EP2879973B1 - Combination product having a high viscosity - Google Patents

Description

The present invention relates to combination products for washing or cleaning, preferably for cleaning hard surfaces. In particular, this invention relates to combination products for machine dishwashing and a method for their use.

Detergent compositions and hard surface cleaners as well as dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional solid means increasingly lately increasingly flowable and especially liquid to gel detergent or cleaning agents gain in importance. In order to improve the cleaning performance of flowable detergents or cleaners, combination products have been proposed in the prior art which comprise a packaging means and two separate flowable detergents or cleaners located in this packaging means. This is how the international patent applications disclose WO 2007/025665 and WO 2007/025666 a packaging means and two separate, flowable washing or cleaning agents A and B contained in this packaging means, the composition A having enzymes and the composition B having no enzymes or at least little enzyme. The spatial separation of these two compositions makes it possible to separate other ingredients and characteristics of detergents or cleaners that could affect the stability of the enzymes from these enzymes or other ingredients that can negatively affect each other to separate and so on to increase the storage stability of the flowable agent. In general, therefore, the enzyme-containing composition A and the non-enzyme-containing or only in small amounts of enzymes containing composition B have different pH values. High pH values of, for example, pH 10, 11 or higher destabilize or inactivate enzymes, but are beneficial for the cleaning of stubborn stains.

While in the prior art the problem of destabilization of enzymes in the storage of flowable washing or cleaning compositions by the above-mentioned combination products is solved, there is still the problem of destabilizing enzymes in the dosage of these agents. Regardless of whether a metering by means of a Einspülschublade an automatic washing machine or a Einspülkammer an automatic dishwasher or a dosing or other metering device, the two phases mix in the metering or at least in the first phase of the washing or cleaning cycle, creating a mean pH Value is set lower than the pH of the agent B but higher than that of the agent A, whereby the enzymes are thus exposed to a higher pH than originally provided.

To achieve this object, combination products are proposed which comprise a packaging material and two separate, flowable washing or cleaning compositions A and B contained in this packaging material, wherein the composition A contains from 10 to 75% by weight of builder, 0.1 to 10% by weight. % Of enzyme preparation and 24.9 to 89.9% by weight of water and composition B contains less than 0.1% by weight of enzyme preparation, 0.5 to 90% by weight of water and at least one further ingredient of washing composition. or cleaning agents, wherein the two compositions A and B each have a viscosity of greater than 1500 mPas, wherein at least the composition B has a viscosity between 3500 and 6500 mPas. It is immaterial whether the composition A and the composition B have the same viscosity or different viscosities. At the upper limit of the viscosity, no special requirements. However, both compositions should remain flowable.

The viscosity of the media is measured using a Brookfield Viscometer DV-II + Pro (spindle 25, 50 rpm, 20 ° C). It is preferred that the viscosity of composition A is above 2000 mPas. Should more than 2 compositions be present in the packaging material separately, it is preferred that each of these compositions have a viscosity above 1500 mPas, preferably above 2000 mPas. In a particularly preferred embodiment of the invention, at least one of the compositions A and B, preferably at least the composition B; a viscosity between 3500 and 6500 mPas, especially between 4000 and 6000 mPas, wherein at least the composition B has a viscosity between 3500 and 6500 mPas.

The adjustment of the viscosity of the compositions A and B and thus also, if appropriate, a difference in viscosity between the compositions A and B can be carried out in various ways familiar to the person skilled in the art. One possibility is to add a thickening agent to one of the two compositions or, if necessary, to both compositions. Another possibility is to add to the composition, which is to have the higher viscosity of the two compositions, a thickening agent or a thickening agent in higher amounts than the agent with the lower viscosity.

For the purposes of the present invention, polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers. Preferred thickeners are xanthans and xanthan gum.

Also preferred are thickening polyacrylates, which are available, for example, under the trade name Carbopol®, or known thickening agents based on starch or cellulose.

The content of polymeric thickener is preferably 0.1 to 5 wt .-% and in particular 0.5 to 3 wt .-%, based on the particular composition to be thickened.

Another possibility, which can also be used in combination with a thickener, consists in varying the amounts of certain solid raw materials in compositions A and B. For this purpose, builders, for example, which are added in solid form in the preparation of the compositions, are suitable. For example, in phosphate containing compositions different amounts of phosphate can be used for this purpose. Phosphate-containing compositions, in particular phosphate-containing compositions A, can therefore even be free of additionally added thickening agents.

The combination products according to the invention further comprise, in addition to the two liquid cleaning compositions A and B, a packaging means. In this packaging material, the two cleaning compositions A and B are separated from each other, that is, they do not form a common phase boundary, but rather are located in separate, for example by a partition separate areas of the packaging material.

As such a packaging means, for example, a water-insoluble two- or multi-chamber container is suitable. Such a two- or multi-chamber container does not necessarily, but typically has a total volume of between 100 and 5000 ml, preferably between 200 and 2000 ml. The volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml. Preferred two- or multi-chamber containers have a bottle shape.

For metering the liquid washing or cleaning agent, the two- or multi-chamber container preferably has at least one spout, which may be configured, for example, in the form of a common spout for all compositions contained in the bottle. However, preferred are those two- or multi-chamber container, in which each of the receiving chambers of the container has its own spout. By such a configuration, for example, a contamination of individual chambers by ingredients from another chamber is avoided.

Combination products according to the invention, in which the packaging means is a water-insoluble two- or multi-chamber container, wherein preferably each of the receiving chambers of the packaging means is provided with a spout, are preferred.

In order to put a liquid agent in a pre-portioned form, the use of water-soluble films in the form of bags is common. The person skilled in the art knows how to dissolve water One-chamber or multi-chamber bag can be produced. In a preferred embodiment of the invention, the packaging means therefore consists of a water-soluble multi-chamber bag.

The dosage of the two flowable washing or cleaning compositions A and B can be done in the case of a detergent, for example via a metering drawer of the washing machine or a separate metering device such as a dosing ball, which is placed directly in the washing drum. In the case of a dishwasher detergent product, the dosage can be done, for example, in the metering chamber in the door or an additional metering container in the interior of the dishwasher or directly on the soiled dishes. Alternatively, the two detergents or cleaning agents can also be metered onto one of the inner walls of the dishwasher, for example the inside of the door.

In a preferred embodiment of the invention, a water-soluble multi-chamber bag which has a disposable portion of a machine dishwashing agent is metered via the metering chamber or the cutlery box, but advantageously via the metering chamber.

The washing or cleaning compositions A and B of these embodiments must be flowable under use conditions. This is understood to mean that the compositions A and B can be metered without further aids from the packaging material into the intended machine or metering device. Should the packaging means be made of a flexible material, compositions A and / or B may also exhibit rheological behavior such that they are not flowable in the packaging material at rest, but can be easily compressed by the user on the packaging or by shaking transfer a flowable state and thus can be dosed. Typically, these are liquid agents which are flowable under normal conditions of use and whose viscosities can vary widely. In the context of the present invention, the liquid preparations also include gelatinous or pasty agents.

Preferred combination products of the present invention include flowable, especially liquid to gel, detergents which are suitable for use in automatic dishwashing machines. Water-soluble multi-compartment bags with compositions A and B which differ significantly in their viscosities and / or both viscosities of above 2500 mPas, wherein at least the composition B has a viscosity between 3500 and 6500 mPas, are preferred.

In particular, water-soluble multi-chamber bags have proven to be suitable, in which the composition B has a higher viscosity than the composition A. Such embodiments are particularly preferred when the ingredients of the composition A are to distribute faster in the washing or cleaning liquor and thus the washing or Purification process should be made available earlier than ingredients of the composition B. Especially in the case of water-soluble multi-chamber container, the higher viscosity of the composition B compared to the composition A has proven to be advantageous, since so a time-delayed distribution of the composition B over the composition A can be achieved can, without the film of multi-chamber bag special requirements would have to be made, for example, that the film, which forms a chamber whose content is to be distributed more slowly in the washing or cleaning liquor, compared to the film, which forms the other chamber, by the expert known measures such as coating is modified so that it dissolves more slowly. Nor is it necessary that the multi-chamber containers must be made of different films with different water-dissipation kinetics. On the contrary, due to the different viscosities of the two compositions A and B, the multi-chamber containers can be produced from one and the same film material.

The ingredients which are washing or cleaning-active in the combination products according to the invention include the builders. The builders include, in particular, zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. The builders are included at least in Composition A, but may also be included in Composition B. However, in a preferred embodiment of the invention, the composition B does not contain more than 5% by weight of builder, based on the total composition, and is preferably free of builders.

As silicates come amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, but also crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration.

In the context of the present invention, it is preferred that these silicates, preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, be present in the cleaning compositions A and / or B in amounts of from 2 to 40% by weight, preferably 3 to 30 wt .-% and in particular from 5 to 25 wt .-%, each based on the total composition, are included.

To date, phosphates are still preferred in machine dishwashing detergents in many parts of the world. Among the large number of commercially available phosphates, the alkali metal phosphates have, with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

If phosphates are used as washing or cleaning substances in the liquid cleaning compositions A and / or B in the context of the present application, preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium and / or Pentakaliumtriphosphat (sodium and / or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 8 to 45 wt .-% and in particular from 10 to 40 wt .-%, each based on the total composition. In a preferred embodiment of the invention, the composition A has more phosphates than the composition B. In a further preferred embodiment, the composition A comprises phosphates in amounts of from 20 to 45% by weight and in particular from 20 to 40% by weight, respectively based on the composition A, on. Composition B is preferably free of phosphates.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Another important class of phosphate-free builders are aminocarboxylic acid and / or its salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or their salts and glutamine diacetic acid (GLDA) or their salts. The content of these aminocarboxylic acids or their salts may be, for example, based on the total composition, 0.1 to 15 wt .-%.

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

As a further component, the combination products according to the invention contain enzymes to increase the washing or cleaning performance. These include in particular proteases, amylases, lipases, cutinases, cellulases, hemicellulases, which include in particular mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases, or oxidoreductases, and preferably their mixtures. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-%, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of usable amylases are the Bacillus licheniformis α-amylases , from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

The enzymes can be used in any form known in the art, a so-called enzyme preparation. These include, for example, the solid preparations obtained by granulation, extrusion, encapsulation or lyophilization or, especially in the case of liquid or gel-form compositions, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. In the context of the present invention, enzyme or enzymes are each understood to mean a corresponding enzyme preparation if it is not clearly indicated that the active protein is meant.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule or a single enzyme preparation can have multiple enzyme activities.

As stated at the outset, the proportion by weight of the enzymes in the total weight of the flowable cleaning composition A is from 0.1 to 10% by weight, advantageously from 0.2 to 9% by weight and in particular from 0.5 to 8% by weight. Particularly good cleaning performances are achieved when the proportion by weight of the enzymes in the total composition is 1 to 8% by weight and preferably 2 to 5% by weight.

Although the flowable cleaning composition B may of course also contain enzymes, it is preferred that the enzyme content of the cleaning composition B is as low as possible, and in particular less than 0.1 wt .-%. Particularly preferred combination products are characterized in that the flowable cleaning composition B contains no enzymes and the entire amount of enzyme is provided via the flowable cleaning composition A.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations and / or amylase preparations are used. In a preferred embodiment of the invention, the liquid composition A has an enzyme preparation containing amylase. In a particularly preferred embodiment, the liquid composition A comprises a combination of protease and amylase preparations.

The combination products of the invention may also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.

Other enzyme stabilizers are known to those skilled in the art.

Particular preference is given to using combinations of stabilizers, for example of polyols, such as glycerol, ethylene glycol, propylene glycol or sorbitol, 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 favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

The compositions according to the invention described above may contain, in addition to the ingredients described above, other washing- and cleaning-active substances, preferably washing and cleaning-active substances from the group of surfactants, polymers, glass corrosion inhibitors, corrosion inhibitors, alkali carriers, fragrances and perfume carriers, dyes and preservatives. Bleaching agents and bleach activators, especially liquid bleach activators may also be present. These preferred ingredients will be described in more detail below.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

The anionic surfactants include those having at least one sulfate or sulfonate group, preferably selected from fatty alcohol sulfates, alkyl ether sulfates, alkanesulfonates and alkylbenzenesulfonates. Preference is given here to C ₁₂ -C ₁₈ fatty alcohol sulfates, for example sulfophone K 35 (BASF, Germany), ethoxylated C ₁₂ -C ₁₄ -alcohol sulfates, for example Texapon N70 (BASF, Germany), secondary C ₁₃ -C ₁₇ -alkanesulfonates, eg Hostapur SAS 93 (Clariant, Germany), and also linear C ₈ -C 18 -alkylbenzenesulfonates, in particular dodecylbenzenesulfonate or C ₉ -C ₁₃ -benzenesulfonate.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. These include, for example, ethoxylated and / or propoxylated alcohols or fatty alcohols as well as nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides.

Nonionic surfactants from the group of the alkoxylated alcohols, in particular the alkoxylated linear C ₈ -C ₁₈ -alcohols or the methyl-branched straight-chain or odd-chain alcohols, particularly preferably from the group of the mixed alkoxylated alcohols and in particular from the group of the EO-AO-EO-nonionic surfactants, are used with particular preference.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which comprise alternating ethylene oxide and alkylene oxide units exhibit. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 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 have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -R ² ,

in the R ¹ and R ² independently of one another for a straight-chain or branched, saturated or ein- or. polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.

Very particularly preferred nonionic surfactants in a preferred embodiment have the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH ( OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, in particular 4 to 20 carbon atoms, or mixtures thereof and x and z are values between 0 and 40 and y is a value of at least 15.

The addition of these nonionic surfactants has proved to be advantageous, in particular with regard to the rinse power and the drying. In a preferred embodiment, the automatic dishwashing detergent, based on the sum of the compositions A and B, contains nonionic surfactant of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (CH ₃ ) O] _z CH ₂ CH (OH) R ² in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1.0 to 6 wt .-%.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y, contain CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20 carbon atoms or mixtures thereof and y is a value between 15 and 120, preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants includes, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _{2 -26} , for example the C _8-12 fatty alcohol (EO) ₂₂ - 2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

Another nonionic surfactant is a surfactant of the general formula R ¹ CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 -R ² , where R ¹ and R ² independently of one another are a linear or branched aliphatic hydrocarbon radical From 2 to 20 carbon atoms are particularly preferred.

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.

Also surfactants of the general formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² are preferred in the R ¹ for a linear or branched aliphatic hydrocarbon radical 4 to 22 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH ₂ CH (CH ₃ ) O] and [CH ₂ CH ₂ O] randomized, ie in the form of a random random distribution.

The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ^{2 are} independent each represent 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 represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0 , 5 and 1.5 are very particularly preferred.

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 [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

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

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined 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 here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) 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 zu

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

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is 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 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Further preferably used nonionic surfactants are nonionic surfactants of the general formula R ¹ O (AlkO) _x M (OAlk) _y OR ² , where
R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms;
x and y independently represent values between 1 and 70; and
M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH ₂ CHR ³ and CHR ³ CHR ⁴ , where
R ³ and R ⁴ independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.

• R, R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen;
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen

Nonionic surfactants of the general formula are preferred here

R ^{1 is} -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₃ CH (OH) -R ² ,

in which

• R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 6 to 22 carbon atoms;
• x and y independently represent values between 1 and 40

Particular preference is given here to compounds of the general formula R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) _x CH ₂ CHR (OCH ₂ CH ₂ ) _y O-CH ₂ CH (OH) -R ² , in where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH ₂ -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.

• R¹ und R² unabhängig voneinander für einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen;
• R³ und R4 unabhängig voneinander für H oder für einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und
• x und y unabhängig voneinander für Werte zwischen 1 und 40 stehen.

In a further preferred embodiment, the nonionic surfactant is selected from nonionic surfactants of the general formula

R ^{1 is} -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² ,

in the

• R ¹ and R ² independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;
• R ³ and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
• x and y independently represent values between 1 and 40.

Preference is given here in particular to compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, are provided in the OR ³ and R ⁴ is H, and the subscripts x and y are independently of one another assume values from 1 to 40, preferably from 1 to 15.

Especially preferred particular compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the radicals R ¹ and R ² are independently saturated alkyl radicals having from 4 to Represent 14 carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.

Also preferred are those compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH ₂ ) _y OR ² , in which one of the radicals R ¹ and R ^{2 is} branched.

Very particularly preferred compounds of the general formula R ¹ -O (CH ₂ CH ₂ O) _x CR ³ R ⁴ (OCH ₂ CH _{2) y} OR ^2, in which the indices x and y are independently values 8-12 accept.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the rinse performance and drying can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

The content of the nonionic surfactants, based on the total composition, in a preferred embodiment is 0.1 to 20 wt .-%, more preferably 0.5 to 15 wt .-%, in particular 2 to 10 wt .-%.

Preferred embodiments of the present invention contain as further constituent at least one anionic polymer. Preferred anionic polymers here are the copolymeric polycarboxylates and the copolymeric polysulfonates (sulfopolymers). Mixtures of these polymers can also be used. The proportion by weight of the anionic polymer based on the total compositions is in a preferred embodiment from 0.1 to 20 wt .-%, preferably from 0.5 to 18 wt .-%, particularly preferably from 1.0 to 15 wt .-% and in particular from 4 to 14 wt .-%.

A particularly preferred subject of the present invention comprises one or more copolymeric anionic polymers selected from the group of hydrophobically modified polycarboxylates and sulfopolymers. By means of such a mixture of anionic copolymers, it is possible to achieve an improvement in the rinsing and drying properties of these agents with at the same time a low deposit formation.

The copolymers may have two, three, four or more different monomer units.

Preferred copolymeric sulfopolymers contain not only sulfonic acid-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH, in which R ¹ to R ^{3 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, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.

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

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

in which R ⁵ to R ⁷ independently of one another are -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 or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O ) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

Preferred in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of 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 .

In a further preferred embodiment, in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

1. i) Carbonsäuregruppen-haltige Monomer(e)
2. ii) Sulfonsäuregruppen-haltige Monomer(e)
3. iii) nichtionische Monomer(e).

In a further preferred embodiment of the invention, the agents contain at least one anionic copolymer comprising

1. i) carboxylic acid group-containing monomer (s)
2. ii) sulfonic acid group-containing monomer (s)
3. iii) nonionic monomer (s).

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another are -H, -CH ₃ or -C ₂ H ₅ , X represents an optionally present spacer group selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α Methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate, N - (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N - (2-ethylhexyl) acrylamide, Acrylsäurectctyle ster, Methacrylsäureoctylester, N - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N - (stearyl) acrylamide, behenyl acrylate, Methacrylsäurebehenylester and N - (behenyl) acrylamide or mixtures thereof.

1. a) mindestens ein Monomer gemäß der Formel
   
   wobei
   • R¹ und R⁴ unabhängig voneinander für Wasserstoff oder C_1-6-Alkyl stehen;
   • R² und R³ unabhängig voneinander für C_1-6-Alkyl, Hydroxy-C_1-6-alkyl oder Amino-C_1-6-alkyl stehen;
   • m und n unabhängig voneinander für einen Wert von 1 bis 3 stehen;
   • X^- für ein Gegenion steht;
2. b) mindestens ein hydrophiles Monomer, das mindestens eine Säure-Gruppe trägt;
3. c) mindestens ein hydrophiles nichtionisches Monomer.

Cationic or amphoteric polymers may also be suitable. These include, for example, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF), condensation products of polyglycols and amines, polyethyleneimine, copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyamino-polyamides and their crosslinked water-soluble polymers, quaternized ammonium salt polymers. Particular preference is given to amphoteric polymers, as described in the published patent applications WO 2010/107554 and WO 2010/000629 to be discribed. These are polymers containing

1. a) at least one monomer according to the formula
   
   in which
   • R ¹ and R ^{4 are} independently hydrogen or C _1-6 alkyl;
   • R ² and R ^{3 are} independently C _1-6 alkyl, hydroxyC _1-6 alkyl or aminoC _1-6 alkyl;
   • m and n independently represent a value of 1 to 3;
   • X ^{- stands} for a counterion;
2. b) at least one hydrophilic monomer bearing at least one acid group;
3. c) at least one hydrophilic nonionic monomer.

Examples of alkali carriers are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates or alkali metal bicarbonates or alkali metal sesquicarbonates, preference being given to using the alkali metal hydroxides and alkali metal carbonates, in particular sodium hydroxide, potassium hydroxides, sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.

It has been shown that the performance of the cleaning agents can be improved by organic solvents. These organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the sense of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t- Butyl ether and mixtures of these solvents.

The organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of tea stains.

Preferred dyes, the selection of which presents no difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic crockery do not stain them.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as Isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

Phosphonates are usually used as a complexing agent; they can be used in composition A or in composition B or in both composition A and composition B. Preferred phosphonates are hydroxyethane di-phosphonates and diethylene triamine penta (methylene phosphonates). In a preferred embodiment of the invention, at least composition B contains phosphonate, preferably both composition A and composition B contain phosphonates. The content of the agents in phosphonates is preferably 1 to 10 wt .-%.

The pH at 20 ° C of compositions A and B is within the usual limits. Preferably, the enzyme-containing composition A has a pH (20 ° C) between 6 and 9; the pH of the composition B is dependent on the particular ingredients chosen, but may well be higher than the pH of the composition A.

In a preferred embodiment of the invention, composition B contains a peroxy bleach, bleach activators and / or bleach catalysts. While in principle any of the known peroxygen bleaches can be used, it is particularly preferred that the composition B contains a percarbonate or a peroxycarboxylic acid, for example from the class of imidoperoxycarboxylic acids.

Peroxoic acid, peroxoacetic acid, peroxo-propionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, mono- or di-peroxophthalic acids, 1,12-diperoxododecanedioic acid, nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid, and mixtures of these. The use of imidoperoxycarboxylic acids is preferred. Particularly preferred imidoperoxycarboxylic acids include 6-phthalimidoperoxohexanoic acid.

The individual partial compositions may be solid, pasty or liquid or may also contain mixtures of solid with liquid or pasty components. In a preferred embodiment of the invention, the composition B comprises an aqueous dispersion of a peroxycarboxylic acid which may contain between 1 and 40% by weight of a peroxycarboxylic acid. Advantageously, the aqueous dispersion contains between 1 and 20 wt .-% imidoperoxycarboxylic acid and particularly preferably 1 to 10 wt .-% imidoperoxycarboxylic acid, especially 6-Phthalimidoperoxohexansäure.

In a preferred embodiment of the invention, composition B contains both peroxy bleach and phosphonate. Advantageously, the weight ratio of the peroxygen bleach to the phosphonate is 0.5: 1 to 5: 1, preferably 1: 1 to 4: 1, with an to-peroxy bleach to the phosphonate 0.5: 1 to 5: 1, preferably 1: 1 to 4: 1, wherein a composition B is particularly preferred which peroxo bleach, especially of the imidoperoxycarboxylic acid type, and phosphonate in a weight ratio above 1: 1 having.

The compositions A and B may be present in any desired ratio. However, in a preferred embodiment of the invention, the proportion of composition A in the total composition is from 40 to 98% by weight and in particular from 50 to 95% by weight, while the proportion of composition B in the total composition is from 2 to 60% by weight. and in particular 5 to 50 wt .-% makes.

1. A:
   • 10 bis 75 Gew.-% Gerüststoff(e);
   • 0,1 bis 10 Gew.-% Enzympräparation;
   • 24,9 bis 89,9 Gew.-% Wasser; und
2. B:
   • weniger als 0,1 Gew.-% Enzympräparation;
   • 0,5 bis 90 Gew.-% Wasser;
   • sowie mindestens einen weiteren Inhaltsstoff von Wasch- oder Reinigungsmitteln, vozugsweise mindestens ein Peroxobleichmittel,

wobei die beiden Zusammensetzungen A und B jeweils auf eine Viskosität von größer als 1500 mPas eingestellt worden sind, wobei mindestens die Zusammensetzung B eine Viskosität zwischen 3500 und 6500 mPas aufweist.In a further embodiment of the invention, an automatic washing or cleaning agent process, in particular automatic dishwashing process is claimed, wherein from a combination product according to the invention, comprising a packaging material and at least two separate, flowable washing or cleaning compositions A and B in this packaging means in a in the machine provided or dosed into a separate metering device or directly into the machine and then the washing or cleaning process is set in motion. The two compositions A and B have the following compositions

1. A:
   • From 10% to 75% by weight of builder (s);
   • 0.1 to 10% by weight of enzyme preparation;
   • 24.9 to 89.9% by weight of water; and
2. B:
   • less than 0.1% by weight of enzyme preparation;
   • 0.5 to 90% by weight of water;
   • and at least one further ingredient of washing or cleaning agents, preferably at least one peroxygen bleach,

wherein the two compositions A and B have each been adjusted to a viscosity of greater than 1500 mPas, wherein at least the composition B has a viscosity between 3500 and 6500 mPas.

Examples

In the case of the product according to the invention, 20 g each of compositions A and B from a two-chambered bottle were placed in the dosing chamber of a Miele G698SC dishwasher (program 50 ° C., water hardness 21 ° dH) and tested against a reference product under standard conditions of IKW , wherein the composition B of the comparative product had a significantly lower viscosity than the composition B of the product according to the invention. Table 1: Composition A in% by weight Composition A product comparison tripolyphosphate 23 23 Protease preparation 3.0 3.0 Amylase preparation 1.00 1.0 Fatty alcohol (EO) ₂₂ -2-hydroxyalkyl ether 5.0 5.0 Acrylic acid sulfopolymer (Na salt) 12.0 12.0 phosphonate 2.4 2.4 sodium citrate 5.0 5.0 Monoethanolamine 7.0 7.0 Leftovers and water Ad 100 Ad 100 Viscosity (Brookfield Viscometer DV-II + Pro, spindle 25, 50 rpm, 20 ° C) 4200 mPas 4200 mPas Composition B product comparison 6-phthalimidoperoxyhexanoic acid 4 4 phosphonate 0.6 0.6 Xanthan gum 1.5 <0.5 water Ad 100 Ad 100 Viscosity (Brookfield Viscometer DV-II + Pro, spindle 25, 50 rpm, 20 ° C) 4000 mPas 350 mPas tea egg yolk Stärkemix product 9.0 2.4 8.0 comparison 8.0 2.1 7.0

While contaminations such as milk, minced meat and oats for the product according to the invention and the comparative product almost identical cleaning performance were found in egg yolk and especially in tea and starch soiling the advantages of the product according to the invention over the comparison product are clearly visible.

Claims (10)

1. A combination product, comprising a packaging means and at least two flowable washing or cleaning compositions A and B which are separated from one another and located in said packaging means, the compositions A and B containing in each case:

   A:

   - 10 to 75 wt.% builder(s);

   - 0.1 to 10 wt.% enzyme preparation;

   - 24.9 to 89.9 wt.% water; and

   B:

   - less than 0.1 wt.% enzyme preparation;

   - 0.5 to 90 wt.% water; and

   - at least one additional ingredient of washing or cleaning agents; characterized in that the two compositions A and B each have a viscosity of greater than 1500 mPas (measured using a Brookfield Viscometer DV-II+Pro, spindle 25, 50 rpm, 20 °C), at least composition B having a viscosity of between 3500 and 6500 mPas.
2. The combination product according to claim 1, characterized in that the packaging means is a water-insoluble two- or multi-component container, preferably each of the receiving chambers of the packaging means being provided with an outlet.
3. The combination product according to one of claims 1 or 2, characterized in that the viscosity of composition A is over 2000 mPas.
4. The combination product according to one of claims 1 to 3, characterized in that composition B comprises a peroxy bleaching agent, preferably a peroxycarboxylic acid, in particular an imidoperoxycarboxylic acid.
5. The combination product according to one of claims 1 to 4, characterized in that composition B is an aqueous dispersion which contains 1 to 40 wt.% of a peroxycarboxylic acid, preferably 1 to 20 wt.%, in particular 1 to 10 wt.% of an imidoperoxycarboxylic acid.
6. The combination product according to one of claims 1 to 5, characterized in that phosphonates are contained in composition A and/or B.
7. The combination product according to one of claims 1 to 6, characterized in that composition B contains peroxy bleaching agent and phosphonate, phosphonate preferably also being contained in composition A.
8. The combination product according to one of claims 1 to 7, characterized in that, in composition B, peroxy bleaching agent is present in a weight ratio to phosphonate of 0.5:1 to 5:1, preferably 1:1 to 4:1, a composition B which comprises peroxy bleaching agent, in particular of the imidoperoxycarboxylic acid type, and phosphonate in a ratio above 1:1 being particularly preferred.
9. The combination product according to one of claims 1 to 8, characterized in that the proportion of composition A in the total composition makes up 40 to 98 wt.% and in particular 50 to 95 wt.%, while the proportion of composition B in the total composition makes up 2 to 60 wt.% and in particular 5 to 50 wt.%.
10. An automatic washing or cleaning agent method, in particular an automatic dishwashing agent method, characterized in that, from a combination product according to one of claims 1 to 9, the washing or cleaning compositions A and B are dosed into a dosing apparatus that is provided in the machine or is separate or are dosed directly into the machine, and subsequently the washing or cleaning process is started.