WO2006045450A1 - Detergent or cleaning agent dosing unit - Google Patents

Detergent or cleaning agent dosing unit Download PDF

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Publication number
WO2006045450A1
WO2006045450A1 PCT/EP2005/011064 EP2005011064W WO2006045450A1 WO 2006045450 A1 WO2006045450 A1 WO 2006045450A1 EP 2005011064 W EP2005011064 W EP 2005011064W WO 2006045450 A1 WO2006045450 A1 WO 2006045450A1
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Prior art keywords
preferably
ch
characterized
wt
combination product
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PCT/EP2005/011064
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German (de)
French (fr)
Inventor
Pavel Gentschev
Arnd Kessler
Ulrich Pegelow
Christian Nitsch
Arno DÜFFELS
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority to DE102004051560.3 priority Critical
Priority to DE200410051560 priority patent/DE102004051560A1/en
Priority to DE102004055075.1 priority
Priority to DE200410055075 priority patent/DE102004055075A1/en
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2006045450A1 publication Critical patent/WO2006045450A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/04Detergent materials characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/04Detergent materials characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means

Abstract

Disclosed are combination products for mechanical dishwashing, comprising a) a compartment that contains a detergency booster, b) another compartment which contains a main cleaning agent, and c) instructions which tell the user to use the detergency booster in the preliminary washing cycle and the main cleaning agent in the main washing cycle of a mechanical dishwashing process. The inventive combination products are characterized by an improved cleaning power while the water consumption and energy consumption during the mechanical dishwashing process are reduced.

Description

Washing or Reinigungsmitteldosiereinheit

The present invention is in the field of laundry detergents or cleaning compositions, especially combination products for machine dishwashing.

Machinery GeschirrspDImittel are available to the consumer in various supply forms. In addition to powders and granules offer this example also includes cleaning concentrates in the form of extruded or tableted compositions. These solid, concentrated or compacted forms are characterized by a reduced volume per dosage unit and thus reduce the cost of packaging and transport. In particular, the washing or cleaning agent tablets also fulfill the wish of the consumer for easy dosing. The respective means are described comprehensively in the prior art. In addition to the cited advantages, however, compacted detergents also a number of disadvantages. In particular, the form of tablets are distinguished for their high compaction frequently delayed disintegration and thereby a delayed release of their ingredients. To dissolve this "conflict" between adequate tablet hardness and short disintegration times numerous technical solutions have been disclosed in the patent literature, is to be being made at this point by way of example to the use of so-called tablet disintegrators. This disintegration accelerators are the tablets additionally added to the washing or cleaning-active substances , themselves generally have no active washing or cleaning properties, and thus increase the complexity and cost of these funds. A further disadvantage of tableting active substance mixtures, in particular washing or cleaning active-substance-containing mixtures, the inactivation of the contained active substances by the occurring during tableting compacting. inactivation of the active ingredients can also be due to the increased in consequence of the tableting contact surfaces of the ingredients by chemical reaction e rfolgen.

As an alternative to the above described particulate or compacted detergents solid or liquid washing or cleaning agents are described in recent years, increasingly, which have a water-soluble or water-dispersible packaging. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer package in the washing machine or dishwasher, but on the other hand they allow the same time the formulation of liquid or powdered detergents, which is improved over the compacts by a dissolution and more rapid activity are characterized. For example, the EP 1 314654 A2 (Unilever) discloses a dome-shaped pouch open with a receiving chamber which contains a liquid.

however, the subject of WO 01/83657 A2 (Procter & Gamble) are bags containing two particulate solids in a receiving chamber, each of which are present in fixed regions and do not mix with each other.

In addition to packaging, that only have a receiving chamber disclosed in the prior art, other product forms which comprise more than one receiving chamber or more than one formulation form.

The subject of European Application EP 1,256,623 A1 (Procter & Gamble) is a kit comprising at least two bags with different composition and different optics. The bags are separated from one another and not as a compact single product.

A method for the production of multi-chamber bags by gluing two single chambers describes the international application WO 02/85736 A1 (Reckitt Benckiser).

Despite the previously described wide variety of presentation forms for dishwasher detergents it is still a need to improve the cleaning performance of these products, preferably at the same time saving energy and water in the implementation of machine dishwashing. To solve this problem in the prior art in the past in particular, new agents such as new enzymes, new surfactants or new polymers have been disclosed. However, the production and use of such new compounds are limits as to provide new active substances is usually associated with high effort and cost.

Therefore, the present application was the object 2ugrunde to provide a dishwasher detergent comprising, based on the previously known forms and offer raw materials, preferably while reducing water and energy consumption during the automatic dishwashing process, an improved cleaning and Klarspülprofil.

This object was achieved by a combination product for machine dishwashing, comprising a wash booster for the prewash, a main detergent for the main wash cycle and instructions for the proper dosing of these agents. A first object of the present application is therefore a Kombinatiorisprodukt for machine dishwashing, comprising a) a compartment containing a detergency booster; b) a further compartment containing a main cleaning agent; and c) instructions for use, which instructs the user to use the washing power amplifier in the pre-rinse cycle and the use of the main detergent in the main wash cycle of an automatic dishwashing process.

The included in the inventive compositions detergency booster and main cleaning agents act in successive wash cycles of a machine Geschirrspülgangs, supplement and / or reinforce each other in terms of their effect and provide improved cleaning and rinsing performance. The instructions allow the presentation and communication of the exact operating manner of detergency boosters and main cleaning means for achieving the beneficial effect of the agent. This representation or communication can occur for example in pictorial and / or written and / or acoustic means.

In the detergency booster and the main detergent is two machine dishwashing detergents of different composition. For the assembly of these two means of combination product are open to a variety of different ways, one of which subsequently the most preferred in the context of the present application possibilities will be discussed in more detail.

In a first preferred embodiment of the detergency booster and the main cleaning means comprises at least one common packaging system. In such a presentation form of detergency boosters and the main detergent are available in a common primary and / or secondary packaging. the packaging case is referred to as primary packaging which is on its inner side directly to the detergency boosters and / or the main cleaning agent in contact. As a common primary packaging for laundry booster and main cleaning agent, for example, sacks or bags are suitable. The group of these sacks and bags, including for example those packaging systems, has come to be to their name in the art, the term "flow pack". The secondary packaging serves to further packaging and labeling of the funds contained in the primary packaging and is not directly with these agents contact. the secondary packaging typically corresponds to the outer packaging of the sales product. Examples of such secondary packaging cardboard or foil pouch, for example in the form of a stand-up pouch.

The preferred use as packaging systems sacks or bag of single-layer or laminated paper or plastic film can be designed in different ways, for example as inflated pouches without seam or as a bag with a center seam which by heat (heat fusing), adhesives or adhesive tapes closed become. Single-layered bag or bag materials are the known papers, which may be optionally impregnated, and plastic films, which may be co-extruded, if necessary. Plastic films which can be used in the present invention as a packaging system, "Plastics and their Properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 shown, for example, in Hans Domininghaus. The illustration 111 shown there are simultaneously indications of the water vapor permeability of the said materials.

In the present invention, particularly preferred combinations comprise a packaging system comprising a sack or bag of single-layer or laminated plastic film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and especially from 25 to 50 microns.

Combination products, characterized in that the detergency booster and the main cleaning agent have different packaging systems are preferred in this invention. As the "different" packaging systems are thereby referred to packaging systems which differ (composition, thickness, etc.) due to their chemical or physical properties. An example is a detergency booster and a main cleaning agents, which are present packed into different bags or sacks.

in the context of the present application in particular such combination products in which the detergency booster and the main cleaning means are surrounded by a common primary packaging are preferred, wherein the amount of the automatic dishwashing agent present in the primary packaging is preferably of the dosing unit for an application, that is for a machine wash cycle, corresponding to , With particular preference, several of these packaged primary dosing machine for a wash cycle are packaged together in an additional secondary packaging. In a particularly preferred embodiment, this first secondary packaging is surrounded by a second secondary packaging. In a further preferred embodiment, the detergency booster and the main detergent different primary packaging, however, a common secondary packaging. This common secondary packaging may optionally be surrounded by a second secondary packaging.

Packaging systems in which the detergency booster and the main detergent neither primary nor a joint having a common secondary packaging continue to be preferred. Combination product, characterized in that the detergency booster and the main cleaning agent having no common packaging system are preferable in the invention.

Some preferred packaging systems are summarized in the following table, with one row of the table contains each the data for a preferred packaging system. The primary packaging 1 and 2 and the secondary packages 1 and 2 may consist of the same or of different material.

Figure imgf000006_0001
At least one of the packages used (primary or secondary packaging) preferably has a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system at 23 ° C and a relative equilibrium humidity of 85 is stored%. The temperature and humidity conditions are the test, which are mentioned in the DIN standard 53122, in which, according to DIN 53122 minimal deviations (23 ± 1 ° C, 85 ± 2% rel. Humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods, and for example, in ASTM Standard E-96-53T ( "test for measuring Water Vapor transmission of Materials in Sheet form") and TAPPI Standard T464 m-45 ( "Water Vapor Permeability of Sheet Materials at high temperature to Humidity") described below. The measurement principle of common techniques is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, which container at the top is closed by the material to be tested. From the surface of the container which is sealed with the material to be tested (permeation), the weight increase of the calcium chloride and the exposure time, the moisture vapor transmission rate subsides

FDDR = 2A .lambda..sub.m ".ϊ- [g lm> mh] A y

calculate, where A is the area of the material to be tested in cm 2, x, the weight gain of the calcium chloride in g and y is the time of exposure in h.

The equilibrium relative humidity, often referred to as "relative humidity", in the measurement of moisture vapor transmission rate within the scope of the present invention is 85% at 23 ° C. The ability of air to water vapor increases with temperature up to a particular maximum content, the so-called saturation level, and is indicated in g / m 3. for example, 1 m 3 of air at 17 ° saturated with 14.4 g of water vapor, at a temperature of 11 ° saturation is before with 10 g of water vapor. the relative humidity is in expressed as a proportion ratio of the actually existing water vapor content at the prevailing temperature the corresponding saturation content. If, for example, air at 17 ° 12 g / m 3 of water vapor, the relative humidity = (12 / 14.4) -100 is = 83% . on cooling this air, the saturation is the so-called dew point (100% r L..) (in this example: 14 °) is reached, that is, when w eiterem cooling, a precipitate in the form of mist (Tau) forms. For the quantitative determination of moisture to use hygrometers and psychrometers. The relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control, depending on the type of device to +/- 2% RH precisely adjusted. Also over-saturated solutions of certain salts constant and well-defined relative humidities are formed from in closed systems at a given temperature, based on the phase equilibrium between the partial pressure of the water, a saturated solution and solid substance.

Combination product, characterized in that at least one of the packaging systems having a moisture vapor permeability rate of 0.1 g / m2 / day to less than 20g / m2 / day when the packaging system at 23 0 C and a relative equilibrium humidity is supported by 85% are prefers.

In the present invention, preferred packaging systems have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day.

The packaging system of the combination of the invention can be made of many different materials and may assume any desired outer shapes. For economic reasons and for reasons of ease of processing, packaging systems, however, are preferred in which the packaging material is lightweight, easy to handle and is inexpensive. In accordance with the invention preferred combinations of the packaging system consists of a sack or bag of single-layer or laminated paper and / or plastic film.

The agents may unsorted, ie to be filled as a loose bed, in a pouch made of said materials. However, it is preferred for aesthetic reasons and for sorting of the combinations in secondary packaging, the washing and cleaning composition shaped bodies individually or sorted to a plurality of filling into bags or pouches. For individual application units of washing and cleaning tablets, which are in a bag or pouch, are suitable, for example, the aforementioned "flow packs".

As mentioned above, the detergency boosters and the main cleaning agent of the inventive combination contain, depending on their intended use ingredients of machine Geschirrspülmitten in varying amounts. Preferred detergency booster and main detergent are characterized in that the detergency booster or the main cleaning means has / have a relative equilibrium humidity of less than 30% at 35 ° C. The equilibrium relative humidity of the detergency booster and main detergent may be determined by conventional methods, one using the following procedure was chosen in the present studies: A water-impermeable 1 -Liter- vessel with a lid having a closable opening for the introduction of samples was charged with filling a total of 300 g detergency booster or main detergent and 24 h maintained at a constant 23 C C to ensure a uniform temperature of vessel and substance. The water vapor pressure in the space above funds can then be determined using a hygrometer (hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes, until two successive values ​​show no deviation (Gleichgeichtsfeuchtigkeit). The above hygrometer allows direct display of the recorded values ​​in% relative humidity.

In summary, both such means are within the scope of the present application as combination products in the context of the present application, in which the detergency booster and the main cleaning agent are present together in a primary and / or secondary packaging, as well as those compositions in which the detergency booster and the main detergent in one another be separated primary or secondary packaging.

The detergency boosters and main detergent contained in the inventive combination products may be in solid or liquid form. As formulation forms, for example, liquid (e) are t (s), in particular melting, and / or gel (e) and / or powder and / or granular material (s) and / or extrudate (s) and / or compact.

The term "liquid" means in the present application substances or mixtures, as well as solutions or suspensions, which are present in the liquid state.

Combination products, characterized in that the detergency booster and / or the main cleaning agent in the form of liquid is / are present, are preferred in the invention.

Powder is a general term for a form of fragmentation of solids and / or mixtures of substances which are obtained by crushing, i.e., grinding or crushing in a mortar (pulverizing), grinding in mills, or as a result of atomization or freeze dryings. A particularly fine division is often called atomization or micronization; the respective powders are referred to as micro-powder. After the grain size is a rough division of the powders in coarse, fine u. Impalpable powder usual; a more accurate classification of powdered bulk goods via bulk density and by sieve analysis. In the present application, preferred powder, however, have lower particle sizes below 5000 microns, preferably less than 3000 microns, preferably less than 1000 microns, most preferably between 50 and 1000 .mu.m and in particular between 100 and 800 microns.

Powders can be compacted by extrusion, pressing, rolling, briquetting, pelletizing and related methods and agglomerate. Each of the known particulate mixtures in the prior art for the agglomeration method is in principle suitable for producing the solids contained in the agents. In the present invention, preferably as a solid (s) used agglomerates in addition to the granules, the compacts and extrudates.

Combination products, characterized in that the detergency booster and / or the main cleaning agent is / are present in the form of a powder are preferable in the invention.

As granules clusters of granules are referred. A Granulatkom (granule) is an asymmetric aggregate of powder particles. Granulation are described in the prior art wide. Granules can be prepared by wet granulation, by dry granulation or compaction and by granulation of solidified melts.

The most common granulation is wet, as this technique is subject to the fewest restrictions and most reliable for producing granules with favorable properties. Wet granulation is effected by moistening the powder mixtures with solvents and / or Lösungsmitteigemischen and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds, or spray towers, said mixer can be equipped for example with stirring and kneading tools. However, combinations of the fluidized bed (s) and mixer are various mixers for granulation (s), or combinations of these. The granulation is carried out depending on the starting material and the desired product properties, under the action of low to high shear forces.

When the granulation in a spray tower may have as starting materials, for example melting (melt solidification) or preferably aqueous, slurries (spray drying) of solid substances are used, which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and at the incurred bottom of the tower as granules. The melt solidification is generally very low melting point for forming substances which are stable in the range of the melting temperature (eg. As urea, ammonium nitrate u. Diverse formulations such as enzyme concentrates, drugs, etc.), the respective granulates are also referred to as prills. Spray drying is used especially for the manufacture of detergents or detergent ingredients.

Other agglomeration techniques described in the prior art, the extruder or Lochwalzengranulierungen in which optional granulation offset Puivergemische during pressing through perforated plates (extrusion) or are plastically deformed to piercing rolls. The products of the extruder granulation are also known as extrusions.

Combination products, characterized in that the detergency booster and / or the main cleaning agent is / are present in the form of granules are preferred in the invention.

As additional offer form for the detergency boosters and the main detergent especially the compacts and especially the tablets are. Combination products, characterized in that the detergency booster and / or the main cleaning agent in the form of a compacted, preferably in the form of a tablet are preferred in the invention.

Of particular advantage with regard to the improved cleaning and rinsing results are combination products according to the invention, in which the detergency booster in particulate form, preferably in the form of a powder or granules, while the main detergent in the form of a compact dosage unit, preferably in the form of a tablet or a filled water-soluble container is present ,

As explained above, it is in the detergency booster and the main detergent to machine dishwashing detergents of different composition. As ingredients of washing power amplifier is in principle all the skilled person are known as ingredients of dishwasher detergents active substances. To be particularly advantageous, however, such washing power amplifiers have proven to contain at least one member selected from the group of builders or bleaching agent. Combination products, characterized in that the detergency booster a builder and / or a bleaching agent, preferably in quantities above 10 wt .-%, preferably contain above 20 wt .-% and in particular above 40 wt .-%, are preferred in the invention. Among the Builders in particular include the phosphates, silicates and alkali carrier.

Among the multitude of commercially available phosphates, the alkali metal phosphates are the most important with particular preference for pentasodium or Pentapotassium (sodium or potassium) in the detergents and cleaners industry.

Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which n and orthophosphoric acid H 3 PO may in addition to higher molecular weight representatives metaphosphoric acids (HPO 3). 4 The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime encrustations in fabrics, and furthermore contribute to cleaning performance.

Suitable phosphates, for example, the sodium dihydrogen phosphate, NaH 2 PO 4, in the form of the dihydrate (density 1, 91 like "3, melting point 60 °) or in the form of the monohydrate (density 2.04 liked" 3), disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4, which is in anhydrous or with 2 mol (density 2.066 gcm -3, water loss at 95 °), 7 mol (density 1, 68 like "3, melting point 48 ° with loss of 5 H2O) and 12 mol water (density 1, 52 gcm -3, melting point 35 ° with loss of 5 H2O) may be used, but in particular trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4, which (as the dodecahydrate, as the decahydrate corresponding to 19-20% P Z O 5) and (in anhydrous form, corresponding to 39-40% P 2 O 5) can be used.

Another preferred phosphate is tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4. Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 are further preferred, which in anhydrous form (density 2.534 like "3, melting point 988 °, 880 ° shown) and as the decahydrate (density 1, 815-1, 836 like" 3, melting point 94 ° there is loss of water), and the corresponding potassium salt, potassium diphosphate (potassium pyrophosphate), K 4 P 2 O. 7

The industrially important pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) is an anhydrous or with 6 H 2 O crystallizing, non-hygroscopic, colorless, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n Na with n =. 3 The corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 0 (potassium tripolyphosphate), is marketed for example in the form of a 50 wt .-% - solution (> 23% P 2 O 5, 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the detergents and cleaners industry. Sodium potassium tripolyphosphates, which may also be used in the present invention exist. These are formed for example when sodium trimetaphosphate hydroiysiert with KOH:

(NaPO 3) 3 + 2 KOH → Na 3 K 2 P 3 O 10 + H 2 O

These are according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and sodium, or mixtures of and Kaliumtripoiyphosphat and sodium are used according to the invention.

Used in the context of the present application phosphates as part of the washing power amplifier, these means comprise the / the phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium), preferably in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent booster.

Preferably, it is in particular potassium tripolyphosphate and sodium tripolyphosphate at a weight ratio of more than 1: 1, preferably more than 2: 1, preferably greater than 5: 1, more preferably greater than 10: 1 insert: 1 and in particular more than the twentieth It is particularly preferred to use exclusively potassium tripolyphosphate without additions of other phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1

H 2 O wherein M is sodium or hydrogen, x is a number from 1: 9 to 4 and y is a number from 0 to 20, preferred values for x being 2, 3 or. 4 Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. In particular, both .beta.- and δ-sodium Na 2 Si 2 O 5 y H 2 O are preferred.

With particular preference, in particular as part of the washing power amplifier, crystalline layered silicates of general formula NaMSi x O 2x + 1 y H 2 O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1 , 9 to 4 and y is a number from O to 33rd The crystalline layered silicates of the formula NaMSi x O 2x + I

y H 2 O, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 x H 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 x H 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 Oi x 7 H 2 O) or Na SKS-4 (Na 2 Si 4 O 9 x H 2 O, makatite). Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi x O 2x + I "y H 2 O, in which x stands for 2 h. Of these, especially Na-SKS-5 (CX-Na are 2 Si 2 O 5), Na-SKS-7 (B-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 H 2 O), Na-SKS-10 (NaHSi 2 O 5 3 H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 0 5) and Na-SKS-13 (NaHSi 2 O 5), but in particular Na-SKS-6 (5-Na 2 Si 2 O 5).

When the silicates are used as part of the washing power amplifier, these means preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x O 2x + 1 y H 2 O from 0.1 to 20 wt .-%, from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred, especially if such weight dishwasher detergents have a total silicate content below 7 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, more preferably below 4 wt .-%, most preferably below 3 .-% and in particular below 2.5 wt .-% have, wherein this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to at least 90 wt .-% to silicate of the formula NaMSi x O 2x + - is I y H 2 O.

Other useful builders are amorphous sodium silicates with an Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and more preferably 1: 2 to 1: 2.6, which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention is also meant "X-ray", the term "amorphous". This means that the silicates do not produce sharp X-ray reflexes in X-ray diffraction experiments, as it is typical of crystalline substances, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, it may very well even lead to particularly good builder properties if the silicate particles yield blurred or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted so that the products have microcrystalline regions with a size ten to several hundred nm, values ​​up to max. 50 nm and especially up to max. 20 nm are preferable. Such X-ray amorphous silicates likewise have retarded dissolution compared with traditional water glasses. Particular preference is given to compressed / compacted amorphous silicates, compounded amorphous silicates and over dried X-ray amorphous silicates. In the present invention, it is preferred that these (s) silicate (s), preferably alkali metal silicates, with particular preference crystalline or amorphous alkali metal disilicates, in amounts of from 10 to 60 wt .-%, preferably from 15 to 50 wt .-%, and in particular from 20 to 40 wt .-%, in each case based on the weight of the washing power amplifier.

Other preferred builders are the alkali carriers. As alkali carriers, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonate, said alkali metal silicates, alkali metal metasilicates and mixtures of the aforementioned substances are, with the purposes of this invention, preferably, the alkali metal carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. The alkali metal hydroxides are preferred in the Waschkraftverstäreker only in small amounts, preferably in quantities below 30 wt .-%, preferably below 20 wt .-% relative, more preferably below 15 wt .-% and particularly below 12 wt .-%, in each the total weight of the washing power amplifier used.

Particularly preferred is the use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular 7.5 to 30 wt .-%, each based on the weight of the detergent booster.

As organic cobuilders polycarboxylates / polymeric polycarboxylates, polyacetals, dextrins, other organic cobuilders are in particular (see below) and to name phosphonates. These classes are described below.

Useful organic builders are, for example usable in the form of their sodium salts polycarboxylic acids, with such carboxylic acids are understood to polycarboxylic acids which carry more than one acid function. For example, this citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic are (NTA), providing their use for environmental reasons is not objectionable, and mixtures thereof. 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 per se can be used. The acids Besides their builder effect also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergents or cleaners. Citric acid, succinic acid, adipic acid, gluconic acid and any mixtures thereof are particularly mentioned.

As builders, polymeric polycarboxylates are also suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

At the indicated for polymeric polycarboxylates molecular weights are within the meaning of this specification, weight-average molecular weights Mw of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV-detector. The measurement was made against an external polyacrylic acid standard, which owing to its structural similarity to the polymers under investigation, provides realistic molecular weight. These figures differ significantly from the molecular weights measured against polystyrene sulfonic acids as standard. The measured against polystyrenesulfonic acids are significantly higher than the molecular weights mentioned in this specification generally.

Particularly suitable polymers are 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 molecular weights of 2,000 to 10,000 g / mol in this group may in turn, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Particularly suitable copolymers of acrylic acid with maleic acid which contain from 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% of maleic acid. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and especially 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The amount of washing or cleaning agents (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

In order to improve the water solubility of the polymers can also contain allyl sulfonic acids such as allyloxybenzenesulfonic acid and Methallyisulfonsäure, as monomers. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or the salts of acrylic acid and of 2-Alkyla lylsulfonsäure as monomers as monomers! And sugar are derivatives.

Other preferred copolymers are those which contain as monomers, acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Similarly, other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Particularly preferably polyaspartic acids or their salts.

Combination products, characterized in that the detergency booster a builder, preferably in quantities above 10 wt .-%, preferably above 20 wt .-% containing and in particular above 40 wt .-%, are preferred in the invention.

In a further preferred embodiment of the detergency booster containing a chlorine bleach or a Brombleichmittel. Suitable chlorine- or bromine-releasing materials, examples include heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, Tribromisocyanu 'rsäure, dibromoisocyanuric and / or

Dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. The content of the washing power amplifier to chlorine or Brombleichmitteln is preferably between 0.1 and 30 wt .-%, preferably between 0.2 and 25 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0 , 8, and 15 wt .-%. The chlorine or Brombleichmittel-containing detergency boosters are preferably packaged in liquid form.

Alternatively, or in addition to the chlorine or Brombleichmittel the detergency booster may contain an oxygen bleach. Preferred combination products are characterized in that the detergency booster containing an oxygen bleaching agent. Among the compounds used as bleaching agents in water H 2 O 2 compounds, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H2 O2 -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or Phthaloiminopersäure. Furthermore, bleaching agents from the group of organic bleaches can be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids being mentioned in particular as examples the alkyl and aryl peroxyacids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid

[Phthaliminoperoxyhexansäure (PAP)], o-Carboxybenzamidoperoxycapronsäure, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids which, 2- Decyldiperoxybutan- 1, 4-dioic acid, N, N-terephthaloyl-di (6-aminopercaproic acid) may be used. With particular preference, the wash booster dibenzoyl peroxide and / or sodium included. The content of the washing power amplifier of oxygen bleaching agents is preferably between 0.1 and 30 wt .-%, preferably between 0.2 and 25 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 15 wt .-%. The oxygen bleach-containing detergency booster are preferably formulated in liquid form or in the form of particulate compositions. The average particle size of these particulate compositions is preferably between 100 and 5000 .mu.m, more preferably between 100 and 2000 microns, and more particularly between 100 and 1000 microns.

Combination products, characterized in that the detergency booster by weight, preferably a bleaching agent in amounts above 10, -%, preferably above 20 wt .-%, and contains in particular above 40 wt .-%, are preferred in the invention.

The detergency reinforced contained in the inventive combination product exerts its effect in the pre-wash cycle of the automatic dishwashing process, wherein the detergency booster is preferably used to a large proportion as possible, that is, in the aqueous solution is Flottein or dispersed. Such washing power amplifiers which consume in the pre-rinse cycle at least 30 wt .-%, preferably at least 50 wt .-%, preferably at least 60 wt .-% and in particular at least 80 wt .-% being preferred.

Combination product, characterized in that the detergency booster during the prerinse cycle completely consumed, are particularly preferred in the context of the present application. Of course, often over of active substances occur in the main wash cycle of the dishwashing process when using a dishwasher detergent in the prewash cycle of an automatic dishwashing process. As "completely consumed" in the sense of the present application therefore such detergency boosters, of the ingredients is less than 15 wt .-% is considered, preferably less than 10 wt .-%, preferably less than 8 wt .-%, more preferably less than 6 are dragged wt .-% and in particular less than 3 wt .-% in the main wash cycle. particularly preferred, however, such washing power amplifier whose ingredients to less than 1 wt .-%, in particular less than 0.5 wt .-% in the are main wash will be deported.

Combination products according to, characterized in that the main cleaning agent during the course of the main wash completely consumed, according to the invention are also preferred. Of course, often over of active substances associated with the use of a dishwasher detergent in the main wash of a dishwashing machine in the rinse cycle of the dishwashing process. As "completely consumed" in the sense of the present application, therefore, such a main cleaning agents, whose contents less than 15 wt .-% is considered, preferably less than 10 wt .-%, preferably less than 8 wt .-%, more preferably less than 6 are dragged wt .-% and in particular less than 3 wt .-% in the rinse cycle. particularly preferred, however, such main detergent whose ingredients to less than 1 wt .-%, in particular less than 0.5 wt .-% in the are rinse cycle will be deported.

With particular preference, combination product of the invention in addition to the detergency booster, the main cleaning means and the instructions for use further comprises a dosing aids. Combination products, characterized in that the combination product further comprises a dosing aids for the detergency booster and / or for the main cleaning agents, are preferred in the invention. When dosing aids, for example, all the devices and articles are suitable which are suitable to dose the washing power amplifier or the main detergent in the dishwasher or the metering chamber; and / or are suitable for the dimension of a given volume or weight. Dosing aids are used with particular preference in particular for flowable laundry booster or main cleaning agent. Examples of such free-flowing agents are liquids and gels, as well as particulate compositions as powders, granules, agglomerates, or extrudates. Suitable dosing aids are, for example (measured) - or cup (measuring) vanes (measuring) spoon. This dosing aids may be made, for example, from polymeric plastics, glass, paper or plastic.

Another essential component of the combination product according to the invention is the instructions for use. For ease of handling, and information for the consumer these instructions is preferably contained in or on the outer packaging of the washing power amplifier and / or the main cleaning agent. The instructions for use will be printed with particular advantage to the primary or secondary packaging of the washing power amplifier and / or the main cleaning agent. But of course it is also possible to provide access to the instructions for use by a package insert.

As previously discussed, the instructions directs the user to the use of detergency boosters and main detergent in the pre-wash and main wash cycle of an automatic dishwashing process. The instructions are preferably further instructions regarding the dosage level, the kind of dosage, the choice of the cleaning program, the type of cleaning utensil (eg glass, porcelain, plastic, wood, etc.) and the type of possibly in combination with the inventive combination products employed other cleaning agents (eg deodorant, silver protection, protective glass, etc.)

The compositions of the invention are characterized by improved cleaning and rinsing effect. This improved efficiency allows the consumer or user the choice of water and / or energy-saving mechanical dishwashing. For this reason, such combination products according to the invention are particularly preferred in which the instructions for carrying out an energy and / or water-saving guides machine dishwashing.

The wash booster especially when used in combination with modern "2in1" and "3in1" dishwashing detergents outstanding cleaning and Klarspülleistungen. As the main cleaning agent combination products of the invention therefore comprise with preference a "2in1" - "3in1" detergent or a. Combination products in which the instructions for carrying out a "2in1" - or "3in1" -maschinellen dishwashing guides are therefore preferred in the invention.

The compositions of the invention show their improved cleaning action particularly on difficult-to-clean residues on glass, plastic or dishes. These residues, which are traditionally often pre-cleaned by manual, can be removed without using a manual cleaning with the use of the combination product according to the invention. Combination products in which the operating instructions for dispensing with a manual precleaning of the dishes guides are therefore according to the invention particularly preferred.

In addition to the pre-cleaning, however, the post-cleaning has been found to the wash items as superfluous when using the compositions of the invention now. The present application is, therefore, an inventive combination product, characterized in that the operating instructions for dispensing with a post-cleaning of the crockery, preferably for dispensing with a manual cleaning of the dishes guides.

To be particularly effective are combination products of the invention in the cleaning of metal surfaces, particularly stainless steel surfaces and coated in the cleaning of enamel surface or scratch-resistant surfaces, as evidenced, for example, surfaces of Teflon ®.

A further subject matter of this application is, therefore, an inventive combination product, characterized in that the instructions for use of the combination product for cleaning metal surfaces, preferably for cleaning stainless steel surfaces, or for cleaning enamel surfaces or for cleaning scratch resistant coated surfaces, preferably surfaces made of Teflon ® instructs.

The present application thus relates to the use of a combination product according to the invention for the cleaning of metal surfaces, preferably stainless steel surfaces or for cleaning enamel surfaces or for cleaning scratch resistant coated surfaces, preferably surfaces made of Teflon ®.

As enamel are called vitrified melt mixtures in this application there. The mixtures preferably comprise predominantly oxidic composition and more preferably are based on a glass matrix, preferably an alkali borate silicate matrix in which are dispersed in the opacifiers and colorants ceramic pigments.

The combination products of the invention act in particular against tea stains and against baked dirt like Fettverkrustungen, branded minced meat or baked cheese.

Also claimed is therefore an inventive combination product, characterized in that the instructions for use for the purification of tea stains, or baked-on soils as Fettverkrustungen, branded minced meat or cheese branded guides.

Also claimed is the use of inventive combination products for the removal of tea stains, or baked-on soils as Fettverkrustungen, branded minced meat or branded cheese. Another object of the present application is a machine dishwashing using a combination product of the invention described above, comprising the steps of a) reading a user manual, which instructs the user to use the washing power amplifier in the pre-rinse cycle and the use of the main detergent in the main wash of an automatic dishwashing process; b) introducing a washing power amplifier in the pre-wash cycle of a machine dishwashing process; c) introducing a main detergent in the main wash of an automatic dishwashing process.

The wash booster exerts its effect in the pre-rinse cycle of machine dishwashing. A direct dosage of the washing power amplifier in the interior of the dishwasher has been found to be particularly advantageous for the effect of the washing power amplifier. Machine dishwashing, characterized in that the detergency booster is preferably manually metered into the interior of the dishwasher, are particularly preferred.

As a particular preference, it has now been found to dose the washing booster on the inside of the dishwasher.

Another object of this additional application is a machine dishwashing using a combination product according to the teaching of DE 102004051560.3, comprising the steps of a) reading a user manual, which instructs the user to use the washing power amplifier in the pre-rinse cycle and the use of the main detergent in the main wash of an automatic dishwashing process; b) dosing a washing power amplifier to the inside of the dishwasher door; c) introducing a main detergent in the main wash of an automatic dishwashing process.

"3in1" main cleaning agent or through improved cleaning and rinsing results from - As stated previously, the detergency booster are characterized in particular in combination with a "2in1". Such agents are known as well as the dishwashing detergent powder typically dosed over the dosing chamber. Machine dishwashing, in which the main cleaning agent preferably is manually metered into the dosing chamber of the dishwasher, are particularly preferred.

The inventive combination products described above of detergency boosters and Hauptreinigungsmittei containing washing- and cleaning-active substances, preferably washing and cleaning-active substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, perfumes and perfume carriers. These preferred ingredients are, if they have not already been described, described in more detail below.

surfactants

The group of surfactants are the nonionic, anionic, cationic and amphoteric surfactants.

Suitable nonionic surfactants are all known in the art nonionic surfactants may be used. As preferred surfactants, low-foaming nonionic surfactants are used. With particular preference, washing or cleaning agents, in particular cleaning agents for automatic dishwashing nonionic surfactants, especially nonionic surfactants from the group of alkoxylated alcohols. can be used as nonionic surfactants alcohol are preferably alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of used, in which the alcohol methyl-branched linear or preferably in the 2-position or linear and methyl-branched radicals may contain the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol preferably. Preferred ethoxylated alcohols include, for example, Ci 2- i 4 alcohols containing 3 EO or 4 EO, C g. ir alcohol containing 7 EO, C 13 .i 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C12-18 -Alkoho- Ie with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 -alcohol with 3 EO and C 12 _iβ alcohol containing 5 EO. The degrees of ethoxylation given are statistical Mit¬ represents mean values ​​which may correspond to a specific product of a whole or a fractional number. Preferred alcohol ethoxylates have a narrow Homologenverteiiung (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants, alkyl glycosides of the formula RO (G) x employed in which R is a primary linear or methyl-branched, more particularly 2-methyl-branched, aliphatic radical containing 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which measures a glycose unit having 5 or 6 C-Ato, preferably for glucose. The degree of oligomerization x, which glycosides the distribution of mono- and oligoglycosides, is any number between 1 and 10; x is preferably 1, 2 to 1; 4.

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

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 alkanolamide may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fat alcohols, especially not more than half of them.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula,

Figure imgf000024_0001

in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 represents hydrogen, an alkyl or hydroxyalkyl having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which can be obtained with a fatty acid, a fatty acid or a fatty acid chloride by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation.

The group of polyhydroxyfatty acid amides also includes compounds of the formula

R1-O- R2 R-CO-N- [Z]

in which R is a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, where C M alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of that group.

[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 may be converted as a catalyst in the desired polyhydroxy fatty acid methyl ester by reaction with in the presence of an alkoxide.

With particular preference, surfactants are used further containing one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of the mixed alkoxylated alcohols and in particular from the group of AO EO-EO-nonionic surfactants are likewise used with particular preference.

Especially preferred nonionic surfactants which have a melting point above room temperature are. Nonionic surfactant (s) (e) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 6O 0 C and particular between 26.6 and 43.3 ° C, is / are particularly preferred ,

Suitable nonionic surfactants have melting or softening temperature range mentioned above are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa-s, preferably above 35 Pa-s and especially above 40 Pa-s have. Non-ionic surfactants that have a waxy consistency at room temperature are preferred.

Preferably used surfactants which are solid at room temperature, come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / Poiyoxyethylen / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) - nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature an ethoxylated nonionic surfactant derived from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 moles of ethylene oxide has emerged per mole of alcohol or alkylphenol.

A particularly preferred, solid at room temperature nonionic surfactant is derived from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 -alcohol), preferably a C 18 alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Among these, the "narrow range ethoxylates" (see above) are particularly preferred.

With particular preference, therefore, ethoxylated nonionic surfactant selected from C 6-20 - ettalkoholen monohydroxy alkanols or C 6-20 alkylphenols or C 16-20 -F and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were recovered used.

The solid at room temperature nonionic surfactant preferably also contains propylene oxide units in the molecule. Preferably, such PO units up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkylphenols, which additionally comprise polyoxyethylene-polyoxypropylene block copolymer. The alcohol or alkylphenol such nonionic surfactant preferably makes up more than 30 wt .-%, particularly preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred compositions are characterized in that they comprise ethoxylated and propoxylated nonionic surfactants in which the Propyienoxideinheiten in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant account.

Further particularly preferred nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the weight 75 wt .-% of a reverse block copolymer of polyoxyethylene and polyoxypropylene having 17 moles of ethylene oxide and 44 moles propylene oxide and 25th - contains% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from Olin Chemicals. Surfactants of the formula

R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 OIyCH 2 CH (OH) R 2,

in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is a value between 0.5 and 1, 5 and y is a value of at least 15, are more particularly preferred nonionic surfactants.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH (R 3) 0] x [CH 2] k CH (OH) [CH 2] J0R 2,

are in the 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 is a value between 1 and 30 k and j are values ​​between 1 and 12, preferably have 1 to 5 If the value is x ≥ 2, each R 3 may be different in the above formula R 1 O [CH 2 CH (R 3) 0] x [CH 2] k CH (0H) [CH 2] j 0R. 2 R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, said radicals having 8 to 18 carbon atoms are particularly preferred. Of the radical R 3 is H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, in particular 6 to 15

As described above, each R 3 may be different in the above formula, if x ≥ 2. The alkylene oxide can be varied within the square brackets. Is for example, x 3, the radical R may be selected 3 to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3) units which can be joined together in any order, for example, (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected as an example and may be larger, whereby the variation increases with increasing values ​​of x and, for example, a large number of (EO), combined with a small number of (PO) - includes groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula to R 1 O [CH 2 CH (R 3) O] X CH 2 CH (OH) CH 2 OR 2

simplified. In this formula, R 1, R 2 and R 3 are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values 6 to 15

Summing up the latter statements are summarized, are end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 OTCH 2 CH (R 3) O] x [CH 2] κCH (OH) [CH 2] j OR 2,

are in the 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 is a value between 1 and 30 k and j are values ​​between 1 and 12, preferably between 1 and 5, preferably, surfactants of the type

R 1 O [CH 2 CH (R 3) O] X CH 2 CH (OH) CH 2 OR 2,

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Particularly preferred nonionic surfactants in the context of the present invention, low-foaming nonionic surfactants have been found to comprise alternating ethylene oxide and alkylene oxide units. Among these surfactants with EO-AO-EO-AO-blocks are preferred, wherein one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nichionisches surfactants of the general formula

Ri-O- (CH 2 -CH 2 -O) - (C

Figure imgf000028_0001

preferably, R 1 6-24 alkyl or alkenyl is a straight or branched, saturated or mono- or polyunsaturated C; each group R is -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, 2 is 2 and R 3 are independently selected from -CH 3, independently of one another are integers 1 to 6

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene. The radical R 1 in the above formula may vary depending on the origin of the alcohol. If natural sources are used, the radical R 1 has an even number of carbon atoms and is unbranched, as a rule, the linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow fat or oleyl are preferred. From synthetic sources accessible alcohols are for example the Guerbet alcohols or the 2-position methylver¬ branched or linear and methyl-branched residues in the mixture, as are typically present in oxoalcohol radicals. Regardless of the type of alcohol used for preparing the nonionic surfactants contained in the agents are nonionic surfactants are preferred in which R 1 in the above formula is an alkyl radical having from 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and especially 9 to 11 is carbon atoms.

The alkylene oxide unit that is alternatingly contained with the ethylene oxide in the preferred nonionic surfactants, especially butylene addition to propylene into consideration. However, other alkylene oxides in which R 2 and R 3 are independently selected from - CH 2 CH 2 -CH 3 or CH (CH 3) 2 are suitable. Preferably, nonionic surfactants of the above formula in which R 2 and R 3 are a radical -CH 3, w and x independently of one another for values of 3 or 4 and y and z are independently values of 1 or second

In summary, non-ionic surfactants are particularly preferred which have a C. 9 15 having alkyl with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants exhibit in aqueous solution, the required low viscosity, and are according to the invention with particular preference.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH (R 3) O] X R 2,

1 in which R is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which is preferably between 1 and having 5 hydroxy groups and are preferably further functionalized with an ether group, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- is butyl and x is values ​​between 1 and 40th

In a particularly preferred embodiment of the present application, R 3 is in the aforementioned general formula for H. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH 2 O] x R 2

Such nonionic surfactants are especially preferred in which R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, having preferably from 1 to 5 hydroxy groups, and x stands for values ​​between 1 and 40th

In particular, such end-capped poly (oxyalkylated) nonionic surfactants are preferred, according to the formula

R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2

addition to a group R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having from 4 to 20 carbon atoms, further comprising a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms R 2, which a monohydroxylated intermediate group - CH (OH) CH 2 - is adjacent. x in this formula for values ​​between 1 and 90th

Particularly preferred are nonionic surfactants of the general formula

R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2,

which in addition to a group R 1, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further comprising a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon Official omen having which a monohydroxylated intermediate group -CHaCH (OH) - is adjacent and in which x stands for values between 40 and 80, preferably between 40 and 60th

The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be, for example, by reacting a terminal epoxide of formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 CH obtain 2 OH.

Especially preferred are further those end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH 2 O] x [CH 2 CH (CH 3) OIyCH 2 CH (OH) R 2,

in which R 1 and R 2 are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2, but preferably is -CH 3, and x and y are independently values between 1 and 32, wherein nonionic surfactants with values for x from 15 to 32 and y is from 0, 5 and 1, 5 are very particularly preferred.

Surfactants of the general formula

Figure imgf000031_0001

in which R 1 and R 2 are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2, but preferably is -CH 3, and x and y are independently values between 1 and 32, according to the invention are preferred, wherein nonionic surfactants with values for x from 15 to 32 and y of 0.5 and 1, 5 are very particularly preferred.

The carbon chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants are statistical average values ​​which may be an integer or a fractional number for a specific product. Due to the manufacturing process do not exist commercial products of the cited formulas of an individual representative, but instead of mixtures, whereby not only the C-chain lengths but also for the ethoxy lierungsgrade or alkoxylation average values ​​and can thus be fractional numbers.

Of course, the above-mentioned nonionic surfactants may be used not only as single substances, but also as surfactant mixtures of two, three, four or more surfactants. not mixtures of nonionic surfactants as surfactant referred covered in its entirety by one of the general formulas above, but rather those mixtures which contain two, three, four or more non-ionic surfactants which may be described by various of the aforementioned general formulas ,

The anionic surfactants used are used for example on the type of sulfonates and sulfates. Suitable surfactants of the sulfonate type are preferably C. 9 13 -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as they i receives 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, for example, from C 2- , into consideration. Also suitable are alkanesulfonates, which are obtained from C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example, are suitable for the α-sulfonated Methylester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated Fettsäureglycerinester. Under Fettsäureglycerinestern the mono-, di- and triesters and mixtures thereof are to be understood as they are obtained in the production by esterification of a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sul¬ fierte Fettsäureglycerinester are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alkali and especially the sodium salts of the Schwefelsäurehalbester C12 alk (en) yl sulfates 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o oxo alcohols and those Halbester secondary alcohols of these chain lengths. Further preferred are alk (en) yl sulfates of said chain length which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on oleochemical raw materials. From the washing are the C 12 -C 16 alkyl sulfates and C 12 -C 15 - alkyl sulfates and C 14 -C preferably 5 alkyl sulfates. 2,3-AlkyIsulfate which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.

Also, the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C. 7 2 i-alcohols such as 2-methyl-branched C. 9 ir alcohols containing on average 3.5 mol ethylene oxide (EO) or C 12-i 8 fatty alcohols containing 1 to 4 EO, are also suitable. They are used in detergents because of their high foaming behavior, only in relatively small amounts, spielsweise in amounts of from 1 to 5 wt .-%, are used.

Other suitable anionic surfactants include the salts of alkylsulfosuccinic acid, which are also known as sulfosuccinates or as sulfosuccinic esters and which Monoester and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain C 8 - I8 - fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants. Of these sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Likewise, it is also possible to use alk (en) yl succinic acid preferably containing 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other anionic surfactants in particular, soaps. Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, for example coconut, palm kernel or tallow soap mixtures derived.

The anionic surfactants including the soaps can exist in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Are the anionic constituent of machine dishwasher detergents, is their content, based on the total weight of the agent is preferably less than 4 wt .-%, preferably less than 2 wt .-% and most preferably less than 1 wt .-%. Automatic dishwashing agents that contain no anionic surfactants are particularly preferred.

In place of the above-mentioned surfactants or in conjunction with them surfactants may also be used cationic and / or amphoteric. As cationic active substances, cationic compounds of the following formulas can be used:

Figure imgf000034_0001

Figure imgf000034_0002

Figure imgf000034_0003

wherein each R 1 group is independently selected from

Figure imgf000034_0004
Alkenyl or hydroxyalkyl groups; each group R 2 is independently selected from C. 8 28 alkyl or alkenyl groups; R 3 = R 1 or (CH 2) n -TR 2; R 4 = R 1 or R 2 or (CH 2) n -TR 2; T = -CH 2 -, -O- CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing agents, the content of cationic and / or amphoteric surfactants is preferably less than 6 wt .-%, preferably less than 4 wt .-%, most preferably less than 2 wt .-% and in particular less than 1 wt %. Machine dishwashing detergents which contain no cationic or amphoteric surfactants are particularly preferred.

polymers

The group of polymers includes in particular the washing or cleaning action Poylmere, for example rinsing and / or polymers active as softeners. Generally, cationic, anionic and amphoteric polymers can be used in washing or cleaning agents in addition to non-ionic polymers.

"Cationic polymers" in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized ammonium groups or other positively charged groups for example, present in the polymer chain (alkyl). Particularly preferred cationic polymers derived from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinyl pyrrolidone Methoimidazoliniumchlorid- copolymers, quaternized polyvinyl alcohols or of the polymers indicated under the INCI designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27th

"Amphorere polymers" for the purposes of the present invention, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units. These groups can be carboxylic acids, sulfonic acids or phosphonic acids, for example.

Preferred washing or cleaning agents, particularly preferred automatic dishwashing agents, are characterized in that they contain a polymer a) having monomer units of formula having R 1 R 2 C = GR 3 R 4, in which each R 1, R 2, R 3, R 4 is independently selected from hydrogen, derivatized hydroxy, C 1-30 linear or branched alkyl, Aryi, aryl substituted Ci -30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group with a positive charge in the portion of the pH range of 2 to 11, or salts thereof, with the proviso that at least one R 1, R 2, R 3, R 4 is a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one Aminogr is uppe with a positive charge.

In the context of the present application particularly preferred cationic or amphoteric polymers containing as a monomer a compound of the general formula

Figure imgf000035_0001

independently wherein R 1 and R 4 from each other is H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 independently represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl moiety is linear or branched and has between 1 and 6 carbon atoms, it preferably is a methyl group; x and y independently represent integers 1 to 3 X 'represents a counterion, preferably a counterion selected from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, Lauryisulfat, dodecylbenzene sulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CHs) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, and - (CH 2 CH 2 -O) n H.

Very particularly preferred are polymers having a cationic monomer unit of the above general formula are wherein R 1 and R 4 is H, R 2 and R 3 is methyl and x and y are each 1. The respective monomer unit of the formula

H 2 C = C H- (CH 2) -N (CH 3) 2 - (CH 2) -CH = CH 2

X '

in the case of X "= chloride referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer of the general formula

R1 HC = C Rz-C (O) -NH- (CH 2) - N + RsRtRs

X "in which R 1, R 2, R 3, R 4 and R 5 are independently a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from - CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, and - (CH 2 CH 2 -O) n H, and x represents an integer 1 to 6

Are very particularly preferred in the context of the present application polymers having a cationic monomer unit of the above general formula are wherein R 1 is H and R 1 R, R 4, and R is methyl, and x stands for 3 hours. The corresponding monomer units of the formula

H 2 C = C (CH3) -C (O) -NH- (CH2) χ-N + (CH 3) 3

also referred to as MAPTAC (Methyacrylamidopropyl- trimethylammonium chloride) in the case of X "is chloride.

Polymers are used According to the invention, which contain as monomer diallyldimethylammonium salts and / or acrylamidopropyl.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units originate for example from the group of linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, the (meth) acrylic acid, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, vinyl essing acid Allyiessigsäure, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, DIE allylsulfonic acids such as allyloxybenzenesulfonic and methallyl or the allylphosphonic.

Preferred usable amphoteric polymers derive from the group of alkyl acrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methyl methacrylic acid copolymers, alkylacrylamide / acrylic acid / alkyl amino alkyl (meth) acrylic acid copolymers, the

Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the

Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / Alkymethacrylat / Alkylaminoethylmethacrylat / alkyl methacrylate copolymers as well as copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Preferably usable zwitterionic polymers derive from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium / methacrylic acid copolymers and their alkali and ammonium salts, and methacroylethylbetaine / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, besides one or more anionic monomers and cationic monomers methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers derive from the group of methacrylamidoalkyltrialkylammonium trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the

Methacrylic amidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid

Copolymers and

Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / alkyl

(Meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particularly preferred amphoteric polymers from the group of

Methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid

Copolymers of methacrylamidopropyltrimethylammonium chloride / DimethyKdiallyOammonium- chloride / acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.

In a particularly preferred embodiment of the present invention, the polymers are present in pre-assembled form. For fabrication of the polymers, among others, the encapsulation of the polymers by means of water soluble or water is thereby

Coating means preferably by means of water-soluble or water-dispersible natural or synthetic polymers; Encapsulation of the polymers by water-insoluble, meltable

Coating means, preferably by means of water-insoluble coating agents from the

Group of waxes or paraffins having a melting point above 30 ° C; the co-granulation of the polymers with inert carriers, preferably with

Carrier materials from the group of washing or cleaning-active substances, more preferably from the group of builders (builders), or co-builder.

Washing or cleaning composition containing the aforementioned cationic and / or amphoteric polymers in quantities of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent. however, such washing or cleaning agents are preferred in the context of the present application, in which the proportion by weight of cationic and / or amphoteric polymers is between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, preferably between 0.01 and 4 wt .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent.

Polymers effective as softeners are, for example, the sulfonic acid group-containing polymers which are used with particular preference.

Particularly preferably used as a sulfonic acid group-containing polymers are copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid, and optionally further ionic or nonionic monomers.

In the present invention, unsaturated carboxylic acids of formula

R 1 (R 2) C = C (R 3) COOH

preferably in which R 1 to R 3 are each independently -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 Kohienstoffatomen, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH 2, -OH or -COOH-substituted alkyl or alkenyl, or -COOH or -COOR 4 wherein R 4 is a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula, especially acrylic acid (R 1 = R 2 = R 3 = H), methacrylic acid (R 1 = R 2 = H; R 3 = CH 3) and / or maleic acid (R 1 = COOH; R 2 = R 3 = H) is preferred.

In the sulfonic acid group-containing monomers are those of formula

R 5 (R 6) C = C (R 7) -X-SO 3 H

preferably, R s to R 7 are independently -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH 2, -OH or -COOH-substituted alkyl or Alkenyireste or -COOH or -COOR 4 wherein R 4 is a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer which is selected from - (CH 2) n - with n = O to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) 2 - and -C (O) -NH-CH (CH 2 CH 3) -. those of the formulas Among these monomers,

H 2 C = CH-X-SO 3 H

Figure imgf000040_0001

HO 3 SX (R 6) C = C (R 7) -X-SO 3 H

in which R 6 and R 7 are independently selected from -H, -CH 3, -CH 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2 and X is an optionally present spacer group is selected from - (CHa) n - with n = O to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) Z - and -C (O) -NH- CH (CH 2 CH 3) -.

Particularly preferred sulfonic acid group-containing monomers are propanesulfonic acid 1-acrylamido-1, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2- propeni-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3- sulfopropyl methacrylate , sulfomethylacrylamide, sulfomethylmethacrylamide and water soluble salts of said acids.

As a further ionic or nonionic monomers unsaturated compounds in particular, ethylenically. Preferably, the content of the polymers used in these further ionic or nonionic monomers less than 20 wt .-%, based on the polymer. Particularly preferred polymers for use consist solely of monomers of the formula R 1 (R 2) C = C (R 3) COOH and monomers of the formula R 6 (R 6) C = C (R 7) -X-SO 3 H.

In summary, copolymers of i) unsaturated carboxylic acids of the formula R 1 (R 2) C = C (R 3) COOH in which R 1 to R 3 are each independently -H, -CH 3, a straight-chain or branched saturated alkyl radical having from 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, -NH 2, -OH or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR 4, wherein R 4 is a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 12 carbon atoms, ii) monomers of formula containing sulfonic acid R 5 (R 6) C = C (R 7) -X-SO 3 H in which R 5 to R 7 is independently -H, -CH 3, a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, -NH 2, - OH or -COOH-substituted alkyl or alkenyl radicals as defined above, or -COOH or -COOR 4 wherein R 4 is a saturated or unsaturated, linear or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group, selected from - (CH z) n - with n = O to 4, -COO- (CH 2) IC with k = 1 to 6, -C (O) -NH-C (CH 3) 2 - and - C (O) -NH-CH (CH 2 CH 3) - iii) optionally further ionic or nonionogenic monomers.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid,

Methacrylic acid and / or maleic acid, ii) one or more monomers containing sulfonic acid of the formulas:

H 2 C = CH-X-SO 3 H

H 2 C = C (CHs) -X-SO 3 H

HO 3 SX (R 6) C = C (R 7) -X-SO 3 H

in which R 6 and R 7 are independently selected from -H, -CH 3, -CH 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2 and X is an optionally present spacer group is selected from - (CH 2) ,, - where n = O to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH- C (CHa) 2 - and - C (O) -NH-CH (CH 2 CH 3) - iii) optionally further ionic or nonionic monomers.

The copolymers may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, where all members of the group i) can be combined with all representatives of group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

Such copolymers are preferred, for example the structural units of the formula

- [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

included, in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) n - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3) - being preferred.

These polymers are prepared by copolymerizing acrylic acid with a sulfonic acid group-containing acrylic acid derivative. Copolymerizing the sulfonic acid group-containing acrylic acid derivative with methacrylic acid leads to another polymer, the use is also preferred. The corresponding copolymers contain structural units of the formula

- [CH 2 -C (CH 3) COOHU- [CH 2 -CHC (O) -Y-SO 3 H] P-

in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group selected from aüphatischen unsubstituted substituted or aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is - O- (CH 2) n - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3) - are preferred.

Acrylic acid and / or methacrylic acid can be completely analogously also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, whereby the structure units are changed in the molecule. Thus, copolymers which contain structural units of the formula

- [CH 2 -CHCOOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H] p -

included, in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group selected from substituted or unsubstituted aüphatischen, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) n - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3 ) - might also preferred as copolymers which contain structural units of the formula

- [CH 2 -C (CH 3) COOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H] p -

included, in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) π - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3) - being preferred. Instead of acrylic acid and / or methacrylic acid or in addition to maleic acid can also be used as a particularly preferred monomer from group i). Can be reached in this way according to the invention preferred copolymers which contain structural units of the formula

- [HOOCCH-CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p

included, p is on the m and each a whole natural number between 1 and 2000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) n - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CHa) 2 - or -NH-CH (CH 2 CH 3) - stands are preferred. According to the invention, the structural units of the formula are copolymers,

- [HOOCCH-CHCOOHJn 1 - [CH 2 -C (CH 3) C (O) OY-SO 3 H] p -

included, in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) n - with n = 0 to 4, is -O- (C 6 H 4) -, -NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3) - stands.

In summary, such copolymers contain structural units of the formulas are preferred in the invention,

- [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3) COOKI 1n - [CH 2 -CHC (O) -Y SO 3 H] p - - [CH 2 -CHCOOHL- [CH 2 -C (CH 3) C (O) -Y-SO 3 H] P- - [CH 2 -C (CH 3) COOKL- [CH 2 -C (CH 3) C (O) -Y-SO 3 H] P-

- [HOOCCH-CHCOOH] nT [CH 2 -CHC (O) -Y-SO 3 H] p -

- [HO0CCH-CHCOOH] m - [CH 2 -C (CH 3) C (O) 0-Y-S0 3 H] p -

included, in which m and p are each a whole natural number between 1 and 2000, and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y -O- (CH 2) n - with n = O to 4, is -O- (C 6 H 4) -, -NH-C (CHs) 2 - or -NH-CH (CH 2 CH 3) - being preferred. In the polymer, the sulfonic acid groups may be present wholly or partially in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group may be in some or all sulfonic acid groups with metal ions, preferably alkali metal ions and in particular with sodium ions. The use of partially or completely neutralized sulfonic acid copolymer is inventively preferred.

The monomer distribution of the copolymers according to the invention preferably is used with copolymers containing only monomers from groups i) and ii), preferably 5 to 95 wt .-% of i) or ii), particularly preferably 50 to 90 wt .-% monomer from group i) and 10 to 50 wt .-% of monomer from group ii), based in each case on the polymer.

In such terpolymers are particularly preferred which contain 20 to 85 wt .-% of monomer from group i), 10 to 60 wt .-% of monomer from group ii) and 5 to 30 wt .-% of monomer from group iii) ,

The molecular weight of the present invention preferably sulfo-copolymers can be varied to adjust the properties of the polymers to the desired application. Preferred washing or cleaning agents are characterized in that the copolymers have molecular weights from 2000 to 200,000 gmol "1, preferably from 4000 to 25,000 gmol" 1 and in particular from 5000 to 15,000 gmol '1.

Bleach activators

Bleach activators are used in washing or cleaning agents, for example, in order to achieve cleaning at temperatures of 60 0 C and below, an improved bleaching effect. Suitable bleach activators are compounds which, under perhydrolysis conditions produce aliphatic peroxocarboxylic acids preferably containing 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances which carry O- and / or N-acyl groups of said number of carbon atoms and / or gege¬ appropriate, substituted benzoyl groups are suitable. Acylated alkylene diamines are preferred multiple, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1 r 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran. Other bleach activators preferably used in the present application are compounds from the group of cationic nitriles, particularly cationic nitriles of the formula

Figure imgf000045_0001

in which R 1 is -H, -CH 3, a C 2nd 24 -alkyl or -alkenyl radical, a substituted C. 2 24 alkyl or alkenyl group having at least one substituent from the group -Cl, -Br, -OH, -NH 2, -CN, an alkyl or alkenylaryl radical with a C ^ alkyl group, or a substituted alkyl or alkenylaryl radical is a Ci -24 alkyl group, and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 - CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

Particularly preferred is a cationic nitrile of the formula

Figure imgf000045_0002

in which R 4, R 5 and R 6 are independently selected from -CH 3, -CH 2 -CH 3, -CH 2 -CH 2 - CH 3, -CH (CH 3) -CH 3, wherein R 4 is additionally also be -H and X is an anion, preferably R 5 = R δ = -CH 3 and, in particular R 4 = R 5 = R 6 = CH 3 and compounds of the formulas (CH 3) 3 N (+) CH 2 -CN X, (CH 3 CH 2) 3 N (+) CH 2 -CN X ", (CH 3 CH 2 CH 2) 3 N {+) CH 2 -CN X", (CH 3 CH ( CH 3)) 3 N (+) CH 2 -CN X ', or (HO-CH 2 -CH 2) 3 N (+) CH 2 -CN X "are particularly preferred, and, to the cationic selected from the group of these substances nitrile of the formula (CH 3) 3 N (+) CH 2 -CN X, "in which X" represents an anion, iodide from the group chloride, bromide, hydrogen sulfate, methosulfate, p-toluene sulfonate (tosylate) or xylene sulfonate is selected, is particularly preferred.

Bleach activators may further compounds which under perhydrolysis conditions produce aliphatic peroxocarboxylic acids preferably containing 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances which carry O- and / or N-acyl groups of said number of carbon atoms and / or optionally substituted benzoyl groups. Acylated alkylene diamines are preferred multiple, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) 1 N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol, 2,5- diacetoxy-2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and acetylated, optionally N-alkylated Giucamin and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam. Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional Bieichaktivatoren can be used.

Provided that in addition to the nitrile other bleach activators to be used, are preferred bleach activators from the group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate ( n- or iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA), preferably in amounts wt .-% to 10, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-%, and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleaching activator.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can be used. These substances are bleach-boosting transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru - or Mo salt complexes or carbonyl complexes. Also, Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- and Cu-complexes with N-containing tripod ligands and Co-, Fe-, Cu- and Ru- ammine complexes may also be used as bleach catalysts.

Bleach-boosting transition metal complexes, more particularly containing the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammine) - complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate, are used in conventional amounts, preferably in an amount up to 5 wt .-%, particularly 0.0025 .-% to 1 wt .-% and particularly preferably of 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleaching activator. However, in special cases, more bleach activator can be used. enzymes

To increase the washing or cleaning performance of detergents or cleaners use enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; starting from the natural molecules are available for use in detergents and cleaning agents, improved variants are available that can be preferably used accordingly. Washing or cleaning composition preferably contain enzymes in total amounts of I x IO -6 Ws 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases are those of the subtilisin type are preferred. Examples include the subtilisins BPN 'and Carlsberg, protease PB92, subtilisins 147 and 309, the alkaline protease from Bacillus lentus subtilisin DY and the subtilases, but not more subtilisins in the strict sense as enzymes thermitase, proteinase K, and proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaard, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. Of the protease from Bacillus lentus DSM 5483 listed under the name BLAP ® variants derive.

Other usable proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Firnia Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of the present invention can be used amylases are the α-amylases from Bacillus licheniformis,. amyloliquefaciens or from B.. stearothermophilus as well as their improved for use in detergents and cleaning compositions. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. 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 ®. The α-amylase of ß. amyloliquefaciens is sold by Novozymes under the name BAN ®, and derived variants from the α- amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.

Furthermore, the α-amylase from Bacillus sp for this purpose. A 7-7 (DSM 12368), and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) emphasized.

In addition, the enhancements available under the Handeisnamen Fungamyl.RTM ® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product Amylase-LT example ®.

According to the invention used are lipases or cutinases, also to generate from suitable precursors in situ peracids in particular because of their triglyceride-cleaving activities, but. These include, for example, originally from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular those with the D96L amino acid substitution. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®. Furthermore, the cutinases are for example used, which were originally isolated from Fusarium solani pisi insolens and Humicola. Likewise useable lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ®, lipase AP ®, Lipase M-AP ® and lipase AML ® available. From Genencor, for example, the lipases and cutinases used are those whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ® and Lipomax® ® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ®, Lipase OF ® and lipase PL ® to mention, furthermore, the product Lumafast® ® from Genencor.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and beta-glucanases. Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States. From ß. subtilis derived beta-glucanase is available under the name Cereflo ® from Novozymes.

To enhance the bleaching effect, oxidoreductases such as oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese dioxygenases or laccases (phenol, Polyphenoioxidasen) are used. Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned. Advantageously, preferably organic, more preferably aromatic compounds that interact with the enzymes are added in order to enhance the activity of the oxidoreductases (enhancers) or to ensure the flow of electrons at very different redox potentials between the oxidizing enzymes and the stains (mediators).

The enzymes derived, for example, either originally from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are produced according to known biotechnological processes using suitable microorganisms such as by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the enzymes in question are preferably using established methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, the action of chemicals, deodorization or suitable combinations of these steps.

The enzymes may be used in any well-established in the prior art form. These include, for example, obtained by granulation, extrusion or lyophilization or solid preparations, in particular in liquid or gel form, solutions of the enzymes, advantageously highly concentrated, water and / or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated for both the solid and the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzyme is embedded in a solidified gel or those of the core-shell type in which an enzyme-containing core with a water, air and / or chemical-impermeable protective layer is coated. In superimposed layers further active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes may be applied in addition. Such capsules are applied by known methods, for example by shaking or rolling granulation or in fluid bed processes. Advantageously, such granules, for example, by applying a polymeric film former, and stable in storage due to the coating.

Furthermore, it is possible to formulate two or more enzymes together, so that a single granule has a plurality of enzymatic activities.

A protein and / or enzyme can be protected especially during storage, from damage, such as inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. Microbial recovery of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially when the compositions also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such compositions represents a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or salts or esters thereof are used, including in particular derivatives having aromatic groups such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or salts or esters thereof. As peptidic protease inhibitors include ovomucoid and leupeptin are to be mentioned; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are aminoalcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide are suitable. Certain used as Buiider organic acids are additionally capable of stabilizing an enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol, are other frequently used enzyme stabilizers. Calcium salts are used, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation inter alia against physical influences or pH variations. Polyamine-N-oxide-containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of enzymes against oxidative decay. A sulfur-containing reducing agent, for example sodium sulfite.

Combinations of stabilizers are preferably used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is enhanced by combination with boric acid and / or boric acid derivatives and polyols, and further enhanced by the additional use of divalent cations such as calcium ions.

one or more enzymes and / or enzyme preparations are preferred, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, based in each case on the overall composition containing enzyme.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of cloudiness, streaks and scratches as well as iridescence of the glass surface of machine washed glassware. Preferred glass corrosion inhibitors originate from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds which can be used to prevent glass corrosion are insoluble zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of not more than 10 gram of zinc salt per liter of water at 20 0 C. Examples of the particularly preferred insoluble zinc salts are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4) 2) and zinc pyrophosphate (Zn 2 (P 2 O 7)).

The zinc compounds are preferably used in amounts that a content of the compositions of zinc ions between 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1, 0 wt .-%, each based on the entire glass corrosion inhibitor containing agents cause. The exact content of the compositions of the zinc salt or zinc salts of course depends -depending on the type of zinc salts less soluble zinc salt used, the higher its concentration in the media should be.

Since the insoluble zinc salts during the dishwashing operation remain largely unchanged, the particle size of the salts is a criterion to be considered, so that the salts do not adhere to glassware or machine parts. Presently preferred are compositions wherein the insoluble zinc salts have a particle size below 1, 7 millimeters.

When the maximum particle size of the insoluble zinc salts is below 1, 7 mm, insoluble residues in the dishwashing machine are not to be feared. Preferably, the insoluble zinc salt has an average particle size which is well below this value in order to minimize the danger of insoluble residues, for example, a mean particle size less than 250 microns. This in turn is all the more, the less the zinc salt is soluble. In addition, the glass corrosion-inhibiting effectiveness increases with decreasing particle size. At very sparingly soluble zinc salts, the average particle size is preferably below 100 microns. For even more sparingly soluble salts, it may be even lower; For example, average particle sizes are preferably less than 60 microns for very poorly soluble zinc oxide.

A further preferred class of compounds are magnesium and / or zinc salt (s) at least one monomeric and / or polymeric organic acid. These cause non-corrosive changed the surfaces of glassware, even with repeated use, in particular no clouding, smears or scratches caused no iridescence of the glass surfaces.

can be used even though all the magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids, the magnesium and / or zinc salts are however, of monomeric and / or polymeric organic acids from the group of unbranched, saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, of saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, of the sugar acids, of the hydroxy acids, of the oxo acids, of the amino acids and / or polymeric carboxylic acids.

The spectrum of the inventive preferred zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts which are sparingly water soluble or insoluble, so a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l have, to those salts, which in water has a solubility greater than 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 0 C water temperature). The first group of zinc salts include, for example, zinc citrate, zinc oleate, and zinc stearate, the group of soluble zinc salts include, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference, the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt selected from the group of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Also ricinoleate, zinc abietate and zinc oxalate are preferred.

In the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular from 0.4 to 3 wt .-%, or the content of zinc in an oxidized form (calculated as Zn 2+), in particular between 0.04 to 0.2 percent by between 0.01 to 1 wt .-%, preferably from 0.02 to 0.5 wt .-% and. -%, each based on the total weight of the glaskorrosionsinhibitorhaitigen agent.

corrosion inhibitors

Corrosion inhibitors serve to protect the ware or the machine, in the field of machine dishwashing particularly silver protectants have a special meaning. The known substances of the prior art are. In general, silver protectants selected from the group of triazoles, benzotriazoles, bis-benzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or - complexes. preferred to use benzotriazole and / or alkylaminotriazole. As examples of the present invention are preferably to be 3-amino-5-alkyl- 1, 2,4-triazoles may be mentioned propyl, -butyl, -pentyl, -heptyl, octyl, nonyl, decyl -, undecyl, dodecyl, -Isononyl-, -Versatic-10 säurealkyl-, -phenyl-, -p-tolyl, - (4-tert-butylphenyl.) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5- oxo-2-pyrrolidinyl) -, -3 amino-1, 2,4-triazole. In dishwashing detergents are the triazoles or alkyl-amino-1,2,4 their physiologically tolerable salts in a concentration of 0.001 to 10% by weight, preferably from 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric acid, succinic acid. Very particularly effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5- isononyl, 5-Versatic 10 acid alkyl-3-amino-1, 2,4-triazoles, and mixtures these substances.

Often found containing active chlorine addition, agents that can reduce corrosion of the silver surface in cleaning formulations. In chlorine-free cleaners, particularly oxygen and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of these compounds can be used. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Of these, the transition metal salts, which are selected from the group of complexes of manganese and / or cobalt salts and / or, more preferably the cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) - complexes, chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can be used to prevent corrosion on the ware also.

Instead of or in addition to the above-described silver protection agents, such as the benzotriazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation stages II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The suitable salt-forming counterions include all conventional one-, two-, or three-fold negatively charged inorganic anions, such as the oxide, sulfate, nitrate, fluoride, as well as organic anions such as stearate.

Metal complexes according to the invention are compounds which consist of a central atom and one or more ligands, and, optionally, one or more of the above-mentioned anions. The central atom is one of the abovementioned metals in one of the aforementioned oxidation states. The ligands are neutral molecules or anions which are mono- or polydentate; the term "ligand" within the meaning of the invention, eg "Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart / New York, 9th edition, 1990, page 2507" in explanation. the charge of the central atom and the charge of the ligand / not complement each other in a metal complex to zero, then according to whether a cationic or an anionic charge excess, either one or more of the abovementioned anions or one or more cations, for example sodium -, potassium, ammonium ions to balance the charge. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The customary in chemistry definition of "oxidation state" is shown for example in "Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart / New York, 9th edition, 1991, page 3168". Particularly preferred metal salts and / or metal complexes are selected from the group MnSO 4, Mn (ll) citrate, Mn (ll) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5, V 2 O 4, VO 2, TiOSO 4, K 2 TiF 6, K 2 ZrF 6, CoSO 4, Co (NO 3) 2, Ce (NO 3) 3, and mixtures thereof, so that the metal salts and / or metal complexes selected from the group MnSO 4, Mn (ll) citrate, Mn (ll) stearate, Mn (II) acetylacetonate, Mn (II) - 1 [I-hydroxyethane-1, - are diphosphonate], V 2 O 5, V 2 O 4, VO 2, TiOSO 4, K 2 TiF 6, K 2 ZrF 6, CoSO 4, Co (NO 3) 2, Ce (NO 3) 3 used with particular preference ,

These metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior cleaning in the washing or cleaning agents. Thus, for example selected from the SO 3 -Her- position (contact method) suitable known mixture of pentavalent and tetravalent vanadium (V 2 O 5, VO 2, V 2 O 4), as well as the by diluting a Ti (SO 4) 2 solution resulting titanyl sulphate, TiOSO. 4

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, that is entirely coated with a water-proof, but easily soluble in the cleaning material temperatures to prevent their premature decomposition or oxidation during storage. Preferred coating materials strie by known processes, such as melt coating method according Sandwik from the Lebensmittelindu¬ be applied, paraffins, microcrystalline waxes, waxes of natural origin such as carnauba wax, candelilla wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. Here, the solid at room temperature Coating material is applied to the material to be coated in the molten state, for example, by fine-particle is thrown material to be coated in a continuous stream through a likewise continuously produced spray mist zone of the molten coating material. The melting point must be chosen such that the coating material while the silver treatment readily dissolves or rapidly melts. The melting point should ideally be in the range between 45 0 C and 65 ° C and preferably in the range 50 0 C and 60 ° C.

The metal salts and / or metal complexes are in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent.

disintegration aid

In order to facilitate the disintegration of prefabricated shaped bodies, it is possible disintegration aids, so-called tablet disintegrators, may be incorporated in the means in order to shorten the disintegration times. Tablet disintegrants or disintegration accelerators are according to Römpp (9th Edition, Vol. 6, p 4440) and Voigt understood "Textbook of pharmaceutical technology" (6th edition, 1987, pp 182-184) auxiliaries which the rapid disintegration of tablets in water or gastric juices and the release of the pharmaceuticals in an absorbable form care.

These substances, which are also known because of their action as "explosive" means to enlarge contact with water in volume, wherein the one hand, the intrinsic volume (swelling), a pressure can be generated on the other hand also by the release of gasses, which the tablet into smaller particles can disintegrate. Well-known disintegrators are, for example, carbonate / citric acid systems, although other organic acids may be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Disintegration aids are preferably used in amounts of from 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%, each based on the total weight of the disintegration aids containing agent used.

As preferred disintegration agents based on cellulose are used, so that preferred detergent and cleaning agent, a disintegrator Ceilulosebasis in amounts of from 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and especially 4 to 6 parts by weight % contain. Pure cellulose has the formal empirical composition (C 6 H 10 O) n and, formally, is a beta-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of ca. 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. used as a disintegration agent based on cellulose are within the scope of the present invention, cellulose derivatives which are obtainable by polymer-analogous reactions from cellulose. Such chemically modified celluloses include, for example, products of esterification or etherification reactions in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxy groups by functional groups that are not attached by an oxygen atom, can be replaced, used as cellulose derivatives. for example, fall within the group of cellulose derivatives, alkali metal celluloses, carboxymethyl cellulose (CMC), Celluloseester and ethers, and amino. The cellulose derivatives mentioned are preferably not used alone as the disintegration agent based on cellulose, but in a mixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50 wt .-%, more preferably below 20 wt .-%, based on the disintegration agent based on cellulose. Is particularly preferably used as disintegration agent based on cellulose, pure cellulose free from cellulose derivatives. The cellulose used as disintegration aid is preferably not used in fine-particle form, but instead is converted prior to admixing the premixes to be tabletted into a coarser form, for example granulated or compacted. The particle sizes of such disintegration aids is mostly above 200 microns, preferably at least 90 wt .-% 300-1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred in the present invention as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier.

As a further disintegration agent based on cellulose or as a constituent of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions that only the amorphous areas (ca. 30% of the total cellulose mass) of the celluloses, but leave the crystalline regions (ca. 70%) but leave intact. Subsequent disaggregation of formed by the hydrolysis microfine celluloses provides the microcrystalline celluloses which have primary particle sizes of about 5 microns, and for example can be compacted to granules having an average particle size of 200 microns.

Preferred disintegration aid, preferably a disintegration assistant based on cellulose, preferably in granular, co-granulated or compacted form, are in agents containing the disintegrant in amounts of from 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant containing the composition.

According to the invention effervescing systems can still be used as tablet disintegrants beyond. The gas-evolving effervescent system may consist of a single substance which releases a gas on contact with water. Among these compounds, particular mention is made of magnesium peroxide, which releases oxygen on contact with water. However, the gas-releasing effervescent system in turn consists of at least two components which react together to form gas. While a variety of systems conceivable and is executable, which release, for example nitrogen, oxygen or hydrogen, the effervescent system used in the detergent and cleaning agent selected with both economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts release carbon dioxide in an aqueous solution. Among the alkali metal carbonates or bicarbonates of sodium and potassium salts for reasons of cost over the other salts are clearly preferred. Of course, not pure alkali metal or bicarbonates in question must be used; instead mixtures of different carbonates and bicarbonates may be preferred.

are preferred as the effervescent system 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 wt .-% and in particular 3 to 10 wt .-% of an acidifying agent, based the total weight of the agent used.

Suitable acidifying agents that are free from the alkali metal salts in aqueous solution carbon dioxide, for example, boric acid and alkali metal hydrogen sulfates,

Alkalimetalldihydrogenphosphate and other inorganic salts can be used. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. Can be used but are also especially the other solid mono-, oligo- and polycarboxylic acids. Within this group, preferred are tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid may also be used. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (adipic acid and max. 33 wt .-%).

Preferred acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof.

fragrances

Suitable perfume oils or fragrances in the context of the present invention include individual perfume compounds, for example synthetic products are used of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinylacetat, phenylethyl acetate, Linalyl benzoate, benzyl formate, Ethylmethylphenyl glycinate, Allylcyclohexylpropionat, Styrallylpropionat and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8-18 carbon atoms, citral, Citronellai, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, the ionones, isomethylionone and oc-methyl cedryl ketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include primarily the terpenes such as limonene and pinene. Preferably, however, mixtures of different odorants, which together produce a pleasing fragrance note. Such perfume oils may also contain natural odorant mixtures, as are accessible from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, galbanum oil and laudanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.

The general description of the employable perfumes (see above) is a general representation the different substance classes of perfumes. In order to be perceptible, an odorant must be volatile; in addition the nature of the functional groups and the structure of the chemical compound, the molecular weight an important role plays. Thus, most perfumes have molecular weights up to about 200 Dalton, while molar masses of 300 Dalton and above an exception rather. Because of the different volatilities of perfumes, the smell of a composite of a plurality of odoriferous perfume or fragrance during evaporation altered, wherein the odor impressions in "top note" (top note), "middle or middle note" (middle note and body ) and "base notes" (end note or divided dry out). Since the odor perception is based to a large extent on the odor intensity, the top note of a perfume or fragrance does not consist only of volatile compounds, while the end note for the most part of less volatile, ie adherent odorants. In the composition of perfumes, more volatile odorants can be bound for example to certain fixatives, so is prevented from evaporating too quickly. The subsequent classification of the odorants "more volatile" or "tenacious" perfumes, nothing is mentioned about the odor impression or about whether the odorant is perceived as a top or middle note says nothing.

Tenacious odoriferous substances which are usable in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, silver fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine needle oil,

Kopaϊvabalsamöl, coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, ambrette seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, oregano, palmarosa oil, patchouli, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil. But the higher boiling or solid odorants of natural or synthetic origin can be used in the present invention as adherent odorants or odorant mixtures, ie fragrances. These compounds include the compounds listed below and mixtures thereof: ambrettolide, α-amyl cinnamic aldehyde, anethole, anisaldehyde, anisyl alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzylvalerianat, borneol , bornyl acetate, α-bromostyrene, n-decyl, n-dodecyl aldehyde, eugenol, eugenol, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin,

Heptincarbonsäuremethylester, heptaldehyde, hydroquinone dimethyl ether,

Hydroxyzimtaldehyd, Hydroxyzimtalkohol, indole, Iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, Karvakrol, carvone, p-Kresolmethylether, coumarin, p-methoxy acetophenone, methyl n-amyl ketone, Methylanthranilsäuremethylester, p-methylacetophenone, Methylchavikol, p-methylquinoline, methyl-beta-naphthyl ketone, methyl-n-nonylacetaldehyd, methyl-n-nonylketon, Muskon, ß-Naphtholethylether, .beta.-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, Nonylakohol, n-octyl, p-oxy-acetophenone, Pentadekanolid, beta-phenylethyl alcohol, phenylacetaldehyde Dimethyacetal, phenylacetic, pulegone, safrole, Salicylsäureisoamylester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santaiol, skatole, terpineol, thymuses. Thymol, γ-Undelacton, vanillin, veratraldehyde, cinnamic aldehyde, Zimatalkohol, cinnamic acid, cinnamic acid ethyl ester, Zimtsäurebenzylester. The more readily volatile odoriferous substances particularly include the low boiling perfumes of natural or synthetic origin, which may be used alone or in mixtures. Examples of volatile odorants are alkyl isothiocyanates (alkyl), butanedione, limonene, linalool, and Linaylacetat propionate, menthol, menthone, methyl-n-heptenon, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a slower release of fragrance, long lasting scent. Suitable carrier materials are, for example, cyclodextrins have proved, the cyclodextrin-perfume complexes can also be coated with further excipients.

dyes

Preferred dyes, whose selection the skilled person any difficulty, have high storage stability and insensitivity to the other ingredients of the detergents or by light, and no marked substantivity towards the the dye-containing compositions substrates to be treated, such as textiles, glass, ceramics or plastic dishes to not to color.

In selecting the dye, it must be noted that the coloring agents in the case of laundry detergents do not exhibit too great an affinity for the textile surfaces and, in particular with respect to synthetic fibers, while in the case of detergents too strong affinity for glass, ceramic or plastic dishes must be avoided. At the same time must also be considered when choosing suitable colorants that colorants have different stabilities with respect to oxidation. Generally the case that water dyes to oxidation are more stable than water-soluble colorants. Depending on the solubility and hence its sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble colorants, such as the Basacid Green ® above or also above Sandolan Blue ®, dye concentrations in the range of some 10 'are typically 2 to 10 wt .-% ~ 3 is selected. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ® - dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 "3 to 10" 4 wt .-% ,

There are coloring agents preferred which can be destroyed by oxidation in the washing process and mixtures thereof with suitable blue dyes. Blautönem. It has proven to use dyes which are soluble in water or at room temperature in liquid organic substances to be advantageous. Suitable examples are anionic colorants, eg anionic nitroso. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable. blue dyes. Further suitable colorants Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.

As stated previously, containing detergency booster of the combination products preferably builders and / or bleaching compositions of the invention, wherein detergency boosters are particularly preferred with a Gerüststoff- and / or bleaching agent content above 10 wt .-%. Particularly preferred detergency amplifiers further comprise, among other conventional components of machine detergents enzymes, bleach activators / bleach catalysts and / or surfactants, preferably surfactants nichtionsiche. The following table provides an overview of some particularly preferred formulations for inventive laundry detergent booster. The proportions by weight indicated in wt .-% relate to the total weight of the respective wash booster.

Figure imgf000062_0001

Figure imgf000063_0001

As detergency boosters to "sour" as well as "alkaline" recipes are suitable.

Solution of the washing power amplifier in distilled water at 20 c C has a pH value above 10, preferably above 11 - such combination products in which a 1 wt .-% being particularly preferred. Such combination products contain as builders preferably carbonates and / or phosphates and / or silicates or alkali carrier, preferably alkali carriers from the group of metal hydroxides, preferably sodium or potassium hydroxide. Combination products containing these "alkaline" detergency boosters, are distinguished from conventional cleaners in particular by improving cleaning performance on stubborn stains such as tea or starch soiling and baked-on soils as Fettverkrustungen, branded minced meat or baked cheese.

Figure imgf000063_0002

Figure imgf000064_0001

As an alternative to the "alkaline" recipes but also "sour" Recipes can be used. Therefore continue to be combination products, preferably in which a 1 wt .-% - solution comprising the wash booster in distilled water at 20 0 C a pH below 6, preferably below fourth This "acidic" formulations contain as the acid source preferably organic acids, especially organic mono-, di- or polycarboxylic acids and / or polymeric organic acids. Particularly preferred are detergency boosters having a content of citric acid above 10 wt .-%, preferably above 20 wt by weight, preferably above 30% wt .-% and especially above 40.%.

In preferred washing power amplifiers, the sum of the parts by weight of phosphate and the weight of the carbonate and the weight of percarbonate 40-95 wt .-%, preferably between 50 and 95 wt .-%, particularly preferably between 60 and 95 wt .-% and in particular between 70 and 95 wt .-%.

Preferred detergency boosters have a surfactant content below 10 wt .-%, preferably below 6 wt .-%, preferably dependent on 4 wt .-% and in particular below 2 wt .-%.

Claims

claims:
1. Combination product for machine dishwashing, comprising a) a compartment containing a detergency booster; b) a further compartment containing a main cleaning agent; and c) instructions for use, which instructs the user to use the washing power amplifier in the pre-rinse cycle and the use of the main detergent in the main wash cycle of an automatic dishwashing process.
2. Combination products according to claim 1, characterized in that the
have detergency boosters and the main detergent different packaging systems.
3. Combination products according to claim 1 or 2, characterized in that the detergency booster and the main cleaning means comprises at least one common packaging system.
4. Combination product according to one of claims 1 or 2, characterized in that the detergency booster and the main cleaning agent having no common packaging system.
5. Combination product according to one of claims 2 to 4, characterized in that at least one of the packaging system has a moisture vapor permeability rate of 0.1 g / m2 / day to less than 20g / m2 / day when the packaging system at 23 0 C and a equilibrium relative humidity is supported by 85%.
6. Combination products according to any one of claims 1 to 5, characterized in that the detergency booster and / or the main cleaning agent is in the form of a powder.
7. Combination product according to one of claims 1 to 6, characterized in that the detergency booster and / or the main cleaning agent is in the form of a liquid.
8. Combination product according to one of claims 1 to 7, characterized in that the detergency booster and / or the main cleaning agent in the form of a compacted, preferably in the form of a tablet.
9. Combination product according to one of claims 1 to 8, characterized in that the detergency booster a builder, preferably in quantities above 10% by weight, preferably contains above 20 wt .-% and in particular above 40 wt .-%.
10. Combination product according to one of claims 1 to 9, characterized in that the detergency booster, preferably in amounts above 10 wt .-%, preferably above 20 wt .-% and especially above 40 containing a bleaching agent, wt .-%.
11. A combination product according to claim 10, characterized in that the detergency booster containing a chlorine bleach.
12. Combination product according to one of claims 10 or 11, characterized in that the detergency booster containing an oxygen bleaching agent.
13. Combination product according to one of claims 1 to 12, characterized in that the detergency booster completely consumed during the prerinse cycle.
14. Combination product according to one of claims 1 to 13, characterized in that the main cleaning means completely consumed in the course of the main wash.
15. Combination product according to one of claims 1 to 14, characterized in that the combination product further comprises a dosing aids for the detergency booster and / or for the main cleaning agent.
16. Combination product according to one of claims 1 to 15, characterized in that the instructions contained in or on the outer packaging of the washing power amplifier and / or the main cleaning agent.
17. Combination product according to one of claims 1 to 16, characterized in that the instructions for carrying out a power and / or water-saving instructs automatic dishwashing process.
18. Combination product according to one of claims 1 to 17, characterized in that the instructions for carrying out a "2in1" - or "3in1" instructs -maschinellen dishwashing.
19. Combination product according to one of claims 1 to 18, characterized in that the instructions instructs to renounce to a manual precleaning of the dishes.
20. Combination product according to one of claims 1 to 19, characterized in that the operating instructions for dispensing with a post-cleaning of the crockery, preferably for dispensing with a manual cleaning of the dishes guides.
21. Combination product according to one of claims 1 to 20, characterized in that the instructions for use of the combination product for cleaning metal surfaces, preferably for cleaning stainless steel surfaces, or for cleaning enamel surfaces or for cleaning scratch resistant coated surfaces, preferably surfaces made of Teflon ® instructs.
22. Machine dishwashing method using a combination product according to any one of claims 1 to 21, comprising the steps of a) reading a user manual, which instructs the user to use the washing power amplifier in the pre-rinse cycle and the use of the main detergent in the main wash of an automatic dishwashing process; b) introducing a washing power amplifier in the pre-wash cycle of a machine dishwashing process; c) introducing a main detergent in the main wash of an automatic dishwashing process.
23. Machine dishwashing method according to claim 22, characterized in that the detergency booster, preferably manually, is preferably on the inside of the GeschirrspDImaschinentür, metered, into the interior of the dishwasher.
24. Machine dishwashing method according to any one of claims 22 or 23, characterized in that the main cleaning means is preferably manually metered into the dosing chamber of the dishwasher.
25. Use of a combination product according to any one of claims 1 to 21 for cleaning metal surfaces, preferably stainless steel surfaces or for cleaning enamel surfaces or for cleaning scratch resistant coated surfaces, preferably surfaces made of Teflon ®.
PCT/EP2005/011064 2004-10-22 2005-10-14 Detergent or cleaning agent dosing unit WO2006045450A1 (en)

Priority Applications (4)

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DE102004051560.3 2004-10-22
DE200410051560 DE102004051560A1 (en) 2004-10-22 2004-10-22 Combination product, useful for dish washing machine, comprises compartments containing wash pack and main cleaning agent; and instructions for using wash pack and cleaning agent in the pre-washing and main washing cycle
DE102004055075.1 2004-11-15
DE200410055075 DE102004055075A1 (en) 2004-10-22 2004-11-15 Washing or Reinigungsmitteldosiereinheit

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0593952A1 (en) * 1992-10-17 1994-04-27 DISPO-Kommerz AG Product for releasing treatment agents into the wash liquid of an automatic washing or dishwashing machine
DE19845602A1 (en) * 1998-10-05 2000-04-06 Henkel Kgaa Detergent tab pack for dishwashers
EP1026230A1 (en) * 1999-02-05 2000-08-09 Unilever N.V. A machine dishwashing kit
DE10035781A1 (en) * 1999-12-13 2001-07-12 Henkel Kgaa Washing or cleaning composition portions with controlled drug release
WO2004081161A1 (en) * 2003-03-11 2004-09-23 Reckitt Benckiser N.V. Package comprising a detergent composition

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Publication number Priority date Publication date Assignee Title
GB8605734D0 (en) * 1986-03-07 1986-04-16 Unilever Plc Dispensing treatment agents
CA2425641A1 (en) * 2000-11-27 2002-05-30 The Procter & Gamble Company Dishwashing method
GB2374580B (en) * 2001-04-20 2003-07-16 Reckitt Benckiser Water-soluble containers
GB2374581B (en) * 2001-04-20 2004-01-28 Reckitt Benckiser Water soluble containers
MXPA04004523A (en) * 2001-11-14 2004-08-11 Procter & Gamble Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer.
US7033980B2 (en) * 2002-11-14 2006-04-25 The Procter & Gamble Company Automatic dishwashing detergent composition comprising encapsulated glasscare active salt

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0593952A1 (en) * 1992-10-17 1994-04-27 DISPO-Kommerz AG Product for releasing treatment agents into the wash liquid of an automatic washing or dishwashing machine
DE19845602A1 (en) * 1998-10-05 2000-04-06 Henkel Kgaa Detergent tab pack for dishwashers
EP1026230A1 (en) * 1999-02-05 2000-08-09 Unilever N.V. A machine dishwashing kit
DE10035781A1 (en) * 1999-12-13 2001-07-12 Henkel Kgaa Washing or cleaning composition portions with controlled drug release
WO2004081161A1 (en) * 2003-03-11 2004-09-23 Reckitt Benckiser N.V. Package comprising a detergent composition

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