EP4008764A1 - Improved cleaning by means of hydrogen carbonate in mechanical dishwashing - Google Patents

Abstract

The present invention relates to an automatic dishwashing agent comprising at least one bleach, at least one builder and at least one bicarbonate, and the use of bicarbonate to improve the cleaning performance of an automatic dishwashing agent which contains at least one bleach and at least one builder, and a method for cleaning dishes using such a dishwashing detergent.

Description

The present invention relates to an automatic dishwashing agent comprising at least one bleach, at least one builder and at least one bicarbonate, and the use of bicarbonate to improve the cleaning performance of an automatic dishwashing agent which contains at least one bleach and at least one builder, and a method for cleaning dishes under Use of such a dishwashing detergent.

The most important criterion in automatic dishwashing is the cleaning performance on a wide variety of soiling, which is brought into the dishwasher in the form of food residues. In this respect, there is a general need for dishwashing detergents with increased cleaning performance. In addition, there is a general trend towards avoiding the use of phosphates in machine dishwashing for environmental reasons. The problem thus arises of providing phosphate-free machine dishwashing detergents without the cleaning performance being impaired.

However, bleachable stains, particularly tea stains, are stubborn stains that are often not removed satisfactorily. Modern dishwashing detergents, in particular machine dishwashing detergents, often do not meet the requirements with regard to removing such soiling. There is therefore still a need for dishwashing detergents and, among these, in particular for automatic dishwashing detergents, very particularly for phosphate-free automatic dishwashing detergents, which reliably remove stains that can be bleached.

Surprisingly, it has now been found that by adding even small amounts of hydrogen carbonate to dishwashing detergents containing bleach and builders, a generally improved cleaning performance, in particular of tea-based stains, can be achieved.

1. a) mindestens ein Bleichmittel sowie optional mindestens einen Bleichaktivator und/oder mindestens einen Bleichkatalysator;
2. b) mindestens einen Builder und
3. c) mindestens ein Hydrogencarbonat.

In a first aspect, the present invention is therefore directed towards an automatic dishwashing detergent

1. a) at least one bleach and optionally at least one bleach activator and/or at least one bleach catalyst;
2. b) at least one builder and
3. c) at least one bicarbonate.

In a further aspect, the present invention is directed to the use of a dishwashing detergent according to the invention for machine cleaning of dishes.

In yet another aspect, the present invention is directed to a method for machine dishwashing, characterized in that a dishwashing detergent according to the invention is used in at least one method step.

The invention further relates to the use of at least one hydrogen carbonate to improve the cleaning performance of a bleach- and builder-containing dishwashing detergent, in particular on tea-based stains. Specifically, the invention is also directed to the use of hydrogen carbonate to improve the bleaching performance of a bleach and builder-containing dishwashing detergent, in particular on tea-based soiling, and the use of hydrogen carbonate in bleach and builder-containing dishwashing detergents to improve them the cleaning performance, especially on tea-based soiling.

According to the invention, a dishwashing detergent is understood to mean all detergents which are suitable for washing or cleaning hard surfaces, in particular dishes. Other suitable ingredients are described in detail below.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples. All percentages are % by weight unless otherwise indicated. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

"At least one" as used herein refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

"About" or "about" as used herein in connection with a numerical value refers to the numerical value ±10%, preferably ±5%.

"Improvement in cleaning performance" or "improvement in bleaching performance" as used herein refers to an improvement in the respective performance, for example evaluated as described herein, over a composition which does not contain the ingredient in question, i.e. present bicarbonate, but does is otherwise identical.

When reference is made herein to molar masses, this information always relates to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF be determined as eluent. The mass-average molar mass M _w can also be determined by GPC, as described for M _n .

In the context of the present invention, fatty acids or fatty alcohols or their derivatives—unless otherwise stated—are representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms. In particular, the oxo-alcohols or their derivatives which can be obtained, for example, by _Roele 's oxo-synthesis can also be used accordingly.

Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient for charge equalization - as the anion.

Substances that are also used as ingredients in cosmetic products are referred to below, where appropriate, in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are listed exclusively in Latin according to Linnaeus, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI designations are dem International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997) published by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , is published and contains more than 9,000 INCI designations as well as references to more than 37,000 trade names and technical designations including their associated distributors from over 31 countries. That The International Cosmetic Ingredient Dictionary and Handbook assigns ingredients to one or more chemical classes ), for example polymeric ethers, and one or more functions (functions), for example surfactants - cleansing agents, which in turn are explained in more detail and to which reference may also be made below.

The indication CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

"Solid" as used herein in the context of the present invention means a powder, granule, extrudate or compact composition.

"Liquid" as used in the context of the present invention refers to all flowable compositions (at 20°C, 1.013 bar), including gels and paste-like compositions, as well as non-Newtonian liquids that exhibit a yield point.

"Phosphate-free" and "phosphonate-free" as used herein means that the composition in question is essentially free of phosphates and phosphonates, respectively, ie in particular Contains phosphates or phosphonates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.

A machine dishwashing detergent according to the invention comprises a) at least one bleach and optionally at least one bleach activator and/or at least one bleach catalyst; b) at least one builder and c) at least one bicarbonate.

The bleaching agents that can be used according to the invention are washing or cleaning-active substances. In various embodiments, the bleaching agent comprises at least one source of active oxygen. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and yield H ₂ O ₂ in water. Examples of other bleaches which can be used are peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which supply H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

In various embodiments, the at least one bleach is a bleach selected from the group of percarbonates. In various such embodiments, the at least one bleaching agent is sodium percarbonate.

Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids. All other inorganic or organic peroxy bleaches known to those skilled in the art from the prior art can also be used. Substances which release chlorine or bromine can also be used as bleaching agents. Suitable chlorine or bromine releasing materials include N-bromo and N-chloro heterocyclic amides, e.g. trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also useful.

Preferably the bleaching agent is present in an amount of from 1-35% by weight and more preferably from 2-30% by weight, 3.5-25% by weight, from 4-20% by weight and most preferably from 5 -15% by weight contained in the dishwashing detergent according to the invention, based in each case on the total weight of the dishwashing detergent. Preferred dishwashing detergents are further characterized in that the dishwashing detergent contains 2 to 20% by weight, preferably 3 to 18% by weight and in particular 4 to 15% by weight sodium percarbonate, based in each case on the total weight of the dishwashing detergent.

In various embodiments, a dishwashing detergent according to the invention also contains at least one bleaching catalyst and/or at least one bleaching activator in addition to the at least one bleaching agent.

Accordingly, in some embodiments, a dishwashing detergent according to the invention contains at least one bleach catalyst. In some embodiments, this is a bleach catalyst selected from the group of bleach-boosting transition metal salts or transition metal complexes. Suitable bleach-boosting transition metal salts or transition metal complexes are, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN ) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Examples of suitable manganese complexes are [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ](ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ](BPh ₄ ) ₂ , [Mn ^IV ₄ (µ-O) ₆ (TACN) ₄ ](ClO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ ](ClO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ](ClO ₄ ) ₃ , [Mn ^IV ₂ (µ-O) ₃ ( Me-TACN) ₂ ](PF ₆ ) ₂ and [Mn ^IV ₂ (µ-O) ₃ (Me/Me-TACN) ₂ ](PF ₆ ) ₂ (with OAc = OC(O)CH ₃ ).

In various embodiments, the at least one bleach catalyst is selected from the group of bleach-boosting transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) or 1, 2,4,7-tetramethyl-1,4,7-triazacyclononane (Me/Me-TACN) are preferred according to the invention, since the abovementioned bleaching catalysts in particular can significantly improve the cleaning result.

The aforementioned bleach-boosting transition metal complexes, in particular with the central atoms Mn and Co, are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.1% by weight and particularly preferably from 0.01% by weight. % to 0.05% by weight, based in each case on the total weight of the agent. In special cases, however, more bleach catalyst can also be used.

In various embodiments, the bleach catalyst is selected from the group of bleach-boosting transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) or 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane (Me/Me-TACN), and/or the hydrogen peroxide source is sodium percarbonate, sodium perborate tetrahydrate, or sodium perborate monohydrate, or a combination thereof. The bleaching catalyst is very particularly preferably a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), in particular [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ , or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me/Me-TACN) or a mixture thereof, and the Source of hydrogen peroxide is sodium percarbonate. In the aforesaid combinations, the bleach catalyst and the hydrogen peroxide source are preferably present in the amounts specified above for each.

In addition, in some embodiments it is correspondingly provided that a dishwashing detergent according to the invention contains at least one bleach activator.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Of all the bleach activators known to those skilled in the art from the prior art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) , Acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. TAED is very particularly preferred. Combinations of conventional bleach activators can also be used.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based in each case on the total weight of the agent used.

In various embodiments, a dishwashing detergent according to the invention contains at least one bleach as defined above, at least one bleach catalyst as defined above and at least one bleach activator as defined above, preferably in each case in the amounts specified above.

A dishwashing detergent according to the invention contains at least one builder as a further component. In particular, silicates, aluminum silicates (particularly zeolites), carbonates, organic dicarboxylic and polycarboxylic acids and aminocarboxylic acids or their salts are used as builders that can be contained in the dishwashing detergent, and—where there are no ecological prejudices against their use—also the phosphates. Mixtures of these substances can of course also be used. The agents are preferably phosphate-free.

For example, crystalline layered silicates of the general formula NaMSi _x O _2x+1 · y H ₂ O can be used, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _2x+1 · y H ₂ O are marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ × H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .×H ₂ O, makatite). Crystalline phyllosilicates of the formula NaMSi _x O _2x+1 .yH ₂ O, in which x is 2, are particularly suitable for the purposes of the present invention. In particular, both ß- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ · y H ₂ O and, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (ß-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3 H ₂ O, kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

Automatic dishwashing detergents typically contain a proportion by weight of the crystalline layered silicate of the formula NaMSi _x O _2x+1 y H ₂ O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0 4 to 10% by weight, based in each case on the total weight of these agents.

Amorphous sodium silicates with an Na ₂ O:SiO ₂ modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, can also be used are preferably delayed in dissolution and have secondary washing properties. The delay in dissolving compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting/densification or by overdrying. In the context of this invention, the term "amorphous" means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle , cause.

In the context of the present invention, it is preferred that these silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are present in the agents in amounts of 1 to 40% by weight, preferably 2 to 35% by weight. -%, each based on the weight of the automatic dishwashing detergent, are included.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use is not to be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) being particularly preferred, are the most important in the detergent and dishwashing detergent industry. However, it is preferred that the agents contain no phosphates, i.e. are phosphate-free.

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

Industrially particularly important phosphates are pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate) and corresponding mixed salts (sodium potassium tripolyphosphate). However, the agents are preferably phosphate-free.

If, in the context of the present application, phosphates are used as active cleaning substances in automatic dishwashing detergents, preferred detergents contain this phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in Amounts from 5 to 80% by weight, preferably from 10 to 60% by weight and in particular from 18 to 45% by weight, based in each case on the weight of the machine dishwashing detergent.

The dishwashing detergents can also contain, in particular, phosphonates as a further builder. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. The detergents preferably contain phosphonates in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent. In the context of this invention, phosphonates do not come under the category of phosphates, i.e. agents that are designated as phosphonate-free can also contain such phosphonates.

Other builders are the alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal metasilicates and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Due to their low chemical compatibility with the other ingredients of machine dishwashing detergents compared to other builder substances, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight % by weight and in particular below 2% by weight, in each case based on the total weight of the machine dishwashing detergent. Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.

Particular preference is given to using carbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30% by weight %, based in each case on the weight of the machine dishwashing liquid. Particular preference is given to detergents which, based on the weight of the automatic dishwashing detergent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate(s ), preferably alkali metal carbonate(s), particularly preferably sodium carbonate.

Organic builders which should be mentioned in particular are polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders. These substance classes are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and are therefore also used to set a lower and milder pH in the machine dishwashing detergents. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.

The use of citric acid and/or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of the agents described herein. Automatic dishwashing detergents are therefore preferred, characterized in that the automatic dishwashing detergent contains citric acid or a salt of citric acid.

Another important class of phosphate-free builders are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts and glutamicdiacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). The content of these aminocarboxylic acids or their salts can be, for example, between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight. Aminocarboxylic acids and their salts can be used together with the aforementioned builders, in particular also with the phosphate-free builders.

In addition, all compounds capable of forming complexes with alkaline earth metal ions can be used as builders. In various embodiments, the at least one builder is selected from the group consisting of chelators for Ca and/or Mg ions.

In further embodiments, the at least one builder is present in the dishwashing detergent according to the invention in an amount of approximately 5 to 80% by weight, preferably 10 to 60% by weight, in particular >30% by weight, based in each case on the total weight of the detergent contain.

In some embodiments, the at least one builder is selected from the group consisting of citrate, sodium carbonate, methylglycine diacetic acid (MGDA), and mixtures thereof. Mixtures of citrate and soda and/or MGDA are particularly preferred.

The at least one hydrogen carbonate used according to the invention can be any hydrogen carbonate known in the prior art. In various embodiments, however, it is preferred that the at least one bicarbonate is selected from the group consisting of bicarbonates of alkali metals, bicarbonates of alkaline earth metals and ammonium bicarbonate. In various embodiments, alkali metal bicarbonates are preferred. Of course, it is also possible and provided that mixtures of the aforementioned can be used. In various embodiments, the at least one bicarbonate is selected from the group consisting of sodium bicarbonate, calcium bicarbonate and ammonium bicarbonate. Mixtures of the aforementioned are also possible. The at least one bicarbonate is particularly preferably sodium bicarbonate.

In some embodiments, the amount of at least one hydrogen carbonate in the dishwashing detergent according to the invention is approximately 0.1 to 10% by weight, for example approximately 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 , 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2.0, 2.5, 3.0, 3 .5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 or 10 wt. -%, each based on the total weight of the agent.

The hydrogen carbonates are used according to the invention in order to improve the cleaning performance of the agent, especially on bleachable stains. Surprisingly, the inventors have found that the addition of hydrogen carbonate increases the cleaning performance and in particular the bleaching performance compared to agents that do not contain such a hydrogen carbonate. The corresponding use of the hydrogen carbonates is therefore also part of the invention.

In various embodiments, the dishwashing detergent according to the invention is a multiphase dishwashing detergent, in other words a dishwashing detergent containing at least two phases.

A phase within the meaning of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various features, for example ingredients, physical properties, external appearance, etc. Various phases can preferably be distinguished visually. So for the consumer, the at least one first phase is clearly of the to distinguish at least a second phase. If the agent according to the invention has more than one first phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example in terms of colour. The same applies if there are two or more second phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a difference in color or transparency. Phases within the meaning of the present invention are therefore self-contained areas which the consumer can visually distinguish from one another with the naked eye. The individual phases can have different properties when used, such as the speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase. The phases are typically spatially separated from each other. In various embodiments, this can be done in such a way that if one or both of the phases are liquid phases, the liquid phase is present separately from the other phase in a separate, closed area, for example the chamber of a pouch. Such ready-made forms are known in the prior art. In the case of solid agents, ie agents in which both phases are solids, the two phases are also made up separately from one another, for example in the form of a multi-chamber pouch, with each of the phases being present in a separate chamber. Alternatively, in the case of compacted agents, such as tabs or tablets, in particular multi-phase tabs as are known in the prior art, the two phases can be arranged spatially directly adjacent in such a way that the phases are formulated separately and contact each other, but cannot mix.

In various embodiments, it is preferred if the at least one bleach and optionally the at least one bleach catalyst and/or the at least one bleach activator, particularly preferably such a bleach system consisting of the aforementioned components, is contained in a single phase of the multiphase dishwashing detergent. However, one or more of the individual components of the bleaching system, i.e. a bleaching agent, a bleaching catalyst and/or a bleaching activator, can also be present in at least one further phase of a multiphase dishwashing detergent according to the invention. However, agents according to the invention can also comprise more than one such bleaching phase.

In various embodiments in which a multi-phase dishwashing detergent according to the invention contains at least one bleaching phase, i.e. at least one phase comprising at least one bleaching agent and optionally at least one bleaching catalyst and/or at least one bleaching activator, preferably such a bleaching system, the at least one hydrogen carbonate is in an amount of about 0.5 to 10% by weight, for example about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 1.2.0, 2.5 , 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9 0, 9.5 or 10.0% by weight, preferably about 0.7 to 2% by weight, based in each case on the total weight of the bleaching phase, in the agent according to the invention.

In various embodiments, the at least one bleaching agent in the at least one bleaching phase of a dishwashing detergent according to the invention is in an amount of from about 3 to 40 % by weight, preferably about 5 to 35% by weight, in particular about 7 to 30% by weight, for example about 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 , 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 20% by weight, based in each case on the total weight of the bleaching phase.

In various embodiments, the at least one bleaching phase of the dishwashing detergent according to the invention, as defined above, contains at least one bleaching catalyst in an amount of about 0.005 to 0.7% by weight, preferably about 0.01 to 0.5% by weight, even more preferably about 0.02 to 0.03% by weight, based on the total weight of the bleaching phase.

In various embodiments, the at least one bleaching phase of the dishwashing detergent according to the invention, as defined above, contains at least one bleach activator in an amount of about 1 to about 10% by weight, preferably about 3 to 8% by weight, more preferably about 5 to 7% by weight %, in each case based on the total weight of the bleaching phase.

In various embodiments, the at least one bleaching phase as defined above comprises at least one bleaching agent; at least one bleach catalyst; at least one bleach activator, in each case in the aforementioned amounts based on the total weight of the bleaching phase; at least one builder, preferably in an amount of about 10 to 90% by weight, more preferably about 20 to 70% by weight, even more preferably about 30 to 70% by weight, for example about 30, 31, 32, 33, 34 , 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 , 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70% by weight, in each case based on the total weight of the bleaching phase; and at least one bicarbonate in the aforesaid amounts based on the total weight of the bleaching phase.

In various embodiments, the at least one bleaching phase as defined and described above makes up about 20 to 90% by weight, preferably about 30 to 80% by weight, more preferably about 35 to 70% by weight, most preferably about 40% up to 65% by weight of the total weight of the agent according to the invention. In various other embodiments, the at least one bleaching phase has a pH in the range from about 6 to 12, preferably 6.5 to 11, more preferably 8 to 11, in particular greater than 8.8, especially in the range 8.5 to 10. The above pH values relate to a 10% dilution of the bleaching phase in water at a temperature of around 20°C.

In preferred embodiments, the dishwashing detergent according to the invention contains at least one other ingredient, ie ingredients that are commonly used as ingredients in dishwashing detergents, in particular machine dishwashing detergents, preferably selected from the group consisting of surfactants, polymers, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors , foam inhibitors, dyes, pigments, additives to improve sagging and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers.

In the case of a multi-phase dishwashing detergent, as defined herein, the other ingredients can be present in any phase. Furthermore, two or more different phases can each contain ingredients of the same type; for example, a surfactant may be included in more than one phase of a multi-phase dishwashing detergent. Likewise, a builder can also be present in more than just one phase of a multi-phase dishwashing detergent. However, the components of a respective phase are preferably combined with one another in such a way that they do not impede each other in their respective mode of action. Exemplary embodiments in which certain ingredients are preferably not formulated together in the same phase are set forth below.

The compositions described herein preferably contain at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.

Examples of suitable nonionic surfactants are alkyl glycosides of the general formula RO(G) _x , where R is a primary straight-chain or methyl-branched aliphatic radical, especially methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which is a glucose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.2 to 1.4.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.

Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

However, preference is given to using low-foaming nonionic surfactants, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.

One class of nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants is accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with surfactants with a more complex structure such as Polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are distinguished by good foam control.

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.Particularly preferred nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferably 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 are independent of one another are integers from 1 to 6.

Thus, particularly preferred are nonionic surfactants having a C _9-15 alkyl radical containing 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.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A, A', A" und A'" unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH2-CH3) stehen,
• w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula

R ^1- CH(OH)CH ₂ O-(AO) _w -(A′O) _x -(AʺO) _y -(A‴O) _z -R ² ,

in the

• R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• 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 ),
• w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0.

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] _x CH ₂ CH(OH)R ² , in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, where x is a value between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60. 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 are particularly preferred, in which R ¹ represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 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 has values between 0.5 and 1.5 and y has a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ -(EO) _15-40 -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ -(EO) ₂₂ -2 -hydroxydecyl ether. Particular preference is also given to end-capped poly(oxyalkylated) 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 represents 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 represent values between 1 and 32, where nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are most preferred.

Other preferably usable 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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ³ represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. When the value of 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 can 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH ₃ are particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, when x ≥ 2, each R ³ in the above formula may be different. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group may be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) moieties which may be joined in any order, e.g. (EO)( PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)( PO)(PO). The value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Particularly preferred endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula translates to 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 a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R ¹ and R ² have 9 to 14 carbon atoms, R ³ is H and x has a value of 6 to 15 are particularly preferred.

• R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula R ¹ -CH(OH)CH ₂ O-(AO) _w -R ² have proven to be particularly effective

• R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical;
• R ² represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH(CH ₃ ), preferably CH ₂ CH ₂ , and
• w is between 1 and 120, preferably 10 to 80, especially 20 to 40

The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ether.

In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers defined above, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These may satisfy the formulas above except that R ² is hydrogen and R ¹ , R ³ , A, A', Aʺ, A‴, w, x, y and z are as defined above.

The agents described herein, which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the agent of at least 2% by weight, preferably at least 5% by weight. %. The absolute amounts used per application can be, for example, in the range from 0.5-10 g/job, preferably in the range from 1-5 g/job.

All anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts having 2 to 4 carbon atoms in the alkanol group.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

In various embodiments, the dishwashing detergents therefore contain at least one surfactant of the formula R ⁴ -O-(AO) _n ^-SO ₃ -X ⁺ .

In this formula, R ⁴ is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety. The index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-1).Particularly preferred anionic surfactants are selected from fatty alcohol ether sulfates of formula A-1

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula A-1).

The agents can additionally or alternatively contain at least one surfactant of the formula R ⁵ -A-SO ₃ ^{-Y +} .

In this formula, R ⁵ represents a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical and the group -A- represents -O- or a chemical bond. In other words, the above formula can be used to describe sulfate (A=O) or sulfonate (A=chemical bond) surfactants. Depending on the choice of grouping A, certain radicals R ⁵ are preferred. In the sulfate surfactants (AO), R ⁵ is preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ⁵ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred. Particularly preferred radicals R ⁵ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. Y represents a monovalent cation or the nth part of an n-valent one Cations, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations Y ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13).Such particularly preferred surfactants are selected from fatty alcohol sulfates of the formula

with k=11 to 19. Very particularly preferred representatives are Na—C _12-14 fatty alcohol sulfates (k=11-13).

In the case of the sulfonate surfactants (A=chemical bond), R ⁵ preferably represents a linear or branched, unsubstituted alkylaryl radical. Here, too, X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof. Such surfactants can be selected from linear or branched alkyl benzene sulfonates.

Cationic and/or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and/or amphoteric surfactants are used.

Agents according to the invention can also contain various polymers.

According to the invention, homopolymers of α,β-ethylenically unsaturated carboxylic acids, for example, can be used in various embodiments. The unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R ¹ (R ² )C═C(R ³ )COOH, in which R ¹ to R ³ independently represent —H, —CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, 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 for -COOH or -COOR ⁴ where 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-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Acrylic acid is very particularly preferred. In various embodiments of the invention, therefore, the homopolymer is a polyacrylic acid.

In the polymers, some or all of the carboxylic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized polymers is preferred according to the invention.

The molar mass of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M _n of 1000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g/mol, and particularly preferably from 1200 to 5000 g/mol, may in turn be preferred from this group.

In various preferred embodiments of the invention, the compositions also contain at least one sulfopolymer. The polymers that can be used in this context are, in particular, copolymers which can have two, three, four or more different monomer units, with at least one monomer unit carrying a sulfonic acid group. In addition to monomer(s) containing sulfonic acid groups, preferred copolymers contain at least one monomer from the group of unsaturated carboxylic acids.

The unsaturated carboxylic acids described above are/are used with particular preference as the unsaturated carboxylic acid(s). Acrylic acid is very particularly preferred.

The monomers containing sulfonic acid groups are those of the formula

R ⁵ (R ⁶ )C=C(R ⁷ )-X-SO ₃ H

preferably, in which R ⁵ to R ⁷ independently represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH are substituted alkyl or alkenyl radicals or are -COOH or -COOR ⁴ , where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group 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 -.

Preferred among these monomers are those of the formulas

_H2C =CH-X- _SO3H

H ₂ C=C(CH ₃ )-X-SO ₃ H

HO ₃ SX-(R ⁶ )C=C(R ⁷ )-X-SO ₃ H,

in which R ⁶ and R ⁷ are independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH(CH ₃ ) ₂ and X is an optionally present 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 sulfonic acid group-containing monomers 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the copolymers too, the acid groups can be present in whole or in part in neutralized form, i.e. the acidic hydrogen atom of the sulfonic and/or carboxylic acid group in some or all of the acid groups can be replaced by metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers is preferred according to the invention.

In the case of copolymers which contain only carboxylic acid group-containing monomers and sulfonic acid group-containing monomers, the monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight, the monomers here preferably being selected from those mentioned above.

In various embodiments, the copolymers can contain further monomers, in particular unsaturated carboxylic acid ester group-containing monomers, in addition to the above-described carboxylic acid group-containing monomers and sulfonic acid group-containing monomers. In such terpolymers, the carboxylic acid ester group-containing monomers are, for example, those of the formula R ¹ (R ² )C═C(R ³ )COOR ⁴ , in which R ¹ to R ³ are as defined above and R ⁴ is a saturated or unsaturated, straight-chain or is a branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, sorbic acid, cinnamic acid or mixtures thereof. Very particular preference is given to C _1-8 alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate. Ethyl acrylate is very particularly preferred.

The molar mass of the copolymers used can be varied in order to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized characterized in that the copolymers have molar masses M _n from 2000 to 200,000 g/mol, preferably from 4000 to 25,000 g/mol and in particular from 5000 to 15,000 g/mol.

The homopolymers and copolymers described above can each be used in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the agent. Absolute amounts typically range from 0.1 to 2 g/job, preferably from 0.2 to 1.0 g/job. The mass ratio of the polymers to one another, i.e. homopolymer to copolymer, is 5:1 to 1:5, preferably 2:1 to 1:2, in various embodiments.

The dishwashing detergents can alternatively or additionally contain further polymers. The group of suitable polymers includes in particular the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and/or polymers that act as softeners.

Preferred usable amphoteric polymers come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth )-acrylic acid copolymers, the alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, the alkylacrylamide/alkyl methacrylate/alkylaminoethyl methacrylate/alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

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

Cationic polymers that can be used come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

• die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the abovementioned amphoteric, zwitterionic or cationic polymers are present in a ready-made form. Suitable for packaging the polymers are, inter alia

• the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30°C;
• the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

Machine dishwashing detergents preferably contain the aforementioned cationic and/or amphoteric polymers in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the machine dishwashing detergent. However, within the scope of the present application, preference is given to automatic dishwashing detergents in which the proportion by weight of the cationic and/or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0. 01 and 4% by weight, particularly preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, based in each case on the total weight of the dishwasher detergent.

Dishwashing detergents preferred according to the invention contain one or more enzyme(s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are used with preference accordingly. Cleaning agents according to the invention preferably contain enzymes in total amounts of 1×10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.

An enzyme suitable in the context of the present invention can be any enzyme known in the prior art or useful in the future for use in detergents, especially dishwashing detergents as defined herein.

The enzyme can be a hydrolytic enzyme or other enzyme at a concentration useful for the effectiveness of the composition according to the invention.

All enzymes that can develop a catalytic activity in the agent according to the invention can preferably be used, in particular a protease, lipase, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase, oxidase , or oxidoreductase and mixtures thereof.

The enzymes particularly preferably show synergistic cleaning performance against certain types of soiling or stains, i.e. the enzymes contained in the agent composition support each other in their cleaning performance. Such a synergism is very particularly preferred between a protease and another enzyme of an agent according to the invention, including in particular between a protease and an amylase and/or a lipase and/or a mannanase and/or a cellulase and/or a pectinase. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent according to the invention.

Examples of proteases are the subtilisins BPN' from Bacillus amyloliquefaciens and Carlsberg from Bacillus licheniformis, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, subtilisin DY and the enzymes which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense Thermitase, proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name ^Alcalase® from the Novozymes company. The Subtilisins 147 and 309 are marketed under the trade names ^Esperase® and ^Savinase® by the Novozymes company. The protease variants listed under the name ^BLAP® are derived from the protease from Bacillus lentus DSM 5483. Other usable proteases are, for example, those sold under the trade names ^Durazym® , ^Relase® , ^Everlase® , ^Nafizym® , ^Natalase® , ^Kannase® and ^Ovozyme® from the company Novozymes, which are sold under the trade names Purafect®, ^{Purafect® OxP} , ^Purafect® Prime, Excellase ^® and Properase ^® from Danisco/Genencor sold under the trade name Protosol ^® from Advanced Biochemicals Ltd. sold under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd. sold under the trade names Proleather ^® and Protease P ^® from Amano Pharmaceuticals Ltd., and under the name Proteinase K-16 from Kao Corp. available enzymes. The proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in the international patent applications, are also used with particular preference WO2008086916 and WO2007131656 . Further proteases which can be used advantageously are disclosed in the patent applications WO9102792 , WO2008007319 , WO9318140 , WO0144452 , GB1243784 , WO9634946 , WO2002029024 and WO2003057246 . Further proteases which can be used are those which are naturally present in the microorganisms Stenotrophomonas maltophilia , in particular Stenotrophomonas maltophilia K279a, Bacillus intermedius and Bacillus sphaericus . Protease variants based on Bacillus lentus DSM 5483 protease (BLAP), such as those with the R99E substitution, are particularly suitable. Such particularly suitable proteases are for example in WO 2016/096714 described.

Examples of amylases are the α-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus and, in particular, further developments thereof which have been improved for use in detergents or cleaning agents. The enzyme from Bacillus licheniformis is available from the company Novozymes under the name ^Termamyl® and from the company Danisco/Genencor under the name ^Purastar® ST. Further development products of this α-amylase are available from the company Novozymes under the trade names ^Duramyl® and ^Termamyl® ultra, available from Danisco/Genencor under the name ^Purastar® OxAm and from Daiwa Seiko Inc. as ^Keistase® . Bacillus amyloliquefaciens α-amylase is marketed by the Novozymes company under the name ^BAN® , and variants derived from Bacillus stearothermophilus α-amylase under the names ^BSG® and ^Novamyl® , also by the Novozymes company. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948). Furthermore, the amylolytic enzymes can be used, which are described in the international patent applications WO2003002711 , WO2003054177 and WO2007079938 are disclosed, the disclosure of which is therefore expressly referred to or the relevant disclosure content of which is therefore expressly included in the present patent application. Fusion products of all the molecules mentioned can also be used. In addition, the further developments of α-amylase from Aspergillus niger and A. oryzae available under the trade names ^Fungamyl® from the company Novozymes are suitable. Other commercial products that can be used advantageously are, for example, Amylase- ^LT® and ^Stainzyme® or Stainzyme ^ultra® or Stainzyme ^plus® as well as Amplify ^™ 12L or Amplify Prime ^™ 100L, the latter also from the company Novozymes. Variants of these enzymes obtainable by point mutations can also be used according to the invention.

Examples of cellulases (endoglucanases, EG) are the fungal, endoglucanase (EG)-rich cellulase preparation or its further developments, which is offered by the company Novozymes under the trade name ^Celluzyme® . The products Endolase ^® and Carezyme ^® , which are also available from the company Novozymes, are based on the 50 kD-EG or the 43 kD-EG from Humicola insolens DSM 1800. Other commercially available products from this company are Cellusoft ^® , Renozyme ^® and Celluclean ^® . Cellulases, for example, which are available from AB Enzymes under the trade names ^Ecostone® and ^Biotouch® and which are at least partly based on the 20 kD EG from Melanocarpus , can also be used. Other cellulases from the company AB Enzymes are Econase ^® and Ecopulp ^® . Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp. CBS 670.93 is available from the Danisco/Genencor company under the tradename ^Puradax® . Other usable commercial products from the company Danisco/Genencor are “Genencor detergent cellulase L” and ^IndiAge® Neutra.

Lipases or cutinases, for example, can preferably be used, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or developed therefrom, in particular those with one or more of the following amino acid substitutions starting from the lipase mentioned in positions D96L, T213R and/or N233R, particularly preferably T213R and N233R. Lipases are marketed, for example, by the company Novozymes under the trade names Lipolase®, ^Lipolase® Ultra, ^LipoPrime® , ^Lipozyme® and ^Lipex® . Another lipase that can be used advantageously is available under the trade name ^Lipoclean® from the company Novozymes. Furthermore, for example, the cutinases can be used originally isolated from Fusarium solani pisi and Humicola insolens . Lipases that can also be used are available from the Amano company under the names Lipase ^CE® , Lipase ^P® , Lipase ^B® , or Lipase ^CES® , Lipase ^AKG® , Bacillus sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. From the company Danisco/Genencor, for example, the lipases or cutinases can be used, the starting enzymes of which were originally isolated from Pseudomonas mendocina and Fusarium solanii . Other important commercial products are the preparations M1 ^Lipase® and Lipomax® originally sold by the company Gist-Brocades (now Danisco/ ^Genencor ) and those by the company Meito Sangyo KK under the names Lipase MY- ^30® , Lipase ^OF® and Lipase PL ^® marketed enzymes, as well as the product Lumafast ^® from the company Danisco/Genencor.

According to the invention, oxidoreductases, e.g. oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).

The enzymes to be used in the context of the present invention can originate, for example, from microorganisms such as the Bacillus, Streptomyces, Humicola or Pseudomonas genera and/or be produced by suitable microorganisms using biotechnological methods known per se, for example by transgenic expression hosts, for example the Escherichia genera , Bacillus or by filamentous fungi.

It is emphasized that technical enzyme preparations of the respective enzyme can also be involved, i.e. accompanying substances can be present. Therefore, the enzymes can be packaged and used together with accompanying substances, for example from fermentation or with other stabilizers.

In addition, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are encapsulated as in a set gel or in those of the core-shell type , in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities.

As can be seen from the previous statements, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Enzyme preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0.8 and 10 %wt of enzyme protein. Preference is given in particular to those agents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.

In various embodiments, the one or more enzymes contained in an enzyme-containing agent according to the invention is/are not part of the bleach-containing phase. Accordingly, in preferred embodiments, an enzyme-containing dishwashing detergent is a multi-phase dishwashing detergent. In particular, it is advantageous if neither the at least one bleaching agent nor an advantageously present bleaching catalyst are present in an enzyme-containing phase.

In various other embodiments, the enzyme and the bleach, and optionally the bleach catalyst, are in one and the same phase.

The agent according to the invention, in particular a liquid agent according to the invention, can also advantageously contain one or more enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of said compounds. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, in particular those composed of 2 to 50 monomers, or their hydrogen sulfite adducts are also used for this purpose. Peptidic reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.

In some embodiments, dishwashing detergents according to the invention contain at least one zinc salt as a glass corrosion inhibitor as a further component. The zinc salt can be a act inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20° C. water temperature). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt.

The zinc salt is preferably present in agents according to the invention in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the agent.

In general, the pH of the dishwashing detergent can be adjusted using customary pH regulators, with the pH being selected depending on the desired application. In various embodiments, the pH is in a range from 5.5 to 12, preferably from 5.5 to 11, more preferably from 8 to 11, in particular greater than 8.3, especially in the range from 8.5 to 10.5. The above pH values refer to a 10% dilution of the agent in water at a temperature of around 20°C. Acids and/or alkalis, preferably alkalis, are used as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. In principle, volatile alkalis are also suitable, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.

To adjust and/or stabilize the pH, the dishwashing detergent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of from 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2H ₂ O and tripotassium citrate H ₂ O.

Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Furthermore, preservatives can be contained in the dishwashing detergent according to the invention. For example, preservatives from the groups of alcohols, aldehydes, antimicrobial acids and/or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl carbamate, iodine, iodophors and peroxides. Preferred antimicrobial agents are preferably selected from the group consisting of 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'-methylene-bis(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-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, 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.

In order to facilitate the disintegration of prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these agents in order to shorten the disintegration times. Tablet disintegrants or disintegrants are understood as meaning excipients which ensure that tablets disintegrate rapidly in water or other media and that the active ingredients are released quickly. Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the composition containing disintegration aids.

In general, the machine dishwashing detergents described herein can be packaged in different ways. The agents can be presented in solid or liquid form or as a combination of solid and liquid forms. Powders, granules, extrudates, compacts, in particular tablets, are particularly suitable as solid supply forms. The liquid supply forms based on water and/or organic solvents can be thickened and in the form of gels. The agents are preferably packaged in the form of multi-phase products. The individual phases of such multi-phase agents can have the same or different states of aggregation. The dishwashing detergents can be in the form of shaped bodies. In order to facilitate the disintegration of such prefabricated shaped bodies, it is possible to incorporate disintegration aids, so-called tablet disintegrants, as defined above, into these agents in order to shorten the disintegration times.

The dishwashing detergents described herein are preferably prepackaged to form dosing units. These dosing units preferably comprise the amount of washing or cleaning active substances required for one cleaning cycle. Preferred dosage units have a weight of about 5 and 50 g, preferably about 11 to 30 g, more preferably about 11 to 21 g, for example about 14 to 21 g, most preferably about 18 to 21 g. The volume of the aforementioned dosing units and their three-dimensional shape are selected with particular preference in such a way that the prefabricated units can be dosed via the dosing chamber of a dishwasher. The volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

In various embodiments, the at least one builder is contained in an amount of >5 g in such a pre-portioned dosage form of the agent according to the invention, especially in embodiments in which the weight of such a dosage unit is in the range from about 11 to 30 g, even more preferred about 14 to 21 g, most preferably about 18 to 21 g.

The machine dishwashing detergents, in particular the prefabricated dosing units, particularly preferably have a water-soluble coating. The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent.

The water-soluble packaging can have one or more compartments. The agent can be contained in one or more compartments, if any, of the water-soluble coating. The amount of agent preferably corresponds to the full or half dose required for one rinse.

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.

Suitable water-soluble films for producing the water-soluble casing are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 5,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers can also be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble covering be. A preferred additional polymer are polylactic acids. In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It can be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages of the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400 or M8900. Other suitable films include ^Solublon® PT, ^Solublon® GA, ^Solublon® KC or ^Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.

According to a preferred embodiment, the preferably multiphase dishwashing detergent is tightly enveloped by a water-soluble film.

The water-soluble film, which is preferably used for tight wrapping, particularly preferably comprises polyvinyl alcohol, as described above, with the starting thickness preferably being from 10 μm to 100 μm, in particular from 12 μm to 60 μm, particularly preferably from 15 μm to 50 microns, especially from 20 microns to 40 microns, in particular from 22 microns to 35 microns is used.

In the case of tight wrapping, a single portion of the washing or cleaning agent is wrapped in each case. For the coated single-serving detergent or cleaning agent according to the invention, it is important that the coating lies tightly against the surface of the tablets at every point.

Ideally, the casing is even under tension, but this is not absolutely necessary. This tight fit of the encapsulation is conducive to disintegration: upon first contact with water, the encapsulation will let a small amount of water through at some point, without initially having to detach at all. At this point, the disintegrant contained in the tablet begins to swell. The result of this is that the cover suddenly tears open as a result of the increase in volume of the tablet and the tablet is released. The mechanism described here does not work if the coating is not tight-fitting, since the tablet can swell without the coating being ruptured. The use of a swellable disintegrating agent is superior to a gas-evolving system, since its explosive effect always leads to the shell rupturing. In a gas-evolving system, the explosive effect can be "blown" by gas escaping from a leak in the cladding.

Preferred washing or cleaning agent single portions according to the invention are characterized in that the distance between the single portion and the water-soluble envelope over the entire surface is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 µm.

In a preferred embodiment, the film wrapping is first placed loosely around a single portion of cleaning agent and welded and then shrunk onto it, so that there is close contact between the film packaging and the cleaning agent concentrate. Accordingly, single-serving cleaning agents according to the invention are characterized in that the cover is a foil pack shrunk onto it.

For example, this wrapping can be done by placing a water-soluble lower film on a transport chain or a mold(s), then placing one or more detergent or cleaning agent portion(s) on the lower film; then a water-soluble upper film is placed on the detergent or cleaning agent portion(s) on the lower film and this is then fixed on the lower film, including the detergent or cleaning agent portion(s),

Alternatively, this step can also be carried out using a single-strand film, which is then laid around the single-use portions as a tube. The foils are then sealed and optionally cut. The film can then be shrunk on by using hot air or infrared radiation, optionally with pressure.

Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A , the disclosure of which is hereby incorporated by reference in its entirety.

The corresponding use of the dishwashing detergent according to the invention is also the subject of the invention, in other words the use of a dishwashing detergent according to the invention for cleaning dishes, in particular for machine cleaning of dishes. The invention also relates to a method, in particular an automatic dishwashing method, in which a washing or cleaning agent according to the invention is used in at least one step of the method. The subject matter of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while running through a dishwashing program before the start of the main wash cycle or during the course of the main wash cycle. The agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber. The dishwashing detergents according to the invention are particularly suitable for cascade-like cleaning programs in which a cascade of dilutions/liquor volumes, preferably in the range of 3-6 L each, of the detergent according to the invention with water, preferably with water with a Ca/Mg hardness of max. 21° dH , is generated in a dishwasher, for example a household dishwasher. Dishwashers that have a place to put tea cups or glasses can achieve particularly advantageous cleaning effects. When using the dishwashing detergents according to the invention, it is also possible to use non-softened water, for example water with a Ca/Mg hardness of 18° dH or more, for example 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, or 25 °dH. In these cases, it may be advisable to use the agent according to the invention in combination with conventional rinse aids and/or regenerating salt that are to be dosed separately. Such product combinations are of course also possible with lower water hardnesses, for example a water hardness of less than 18 °dH, for example 17.5, 17, 16.5, 16, 15.5, 15, 14.5, 14, 13.5, 13 , 12.5, 12, 11.5, 11, 10.5, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4 .4, 4, 3.5, 3, 2.5, 2, 1.5, 1, or 0.5.

The invention further relates to the use of bicarbonate to improve the cleaning performance of an automatic dishwashing detergent which contains bleach and optionally also a builder that is different from the bicarbonate, preferably both. The improvement in cleaning performance may include or be an improvement in bleaching performance. It can be used in an automatic dishwashing process. Accordingly, the invention also relates to the use of hydrogen carbonate in a bleach-containing (machine) dishwashing detergent to improve the bleaching effect on bleach-sensitive soiling, in particular in a machine dishwashing process.

The embodiments described in the context of the agents according to the invention can also easily be transferred to the methods and uses according to the invention and vice versa. In particular, the concentration ranges and other ingredients specified for the agents described also apply to the methods and uses according to the invention and vice versa.

examples Example 1: Recipes used

Table 1 ingredients example 1 Example 2 (comparison) Lower phase (blue) % % _{Na2CO3 _} 18.40 19:33 Sodium Citrate Dihydrate 15:17 15:17 Na percarbonate 10.96 10.96 HEDP-Na ₃ 3.98 3.98 end-capped Nio surfactant e.g. Dehypon GRA 3:19 3:19 silicate 2.37 2.37 NaHCOs 0.93 0.00 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 0.86 0.86 Mn-TACN 0.02 0.02 non-active fillers, accompanying, granulating, auxiliary substances, perfume, color, <1% water 6.22 6.22 sum lower phase 62:10 62:10 pH lower phase 10.66 10.91 upper phase Sodium Citrate Dihydrate 12.38 12.38 TAED 2.80 2.80 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 2.25 2.25 silicate 1.35 1.35 end-capped Nio surfactant e.g. Dehypon GRA 1:18 1:18 _{Na2CO3 _} 0.74 0.74 active protease protein, e.g. from Blaze Evity 125 T 0.15 0.15 active amylase protein, e.g. from Stainzyme Plus 36 Evity 0.01 0.01 non-active fillers, accompanying, granulating, auxiliary substances, perfume, color, <1% water 3.80 3.80 sum upper phase 24.67 24.67 core silicate 2.66 2.66 HEDP-Na ₃ 2.29 2.29 NaCO ₃ 3.66 3.66 Na citrate 2H ₂ O 1.45 1.45 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 1:18 1:18 end-capped Nio surfactant e.g. Dehypon GRA 0.03 0.03 non-active fillers, accompanying, granulating, auxiliary substances, perfume, color, <1% water 1.89 1.89 total core 13:16 13:16 PEG based glue for core 0.08 0.08 sum (total) 100 100 pH (total) 10.40 10.60 Table 2 ingredients Example 3 Example 4 (comparison) Lower phase (blue) _{Na2CO3 _} 16.63 17.24 Na percarbonate 12.06 12.06 MGDA 10:16 10:16 non-active fillers, by-products, granulation, auxiliary substances, perfume, 5.03 color, <1% water 8.62 8.62 end-capped Nio surfactant e.g. Dehypon GRA 5.03 5.03 HEDP-Na ₃ 4:23 4:23 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 3.08 3.08 NaHCO ₃ 0.60 0.00 Mn-TACN 0.04 0.04 sum lower phase 60.47 60.47 pH lower phase 10.56 10.61 upper phase non-active fillers, accompanying, granulating, auxiliary substances, perfume, color, <1% water 10.02 10.02 Sodium Citrate Dihydrate 7.34 7.34 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 3.73 3.73 TAED 2.57 2.57 end-capped Nio surfactant e.g. Dehypon GRA 1.59 1.59 silicate 1.27 1.27 active protease protein, e.g. from Blaze Evity 125 T 0.81 0.81 active amylase protein, e.g. from Stainzyme Plus 36 Evity 0.05 0.05 sum upper phase 27.37 27.37 core NaCO ₃ 2.56 2.56 silicate 2.32 2.32 non-active fillers, accompanying, granulating, auxiliary substances, perfume, color, <1% water 1.91 1.91 HEDP-Na ₃ 1.39 1.39 MGDA 1:13 1:13 linear acrylate or acrylate with sulfonic acid groups e.g. Acusol 588 1.03 1.03 Na citrate 2H ₂ O 0.93 0.93 end-capped Nio surfactant e.g. Dehypon GRA 0.17 0.17 total core 11:44 11:44 PEG based glue for core 0.71 0.71 sum (total) 100 100 pH (total) 10.35 10.46

Example 2: cleaning test

To determine the cleaning performance, items of crockery are washed with the above product formulations and then visually inspected. Cleaning grades based on the visual appearance of the dry items to be washed (porcelain, glasses, plastic parts and stainless steel) are assigned as parameters. One tablet is dosed with the above recipe and 100 g of dirt are dosed per wash cycle in order to simulate a normally soiled load. The cleaning result is determined in a Miele GSL in the "Normal 48 °C" program. Water hardness: 21 °dH. Products 1 and 2 were each used after 4 weeks of storage at 50°C. Products 3 and 4 were each used fresh. The rating scale ranges from 0 (no cleaning) to 10 (perfect cleaning). <b>Table 3</b> product Tea (Assam) Creme brulee ground beef egg yolk spaghetti Strength example 1 2.0 6.4 6.8 4.7 1.0 5.1 Example 2 (comparison) 1.5 6.3 6.9 5.1 1.0 5.5 product Tea (Assam) Tea (BOP) Creme brulee ground beef egg yolk spaghetti Strength Example 3 7.0 9.0 9.4 9.9 9.3 5.0 9.9 Example 4 (comparison) 6.5 7.7 8.5 9.6 9.2 4.8 10.0

It can be clearly seen that with the product formulations 1 and 3 according to the invention, a superior cleaning performance compared to the comparison formulations can be achieved, in particular on tea stains.

Claims (14)

Use of at least one bicarbonate. for improving the cleaning performance, in particular the bleaching performance, of an automatic dishwashing detergent which a) at least one bleach and optionally at least one bleach activator and/or at least one bleach catalyst; and b) contains at least one builder. The use according to claim 1, wherein the use is in an automatic dishwashing process. Automatic dishwashing detergent comprising a) at least one bleach and optionally at least one bleach activator and/or at least one bleach catalyst; b) at least one builder and c) at least one hydrogen carbonate, the at least one hydrogen carbonate being present in the agent in an amount of approximately 0.1 to 10% by weight, based on the total weight of the agent. The machine dishwashing detergent according to claim 3, characterized in that the at least one bicarbonate is selected from the group consisting of bicarbonates of alkali metals, bicarbonates of alkaline earth metals and ammonium bicarbonate. The automatic dishwashing agent according to any one of claims 3 to 4, characterized in that the at least one bleach comprises at least one source of active oxygen. The machine dishwashing detergent according to any one of claims 3 to 5, characterized in that at least one bleach and at least one bleach catalyst and/or at least one bleach activator is present. The machine dishwashing detergent according to any one of claims 3 to 6, characterized in that - the bleaching agent is selected from the group of percarbonates; and or - the bleach catalyst is selected from the group of bleach-boosting transition metal salts or transition metal complexes; and or - the bleach activator is selected from the group consisting of acylated alkylenediamines, acylated triazine derivatives, acylated glycolurils, N-acylimides, acylated phenolsulfonates, preferably from the group of acylated alkylenediamines. The automatic dishwashing agent according to any one of claims 3 to 7, characterized in that the at least one builder in an amount of about 5 to 80% by weight, preferably 10 to 60% by weight, in particular > 30% by weight, respectively based on the total weight of the agent. The automatic dishwashing agent according to any one of claims 3 to 8, characterized in that the at least one builder is selected from the group consisting of citrate, soda, methylglycine diacetic acid (MGDA) and mixtures thereof. The automatic dishwashing detergent according to any one of claims 3 to 9, characterized in that the dishwashing detergent has at least one other ingredient selected from the group consisting of surfactants, polymers, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, pigments, additives to improve drainage and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers. The machine dishwashing detergent according to any one of claims 3 to 10, characterized in that the dishwashing detergent is a multi-phase dishwashing detergent. The machine dishwashing detergent according to claim 11, characterized in that the dishwashing detergent is a multiphase dishwashing detergent containing at least one bleaching phase and the at least one hydrogen carbonate in an amount of approximately 0.5 to 10% by weight, preferably approximately 0.7 to 2% by weight. -%, each based on the total weight of the bleaching phase contained in the agent. The automatic dishwashing agent according to any one of claims 3 to 12, characterized in that the dishwashing agent is in pre-portioned form, with a unit dose preferably about 5 to 50 g, preferably about 11 to 21 g, more preferably about 14 to 21 g, most preferably is about 18 to 21 g. Method for machine cleaning of dishes, characterized in that a washing or cleaning agent according to one of Claims 3 to 13 is used in at least one method step.