about 10,000 mPas, in particular up to about 1,000 mPas. This information is based on the viscosity measured using a Brookfield LVT-11 viscometer at 20 rpm. and 20 ° C, spindle no. 3.

The Fig. 3 and 4 show the receptacle 1,2 with the outlets 3,4. In this case, the outlets 3,4 are aligned parallel to each other. A pre-alignment of the streams of the active fluids can also be provided by already aligning the outlets 3, 4 of the receiving containers 1, 2 slightly inclined towards one another. In terms of manufacturing, however, the illustrated parallel alignment has advantages.

In principle, it is possible, but not with the actual blow molding process implemented here, to mold the ejection nozzle 6, 7 at the outlet 3, 4 integrally on the receptacle 1, 2. However, this variant has not been chosen in the illustrated embodiment. In the illustrated embodiment, it is rather provided that the ejection nozzle 6, 7 is arranged or formed in a separate, here from a dimensionally stable plastic nozzle head 12 and that the nozzle head 12th at the outlet 3, 4 is placed on the receptacle 1, 2. The nozzle head 12 is identified in the figures by reference numeral 12. In the illustrated embodiment, it is true that the nozzle head 12 is latched onto the receptacle 1, 2. The nozzle head 12 can also be connected to the receptacle 1, 2 in a different way. A snapping is recommended, however, as a particularly simple and convenient manufacturing technique.

For latching the nozzle head 12 on the respective receptacle 1, 2, it is advisable to provide at the outlet 3, 4 of the receptacle 1, 2 corresponding locking connection means for mating locking connection means of the nozzle head 12. Such locking connection means are known in corresponding constructions of the prior art. In principle, other connection techniques such as screw connections are applicable.

The illustrated and preferred embodiments are particularly characterized by the fact that the nozzle heads 12 of the two receptacles 1, 2 are combined in a common nozzle head 12. This common nozzle head 12 can be seen in the Fig. 7, 8, 9 and 10 as well as 12, 14. This is manufacturing technology very convenient and the connection of the two receptacles 1,2 well adapted.

It is advisable to make the nozzle head 12 of a stiffer plastic material, so that the nozzle head 12 undergoes only slight deformation when the receptacle 1.2 of the dispenser bottle are compressed.

There are a number of design options for the nozzle head 12, which will be explained below. It can be seen the nozzle head 12 in the previously mentioned figures, as well as in Fig. 5 and Fig. 6 , On average, you can see the nozzle head 12 particularly well in Fig. 8, 9 . 10 , It is found that it is expedient for the flow of the active substance fluid in the nozzle head 12 that the ejection nozzle 6, 7 is arranged asymmetrically in the nozzle head 12, in particular offset with respect to the center line of the outlet 3, 4 in the direction of the further ejection nozzles 7, 6. This can be seen in Fig. 8 especially good. The flow of the active substance fluid from the respective receptacle 1, 2 is brought to the desired distance to the parallel outflowing active fluid.

One recognizes here a constructive solution that ensures a laminar flow. Namely, it is provided that the nozzle head 12 has an inflow volume 13 tapering from the outlet 3, 4 of the receptacle 1, 2 to the ejection nozzle 6, 7. This Anströmvolumen 13 can be particularly well in FIGS. 8 and 9 comprehend.

The illustrated and preferred embodiment shows a dimensioning such that the lateral center distance of the ejection nozzles 6, 7 is on the outside about 5 mm to about 30 mm, preferably about 15 mm to about 20 mm.

From the Fig. 1a . 1b and 2a . 2 B as well as out Fig. 10 recognizes that it is also provided for the dispenser bottles shown here that the ejection nozzle 6, 7 with a removable cap 14 is closed, which preferably consists of a dimensionally stable plastic. It is provided that the closure cap 14 has a closing stopper 15 entering the ejection nozzle 6, 7. This technique is already proven to avoid cross-contamination (see above) WO 91/04923 A1 ). In another embodiment, as in Fig. 14 15 and 15, the closure cap 14 has, in addition to the closure stopper 15 entering the ejection nozzle 6, 7, a cylinder portion 19 bent convexly relative to the longitudinal axis of the closure cap 14 as a positioning aid. This cylinder portion 19 is spaced from the closure plug 15 such that the free ends of the cylinder portion 19 abut against the ejection nozzles 6, 7 in the closed position. When placing the cap 14 on the dispenser bottle, the lower end of the cylinder portions 19 slide along the inclined surfaces of the ejection nozzles 6, 7, the movement is forced. The placement of the cap 14 with the cylinder portions 19 as positioning aids and the sealing plug 15 on the ejection nozzles 6,7 is in Fig. 14 shown schematically.

The illustrated and preferred embodiments show, particularly well recognizable in Fig. 1a . 1b and 14, that also applies to the cap 14 that this for both Ejector 6,7 of the two receptacles 1,2 is summarized together. This is manufacturing technology appropriate, as well as the nozzle head 12 has been explained as appropriate. Conveniently, the cap 14 is made of a similar or the same plastic material as the nozzle head 12th

It can be seen from the drawings that the ejection nozzles 6, 7-of course-have a nozzle channel 16 or 17, respectively. It could be provided that the nozzle channels 16,17 of the ejection nozzles 6,7 are inclined towards each other. Then, the exiting streams of the active fluid would already have an orientation to a common application field 5. The illustrated and so far preferred embodiment shows, however, that the nozzle channels 16,17 of the ejection nozzles 6,7 are aligned parallel to each other. A slight tilt in the frame for exampleB. the manufacturing tolerances is of course acceptable.

In particular, in the last-explained embodiment shown in the drawing with the nozzle channels 16, 17 oriented substantially parallel to one another, it is particularly expedient if the nozzle channels 16, 17 of the ejection nozzles 6, 7 each have an obliquely arranged cross-sectional constriction 18 to the total flow cross-section.

In the general part of the description has already been pointed to the particular importance of the cross-sectional constriction 18 in the respective nozzle channel 16 and 17 respectively. One can do this by means of Fig. 11a and 11b comprehend.

The cross-sectional constriction 18 in the respective nozzle channel 16, 17 leads to a certain twist being imparted to the streams of the active substance fluids, so that a certain diversion takes place in each case in the exit region of the ejection nozzles 6, 7, so that the streams of the active substance fluids then flow in the application field Distance, which in some way depends on the pressure of the hand of the operator on the receptacles 1,2, impinge mingling.

Thus, a combination of the streams of the active substance fluids is not achieved by aligning the nozzle channels 16, 17, but by influencing the flow.

In addition, complete coverage of the flows of the active fluids in the application field 5 is achieved, and not only a partial coverage achieved by scattering effect, as could occur with non-modified nozzle channels 16, 17.

The last explained, particularly preferred embodiment of the invention now needs further explanation.

Fig. 11a . 11 b shows above the principle of operation of the cross-sectional constrictions 18, below an example of the arrangement of the cross-sectional constrictions 18 in the adjacent nozzle channels 16,17. Here, it can be seen first that in the illustrated preferred embodiment, the cross-sectional constrictions 18 of the nozzle channels 16,17 are executed with angular transitions. In terms of flow, this results in different flow velocities occurring over the flow cross-section of the nozzle channel 16, 17. Distanced from the cross-sectional constriction 18, the active fluid can flow relatively undisturbed, it maintains a high flow velocity with laminar flow. At the cross-sectional constriction 18, on the other hand, there is a substantially increased flow velocity in the narrowest cross section, but when leaving the constriction a strong reduction in the flow velocity is associated with the formation of turbulence. The overall leads to the above-mentioned swirl-like behavior of the streams of drug fluids.

Furthermore one recognizes in Fig. 11a . 11b in that the cross-sectional constrictions 18 are arranged on the mutually facing sides of the nozzle channels 16, 17, such that the flows of the active fluids emerging under pressure have such a twist that they run towards one another.

In contrast to the embodiment of Fig. 11a The embodiment according to FIG Fig. 11b an oblique opening plane of the nozzle channels 16, 17, cf. also nozzle head 12 according to Fig. 12 , The beveling of the ends of the nozzle channels also produces the swirl effect due to different flow rates in the outlet. The swirl effect is caused by the fact that the openings of the nozzle channels of the Austoßdüsen are chamfered against each other. The opening levels of the Nozzle channels 6, 7 are arranged at an angle to one another, wherein the section of the wall of the ejection nozzle lying inwards to the longitudinal axis of the nozzle channel is longer than the section of the wall lying on the outside of the longitudinal axis of the nozzle channel. In an embodiment not shown, only oblique openings at the end of the nozzle channel, but not a cross-sectional constriction in the nozzle channel are provided for generating the swirl effect.

In the illustrated embodiment according to Fig. 11a . 11b is the respective cross-sectional constriction 18 designed as an inwardly curved arc. Fig. 12a and 12b show further expedient cross-sectional designs. Here, with the different active substance fluids, it will also be possible to choose different cross-sectional shapes for the cross-sectional constrictions 18 as well as for the nozzle channels 16, 17.

For the effect of the cross-sectional constriction 18, it has been found to be advantageous if this does not occur over the full length of the nozzle channel 16, 17, but is limited to a short piece of this length. It is therefore recommended that the length of the cross-sectional constriction 18 of the nozzle channel 16, 17 is only a part of the length of the nozzle channel 16, 17 in total. In particular, it is recommended that the aspect ratio is about 1: 2 to 1: 4, preferably about 1: 2.5 to 1: 3.

For the field of application in the household, which is particularly in the eye here, and the use of low-viscosity, preferably thixotropic active substance fluids, it is recommended that the total length of the nozzle channel 16, 17 be about 2 mm to about 6 mm, preferably about 3 mm to about 5 mm, in particular approximately 4 mm. Accordingly, the diameter of the nozzle channel 16, 17 is about 1.0 mm to about 4.0 mm, preferably about 1.5 mm to about 3.5 mm, in particular about 2.0 mm to about 2.5 mm ,

In a further embodiment, it is preferred that the cross-sectional constrictions 18 on the mutually facing sides of the nozzle channels 16, 17 are executed with angular transitions and that the cross-sectional constrictions 18 on the opposite sides of the nozzle channels 16, 17 starting from the inflow side to the center of the nozzle channels 16th ; 17 beveled beveled, so provided on the upstream side with a chamfer. This can be in the respective nozzle channel 16, 17 over about half of Cross-sectional constriction 18 extend, preferably exactly symmetrical. Basically, the present teaching also applies in a corresponding manner when the nozzle channels 16, 17 of the ejection nozzles 6, 7 are aligned inclined towards each other. However, the design discussed here is particularly simple in the case of essentially parallel alignment of the nozzle channels 16, 17. In a preferred embodiment, it is provided that the bevels a bevel angle with respect to the center axes of the nozzle channels 16, 17 of 5 ° to 85 °, preferably from 10 ° to 60 °, in particular from 35 ° to 40 °. The cross-sectional constrictions 18 as a whole are, with the exception of the chamfers, preferably arranged symmetrically to the total flow cross-section of the nozzle channels 16, 17. This can be realized in that the cross-sectional constrictions 18 in total, with the exception of the chamfers, are formed annularly in circular nozzle channels 16, 17. The interaction of the differently contoured regions of the cross-sectional constriction 18 in the respective nozzle channel 16, 17 leads to an even more optimized and well-calculable radiation image of the fluids.

If the structural design of the dispenser bottle according to the invention is therefore described essentially completely, then it will now be further discussed which types of detergents consisting of several partial compositions are applied in a particularly expedient manner with such a dispenser bottle.

In principle it is possible to use as different active fluids for the various receptacles (1,2) such drug fluids, as they are known for two- or multi-phase liquid means, but differing from the known two- or multi-phase means the different Phases of these agents in the various receptacles (1,2) are assembled.

According to the invention, it is essential that the first part composition contains water, hydrogen peroxide and surfactant and has an acidic pH. This means that it has undiluted a pH below 7, preferably in the range from 3.5 to less than 7, in particular from 4 to 6.5 and more preferably from 5.0 to 6.0. A pH in this range can be due to the presence of system-compatible acids, for example mineral acids such as hydrochloric acid, sulfuric acid and / or phosphoric acid, amidosulfonic acid, and / or organic acids such as formic acid and / or Citric acid, but also by the - optionally additional - presence of specified below chelating agents are adjusted in their acid form. The acidic pH contributes to the fact that the hydrogen peroxide present in the first part composition is storage-stable over a prolonged period. The proportion of hydrogen peroxide in the first part composition is preferably 1.5% by weight to 15% by weight, in particular 2.5% by weight to 10% by weight and particularly preferably 5% by weight to 8% by weight. -%.

The second part composition has an alkaline pH (ie above pH 7) of preferably in the range of 9 to 13.5 and is preferably also hydrous, in which case its water content may be up to 99.95% by weight, and preferably in the range of 50 wt .-% to 98 wt .-%, in particular 60 wt.% To 95 wt .-%. If it is anhydrous, which is to be understood to mean the presence of such small amounts of water that do not allow the direct measurement of pH, the characteristic of its alkaline pH refers to containing so much alkaline water-reacting substances. that after mixing with the first part composition in the volume ratio 1: 1, the resulting pH is at least 1 unit, preferably at least 1.5 units above that of the first part composition. The pH resulting from mixing the two partial compositions in a volume ratio of 1: 1 is preferably in the range from 8.5 to 11.

The alkaline pH of the second part composition is preferably characterized by the presence of organic bases such as amines, in particular mono-, di- and / or trialkyl and / or alkanolamines, preferably -ethanolaminen, or inorganic bases such as alkali metal hydroxide, alkali metal carbonate or mixtures causes, wherein sodium and / or potassium is the preferred alkali metal. Amounts up to 5% by weight of such alkalizing agents are normally quite sufficient in the second part composition to set a pH of preferably 11 to 13 for this part composition. When combining the acidic first part composition with an alkaline second part composition, when the alkaline part composition is carbonate, when these two part compositions are mixed (when the agent is used), carbon dioxide is liberated, resulting in foaming of the agent and its cleaning performance, especially in the direct Order on a soiled fabric, for example, a garment in the context of a pre-treatment step before the textile laundry or a carpet or a cushion supported.

An agent according to the invention may also contain fragrances, it being noted that some fragrances are not very stable in the acidic pH range and / or in the presence of bleaching agents. In contrast, the stability of high-quality fragrances in the alkaline medium is to be optimally realized, so that a possible fragrance content of the agent can optionally be limited to the alkaline second partial composition.

The liquid partial compositions may contain, in addition to water, nonaqueous solvents which originate, for example, from the group of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Particularly preferred are non-aqueous solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Nonaqueous solvents which can be used in the dispenser bottles according to the invention are preferably from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n-propanol or isopropanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether as well as mixtures of these solvents.

In addition to the liquids, flowable solids, such as, for example, powders, granules or microcompactates, are also considered as flowable substances / substance mixtures in the context of the present application. The solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form. The particle size of these flowable solids is preferably in the range of 10 to 2000 microns, more preferably in the range of 20 to 1000 microns and in particular in the range of 50 to 500 microns. Particularly preferred are flowable solids in which at least 70 wt .-% of the particles, preferably at least 90 wt .-% of the particles have a particle size below 1000 microns, preferably below 800 microns, more preferably below 400 microns.

The surfactants contained in the first part composition and optionally the second part compositions include in particular anionic surfactants and nonionic surfactants, although cationic surfactants and amphoteric surfactants may also be suitable.

As anionic surfactants, preference is given to using one or more substances from the group of the carboxylic acids, the sulfuric acid half esters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical. Usually, the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. are preferred in the context of the present invention Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated Sezies 9c -Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For cost reasons, it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipolysis. Such mixtures are, for example, coconut oil fatty acid (about 6% by weight C8, 6% by weight C10, 48% by weight C12, 18% by weight C14, 10% by weight C16, 2% by weight C18, 8% by weight C18 ', 1% by weight C18 "), palm kernel oil fatty acid (about 4% by weight C8, 5% by weight C10, 50% by weight C12, 15% by weight C14, 7 Wt% C16, 2 wt% C18, 15 wt% C18 ', 1 wt% C18 "), tallow fatty acid (about 3 wt% C14, 26 wt% C16, 2 wt%) % C16 ', 2 wt.% C17, 17 wt.% C18, 44 wt.% C18', 3 wt.% C18 ", 1 wt.% C18"'), hardened tallow fatty acid (approx 2% by weight C14, 28% by weight C16, 2% by weight C17, 63% by weight C18, 1% by weight C18 '), technical oleic acid (about 1% by weight C12, 3 wt .-% C14, 5 wt .-% C16, 6 wt .-% C16 ', 1 wt .-% C17, 2 wt .-% C18, 70 wt .-% C18', 10 wt .-% C18 ", 0.5 wt .-% C18"'), technical palmitic / stearic acid (about 1 wt .-% C12, 2 wt .-% C14, 45 wt .-% C16, 2 wt .-% C17, 47 Wt% C18, 1 wt% C18 ') and soybean oil fatty acid (about 2 wt% C14, 15 wt% C16, 5 wt% C18, 25 wt% C18', 45 wt%) % C18 ", 7% by weight C18"').

Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants and can be used in the context of the present invention. Their alkali metal salts, in particular sodium salts, the so-called fatty alcohol sulfates, are commercially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to give the corresponding alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters. The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO ₃ / air mixtures in special cascade, falling film, or tube bundle reactors.

Another class of anionic surfactants which can be used according to the invention are the alkyl ether sulfuric acids whose salts, the so-called alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates. Alkyl ether sulfuric acids are synthesized in analogy to the alkyl sulfuric acids from fatty alcohols, which are reacted with ethylene oxide to the relevant fatty alcohol ethoxylates. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids, which are usually used after their neutralization as the alkali metal, in particular sodium salts.

Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants, if appropriate in their acid form. Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons. In the sulfochlorination according to Reed n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to the corresponding sulfochlorides which, upon hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water, the alkanesulfonic provide. Since di- and Polysulfochloride and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.

Another process for producing alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation. In this radical reaction, successive alkylsulfonyl radicals are formed which, with oxygen, continue to form the alkylsulfonyl radical react. The reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid. In order to keep the yield of the two end products alkyl sulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.

Olefinsulfonates are produced industrially by reaction of α-olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.

Alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950's propylene was tetramerized into branched α-dodecylene to produce alkylbenzenesulfonates and the product was reacted via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride to tetrapropylenebenzene, which was subsequently sulfonated and neutralized. This economic possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced soaps as the major surfactant in detergents and cleaners.

Due to the lack of biodegradability of TPS, there was a need to present new alkylbenzenesulfonates that are characterized by improved environmental performance. These requirements are met by linear alkylbenzenesulfonates, which are today almost exclusively produced alkylbenzenesulfonates and are denoted by the abbreviation ABS or LAS.

Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes: When using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt .-%, however, hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer can be reduced to about 20 wt .-% , The sulfonation of linear alkylbenzenes finally succeeds today industrially with oleum, sulfuric acid or gaseous sulfur trioxide, the latter having by far the greatest importance. For sulfonation special film or tube bundle reactors are used, which provide as a product 97 wt .-% alkylbenzenesulfonic acid (ABSS).

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäß bevorzugt als Aniontensid in Säureform sind C8-16-, vorzugsweise C9-13-Alkylbenzolsulfonsäuren. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so dass die eingesetzten C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.By choosing the neutralizing agent, it is possible to obtain a wide variety of salts, that is to say alkylbenzenesulfonates, from the ABSS. For reasons of economy, it is preferred in this case to prepare and use the alkali metal salts and, among these, preferably the sodium salts of ABSS. These can be described by the following general formula:

in which the sum of x and y is usually between 5 and 13. C8-16-, preferably C9-13-alkylbenzenesulfonic acids are preferred according to the invention as anionic surfactant in acid form. It is within the scope of the present invention it is preferable to use C8-16-, preferably C9-13-alkylbenzenesulfonic acids derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C8-16-, preferably C9-13-alkylbenzenesulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight to the alkylbenzenesulfonic acid.

The said anionic surfactants may be used alone or in admixture with each other, with ether sulfates and mixtures of fatty acids and ether sulfates, in particular in weight ratios of 5: 1 to 1: 5, preferably 2: 1 to 1: 2, being particularly preferred. The anionic surfactants described above in their acid form are usually used partially or fully neutralized. Suitable cations for the anionic surfactants are, in addition to the alkali metals (in particular Na and K salts), ammonium and mono-, di- or triethanolammonium ions. Instead of mono-, di- or triethanolamine, the analogous representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen. Diese lassen sich durch bekannte Methoden aus den entsprechenden Alkoholen R¹-OH und Ethylen- bzw. Alkylenoxid herstellen. Der Rest R¹ in der vorstehenden Formel kann je nach Herkunft des Alkohols variieren. Werden native Quellen genutzt, weist der Rest R¹ eine gerade Anzahl von Kohlenstoffatomen auf und ist in der Regel unverzweigt, wobei die linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum BeispielB. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, bevorzugt sind. Aus synthetischen Quellen zugängliche Alkohole sind beispielsweise die Guerbetalkohole oder in 2-Stellung methylverzweigte beziehungsweise lineare und methylverzweigte Reste im Gemisch, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Unanbhängig von der Art des zur Herstellung der erfindungsgemäß in den Mitteln enthaltenen Niotenside eingesetzten Alkohols sind erfindungsgemäße Mittel bevorzugt, bei denen R¹ in der vorstehenden Formel für einen Alkylrest mit 6 bis 24, vorzugsweise 8 bis 20, besonders bevorzugt 9 bis 15 und insbesondere 9 bis 11 Kohlenstoffatomen steht. Als Alkylenoxideinheit, die alternierend zur Ethylenoxideinheit in den Niotensiden enthalten sein kann, kommt neben Propylenoxid insbesondere Butylenoxid in Betracht. Aber auch weitere Alkylenoxide, bei denen R² bzw. R³ unabhängig voneinander ausgewählt sind aus -CH₂CH₂-CH₃ bzw. CH(CH₃)₂, sind geeignet.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example B. from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. Examples of preferred ethoxylated alcohols include C12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols. Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Low-foaming nonionic surfactants may also be used which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Examples of these are surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6. These can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 C atoms, for example B. from coconut, palm, tallow or oleyl alcohol are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants used in the compositions according to the invention, agents according to the invention are preferred in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms. As the alkylene oxide unit which may be contained in the nonionic surfactants in an alternating manner with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also Other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ , are suitable.

In addition, as nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the following formula

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are usually prepared by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Further usable nonionic surfactants are the end-capped poly (oxyalkylated) surfactants of the formula

R ¹ O [CH ₂ CH (R ₃ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the be different from the above formula. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

Among the nonionic surfactants, alkoxylated fatty alcohols, optionally in exchange or in admixture with end-capped polyalkoxylated surfactants, are preferred. In the latter, the weight ratio is preferably 10: 1 to 1: 2, in particular 10: 1 to 2: 1.

It is particularly preferred if the weight ratio of anionic surfactant to nonionic surfactant is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. It is preferred if the first part composition contains 1% by weight to 20% by weight, in particular 1.5% by weight to 10% by weight, of surfactant. Nonionic surfactant, in particular alkoxylated fatty alcohol, and / or anionic surfactant, in particular a sulfation product of an alkoxylated fatty alcohol, are the preferred surfactants. The ratios given relate in one embodiment of the invention to the individual partial compositions and in a further embodiment to the entire composition according to the invention.

In addition, the sub-compositions may contain all ingredients customary in liquid detergents which do not unduly interact negatively with the obligatory ingredients. In the sub-compositions, which preferably contain one or more of the abovementioned non-aqueous solvents, it is possible to use further active substances preferably from the group of polymers, builders, co-builders, enzymes, electrolytes, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, antimicrobial agents, germicides, fungicides, antioxidants and corrosion inhibitors. Preferably, in addition to the obligatory ingredients, the first part composition contains chelating agent, water miscible solvent, free radical scavenger, dye and / or perfume.

The liquid detergent composition according to the present invention preferably does not contain an active ingredient commonly referred to as a bleach activator, that is, a compound which splits a peroxycarboxylic acid or peroxyimidic acid under perhydrolysis conditions.

Proteins, amylase, lipase, hemicellulase and / or cellulase belong in particular to the enzymes which may be present in the partial compositions, in particular in the second partial composition. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. In the second subcomposition or the further subcompositions, agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem. 177 (1948), pp. 751-766 ). The first part composition is preferably free of enzymes. In a preferred embodiment of compositions according to the invention, the second partial composition contains protease, amylase and cellulase.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsværd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase® or Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 (known from the international patent application WO 91/02792 ) derived from the name BLAP® variants, in particular in the international patent applications WO 92/21760 . WO 95/23221 and in the German patent applications DE 101 21 463 and DE 101 53 792 to be discribed. Further useful proteases from various Bacillus sp. and B. gibsonii go out of the German patent applications DE 101 62 727 . DE 101 63 883 . DE 101 63 884 and DE 101 62 728 out. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozymes® from Novozymes, sold under the trade names Purafect®, Purafect® OxP and Properase® by the company Genencor, sold under the trade name Protosol® by the company Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further development products of this α-amylase are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. B. amyloliquefaciens α-amylase is sold by Novozymes under the name BAN®, and variants derived from the B. stearothermophilus α-amylase under the names BSG® and Novamyl®, also from Novozymes. Furthermore, those in the international patent application WO 02/10356 disclosed α-amylase from Bacillus sp. A 7-7 (DSM 12368) and in the international patent application PCT / EP01 / 13278 highlighted cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); furthermore, those belonging to the sequence space of α-amylases, which in the German patent application DE 10131441 A1 is defined. Likewise, fusion products of said molecules can be used, for example those from the German patent application DE 101 38 753 known. In addition, those under the trade name Fungamyl® Further developments of the α-amylase from Aspergillus niger and A. oryzae available from Novozymes are suitable. Another commercial product is, for example, the amylase LT®.

Compositions according to the invention may contain lipases and / or cutinases. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase CE®, Lipase P®, Lipase B® or Lipase CES®, Lipase AKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the preparations M1 Lipase.RTM. And Lipomax.RTM. Originally sold by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.

Compositions according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect. A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG, or the 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® and Renozyme®. Likewise, those in the international patent application WO 97/14804 disclosed cellulases used; for example, the 20 kD EG from Melanocarpus disclosed therein, available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®. Further commercial products of AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are described in the international patent application WO 96/34092 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax® is available. Other commercial products of Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra.

Compositions of the invention may contain other enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example, under the names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA. A suitable β-glucanase from a B. alcalophilus, for example, is that of the international patent application WO 99/06573 out. The β-glucanase obtained from B. subtilis is available under the name Cereflo® from Novozymes.

The enzymes optionally employed in agents according to the invention are either originally derived from microorganisms, such as the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi ,

An enzyme which may optionally be present in an agent according to the invention can be used, in particular, during storage against damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or protected proteolytic cleavage. Compositions according to the invention may contain enzyme stabilizers for this purpose. One group of enzyme stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example according to the international patent application WO 95/12655 ortho-substituted, according to the international patent application WO 92/19707 meta-substituted and according to the US Pat. No. 5,972,873 para-substituted phenylboronic acids or their salts or esters. In the international patent application WO 98/13460 and the European patent application EP 583 534 For the same purpose, peptide aldehydes, that is, oligopeptides with reduced C-terminus, are disclosed. Suitable peptidic protease inhibitors include ovomucoid (according to international patent application WO 93/00418 ) and leupeptin; An additional option is the formation of fusion proteins from proteases and peptide inhibitors. Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, for example from European Patent Application EP 0 378 261 or the international patent application WO 97/05227 known, such as succinic acid, other dicarboxylic acids or salts of said acids. In the German patent application DE 196 50 537 For this purpose, end-capped fatty acid amide alkoxylates are disclosed. Certain organic acids used as builders are capable of, as in the international patent application WO 97/18287 discloses additionally stabilizing a contained enzyme. Lower aliphatic alcohols such as ethanol or propanol, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other useful enzyme stabilizers. According to the European Patent Application EP 0 965 268 also protects di-glycerol phosphate against denaturation by physical influences. Likewise frequent calcium salts are used, such as calcium acetate or in the European Patent EP 0 028 865 calcium formate disclosed for this purpose, and magnesium salts, such as the European Patent Application EP 0 378 262 , Reducing reducing agents and antioxidants, such as in the European Patent Application EP 0 780 466 discloses the stability of enzymes to oxidative degradation. sulfuric Reducing agents are for example from the European patents EP 0 080 748 and EP 0 080 223 known. Other examples include sodium sulfite (according to the European Patent Application EP 0 533 239 ) and reducing sugars (according to the European Patent Application EP 0 656 058 ).

Preference is given to using combinations of stabilizers, for example of polyols, boric acid and / or borax according to the international patent application WO 96/31589 , the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids after the European Patent Application EP 0 126 505 or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts as described in U.S. Pat European patent application EP 0 080 223 disclosed. The effect of peptide-aldehyde stabilizers is according to the international patent application WO 98/13462 increased by the combination with boric acid and / or boric acid derivatives and polyols and according to the international patent application WO 98/13459 further enhanced by the additional use of divalent cations, such as calcium ions.

In addition, the partial compositions may contain all ingredients customary in liquid detergents which do not unduly interact negatively with the abovementioned. These include, for example, builder materials, heavy metal chelating agents, non-aqueous water-miscible solvents, thickeners, grayness inhibitors, foam control agents, dye transfer inhibitors, antimicrobial agents, optical brighteners, dyes, and fragrances. If desired, such further ingredients may also be included in the first part composition, provided that they do not unreasonably affect the storage stability of the peracid component.

Builder materials which may be present in the compositions according to the invention are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O 2 _{x + 1} . y H ₂ O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline sheet silicates are described for example in the European Patent Application EP 0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in US Pat German patent application DE 44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. Zeolite P is zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ) marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX® and represented by the formula n Na ₂ O. (1-n) K ₂ O.Al ₂ O _3. (2 - 2.5) SiO ₂ . 3.5-5.5) H ₂ O can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method, for example by means of Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. The acids typically also have, in addition to their builder effect the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. For the purposes of the present specification, the molecular weights stated for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. These data deviate significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard, the molar masses measured against polystyrenesulfonic acids generally being significantly higher. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. To improve the water solubility, the polymers may also allylsulfonic acids, such as from European Patent EP 0 727 448 B1 known allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example, those according to the German patent application DE 43 00 772 A1 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the German patent DE 42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred organic builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE 195 40 086 A1 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties. Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in US Pat European Patent Application EP 0 280 223 described, can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol. A preferred dextrin is in the European patent application EP 0 703 292 A1 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are, for example from the European patent applications EP 0 232 202 . EP 0 427 349 . EP 0 472 042 and EP 0 542 496 as well as the international patent applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A-196 00 018 , A product oxidized at C6 of the saccharide ring may be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable builder materials. In this case, ethylenediamine-N, N'-disuccinate (EDDS), the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US Pat. No. 4,524,009 . US 4,639,325 , in the European Patent Application EP-A-0 150 930 and the Japanese Patent Application JP 93/339896 to be discribed. Further useful organic builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such builders are described, for example, in the international patent application WO 95/20029 described. Builder substances, and among these, in particular, water-soluble materials, are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 1% by weight to 8% by weight.

The complexing agents for heavy metals (also referred to as chelating agents) optionally contained in the compositions include, in particular, phosphoric acid, aminocarboxylic acids and optionally functionally modified phosphonic acids, for example hydroxy- or aminoalkanephosphonic acids. Examples of useful aminocarboxylic acids include nitrilotriacetic acid, methylglycinediacetic acid and diethylenetriaminepentaacetic acid. Examples of phosphonic acids are triphosphonomethylamine, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the disodium salt or tetrasodium salt of this acid, 2-phosphonobutane-1,2,4-tricarboxylic acid or the trisodium salt of this acid, ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs in question. The N-oxides corresponding to the nitrogen-containing compounds mentioned can also be used. The useful complexing agents include ethylenediamine-N, N'-disuccinic acid (EDDS). The complexing agents mentioned in their acid form can be used as such or in the form of their alkali metal salts, in particular the sodium salts. Preference is given to the use of mixtures of aminocarboxylic acids with phosphonic acids. Complexing agents for heavy metals are preferably contained in agents according to the invention in amounts of from 0.05% by weight to 1% by weight, it being possible for them to be present in the first part composition and / or in the second part composition.

Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils. Preferably, silicone oils are used.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether , As well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances draw on the fiber and cause brightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and with the yellowing of yellowed laundry results in pure white. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished composition.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for example B. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions

Since textile fabrics, in particular of rayon, rayon, cotton and mixtures thereof, may be creased because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction, the compositions according to the invention may contain synthetic crease inhibitors which, however, preferably do not contain the first part composition are included. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions of the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with. In order to avoid germination under unfavorable storage conditions, it may, however, be advantageous for the second alkaline subcomposition to comprise a preservative, in which case apart from the antimicrobial active substances mentioned, in particular also Na-N-hydroxymethylglycinate, 3-iodo-2-propynylcarbamate and / or alkali hypochlorite, preferably in amounts of 0.0001 wt .-% to 0.05 wt .-%, is suitable.

Thickening agents which can be used in the partial compositions according to the invention are, for example, those from the class of polyurethanes, polyacrylates which may also be present at least partially crosslinked, polyacrylamides and / or polysaccharides or their derivatives. In addition to carboxylated and / or alkoxylated cellulose, an optionally modified polymer of saccharides, such as glucose, galactose, mannose, gulose, altrose, allose, etc., is suitable as the polysaccharide thickening active. Preferably, a water-soluble xanthan, as it is commercially available, for example, under the product names Kelzan®, Rhodopol®, Ketrol® or Rheozan®. By xanthan is meant a polysaccharide corresponding to that produced by the bacterial strain Xanthomonas campestris from aqueous solutions of glucose or starch ( J. Biochem. Microbiol. Technol. Engineer. Vol. III (1961), pp. 51 to 63 ). It consists essentially of glucose, mannose, glucuronic acid and their acetylation products and also contains minor amounts of chemically bound pyruvic acid. The use of water-soluble polysaccharide derivatives, as can be obtained, for example, by alkoxylation with, for example, ethylene oxide, propylene oxide and / or butylene oxide, by alkylation with, for example, methyl halides and / or dimethyl sulfate, by acylation with carboxylic acid halides or by saponifying deacetylation from the corresponding polysaccharides, is possible , Thickening agents are in the inventive compositions, in particular in the first H ₂ O ₂ -containing part composition, in amounts of preferably 0.05 wt .-% to 2.5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% , whose proportion does not have to be the same in all sub-compositions. Preferably, the first part composition contains thickening agent in an amount that results in a viscosity of the first part composition in the range of 20 mPa.s to 150mPa.s, especially 40 mPa.s to 70 mPa.s (measured at 20 ° C using a conventional rotational viscometer , 20 revolutions per minute). Although the viscosity of the second part composition is outside the range specified for the first part composition, although it is preferably lower, it may, if desired, assume values in the range of, in particular, 5 mPa.s to 250 mPa.s.

The individual partial compositions, especially if only two are present, are preferably used in equal proportions. This can easily be achieved by adjusting the viscosity of the sub-compositions and / or the type of outflow openings of the chambers of the dispenser bottle, in particular the adjustment of the diameters of the outflow openings, so that the user of the agent can easily do so simply by pouring or expressing the dispenser bottle useful amount, for example, the necessary for a wash in a washing machine amount of liquid detergent receives.

example 1

By simply mixing the ingredients listed in the table below in the stated amounts (in% by weight, based on the particular component composition), partial compositions T1 (pH 5.2, viscosity 40 mPas) and T2 (pH 11.2) were prepared. These were each filled into one chamber of a polyethylene dispensing bottle consisting of two chambers of equal size (750 ml each). Table: Partial compositions [% by weight] T1 T2 hydrogen peroxide 7.5 - Nonionic surfactant ^a) 0.5 - Anionic surfactant ^b) 2 - Na-carbonate - 2.5 NaOH - 0.06 Na citrate - 0.2 Phosphonate ^c ) 0.15 0.001 Aminocarboxylate ^d ) 0.3 - Radical scavengers ^e ) 0.03 - Na-hypochlorite - 0.0005 ethanol 2 - xanthan 0.1 - polydimethylsiloxane 0,015 - Dyes and perfumes 0.05 - water on 100 on 100 a): C _12-14 fatty alcohol, 4-fold propoxylated and 5-fold ethoxylated
b): C _12-14 fatty alcohol + 2-EO-sulfate triethanolamine salt
c): hydroxyethanediphosphonic acid (Turpinal® SL)
d): Methylglycinediacetic acid trisodium salt
e): butylhydroxytoluene

Example 2

Instead of the partial composition T2 mentioned in Example 1, the partial composition T1 was mixed with a 5 weight percent aqueous solution of triethanolamine (T3, pH 10.9), with a 5 weight percent aqueous solution of monoethanolamine (T4, pH 11.7) or an aqueous solution, which was obtained by soaking vopn 3% by weight of monoethanolamine and 1% by weight of citric acid (T5, pH 10.2) in the double-chambered bottle as in Example 1. Upon exiting the ejection nozzles, immediately after mixing the two partial compositions, the pHs of the mixtures were 9.2 (T1 + T3), 10.2 (T1 + T4), and 9.8 (T1 + T5).

Claims (45)

1. Dispenser bottle for a liquid aqueous washing composition which consists of at least two, preferably exactly two, part-compositions kept separate from one another, and the dispenser bottle has a first receiving vessel (1) and at least one, preferably exactly one, second receiving vessel (2) and the first receiving vessel (1) contains a first part-composition and the second receiving vessel (2) a second part-composition, the two receiving vessels (1, 2) either being designed separately or connected to one another or designed together in one piece, the receiving vessels (1, 2) each having an outlet (3, 4) for the part-composition and the outlets (3, 4) being arranged adjacently to one another such that the two part-compositions can be applied in a common application field (5) of an application region, the outlets (3, 4) each further being equipped with at least one, preferably with exactly one, expulsion nozzle (6, 7), so that the part-compositions are not mixed with one another until after they leave the expulsion nozzles (6, 7), the expulsion nozzles additionally being closable (6; 7) with a removeable closure cap (14), characterized in that the first part-composition comprises water, hydrogen peroxide and surfactant and has an acidic pH and the second part-composition has an alkaline pH, the closure cap (14) having a closure stopper (15) which enters into the expulsion nozzle (6; 7) laterally, in addition to the closure stopper (15) entering into the expulsion nozzle (6; 7), in each case a cylinder section (19) arranged convex to the longitudinal axis of the closure cap (14) as a positioning aid, the cylinder section (19) being spaced apart from the closure stopper (15) such that the free ends of the particular cylinder sections (19) adjoin the expulsion nozzles (6, 7) in closure position.
2. Dispenser bottle according to Claim 1, characterized in that the receiving vessels (1, 2) are designed as compressible containers.
3. Dispenser bottle according to Claim 2, characterized in that the receiving vessels (1, 2) consist of a material with resilient characteristics and/or have a shape which supports reset to the original shape.
4. Dispenser bottle according to one of Claims 1 to 3, characterized in that the receiving vessels (1, 2) consist of a polymer material.
5. Dispenser bottle according to Claim 4, characterized in that the material of the receiving vessels (1, 2) is a polyolefin, especially a polypropylene (PP), a polyethylene (PE), a polyvinyl chloride (PVC), a polyethylene terephthalate (PET) or a glycol-modified polyethylene terephthalate (PETG).
6. Dispenser bottle according to one of Claims 1 to 5, characterized in that the receiving vessels (1, 2) have equal volumes and/or an identical shape, especially a shape identical in mirror image.
7. Dispenser bottle according to one of Claims 1 to 6, characterized in that the receiving vessels (1, 2) are designed as in each case complete containers and are only connected to one another via at least one, preferably exactly one, connecting element (8) formed between the receiving vessels (1, 2), the one connecting element (8) preferably being arranged in about the middle and extending essentially - optionally with interruptions - over the full length of the receiving vessels (1, 2).
8. Dispenser bottle according to one of Claims 1 to 7, characterized in that the receiving vessels (1, 2) designed together in one-piece form and preferably produced in a blow-molding process have different transparency and/or different color, and, in particular, one receiving vessel (1) has an opaque design, the other receiving vessel (2) a transparent design.
9. Dispenser bottle according to one of Claims 1 to 8, characterized in that the receiving vessels (1, 2) each have such a cross section that they can be grasped, at least for the most part, by the hand of a user.
10. Dispenser bottle according to Claim 9, characterized in that a holding region (9) to be grasped by the hand of a user is formed and/or indicated by special edge moldings (10, 11) and/or surface configurations on the receiving vessels (1, 2).
11. Dispenser bottle according to Claim 9 or 10, characterized in that the receiving vessels (1, 2) have, in cross section, in the holding region (9) to be grasped by the hand of a user, an outer circumference of from approx. 18 to approx. 30 cm, preferably of from approx. 20 to approx. 28 cm, in particular of from approx. 22 to approx. 26 cm, very particularly of approx. 24 cm.
12. Dispenser bottle according to one of Claims 1 to 11, characterized in that the shape and the dimensions of the expulsion nozzles (6; 7) and the properties of the active substance fluids are adjusted relative to one another such that - with average pressure from the hand of a user and/or by virtue of gravity - the fluid streams overlap at a certain, precalculated distance.
13. Dispenser bottle according to Claim 12, characterized in that the fluid streams overlap at a distance of from about 50mm to about 300 mm, preferably of from about 100 mm to about 250 mm, in particular of about 150 mm.
14. Dispenser bottle according to one of Claims 1 to 13, characterized in that the outlets (3; 4) are aligned so as to be inclined toward one another or, preferably, are aligned essentially parallel to one another.
15. Dispenser bottle according to one of Claims 1 to 14, characterized in that the expulsion nozzle (6; 7) is shaped integrally at the outlet (3; 4) on the receiving vessel (1; 2).
16. Dispenser bottle according to one of Claims 1 to 15, characterized in that the expulsion nozzle (6; 7) is arranged or shaped in a separate nozzle head (12) consisting preferably of a dimensionally stable plastic, and in that the nozzle head (12) is attached to the receiving vessel (1; 2) at the outlet (3; 4).
17. Dispenser bottle according to Claim 16, characterized in that the nozzle head (12) is snap-fitted to the receiving vessel (1; 2).
18. Dispenser bottle according to Claim 16 or 17, characterized in that the nozzle heads (12) of the two receiving vessels (1; 2) are combined in a common nozzle head (12).
19. Dispenser bottle according to one of Claims 16 to 18, characterized in that the expulsion nozzle (6; 7) is arranged asymmetrically in the nozzle head (12), especially offset in the direction of the further expulsion nozzles (7; 6),with respect to the center line of the outlet (3; 4).
20. Dispenser bottle according to one of Claims 16 to 18, characterized in that the nozzle head (12) has an inflow volume (13) narrowing from the outlet (3; 4) of the receiving vessel (1; 2) toward the expulsion nozzle (6; 7).
21. Dispenser bottle according to one of Claims 1 to 20, characterized in that the lateral midpoint separation of the expulsion nozzles (6; 7) externally is from about 5 mm to about 30 mm, preferably from about 15 mm to about 20 mm.
22. Dispenser bottle according to one of Claims 1 to 21, characterized in that the expulsion nozzles additionally being closable (6; 7) with a removable closure cap (14), the removable closure cap (14) consists of a dimensionally stable polymer.
23. Dispenser bottle according to Claim 22, characterized in that the closure caps (14) of the two expulsion nozzles (6; 7) are combined in a common closure cap (14).
24. Dispenser bottle according to one of Claims 1 to 23, characterized in that the nozzle channels (16; 17) of the expulsion nozzles (6; 7) are inclined toward one another.
25. Dispenser bottle according to one of Claims 1 to 23, characterized in that the nozzle channels (16; 17) of the expulsion nozzles (6; 7) are aligned essentially parallel to one another.
26. Dispenser bottle according to Claim 24 or, in particular, Claim 25, characterized in that the nozzle channels (16; 17) of the expulsion nozzles (6; 7) each have a cross-sectional constriction (18) arranged asymmetrically to the overall flow cross section.
27. Dispenser bottle according to Claim 26, characterized in that the cross-sectional constriction (18) of the nozzle channel (16; 17) is designed with angular transitions.
28. Dispenser bottle according to Claim 26 or 27, characterized in that the cross-sectional constrictions (18) are arranged on the sides of the nozzle channels (16; 17) facing one another, in such a way that the streams of the active substance fluids exiting under pressure have such a swirl that they run toward one another.
29. Dispenser bottle according to one of Claims 26 to 28, characterized in that the cross-sectional constriction (18) is designed as a circle section, as a geometric figure projecting inward, especially concavely, in an inwardly curved manner or the like.
30. Dispenser bottle according to one of Claims 26 to 29, characterized in that the length of the cross-sectional constriction (18) of the nozzle channel (16; 17) is only part of the length of the nozzle channel (16; 17) as a whole.
31. Dispenser bottle according to Claim 30, characterized in that the length ratio is from about 1:2 to about 1:4, preferably from about 1:2.5 to about 1:3.
32. Dispenser bottle according to one of Claims 1 to 31, characterized in that the total length of the nozzle channel (16; 17) is from about 2 to about 6 mm, preferably from about 3 to about 5 mm, in particular about 4 mm.
33. Dispenser bottle according to one of Claims 1 to 32, characterized in that the nozzle channel (16; 17) is canted at its end, the opening plane of the nozzle channel (16; 17) being arranged such that the inner section of the wall (20) with respect to the longitudinal axis of the nozzle channel (16; 17) is longer than the outer section of the wall (20) with respect to the longitudinal axis of the nozzle channel (16; 17).
34. Dispenser bottle according to one of Claims 1 to 33, characterized in that the diameter of the nozzle channel (16; 17) is from about 1.0 mm to about 4.0 mm, preferably from about 1.5 mm to about 3.5 mm, in particular from about 2.0 mm to about 2.5 mm.
35. Dispenser bottle according to one of Claims 1 to 34, characterized in that the first part-composition contains from 1.5% by weight to 15% by weight, in particular from 2.5% by weight to 10% by weight, of hydrogen peroxide.
36. Dispenser bottle according to one of Claims 1 to 35, characterized in that the first part-composition contains from 1% by weight to 20% by weight, in particular from about 1.5% by weight to 10% by weight, of surfactant.
37. Dispenser bottle according to one of Claims 1 to 36, characterized in that the first part-composition comprises nonionic surfactant, especially alkoxylated fatty alcohol, and/or anionic surfactant, especially sulfation product of an alkoxylated fatty alcohol.
38. Dispenser bottle according to one of Claims 1 to 37, characterized in that the first part-composition contains from 50% by weight to 95% by weight, in particular from 60% by weight to 90% by weight, of water.
39. Dispenser bottle according to one of Claims 1 to 38, characterized in that the first part-composition has a pH in the range from 3.5 to below 7, in particular from 4 to 6.5 and preferably from 5.0 to 6.0.
40. Dispenser bottle according to one of Claims 35 to 39, characterized in that the first part-composition additionally comprises chelating agent, water-miscible solvent, free-radical scavenger, dye and/or fragrance.
41. Dispenser bottle according to one of Claims 35 to 40, characterized in that the first part-composition additionally comprises thickener in an amount which leads to a viscosity of the first part-composition in the range from 20 mPa.s to 150 mPa.s, in particular from 40 mPa.s to 70 mPa.s (20°C, rotary viscometer, 20 revolutions per minute).
42. Dispenser bottle according to one of Claims 1 to 41, characterized in that the water content of the second part-composition is up to 99.95% by weight and is preferably in the range from 50% by weight to 98% by weight, in particular from 60% by weight to 95% by weight.
43. Dispenser bottle according to one of Claims 1 to 42, characterized in that the second part-composition has a pH in the range from 9.5 to 13.5, in particular from 11 to 13.
44. Dispenser bottle according to one of Claims 1 to 41, characterized in that the second part-composition is anhydrous and contains such an amount of substances alkaline in water that, after mixing with the first part-composition in a volume ratio of 1:1, the resulting pH is at least 1 unit, in particular at least 1.5 units above that of the first part-composition.
45. Use of a dispenser bottle according to one of the preceding claims for applying laundry detergents.

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