EP4015606A1 - Method of cleaning and maintaining an automatic dishwashing machine - Google Patents

Abstract

Method for cleaning and / or care of an automatic dishwasher, in which in a normal cleaning cycle for cleaning items to be washed with an automatic dishwashing detergent, a pre-portioned care product for automatic dishwashers that is formulated separately from the dishwashing detergent is metered in, the care product having at least one bleach and at least one nonionic surfactant and wherein the care product has at least two different portions A and B, wherein portion B has a bleaching agent and/or a surfactant and portion A has at least one bleaching agent.

Description

The present invention relates to a method for cleaning and/or maintaining automatic dishwashing machines, which method removes deposits in an automatic dishwashing machine and can be carried out in a normal dishwashing cycle in the presence of items to be washed.

Limescale and grease deposits in an automatic dishwashing machine that develop through use are nowadays usually removed with special machine care products. These special care products contain acids to remove limescale and surfactants to remove grease. Due to the acid they contain, however, such care products must be used in a separate program, otherwise the cleaning performance of the neutral to alkaline dishwashing detergents is significantly reduced and the acidic detergents can have a damaging effect on the decor and glasses.

The use of such care products therefore increases energy and water consumption. In addition, it is not particularly user-friendly due to the additional time required.

There are already cleaning and care products for automatic dishwashing machines that can be used in a normal cleaning cycle of a dishwashing machine together with a conventional dishwashing detergent. However, cleaning the soiled dishes in the machine while cleaning and caring for the machine at the same time is often unsatisfactory. The overall cleaning performance, in particular the cleaning of starch soiling, proteinaceous soiling and burned-in proteinaceous soiling, is in need of improvement.

There is therefore a need to enable a method that allows the consumer, in addition to removing grease and limescale deposits, to also achieve a clean and hygienic overall impression of the dishwasher, including the items to be cleaned, without having to carry out an additional rinse cycle. In particular, the cleaning of the items to be washed, e.g. of starch soiling, protein-containing soiling and burnt-in protein-containing soiling, should be improved compared to the previous methods while at the same time maintaining the same good level of machine cleaning.

Surprisingly, it has now been found that cleaning and care products for the dishwasher, which have two or more parts and contain bleach, can solve these problems.

1. i) mindestens ein Bleichmittel und
2. ii) mindestens ein nichtionisches Tensid

aufweist und
wobei das Pflegemittel mindestens zwei unterschiedliche Anteile A und B aufweist, wobei Anteil B ein Bleichmittel aus i) und/oder ein Tensid aus ii) aufweist und Anteil A mindestens ein Bleichmittel aus i) aufweist.In a first aspect, the present invention is therefore directed to methods for cleaning and / or care of an automatic dishwasher, wherein in a normal cleaning cycle for cleaning items to be washed, in particular soiled dishes, with a machine dishwashing detergent, a pre-portioned care product for automatic dishwashers formulated separately from the dishwashing detergent is metered in, with the care product

1. i) at least one bleaching agent and
2. ii) at least one nonionic surfactant

has and
where the care product has at least two different parts A and B, where part B has a bleaching agent from i) and/or a surfactant from ii) and part A has at least one bleaching agent from i).

In the process according to the invention, the care product is used together with an automatic dishwashing detergent in a normal cleaning cycle for cleaning soiled items to be washed, i.e. in the presence of items to be washed (or dishes) to be cleaned. This has the advantage that the machine is prevented from idling at high water temperatures. Energy and water are therefore not wasted. Furthermore, the consumer does not have to empty the machine completely in daily operation, but can also clean the machine at the same time as the dishes. Due to this minimal effort for the consumer, regular cleaning of the machine is facilitated. In such a case, there is no accumulation of stubborn soiling in the dishwasher that can only be removed under harsh conditions. Furthermore, the simultaneous use of the care product in the usual dishwashing cycle with dishes saves time, water and energy. The leftovers and soiling, especially in the dishwasher sieve, which represent a breeding ground for unwanted germs, are also significantly reduced and thus contribute to an improvement in the microbiological condition of the machine.

"Normal cleaning cycle" as used herein refers to a program for cleaning dishes (dishes) of an automatic dishwashing machine. Such a cleaning cycle can include one or more prewash cycles, one or more main wash cycles and one or more rinse cycles. Such a cleaning cycle includes the automatic cleaning/rinsing of soiled items to be washed or crockery.

"At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more. "At least two" as used herein includes, but is not limited to, 2, 3, 4, 5, 6 and more.

Unless otherwise stated, the percentages by weight given in this application relate to the active substance content in g, based on the weight of the entire composition in g.

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 specified. 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.

The care product in the method according to the invention contains at least one bleaching agent. The at least one bleach is preferably an oxygen bleach. Among the compounds serving as oxygen bleaches and yielding H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaches are, for example, peroxypyrophosphates, persilicates, peroxymonosulfates, citrate perhydrates and H ₂ O ₂ -supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Further typical organic bleaching agents are the peroxyacids, also called peroxycarboxylic acids, examples being mentioned in particular of the alkylperoxyacids, the arylperoxyacids and the imidoperoxyacid. All other inorganic or organic peroxy bleaches known to those skilled in the art from the prior art can also be used. It is preferably selected from percarbonates, perborates and phthaloimino peracids and mixtures thereof. Sodium percarbonate is particularly preferably used.

A preferred object is accordingly a method in which the care product is designed in such a way that the at least one bleach is an oxygen bleach; this bleach is preferably selected from percarbonates, perborates and phthaloimino peracids and mixtures thereof. In particularly preferred methods, the conditioner contains sodium percarbonate.

In order to convey the desired positive overall impression, certain amounts of bleaching agent are preferably used in the care product. It is preferred that the care product contains bleach in amounts of 5 to 40% by weight, preferably from 9 to 23% by weight, in particular from 13 to 18% by weight, based on the total amount of care product and/or that portion A has the at least one bleaching agent in amounts of 20 to 65% by weight, preferably 30 to 55% by weight, in particular 35 to 50% by weight, based on the total amount of portion A.

A preferred object is therefore a method in which the care product is designed in such a way that the care product contains the at least one bleaching agent in amounts of 5 to 40% by weight, preferably 9 to 23% by weight, in particular 13 to 18% by weight %, based on the total amount of the care product, and/or that part A contains the at least one bleaching agent in amounts of 20 to 65% by weight, preferably 30 to 55% by weight, in particular 35 to 50% by weight. -%, based on the total amount of part A, has.

In addition, a preferred subject matter is a method in which the care product is designed in such a way that the at least one bleach is an oxygen bleach; this bleach is preferably selected from percarbonates, perborates and phthaloimino peracids and mixtures thereof, in particular sodium percarbonate, and wherein the Care product which has at least one bleaching agent in amounts of 5 to 40% by weight, preferably 9 to 23% by weight, in particular 13 to 18% by weight, based on the total amount of the care product, and/or that proportion A which has at least one bleach in amounts of from 20 to 65% by weight, preferably from 30 to 55% by weight, in particular from 35 to 50% by weight, based on the total amount of portion A.

If one or more inorganic persalts are used in the care product, it is preferred that at least one bleach activator is also used. It is particularly preferred that at least one bleach activator is used in at least one proportion A. 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 the person 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 preferably used. Combinations of conventional bleach activators can also be used. If one or more inorganic persalts, preferably a percarbonate bleach, are used in the care product, it is therefore preferred that at least one bleach activator, preferably TAED, is also used in the care product.

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, in each case based on the total amount of part A, preferably used in at least one part A.

If inorganic persalts and optionally bleach activators are used in the care product, the care product preferably also contains at least one bleach catalyst in special processes according to the invention. In this case, the bleach catalyst is preferably present in portion A. Bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, 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 care products which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands , 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-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 ](CIO 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 ](CIO ₄ ) ₄ , [Mn ^III ₂ (µ-O) ₁ (µ-OAc) ₂ (Me-TACN ) ₂ ](CIO ₄ ) ₂ , [Mn ^III Mn ^IV (µ-O) ₁ (µ-OAc) ₂ (Me-TACN) ₂ ](CtO 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 (OAc=OC(O)CH ₃ ).

If inorganic persalts and optionally bleach activators are used in the care product, the care product preferably also contains at least one bleach catalyst in special processes according to the invention, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN). If the aforementioned bleach-boosting transition metal complexes are used, this is preferably done in the usual amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight % to 0.30% by weight or 0.02% by weight to 0.5% by weight, based in each case on the total weight of fraction A, particularly preferably in fraction A. However, more can also be used in special cases Bleach catalyst are used.

In specific embodiments, the care product contains at least one inorganic persalt, preferably a percarbonate, particularly preferably sodium percarbonate, at least one bleach activator, preferably TAED, and optionally a bleach catalyst, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1, 4,7-triazacyclononane (Me ₃ -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN). Processes in which the care product does not contain a bleach catalyst are particularly preferred.

Organic peracids such as alkyl peroxyacids, aryl peroxyacids and imidoperoxycarboxylic acids can also be used as bleaching agents. Particular mention should be made here of phthalimidoperoxycarboxylic acids such as phthalimidoperoxybutanoic acid and phthalimidoperoxyhexanoic acid (PAP). If one or more phthalimidoperoxycarboxylic acids are used in the care product, it is preferred that no bleach activator and/or no bleach catalyst is used in the care product.

Agents that have no bleach activator and/or no bleach catalyst are essentially free of these substances. This means that the care products contain bleach activators in amounts of less than 1% by weight, preferably less than 0.1% by weight, and/or contain no intentionally added bleach activator and/or that the care products contain bleach catalysts in amounts of less than 0.01% by weight. -%, preferably less than 0.001% by weight, and/or contain no intentionally added bleach catalyst. Bleach activators or bleach catalysts are all substances and classes of substances that have been described as such above and all others that are generally known as such to the person skilled in the art.

Methods according to the invention are also preferred in which the at least two different components A and B mentioned above are packaged in such a way that they are released into the washing liquor at different times of the cleaning cycle. This allows the ingredients contained in parts A and B to act on the parts to be cleaned or cared for at different points in time during the cleaning cycle in an automatic dishwasher.

In the context of the method according to the invention, it is therefore preferred that portion B is released into the washing liquor in the pre-wash cycle of the cleaning cycle and/or that portion A is released into the washing liquor in the main washing cycle of the cleaning cycle.

A preferred object is therefore a method according to the invention, in which the care product used has at least two different proportions A and B, and wherein proportion B is released into the rinse liquor in the pre-rinse cycle of the cleaning cycle and/or wherein proportion A is released into the rinse liquor in the main rinse cycle of the cleaning cycle becomes.

Such a time-delayed release can be made possible by packaging parts A and B differently. Various possibilities are conceivable as to what type of proportion A should be made of so that the ingredients are released in the main wash cycle.

For example, it may be preferred according to the invention if the composition of Part A is in the form of one or more compressed tablets. It can likewise be preferred according to the invention if the active substance composition of portion A is embedded in a wax. It can also be preferred according to the invention if the active substance composition of portion A is embedded in a polymer.

Various possibilities are also conceivable as to what type of portion B should be made of so that the ingredients are released in the pre-rinse cycle. For example, it may be preferred according to the invention if the composition of portion B is present in non-compressed form. In the context of this application, non-compressed means that the composition of portion B was not compressed under increased pressure. Examples of non-compressed forms include, but are not limited to, powders, granules, gels, and liquids.

In the context of the method according to the invention, it is therefore preferred if the care product is such that the composition of part A in the form of one or more compressed / r tablet (s) and / or the active ingredient composition of part A embedded in a wax and / or embedded in a polymer and/or that the composition of portion B is present in non-compressed form.

A preferred subject is therefore a method in which the care product is such that the composition of Part A in the form of one or more compressed tablet(s) and/or the active ingredient composition of Part A is embedded in a wax and/or embedded is present in a polymer and/or that the composition of fraction B is present in non-compressed form.

A particularly preferred subject matter is a method in which the conditioner is such that the composition of Part A is in the form of one or more compressed tablet(s) and/or the active ingredient composition of Part A is embedded in a polymer and/or that the composition of portion B is present in non-compressed form.

For example, it may be preferred according to the invention if the composition of portion A is in the form of one or more compressed tablets, the tablet having at least 8 kN/cm ² , preferably at least 10 kN/cm ² , for example 9 to 22 kN/cm ² , that is, for example, with 12 kN/cm ² was pressed.

It can also be preferred according to the invention if the active substance composition of portion A is embedded in a wax, the wax having a melting point of at least 30° C., preferably at least 35° C., very particularly preferably at least 40° C. In this case, the wax is included in the composition of portion A. This can ensure that the ingredients of portion A are not already released in the pre-rinse cycle. It is also preferred according to the invention that the wax has a melting point of at least 30°C, preferably at least 35°C, very particularly preferably at least 40°C, and at most 55°C, preferably at most 50°C. Suitable examples are Kester Wax K-40 or Kester Wax BK-40 from Koster Keunen Holland BV or Naturafin 46/48°C from Reseda Binder AG. If the active substance composition of part A is embedded in such a wax, then the wax is contained in the composition of part A and the proportion of this wax in the overall composition of part A is preferably 10 to 80% by weight.

It can also be preferred according to the invention if the active substance composition of portion A is embedded in a polymer, the polymer being completely soluble in 1 L of water at a water temperature of 50° C. within 2 to 7 minutes. This can ensure that the ingredients of portion A are not already released in the pre-rinse cycle. Solublon EF from Aicello Chemical Europe GmbH is suitable by way of example. The solubility of a polymer can be checked using simple means. 1 liter of water at the desired temperature is kept ready in a beaker. A film (thickness from 30 μm to 100 μm, area 2 cm×2 cm to 3 cm×3 cm) of the polymer to be tested is clamped on two opposite sides of the piece of film in such a way that it neither folds nor tears. The film is immersed in the water parallel to the bottom of the beaker so that it is approximately halfway between the bottom of the beaker and the water surface. The water is stirred at 700 rpm with the aid of a magnetic stirrer/magnetic stirrer core. According to the definition of this method, complete dissolution is given as soon as no polymer particles are visible to the naked eye. If the active substance composition of part A is embedded in such a polymer, then the polymer is present in the composition of part A and the proportion of this polymer in the overall composition of part A is preferably 10 to 80% by weight.

In the context of the method according to the invention, it is therefore preferred if the care product is such that the composition of part A is in the form of one or more compressed / r tablet (s), the tablet with at least 8 kN / cm ² , preferably with at least 10 kN/cm ² , for example with 9 to 22 kN/cm ² , for example with 12 kN/cm ² , and/or that the active substance composition of portion A is embedded in a wax, the wax having a melting point of at least 30° C., preferably at least 35° C., very particularly preferably at least 40° C., and/or that the active substance composition of portion A is embedded in a polymer, the polymer is completely soluble in 1L of water at a water temperature of 50 °C within 2 to 7 minutes.

A preferred object is therefore a method in which the care product is such that the composition of portion A is in the form of one or more compressed / r tablet (s), wherein the tablet with at least 8 kN / cm ² , preferably with at least 10 kN/cm ² , for example with 9 to 22 kN/cm ² , for example with 12 kN/cm ² , and/or that the active substance composition of portion A is embedded in a wax, the wax having a melting point of at least 30 °C, preferably at least 35 °C, very particularly preferably at least 40 °C, and/or that the active substance composition of part A is embedded in a polymer, the polymer being dissolved in 1 L of water at a water temperature of 50 °C within 2 is completely soluble up to 7 minutes.

A particularly preferred subject matter is a method in which the conditioner is such that the composition of Part A is in the form of one or more compressed tablet(s), the tablet having at least 8 kN/cm ² , preferably at least 10 kN/cm ² , for example at 9 to 22 kN/cm ² , for example at 12 kN/cm ² , and/or that the active substance composition of portion A is embedded in a polymer, the polymer being present in 1L of water completely soluble within 2 to 7 minutes at a water temperature of 50 °C.

The terms composition and active substance composition used in this application and in particular in the preceding paragraphs differ in that the active substance composition comprises the ingredients which have a direct effect in the context of the cleaning and/or care of an automatic dishwasher, including, for example and incompletely enumerated acids, Count bases, bleaching agents and/or surfactants, if present. However, the term active substance composition does not include waxes and/or polymers of the type mentioned in the preceding paragraphs and in which the active substance compositions can be embedded as described above. The term composition, on the other hand, is more comprehensive and includes all ingredients belonging to the respective portion or the respective agent.

In order to make it easier for the consumer to carry out the method and to ensure the correct dosage of the care product, the care product is used in pre-portioned form in the process according to the invention. This can be any form of packaging that is in accordance with the stated conditions. Compositions which are present, for example, in the form of a multi-phase tablet or a multi-phase pouch are preferred. Both in multi-phase tablets and in multi-phase Pouches can be the different phases both on top of each other and next to each other or simultaneously on top of and next to each other.

Within the scope of the method according to the invention, it is preferred if the care product is used in an amount of 10 to 30 g/job, preferably 13 to 23 g/job, in particular 15 to 21 g/job.

In preferred embodiments, the care product used in the process is phosphate- and/or phosphonate-free. "Phosphate-free" and "phosphonate-free" as used herein means that the composition in question is essentially free of phosphates or phosphonates, i.e. in particular phosphates or phosphonates in amounts less than 0.1% by weight, preferably less than 0 .01% by weight, based on the entire care product. It is preferred that a total amount of phosphorus in the care product does not exceed 0.3 g/job, preferably 0.03 g/job.

A preferred subject is therefore a method in which the care product is phosphate and/or phosphonate free.

In order to facilitate application, the care product is preferably present in a water-soluble coating. It is particularly preferred if the water-soluble packaging is a film containing polyvinyl alcohol. 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 covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 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 containing (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble covering Polymers can be added. 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.

The care product in the method according to the invention can be made up in such a way that the at least one part A and the at least one part B are in a weight ratio of 3:1 to 1:10, preferably in a weight ratio of 1:1 to 1:8, in particular from 1 :3 to 1:7, for example from 1:4 to 1:6, based on the respective amounts of parts A and B in the care product.

A preferred object is therefore a method in which the care product is such that the at least one part A and the at least one part B are present in a weight ratio of 3:1 to 1:10, preferably in a weight ratio of 1:1 to 1 :8, in particular from 1:3 to 1:7, for example from 1:4 to 1:6, based on the respective amounts of parts A and B in the care product.

In order to facilitate the removal or reduction of greasy stains, the care product in the process according to the invention contains at least one nonionic surfactant. It is preferred that a mixture of two or more nonionic surfactants is used in the care product of the method according to the invention.

A care product that can be used in the methods described herein can have any of the nonionic surfactants known to those skilled in the art. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used in the care product. A class of preferably usable nonionic surfactants, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants in the care product, are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty alcohols.

In various preferred embodiments, a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, is therefore used. In particular, non-capped fatty alcohol alkoxylates are preferred.

In preferred embodiments, the fatty alcohol ethoxylate has the formula

R ¹ -O-(EO) _m -H ,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 12 to 24, in particular 14 to 20, in particular 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 10 to 50, especially 20 to 30, preferably 22 to 27, especially 25.

In particularly preferred embodiments, the fatty alcohol ethoxylate has the formula

R ¹ -O-(EO) _m -H ,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 20 to 30, preferably 22 to 27, especially 25.

In one embodiment, the alkyl group R ¹ is a linear, preferably unsubstituted, alkyl group having 16 to 18 carbon atoms.

The fatty alcohol alkoxylate, preferably the fatty alcohol ethoxylate, in particular the fatty alcohol ethoxylate of the formulas mentioned, can be present in the care product in an amount of 0.1 to 20% by weight, preferably 1 to 13% by weight, particularly preferably 3 to 9% by weight be included on the care product. Such amounts are preferred to ensure adequate grease dissolution and removal.

It is preferred that a nonionic surfactant that can be used in the care products described herein for the methods according to the invention is present in an absolute amount of 0.1 to 6 g/job, preferably 1 to 4 g/job, in particular 2.0 to 3.5 g/job. job, for example 2.9 g/job, is contained in the care products.

It is particularly preferred that a fatty alcohol ethoxylate of the formula

R ¹ -O-(EO) _m -H ,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 12 to 24, in particular 14 to 20, in particular 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 10 to 50, especially 20 to 30, preferably 22 to 27, especially 25; in an absolute amount of 0.1 to 6 g/job, preferably 1 to 4 g/job, in particular 2.0 to 3.5 g/job, for example 2.9 g/job, is contained in the care products.

It is particularly preferred that a fatty alcohol ethoxylate of the formula

R ¹ -O-(EO) _m -H ,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 20 to 30, preferably 22 to 27, especially 25; in an absolute amount of 0.1 to 6 g/job, preferably 1 to 4 g/job, in particular 2.0 to 3.5 g/job, for example 2.9 g/job, is contained in the care products.

The nonionic surfactant is preferably a fatty alcohol ethoxylate which is solid under standard conditions (temperature 25° C., pressure 1013 mbar) and can preferably be used in the form of a powder or granules.

A fatty alcohol alkoxylate of the formula is also suitable as a nonionic surfactant

R ^2- (AO) _w -R ³ ,

where R ² is a linear or branched, substituted or unsubstituted alkyl group having 8 to 16 carbon atoms; R ³ is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; each A independently represents a residue from the group -CH ₂ CH ₂ - and - CH2-CH(CH3)-, CH2- CH2-CH2-, CH2- CH2- CH2-CH2-, -CH2- CH(CH2-CH3) -, -CH2- C(CH ₃ ) ₂ - or - CH ₂ - CH ₂ -CH(CH ₃ )-, where at least one A is -CH ₂ CH ₂ - and at least one A is -CH ₂ -CH(CH ₃ )-, CH2- CH2-CH2-, CH2- CH2- CH2-CH2-, -CH2- CH(CH2-CH3)-, -CH2- C(CH ₃ ) ₂ - or -CH2- CH2-CH(CH ₃ )- is; and w is an integer from 2 to 50, preferably from 10 to 30.

In various embodiments, the ratio of the ethylene oxide units and the higher alkylene oxide units in the fatty alcohol alkoxylate of the formula is 12:1 to 1:1, preferably 10:1 to 2:1, more preferably 6:1 to 3:1. Fatty alcohol alkoxylates of the formula in which R ² is a linear alkyl group having 12-16 carbon atoms and R ³ is H and w=10 to 30 are particularly preferred.

The fatty alcohol alkoxylate of this formula can be contained in the care products, in particular in an amount of 0.01 to 3% by weight, based on the composition. The absolute amount of the fatty alcohol alkoxylate of this formula in the composition can in particular be 0.001 to 3 g/job, preferably 0.01 to 1 g/job, more preferably 0.1 to 0.5, most preferably 0.2 g/job.

Also suitable as nonionic surfactants are, for example, alkyl glycosides of the general formula RO(G) _x , in which R corresponds to a primary linear or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G corresponds to is a symbol that stands for a glucose unit with 5 or 6 carbon atoms, preferably for 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.

Another class of nonionic surfactants that can be used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide 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.

It is preferred according to the invention if a care product is used in the method which nonionic surfactant in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in an amount from 10 to 17% by weight, based on the total amount of care product.

A further preferred object is therefore a method in which the care product contains nonionic surfactant, preferably in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in one Amount of 10 to 17% by weight, based on the total amount of care product.

It is particularly preferred according to the invention if the nonionic surfactant is at least partly an alkoxylated, preferably ethoxylated, alcohol.

Another particularly preferred object is therefore a method in which the care product contains nonionic surfactant, preferably in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in an amount of 10 to 17% by weight, particularly preferably in an amount of 7 to 15% by weight, based on the total amount of care product, wherein the nonionic surfactant is at least partly an alkoxylated, preferably ethoxylated, alcohol.

Furthermore, it is particularly preferred according to the invention if the nonionic surfactant is a mixture of different nonionic surfactants. These can be, for example, mixtures of different alkoxylated alcohols and/or mixtures of one or more alkoxylated alcohols with another type of nonionic surfactant.

Another particularly preferred object is therefore a method in which the care product contains nonionic surfactant, preferably in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in an amount of 10 to 17% by weight, particularly preferably in an amount of 7 to 15% by weight, based on the total amount of care product, the nonionic surfactant being a mixture of different nonionic surfactants.

Furthermore, it is preferred according to the invention if the nonionic surfactant is at least partly a fatty alcohol ethoxylate of the formula

R ¹ is -O-(EO) _m -H,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 20 to 30, preferably 22 to 27, especially 25.

A further preferred object is therefore a method in which the care product contains nonionic surfactant, preferably in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in one Amount of 10 to 17% by weight, based on the total amount of care product, where the nonionic surfactant is at least partly a fatty alcohol ethoxylate of the formula

R ¹ is -O-(EO) _m -H,

where R ¹ is a linear or branched, substituted or unsubstituted alkyl group having 16 to 18 carbon atoms; EO is an ethylene oxide moiety; and m is 20 to 30, preferably 22 to 27, especially 25.

It is preferred for the process according to the invention that in the care product at least 50% by weight of the nonionic surfactant, based on the total mass of nonionic surfactant present, is at least one alkoxylated alcohol, preferably ethoxylated alcohol, particularly preferably at least 70% by weight, in particular at least 85% by weight.

It is preferred that the active substances in the composition required for dissolving the fat are dissolved as quickly as possible and can thus develop their effect before the automatic dishwashing detergent is metered in.

In the context of the method according to the invention, it is therefore preferred that the care product is metered into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the dishwasher detergent.

A preferred object is accordingly a method in which the care product is metered into the interior of the automatic dishwasher at the start of the cleaning cycle, preferably before the automatic dishwashing detergent.

Dosing or dosing into the interior of the dishwasher means that the care product or the automatic dishwashing detergent gets into the interior of the dishwasher, for example by manual insertion, by the possibly program-controlled opening of the dosing flap and/or by automatic addition from an automatic dosing device. It is possible that the detergent portion or the machine dishwashing detergent is completely available in the washing liquor for cleaning and/or care purposes immediately or only after a period of time. This depends on the dissolution rate and thus on the type, composition and nature of the respective agent or composition. According to the definition given here, the dissolving process is not part of the dosing or dosing. The process of dissolving any water-soluble covering, for example a film, is also not part of the dosing or dosing of the care product or the dishwasher detergent.

Dosing the care product at the beginning of the cleaning cycle can make it possible for the care product to already contribute to the cleaning and/or care of the dishwasher in the prewash cycle and/or at the start of the main wash cycle. Dosing an automatic dishwashing detergent only subsequently can contribute to maintaining the conditions necessary for cleaning and/or maintaining the dishwasher.

It is preferred for the course of the care and cleaning cycle and its effect if a pH of 8.0 to 13.0, preferably from 9.5 to 12.0, very particularly preferably from 10.5 to 11.5, is achieved in the existing washing liquor before dosing the automatic dishwashing detergent.

A preferred object is therefore a method in which the washing liquor of the cleaning cycle has a pH value of at least partially dissolving the care product 8.0 to 13.0, preferably from 9.5 to 12.0, very particularly preferably from 10.5 to 11.5, preferably before the machine dishwashing detergent is metered into the interior of the machine.

It is therefore preferred according to the invention that part B is released as quickly as possible in order to obtain an alkaline washing liquor. It is particularly preferred that the time until complete release of part B of a pre-portioned care product with a mass of 20 g in 1 L water at room temperature with stirring (in a 2 liter beaker with a diameter of 12 cm with a propeller stirrer with a diameter of 6 cm (blade of the stirrer at a height of 3 cm above the bottom of the beaker) at 200 rpm) is 0.1 to 15 minutes, preferably 0.3 to 5 minutes, particularly preferably 0.5 to 2 minutes .

A further preferred subject matter is therefore a method in which a care product is used which is of such a nature that the time it takes for portion B to be completely released from 20 g of pre-portioned care product in 1 L of water at room temperature with stirring (in a 2-litre 12 cm diameter beaker with a 6 cm diameter propeller stirrer (stirrer blades at a height of 3 cm above the bottom of the beaker) at 200 rpm) 0.1 to 15 minutes, preferably 0.3 to 5 minutes , more preferably 0.5 to 2 minutes.

For the same reason, it is also preferred that the care product dissolves in 100 times the amount of water, based on the mass of the care product used, in such a way that after 1 minute of stirring (in a 3 liter beaker with a diameter of 13 .5 cm with a 7 cm diameter propeller stirrer (stirrer blades at a height of 3.5 cm above the bottom of the beaker) at 200 rpm) at room temperature a solution with a pH of 8.0 to 13, 0, preferably from 9.5 to 12.0, most preferably from 10.5 to 11.5.

Another preferred object is therefore a method in which a care product is used, which is such that the care product dissolves in 100 times the amount of water, based on the mass of the care product used, such that after 1 minute of stirring (in a 3 liter 13.5 cm diameter beaker with a 7 cm diameter propeller stirrer (blades of stirrer at a height of 3.5 cm above the bottom of the beaker) at 200 rpm) at room temperature a solution with a pH of 8.0 to 13.0, preferably 9.5 to 12.0, most preferably 10.5 to 11.5.

In various processes according to the invention, preference is given to using care products which contain nonionic surfactant either exclusively in portion B or which contain nonionic surfactant both in portion A and in portion B. Furthermore, it may be preferred that Care product containing the nonionic surfactant for the most part in proportion B, based on the total amount of nonionic surfactant in the care product.

In a specific embodiment, processes are therefore preferred in which the care product used in part A also contains at least one nonionic surfactant.

A further preferred object is therefore a method in which the care product in part A also contains at least one nonionic surfactant.

In a further specific embodiment, methods are therefore preferred in which the at least one nonionic surfactant from ii) is contained in proportion B in an amount of 80 to 100% by weight, preferably in an amount of 95 to 100% by weight. , based on the total amount of nonionic surfactant in the care product.

A further preferred object is therefore a process in which the at least one nonionic surfactant from ii) is contained in part B in an amount of 80 to 100% by weight, preferably in an amount of 95 to 100% by weight, based on the total amount of nonionic surfactant in the conditioner.

The care product of the method according to the invention preferably contains acidic and/or basic compounds. This applies to both part A and part B. It goes without saying that the total amounts of acid and base in the individual parts and in the entire care product must be chosen so that the desired pH range is achieved. This applies to both the pH range achieved by dissolving Portion A and the pH range achieved by dissolving Portion B, as well as the pH range achieved by dissolving the overall composition of the care product is obtained. It is also important that a suitable pH value is achieved with the automatic dishwashing detergent. It is therefore preferred according to the invention that the method is designed in such a way that by dissolving the machine dishwashing detergent and dissolving at least a portion of portion A, the resulting washing liquor of the cleaning cycle has a pH of 8.0 to 13.0 in the main wash cycle, preferably from 9.5 to 12.0, most preferably from 10.0 to 11.0.

A further preferred subject matter is therefore a method in which, by dissolving the machine dishwashing detergent and dissolving at least a portion of portion A, the resulting wash liquor of the cleaning cycle has a pH of 8.0 to 13.0, preferably 9, in the main wash cycle. 5 to 12.0, most preferably from 10.0 to 11.0.

A large number of possible alkaline compounds and acids can be used, among other things, to adjust the pH value. Any acids and bases used are preferably solid under standard conditions (temperature 25° C., pressure 1013 mbar) and can preferably be used in the form of a powder, finely crystalline or in the form of granules.

In general, polycarboxylic acids are suitable as acids, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. These are, for example, oxalic acid, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. Representative amino carboxylic acids include aspartic acid, methylglycine diacetic acid (MGDA) and glutamic diacetic acid (GLDA) or ethylene diamine diacetic acid. Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). However, it is preferred that any acids used are not aminocarboxylic acids.

The corresponding bases of the acids mentioned above can be used as the alkaline compound, for example citrates. Alkaline compounds that can be used with preference are one or more, particularly preferably two or more, compounds from the following group of silicates, carbonates, citrates, hydrogen carbonates and amino carboxylates. Particularly suitable compounds are phyllosilicates, alkali metal carbonates, alkali metal bicarbonates and alkali metal salts of amino carboxylates. Sodium carbonate, sodium hydrogen carbonate and the trisodium salt of methylglycine diacetic acid (Na ₃ MGDA) are particularly suitable.

The care products can contain crystalline layered silicates of the general formula NaMSixO _2x+1 .yH ₂ O as a builder, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. 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. Care products used in particularly preferred methods contain silicate as a builder. Furthermore, it is preferred that the amount of silicate in part A, based on the mass of part A, is between 5 and 30% by weight, preferably between 7 and 17% by weight, very particularly preferably between 8 and 15% by weight .-%, amounts to.

In various embodiments of the invention, alkali metal carbonates, in particular sodium carbonate, can be contained in the care product in part A, preferably in an amount of 1 to 40% by weight, preferably 2 to 30% by weight, based on the mass of part A it is preferred that alkali metal carbonates, in particular sodium carbonate, are contained in various embodiments of the invention in the care product in proportion B, preferably in one Amount of 20 to 60% by weight, in particular 30 to 50% by weight, based on the mass of portion B.

In various embodiments of the invention, alkali metal hydrogen carbonates, in particular sodium hydrogen carbonate, can be contained in the care product in proportion A, preferably in an amount of 1 to 30% by weight, preferably 2 to 20% by weight, based on the mass of proportion A.

Aminocarboxylates, in particular alkali metal salts of methylglycine diacetic acid and/or N,N-dicarboxymethylglutamic acid, particularly preferably the trisodium salt of methylglycine diacetic acid (Na ₃ MGDA), can be contained in part A of the care product in various embodiments of the invention, preferably in an amount of 1 to 20 wt. -%, preferably 2 to 10% by weight, based on the mass of portion A. It is also preferred that aminocarboxylates, in particular alkali metal salts of methylglycine diacetic acid and/or N,N-dicarboxymethylglutamic acid, particularly preferably the trisodium salt of methylglycine diacetic acid (Na ₃ MGDA) is contained in various embodiments of the invention in the care product in proportion B, preferably in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on the mass of proportion B.

In various embodiments of the invention, the corresponding bases of the aforementioned acids, preferably citrates, in particular sodium citrate, can be contained in the care product in proportion B, preferably in an amount of 2 to 25% by weight, particularly preferably 5 to 15% by weight. based on the mass of portion B. It is also possible that these bases are contained in portion A.

The care products used in the process according to the invention can contain other components, preferably at least one other component, preferably selected from the group consisting of other builders, surfactants, polymers, enzymes, corrosion inhibitors, glass corrosion inhibitors, thickeners, foam inhibitors, dyes, disintegration aids, fragrances, perfume carriers, Odor neutralizers, preferably one or more polymers and/or fragrances.

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-alkyl esters having 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates can also be used within the scope of the present invention (Fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate. The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali metal or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of sulfonates also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid.

The builders that can also be used include, in particular, organic cobuilders such as polymeric carboxylates, aspartic acid, polyacetals and dextrins. If the builders mentioned are used in the care product, their influence on the buffer system, if any, must be taken into account.

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

Both homopolymers and copolymers as well as terpolymers can be used, and more complex polymer types are also possible. Suitable polymers are, in particular, polyacrylates and/or copolymers and/or terpolymers containing acrylate monomers, which preferably have a molecular weight of 1000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates which have molecular weights of 1000 to 10000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred from this group.

A copolymeric polyacrylate, preferably a sulphopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polycarboxylate. The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

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, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

In the case of the sulfonic acid group-containing monomers, preference is given to those of the formula R ⁵ (R ⁶ )C═C(R ⁷ )—X—SO ₃ H, 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, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH 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, 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 H ₂ C=CH-X-SO ₃ H, H ₂ C=C(CH ₃ )-X-SO ₃ H or 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 stands for 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 -.

According to a particularly preferred embodiment, the care product can contain a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.

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 polymers, some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups in the care product is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers 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 are preferably selected from those mentioned above. The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application. Preferred care products are characterized in that the copolymers have molar masses from 2000 to 200,000 g.mol ^-1 , preferably from 4000 to 25,000 g.mol ^-1 and in particular from 5000 to 15,000 g.mol ^-1 .

In a further preferred embodiment, the copolymers in the care product also comprise at least one nonionic, preferably hydrophobic, monomer in addition to the monomer containing carboxyl groups and the monomer containing sulfonic acid groups.

1. i) Carbonsäuregruppen-haltige Monomere
2. ii) Sulfonsäuregruppen-haltige Monomere
3. iii) nichtionische Monomere, insbesondere hydrophobe Monomere
   eingesetzt wird.

An anionic copolymer can particularly preferably be contained in one embodiment, with a copolymer comprising as an anionic copolymer

1. i) carboxylic acid group-containing monomers
2. ii) sulfonic acid group-containing monomers
3. iii) nonionic monomers, especially hydrophobic monomers
   is used.

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

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-Trimethylpentene-1, 2,4,4-Trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 ,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 α-olefin, 2-styrene, α -Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, Hexyl acrylate, methyl methacrylate, N-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-(2-ethylhexyl)acrylamide, octyl acrylate, octyl methacrylate, N-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, N-( Lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, N-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or mixtures thereof, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

Polyacrylate-containing polymers can be used in amounts of 0.5 to 15% by weight, preferably 0.6 to 10% by weight, particularly preferably in amounts of 0.8 to 3% by weight or 1 to 5% by weight. %, based on the total weight of the care product, be contained in the care product in the method according to the invention. Mixtures of different polymers can also be used here.

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

The conditioner may also contain one or more enzymes. The optional enzyme or enzymes used may be present in one or more enzyme preparations or enzyme compositions.

Suitable enzymes include proteases, amylases, lipases, cellulases and/or pectinases and preferably mixtures thereof. Other enzymes, such as hemicellulases other than pectinases, for example β-glucanases, and/or perhydrolases and/or oxidoreductases, and mixtures thereof, can also be used in combination with at least one of the aforementioned enzymes. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are used with preference accordingly.

Oxidoreductases, for example 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 (enhancer) or in the case of very different ones Redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).

On the other hand, it is preferred if a care product which does not contain any enzymes is used in the method according to the invention. This means that the composition of the care product in question is essentially free of enzymes, i.e. an added amount of enzyme preparation is less than 0.1% by weight, preferably less than 0.01% by weight, based on the care product as a whole . In particularly preferred methods according to the invention, a care product is used which does not contain any intentionally added enzyme.

Methods are particularly preferred in which a care product is used which contains no enzymes and is phosphate-free. The definitions given above apply here.

In the following exemplary embodiment, the method according to the invention is described in a non-limiting manner in the presence of a care product.

Examples: example 1

The following exemplary conditioner was used in the procedure of Example 2. Phase A was pressed into a tablet (16 kN/cm ² ). Phase B was in powder form. All quantities are in percent by weight based on the total amount of composition. Phase A (3g/job) wt% Builders (silicate, bicarbonate, soda) 5 to 12 Nonionic surfactant 0.1 to 3 Sodium percarbonate 4 to 8 Citric acid anhydrate 0 to 2 TAED 0 to 2 Other ingredients 0 to 1 Phase B (16g/job) wt% citrate 4 to 10 soda 20 to 50 sodium sulfate 4 to 10 Trilon Ultimate 1G 2 to 7 TAED 0 to 2 Sodium percarbonate 5 to 15 Nonionic surfactant 10 to 20 Other ingredients 0 to 3

example 2

The cleaning performance of an automatic dishwashing process in the presence of a dish load and using a conventional automatic dishwashing detergent (Somat All-In-1) and a dishwasher care product was determined. The care product was placed on the floor of the machine before the machine dishwashing process began, and the machine dishwashing agent was automatically dosed via the dosing chamber. The dishwashing process was carried out in a Miele GSL2 dishwasher (program: 45° C., 8 min holding time, program duration 55 min) with a water hardness of 21° German hardness according to the IKW method.

This method of the Industry Association for Body Care and Detergents (IKW) is described in the SÖFW-Journal, Volume 142, 6/2016 (pages 34 to 48).

The cleaning performance was evaluated visually on a scale from 1 to 10, with the value 10 being the best rating (no discernible residue). Differences in cleaning performance of one point or more are considered significant. Iterations were performed with 6 internal replicas per machine. The results given are the mean values of the duplicate determinations. care products Creme brulee egg yolk Strength Somat Duo machine cleaner 1.8 1.7 5.7 Means of example 1 5.3 3.4 7.5

The cleaning performance on starch stains, creme brulee stains and egg yolk stains is significantly better in the process according to the invention than in a process using a market product which does not contain any bleaching agent.

Claims (13)

Method for cleaning and / or care of an automatic dishwasher, characterized in that in a normal cleaning cycle for cleaning items to be washed, in particular soiled dishes, with a machine dishwashing detergent, a pre-portioned care product for automatic dishwashers, formulated separately from the dishwashing detergent, is metered in, the care product i) at least one bleaching agent and ii) at least one nonionic surfactant has and
where the care product has at least two different parts A and B, where part B has a bleaching agent from i) and/or a surfactant from ii) and part A has at least one bleaching agent from i). Method according to Claim 1, characterized in that portion B is released into the washing liquor in the pre-wash cycle of the cleaning cycle and/or that portion A is released into the washing liquor in the main washing cycle of the cleaning cycle. Method according to one of the preceding claims, characterized in that the at least one bleaching agent is an oxygen bleaching agent, this bleaching agent is preferably selected from percarbonates, perborates and phthaloimino peracids and mixtures thereof. Method according to one of the preceding claims, characterized in that the care product contains the at least one bleach in amounts of 5 to 40% by weight, preferably 9 to 23% by weight, in particular 13 to 18% by weight, based on the total amount of the care product, and/or that proportion A contains the at least one bleach in amounts of 20 to 65% by weight, preferably 30 to 55% by weight, in particular 35 to 50% by weight, based on the total amount of portion A. Method according to one of the preceding claims, characterized in that the composition of portion A is in the form of one or more compressed tablet(s) and/or the active substance composition of portion A is embedded in a wax and/or embedded in a polymer and/or or that the composition of portion B is uncompressed. Method according to Claim 5, characterized in that any compressed tablet present is compressed with at least 8 kN/cm ² , preferably with at least 10 kN/cm ² was and / or that an optionally present wax is contained in the composition of part A and has a melting point of at least 30 ° C, preferably at least 35 ° C, most preferably at least 40 ° C and / or that an optionally present polymer in the composition of part A and is completely soluble in 1L of water at a water temperature of 50 °C within 2 to 7 minutes. Method according to one of the preceding claims, characterized in that the care product contains nonionic surfactant in an amount of 0.1 to 30% by weight, particularly preferably in an amount of 5 to 20% by weight, particularly preferably in an amount of 10 up to 17% by weight, based on the total amount of care product. Method according to one of the preceding claims, characterized in that the care product in part A also contains at least one nonionic surfactant. Process according to one of the preceding claims, characterized in that the at least one nonionic surfactant from ii) is contained in proportion B in an amount of 80 to 100% by weight, preferably in an amount of 95 to 100% by weight, based on the total amount of nonionic surfactant in the conditioner. Method according to one of the preceding claims, characterized in that the rinsing liquor of the cleaning cycle has a pH of 8.0 to 13.0, preferably 9.5 to 12.0, very particularly preferably 10 .5 to 11.5 is achieved, preferably before the machine dishwashing detergent is metered into the interior of the machine. Method according to one of the preceding claims, characterized in that by dissolving the machine dishwashing detergent and dissolving at least a portion of portion A, the resultant washing liquor of the cleaning cycle has a pH of 8.0 to 13.0, preferably 9, in the main wash cycle. 5 to 12.0, most preferably from 10.0 to 11.0. Method according to one of the preceding claims, characterized in that the at least one portion A and the at least one portion B in a weight ratio of 3: 1 to 1:10, preferably in a weight ratio of 1: 1 to 1: 8, in particular from 1 :3 to 1:7, for example from 1:4 to 1:6, based on the respective amounts of parts A and B in the care product. Method according to one of the preceding claims, characterized in that the care product is metered into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the dishwasher detergent.