DE102013208599A1 - Combination product with improved outflow behavior - Google Patents

Abstract

The present invention relates to combination products for washing and cleaning, in particular for machine dishwashing, and a method for their use, the combination products comprising: a packaging means and at least two separate, flowable washing or cleaning compositions A and B contained in this packaging means, wherein contain the compositions A and B.
A: - 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
B: - 10 to 75% by weight of builder (s);
Less than 0.1% by weight of enzyme preparation;
- 25 to 90 wt .-% water;
wherein the first normal stress difference of the two compositions A and B in the shear rate range up to 5000 s-1 is not higher than 1800 Pa, preferably not higher than 1600 Pa.

Description

The present invention relates to combination products for washing and 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, it has not only been proposed in the prior art to use enzymes, but also combination products are described which comprise a packaging material and two separate flowable detergents or cleaning agents in this packaging material. Thus, the international patent application discloses WO 2007/025665 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 cleaning agents that could affect the stability of the enzymes from these enzymes. 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.

Although the problem of destabilization of enzymes in the storage of flowable washing or cleaning composition is solved by the above-mentioned combination products, the use, in particular the dosage of these agents has the problem that the two formulations show different flow properties due to different ingredients. This is problematic in handling insofar as the jets emerging from the packaging material show different outflow behavior and, for example, divide by "onion-shaped" widening of a jet and the associated deceleration and kinking. This makes the dosage in a dosing of an automatic dishwasher very difficult and raises the consumer displeasure. Furthermore, it also leads to uneven emptying, which leads to the waste of resources and complaints of consumers.

It is known in the prior art that, for as uniform a flow as possible of the components from the two chambers of the packaging means, the viscosities of the two compositions may not differ significantly. Here, the term "viscosity" refers to the total function of viscosity as a function of shear rate, i. H. the two compositions should have similar viscosity functions. In the present application, the viscosity functions were determined by a rotary rheometer type AR G2 from TA Instruments, unless otherwise stated at a temperature of 20 ° C with a cone-plate measuring system with 40 mm diameter and 1 ° or 2 ° cone angle.

However, this adjustment of the viscosities does not necessarily solve the problem of different outflow behavior. In other words, even very similar viscosity functions of the two compositions do not automatically ensure that a satisfactory leakage behavior is produced.

It has now surprisingly been found that the emptying behavior of the two chambers of a two-chamber system is particularly uniform and the metering is particularly favorable if after the nozzle in both components as small strand expansion ("onion") (B _ex = D _ex / D ₀ with D _ex = measured beam diameter, D ₀ = nozzle diameter, B _ex = measured strand expansion).

For strand expansion of non-Newtonian fluids, note the following: It is known from the literature that fluids (non-Newtonian fluids as well as Newtonian fluids) undergo slight strand expansion upon passage through a nozzle. This strand expansion is caused by the change in the velocity profile due to the omission of the wall friction after exiting the nozzle and thus has hydrodynamic reasons B _hydro . In addition, non-Newtonian fluids experience a strand expansion, which is essentially determined by the material properties. In order to determine the strand expansion B caused by these material properties, the measured strand expansion B _ex must be corrected by the hydrodynamic component of the strand expansion (B = B _ex - B _hydro ). In the literature, the value for B _{hydro is} 0, 13 indicated ( Klemens Kohlgruber, "The co-rotating twin-screw extruder, p. 46, Carl Hanser Verlag Munich, 2007 ).

In order to keep the strand expansion B _ex as low as possible, so also the strand expansion component B must be as low as possible. For the purposes of the present invention, the smallest possible strand widening means that, measured with a nozzle of 20 mm length and 2.5 mm diameter, a flow rate of 320 ml / min and a temperature of 23 ° C., the strand expansion B _{ex is} not greater than 38%, preferably not greater than 33%, particularly preferably not greater than 23%, resulting in a strand expansion component B not greater than 25%, preferably not greater than 20%, particularly preferably not greater than 10%. In the ideal case of a Newtonian fluid, the strand expansion component B would therefore be zero. The beam expansion was measured in the context of the present application by means of an optical method: A liquid flow was produced at a flow rate of 320 ml / min vertically downwards through a nozzle with a length of 20 mm and a diameter of 2.5 mm. The temperature was 23 ° C. The beam was recorded with a video camera. In the picture, the maximum diameter of the jet after exit from the nozzle was measured and B _ex calculated. Subsequently, it was corrected according to the above formula and B was calculated.

One reason why the strand expansion ("onion formation") the Ausfließverhalten is particularly unfavorable influenced, as already mentioned above, the following: Due to the strand expansion, the cross-sectional area of the beam increases. In the stationary state, for reasons of continuity, at each point along the jet inside and outside the nozzle, the same amount of liquid must flow past per unit of time. This means that in the expanded beam with increased cross-section, the flow velocity must be reduced. The liquid is thus slowed down by its rheological properties immediately after exiting the nozzle. If a user attempts to dose the product in a direction which is not exactly vertical, the beam slowing caused by the strand expansion causes the jet not to "squirt out" of the nozzle but to quickly bend down vertically in a vertical direction. So the behavior is not what a user would intuitively expect, but the liquid "swells" out of the nozzle and immediately bends down. The nozzle thus "smudges" in the sensation of the user. As the pressure on the bottle increases, so does the expansion of the jet. By pushing harder - against intuition - no further spraying from the nozzle can be achieved. This is considered by the user as a little aesthetic flow behavior and makes it difficult to dosing in the dosing.

A physicochemical quantity which is responsible for the occurrence of the beam expansion ("onion") after the nozzle, among others, is the first normal stress difference N ₁ . The definition of this rheological size is known to the person skilled in the art and described in the relevant literature: In rheology, the stress represents a tensor size. This tensor can be represented by a 3 × 3 matrix with the components (read line by line) σ _xx , σ _xy σ _xz σ _yx , σ _yy σ _yz , σ _zx σ _zy σ _zz . The components σ _xy = σ _yx , represent the shear stress (shear stress), the diagonal components σ _xx , σ _yy , σ _zz are called normal stresses.

The first normal voltage difference N ₁ is the difference of the first two diagonal components of the stress tensor N ₁ = σ _xx - σ _yy . By forming the difference, an isotropic pressure (eg hydrostatic pressure) does not contribute to N1. N1 is therefore exclusively of rheological origin. In contrast to the shear stresses σ _xy , which cause the liquid to flow, the normal stresses act perpendicular to the flow lines and / or the boundaries of the liquid. If a jet exits a nozzle, these voltages, if present, cause the beam diameter to increase. Many non-Newtonian flow fluids, especially surfactant and polymer solutions, exhibit measurable normal stresses at higher shear rates.

It has now been found that the Ausfließverhalten is particularly aesthetically and application technology favorable if the first normal voltage difference N1 is particularly small. In this case, no substantial beam expansion ("onion") forms on exit from the nozzle and the kinking of the jet can be avoided.

In a first aspect, the present invention thus relates to a combination product comprising a packaging means and two separate, flowable detergent or cleaner compositions A and B contained in said packaging means, said composition A being from 10 to 75% by weight of builder (s), 0.1 to 10 wt .-% enzyme preparation and 24.9 to 89.9 wt .-% water and the composition B 10 to 75 wt .-% builder (s), less than 0.1 wt .-% enzyme preparation and 25 to 90 wt .-% water, wherein the first normal stress difference N1 of the two compositions A and B in the shear rate range to 5000 s-1 is not higher than 1800 Pa, preferably not higher than 1700 Pa and more preferably not higher than 1600 Pa. It is preferred that the viscosities of the two compositions at each same shear rate between 0.1 s ^-1 and 5000 s ^-1 by not more than the factor 3, preferably factor 2, particularly preferably not more than the factor 1, 5, ie the ratio of the viscosity of the composition A to the viscosity of the composition B at the same shear rates in the range 0.33-3, preferably 0.5-2, particularly preferably in the range 0.67-1.5.

The first normal voltage difference can be, for example, using a modern rotary rheometer (here, for example, an AR G2 TA-Instruments) using a cone-plate measuring system (here a cone with 40 mm diameter and 2 ° cone angle) based on the normal force on the cone determine. The following applies: N ₁ = 2F _z / πR ² with F _z : normal force on the cone, R: radius of the cone. In particular, for high shear rates, this expression must still be corrected by an inertia term, which is also known from the relevant specialist literature. At high rotational speeds of the measuring system namely cause the centrifugal forces to a negative pressure in the sample and thus to a normal force on the measuring system, which counteracts the rheological normal force. N ₁ = 2 * Fz / (π * R ² ) - 0.15 * ρ * ω ² * R ² .

Where ω is the angular velocity of the measuring system, and ρ is the density of the liquid. The first normal stress differences stated in this application are each retroactively corrected for inertia according to the above formula, provided that they were determined with an AR G2. Similarly, all rheological measurements in this application were made at a temperature of 20 ° C unless otherwise specified.

Another device used to measure normal voltage differences in this application is the Physica MCR 501 from Anton Paar. Here, a cone-plate measuring system with 50 mm diameter and 1 ° cone angle was used, also at a temperature of 20 ° C. In this system, the above-described subsequent inertia correction by the user is not required. The measured values agree well with the expected errors between the two devices.

The combination products described herein further comprise, besides 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 detergent or cleaning agent, 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 in which the packaging means is a water-insoluble two- or multi-chamber container, wherein each of the receiving chambers of the packaging means is provided with a spout, are therefore preferred.

Each spout may in particular have the form of a metering nozzle. Such a metering nozzle preferably has a height of 0.5-10.0, in particular 2.0 to 5.0 mm and / or a width of 0.5 to 10.0, in particular 1.5 to 5.0 mm.

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.

The washing or cleaning compositions A and B must be able to flow under conditions of use. 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. In a further preferred embodiment of the invention, the liquid compositions are based on an aqueous basis.

Preferred combination products of the present invention include flowable, especially liquid to gel, detergents which are suitable for use in automatic dishwashing machines.

The liquid cleaning compositions A and B present separately from one another in the combination products described herein contain builders in addition to other washing- or cleaning-active ingredients. The builders include, in particular, zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

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, 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 silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in the liquid cleaning compositions A and / or B in amounts of 2 to 40 wt .-%, preferably from 3 to 30 wt .-% and in particular from 5 to 25 wt .-%, each based on the weight of the respective cleaning composition A or B, 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, with particular preference of pentasodium and / or pentakalium triphosphate (sodium and / or potassium tripolyphosphate) in the washing and cleaning industry have 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 limescale deposits on machine parts and / 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 weight of the respective cleaning composition. In a preferred embodiment of the invention, the composition A has less phosphates than the composition B. In a further preferred embodiment, the composition A phosphates in amounts of 5 to 15 wt .-%, based on the composition A, and the composition B of 10 to 20 wt .-%, based on the composition B, on, with the proviso that the amount of phosphate in composition B is higher than in composition A.

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 its salts, and glutamic diacetic acid (GLDA) or its salts. The content of these aminocarboxylic acids and / or their salts may be, for example, based on the sum of the compositions A and B, between 0.1 and 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 constituent, the combination products described herein 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 α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, as well as the further developments of the abovementioned amylases, which have been improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the 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 enzyme in the total weight of the cleaning composition A is 1 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 preparation. The amounts of enzyme preparations in the composition A are advantageously between 1 and 10 wt .-%, based on the composition A.

The combination products described herein 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.

In various preferred embodiments, the agents described above contain as further constituent at least one anionic polymer from the group of copolymeric polysulfonates (sulfopolymers). By means of such anionic copolymers, it is possible to achieve an improvement in the rinsing and drying properties of these agents with simultaneously low deposit formation. In addition, it has been found to stabilize the enzymes in the enzyme-containing composition A positive when such a sulfopolymer and a complexing agent, such as HEDP, are included.

The proportion by weight of the anionic polymer based on the sum of the compositions A and B in a preferred embodiment is from 1 to 10 wt .-%, preferably from 3 to 7 wt .-%.

Surprisingly, it was found that the flow behavior of the enzyme-containing composition A is strongly dependent on the particular sulfopolymer used. 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. In various embodiments, the sulfopolymers consist of sulfonic acid group-containing monomer (s) and monomers from the group of unsaturated carboxylic acids, i. H. do not contain other monomer units.

Unsaturated carboxylic acid (s) used are, 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 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, 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.

Particularly preferred copolymeric polysulfonates are copolymers of the abovementioned sulfonic acid group-containing monomers, in particular 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl- 1-propanesulfonic acid and 3-methacrylamido-2-hydroxy-propanesulfonic acid, with acrylic or methacrylic acid.

Particularly favorable effects on the flow behavior showed copolymers of acrylic acid (AA) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) (AA-AMPS copolymers). Such copolymers are 588 under the trade name Acusol ^® (Dow Chemical) are available.

In preferred embodiments, the sulfopolymers contain no further monomer units, in particular no nonionic or hydrophobic monomer, since such monomer units adversely affect the Ausfließverhalten.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, d. H. 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 group-containing copolymers is preferred.

The monomer distribution of the copolymers preferably used 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 the proportion of the sulfonic acid group-containing monomer is from 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molecular weight of the sulfo copolymers preferably used 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 of the invention, the composition A contains 1 to 10 wt .-%, in particular 3 to 7 wt .-% sulfopolymer. Composition B may contain sulfopolymer; the proportion by weight of the sulfopolymer in composition B may even be higher than in composition A. Since it has been found that the distribution of the sulfopolymer has a high influence on the density of compositions A and B, it is left to the skilled person to determine the total amount of sulfopolymer as he wishes to adjust the density of the compositions A and B.

In particular, combination products are preferred in which the weight fraction of the sulfopolymer in composition A is higher than the weight fraction of the sulfopolymer in composition B.

Particularly preferred are compositions containing the sulfopolymer in combination with a polyol as described above in connection with the enzyme stabilizers. Suitable polyols include, but are not limited to, glycerin, ethylene glycol, propylene glycol and sorbitol. These are preferably present in amounts of from 2 to 15% by weight, in particular from 6 to 11% by weight, in the formulation.

In various embodiments, the compositions, i. H. the enzyme-containing composition A and / or composition B, no hydrophobically modified sulfopolymers, especially no terpolymers of monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, such as terpolymers of acrylic acid, 2-acrylamido-2-methylpropanoic acid (AMPS) and ethyl acrylate (EA).

In various embodiments, the viscosity and density of compositions A and B are adjusted by the addition of a thickening agent. Such thickeners can favorably influence the stability of the compositions. Examples of suitable thickeners are polymeric thickeners. 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.

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

The content of polymeric thickener is preferably 0.1 to 5 wt .-% and in particular 0.5 to 3 wt .-%, each based on the sum of the compositions A and B.

Another possibility, which can also be used in combination with a thickener, consists in varying the amounts of certain solid raw materials in the compositions A and B, with a constant total amount of these raw materials in the combination product described herein. For example, builders which are added in solid form during the preparation of the compositions are suitable for this purpose. For example, in phosphate containing compositions different amounts of phosphate can be used for this purpose. In phosphate-containing compositions, the content of thickening agents is preferably 0.5 to 1.5% by weight, based both on the particular composition and on the sum of the compositions A and B.

In addition to the ingredients described above, the agents described above may contain further washing and cleaning-active substances, preferably washing and cleaning-active substances from the group of surfactants, 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, ether sulfates, alkanesulfonates and alkylbenzenesulfonates. Preference is given here C ₁₂ -C ₁₈ fatty alcohol sulfates, z. Sulfopone K 35 (BASF, Germany), C ₁₂ -C ₁₄ ethoxylated alcohol sulfates, e.g. Texapon N70 (BASF, Germany), secondary C ₁₃ -C ₁₇ alkanesulfonates, e.g. B. Hostapur SAS 93 (Clariant, Germany), and linear C8-C18 alkylbenzenesulfonates, in particular dodecylbenzenesulfonate or C ₉ -C ₁₃ alkylbenzenesulfonate.

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- oder mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² und 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 have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferred 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 and R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another integers from 1 to 6 are available.

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 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 which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A "and A" independently of one another are selected from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH _{2 is} -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 z can also be 0, are particularly preferred.

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 0.1 to 15 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%.

Particularly preferred are end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16 carbon atoms or mixtures thereof, R ² denotes 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. The group of these nonionic surfactants include, for example, hydroxy _mixed ethers of the general formula C _6-22 -CH (OH) CH ₂ O- (EO) _20-120 -C _2-25 , 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 is} CH (OH) CH ₂ O- (CH ₂ CH ₂ O) _20-120 -R ² , wherein R ¹ and R ² independently represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms, 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 having 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 for values between 0.5 and 4, preferably 0 , 5 to 1.5, and y represents a value of at least 15.

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 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 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 independently of one another are 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 -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 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 Is 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 selected 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 Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R¹-CH(OH)CH₂-O(CH₂CH₂O)_xCH₂CHR(OCH₂CH₂)_yO-CH₂CH(OH)-R², in denen R für einen linearen, gesättigten Alkylrest mit 8 bis 16 Kohlenstoffatomen, vorzugsweise 10 bis 14 Kohlenstoffatomen steht und n und m unabhängig voneinander Werte von 20 bis 30 aufweisen. Entsprechende Verbindungen können beispielsweise durch Umsetzung von Alkyldiolen HO-CHR-CH₂-OH mit Ethylenoxid erhalten werden, wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen unter Ausbildung eines Dihydroxyethers erfolgt.

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 ₂ CH (OH) -R ² , in which

• R, R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms;
• X and y are independently of one another values between 1 and 40. Preference is given here in particular 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 which 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 radical 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 in which R 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 aforementioned nonionic surfactants represent statistical averages, which may be an integer or a fractional number for a specific product. 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 sum of the compositions A and B, in a preferred embodiment is 0.1 to 20 wt .-%, particularly preferably 0.5 to 15 wt .-%, in particular 2 to 10 wt. %.

Examples of alkali carriers are the hydroxides, preferably alkali metal hydroxides, the carbonates, bicarbonates or sesquicarbonates, preferably alkali metal carbonates and / 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 monoalcohols, diols, triols and / or polyols, ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents for the purposes of the present application are solvents which at room temperature with water completely, d. H. without miscibility, are miscible.

Organic solvents that can be used in the compositions described herein preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified 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 to 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 dishes do not stain them.

Furthermore, preservatives may be included in the compositions. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof 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 can be used as complexing agents. It has been found that also the phosphonates exert an influence on the density of the compositions. Thus, in a further embodiment of the invention, combination products are preferred in which the weight proportion of the phosphonate in composition A is lower than the weight proportion of phosphonate in composition B and at the same time the density of composition A is lower than the density of composition B. Particularly advantageous it proved, when the compositions A is free of phosphonates, while the compositions B contains phosphonates.

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, while the composition B has a pH (20 ° C) between 9 and 14.

In a further embodiment of the invention, an automatic washing or cleaning agent process, in particular automatic dishwashing detergent process is claimed, wherein from a combination product described above, comprising a packaging means and at least two separate, flowable washing or cleaning compositions A and B, located in this packaging means as defined above, metered into a machine or into a separate metering device or directly into the machine, and then the washing or cleaning process is started.

Examples

Example 1:

The viscosity functions were determined by a rotary rheometer type AR G2 from TA Instruments at a temperature of 20 ° C with a cone-plate measuring system with 40 mm diameter and 1 ° or 2 ° cone angle. Beam expansion was measured by an optical method: through a nozzle 20 mm in length and 2.5 mm in diameter, at a temperature of 23 ° C, a liquid flow at a flow rate of 320 ml / min was vertically downwardly generated by means of a suitable pump. The beam was recorded with a video camera. In the picture, the maximum diameter of the jet after exit from the nozzle was measured and B _ex calculated. Then, according to the formula, B = B _ex - 0.13 was corrected and B was calculated.

The first normal voltage difference was determined with the following device: A rotational rheometer (AR G2 from TA-Instruments). Using a cone-plate measuring system was determined using the Normal force on the cone determines the first normal stress difference. The following applies: N ₁ = 2F _z / πR ² with F _z : normal force on the cone, R: radius of the cone. For high shear rates, this expression was corrected for an inertia term according to the following formula: N ₁ = 2 * Fz / (π * R ² ) - 0.15 * ρ * ω ² * R ² .

Where ω is the angular velocity of the measuring system, and ρ is the density of the liquid. The first normal voltage differences given in Table 1 are each corrected for inertia according to this formula. All rheological measurements were carried out at a temperature of 20 ° C. Table 1: Formulations A, all data in wt .-% active substance Composition A Recipe 1 (according to the invention) Recipe 2 (comparison) Recipe 3 (comparison) tripolyphosphate 12.5 12.5 12.5 polyol 9.04 9.04 9.04 calcium salt 0.27 0.27 0.27 zinc acetate 0.19 0.19 0.19 protease 5.2 5.2 5.2 amylase 1.5 1.5 1.5 nonionic surfactant 3.5 3.5 3.5 Acrylic acid-AMPS copolymer (Na salt) 5.7 - - Acrylic acid AMPS-EA terpolymer (Na salt) - 5.7 7.6 phosphonate 1.2 1.2 1.2 protease stabilizer 5.0 5.0 5.0 potassium hydroxide 4.56 4.56 5.5 Crosslinked acrylic acid copolymer thickener 0.83 0.83 0.83 preservative 0.02 0.02 0.02 water Ad 100 Ad 100 Ad 100 pH value (undiluted) 7.5 7.5 7.5 discharge behavior Without onions" With "onion" With "onion" Strand expansion B _ex 20% 40% 60% Strand expansion B 7% 27% 47% First normal voltage difference at 5000 s-1 (Pa) with AR G2 1520 2180 2430 Table 2: Formulation B, all data in wt .-% active substance Composition B tripolyphosphate 12.5 Amphoteric polymer 1.0 Crosslinked acrylic acid copolymer thickener 0.95 phosphonate 3.6 potassium hydroxide 2.35 sodium 10.0 Monoethanolamine 2.7 Crosslinked acrylic acid copolymer thickener 4.0 water Ad 100 pH value (undiluted) 11.2 discharge behavior Without onions"

From composition B, only one formulation according to the invention was used, which was then used in each case in combination with the three different formulations of composition A.

The formulation 1 according to the invention of the composition A shows a good, aesthetic Ausfließverhalten and injected when pressure on the bottle in the horizontal direction in a wide arc. In contrast, Comparative Formulations 2 and 3 of Composition A show a rather unfavorable (Formulation 2) or very unfavorable (Formulation 3) Ausfließverhalten, since the high branch broadening of these formulations when pressure on the bottle of the jet kinks in the vertical direction and the nozzle for Drop tends.

The formulation 1 of the composition B according to the invention also shows a good, aesthetic Ausfließverhalten.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2007/025665 [0002]
• WO 97/18287 [0042]

Cited non-patent literature

• Klemens Kohlgruber, "The co-rotating twin screw extruder, p 46, Carl Hanser Verlag, Munich, 2007 [0007]

Claims (10)

A combination product comprising a packaging material and at least two separate, flowable washing or cleaning compositions contained in this packaging material, in particular automatic dishwashing detergent compositions, A and B, wherein compositions A and B contain 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 B: 10 to 75% by weight of builder (s); Less than 0.1% by weight of enzyme preparation; - 25 to 90 wt .-% water; characterized in that the first normal stress difference of the two compositions A and B in the shear rate range to 5000 s-1 is not higher than 1800 Pa, preferably not higher than 1700 Pa and particularly preferably not higher than 1600 Pa. Combination product according to claim 1, characterized in that the viscosities of the compositions A and B, each at the same shear rate in the range between 0.1 s ^-1 and 5000 s ^-1 by not more than a factor of 3, preferably not more than the factor 2, more preferably no more than a factor of 1.5 differ. Combination product according to claim 1 or 2, characterized in that the packaging means is a water-insoluble two- or multi-chamber container, wherein each of the receiving chambers of the packaging means is provided with a spout. Combination product according to claim 3, characterized in that each spout has the form of a metering nozzle. Combination product according to one of claims 1 to 4, characterized in that the composition A contains 1 to 10 wt .-%, preferably 3-7 wt .-% of a sulfopolymer, wherein the sulfopolymer is preferably a copolymer of (i) acrylic acid or methacrylic acid; and (ii) 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 or mixtures thereof, in particular a copolymer of acrylic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid. Combination product according to claim 5, characterized in that the composition A contains 2 to 15 wt .-%, preferably 6-11 wt .-% of a polyol, wherein the polyol is preferably selected from glycerol, ethylene glycol, propylene glycol and sorbitol. Combination product according to one of claims 1 to 6, characterized in that the corrected strand expansion of composition A and / or composition B is less than 25%, preferably less than 20%, more preferably less than 10%. Combination product according to one of claims 1 to 7, characterized in that the combination product contains in composition A, composition B or both further washing and cleaning active substances, which are preferably selected from the group of surfactants, glass corrosion inhibitors, corrosion inhibitors, alkali carriers, fragrances and perfume carriers , Dyes, preservatives, bleaches and bleach activators. Combination product according to one of claims 1 to 8, characterized in that the density and / or viscosity of the composition A, the composition B or both is adjusted by a thickener. Automatic washing or cleaning agent process, in particular automatic dishwashing process, characterized in that from a combination product according to one of claims 1 to 9, the washing or cleaning compositions A and B in a provided in the machine or are metered into a separate metering device or directly into the machine and then the washing or cleaning process is set in motion.