EP4077610A1 - Methods for cleaning and caring for an automatic dishwasher - Google Patents

Abstract

The invention relates to methods for cleaning and/or caring for an automatic dishwasher. In a normal cleaning cycle for cleaning items to be washed, in particular soiled dishes, a pre-portioned care agent for automatic dishwashers is metered automatically by an automatic dishwashing means, said agent being formulated separately from the dishwashing detergent. The care agent has an acid and/or a buffer system, which consists of at least one acid and at least one base, and at least one non-ionic surfactant. The care agent has at least two different components A and B, wherein component B has an acid made of i) and/or ii) and at least one non-ionic surfactant made of iii), and component A has at least one non-ionic surfactant made of iii) and/or at least one base made of ii).

Description

Method for cleaning and maintaining an automatic dishwasher

The present invention relates to a method for cleaning and / or maintaining automatic dishwashers, which removes deposits in an automatic dishwasher and can be carried out together with an automatic dishwashing agent in a normal dishwashing cycle.

Limescale and fat deposits in an automatic dishwasher, which arise 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. Because of the acid they contain, such care products must be used in a separate program, otherwise the cleaning performance of neutral to alkaline dishwashing detergents is significantly reduced and the acidic agents can have a harmful effect on 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.

Furthermore, the consumer not only finds fat and limescale deposits in the automatic dishwasher troublesome, the machine should also have a positive and clean overall impression after cleaning.

There is therefore a need to enable a method which allows the customer, in addition to removing fat and limescale deposits, to achieve a clean and positive overall impression of the dishwasher without having to carry out an additional wash cycle.

It has now been found, surprisingly, that care agents have at least one acid and / or a buffer system of at least one acid and at least one base and at least one nonionic surfactant and wherein the care agents have at least two different proportions A and B, where portion B is an acid and at least one nonionic surfactant and component A has at least one nonionic surfactant and / or at least one base, meet these requirements by having very good fat and lime-dissolving properties, do not significantly affect the cleaning performance of the dishwashing detergent for the dishes, and gloss and thus create a clean and hygienic overall impression.

In a first aspect, the present invention is consequently directed to a method for cleaning and / or maintaining an automatic dishwasher, wherein in a normal Cleaning cycle for cleaning items to be washed, in particular soiled dishes, with an automatic dishwashing detergent, a pre-portioned care agent for automatic dishwashers formulated separately from the dishwashing detergent is added, the care agent i. an acid and / or ii. a buffer system composed of at least one acid and at least one base and iii. has at least one nonionic surfactant and wherein the care product has at least two different parts A and B, part B having an acid from i) and / or ii) and at least one nonionic surfactant from iii) and part A at least one nonionic surfactant from iii) and / or has at least one base from ii).

In the method according to the invention, the care product is used together with an automatic dishwashing detergent in a normal cleaning cycle for cleaning dirty wash ware, i.e. in the presence of wash ware (or dishes) to be cleaned. This has the advantage that the machine does not run idle at high water temperatures. Energy and water are therefore not wasted. Furthermore, the consumer does not have to completely empty the machine in daily operation, but can also clean the machine at the same time as the dishes. Because of this minimal effort for the consumer, regular cleaning of the machine is made easier. In such a case, there is no accumulation of stubborn dirt on the dishwasher that can only be removed under harsh conditions. Furthermore, the simultaneous use of the care product in the usual dishwashing cycle with items to be washed saves time, water and energy. The food residues and soiling, especially in the dishwasher sieve, which represent a breeding ground for undesirable 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 items to be washed (dishes) in an automatic dishwasher. Such a cleaning cycle can comprise one or more pre-wash cycles, one or more main wash cycles and one or more final rinse cycles. Such a cleaning cycle includes the automatic cleaning / rinsing of soiled items or dishes.

"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 data in% 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 goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are percentages by weight. Numeric ranges specified in the format “from x to y” include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

The care products described herein for use in the method according to the invention contain pH regulators in the form of at least one acid and / or at least one buffer system which contains at least one acid and at least one base. In general, suitable acids are polycarboxylic acids, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are 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 that such use is not objectionable for ecological reasons, as well as mixtures of these. Corresponding buffer systems can contain one or more of the acids mentioned and the respective corresponding base (s) and further bases. Citric acid or a buffer system composed of citric acid and citrate can preferably be used.

Representatives of the aminocarboxylic acids include aspartic acid, methylglycine diacetic acid (MGDA) and glutamine diacetic acid (GLDA) or ethylenediamine diacetic acid. Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable. However, it is preferred that the acids used are not aminocarboxylic acids.

Suitable bases are all bases known in the prior art for dishwashing detergents. However, it is preferred that the base corresponding to the acid is used in the buffer system composed of acid and base, ie for example citrate if citric acid is used as the acid. Organic acids and their corresponding bases are therefore preferably used. Bases that can be used in addition are, in particular, carbonates and silicates, which are described further under the additionally usable builders; the use of acetates is also possible. The acids and optionally 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 the context of the method according to the invention, it is preferred if the care product is such that (i) the at least one acid is an organic acid, in particular citric acid, and / or (ii) the buffer system is at least one organic acid, in particular citric acid, and the corresponding base, in particular citrate, contains.

A preferred subject is accordingly a method in which the care product is such that (i) the at least one acid is an organic acid, in particular citric acid, and / or (ii) the buffer system is at least one organic acid, in particular citric acid, and the corresponding base, in particular citrate, contains.

In order to facilitate the removal or reduction of grease soiling in addition to removing or reducing lime, at least one nonionic surfactant is contained in the care product of the method according to the invention. It is preferred that a mixture of two or more nonionic surfactants is used in the care agent of the method according to the invention.

A care agent that can be used in the methods described herein can contain any of the nonionic surfactants known to the person skilled in the art. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used in the care product. One class of nonionic surfactants that can be used with preference, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants in the care product, is accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty alcohols. Examples of suitable ethoxylated fatty alcohols include Dehydol LS 6, Emulan AT 9, Lutensol AO 7 and Plurafac 220 and 221 from BASF.

It is preferred according to the invention if a care agent is used in the process in which at least one of the surfactants from iii) is a rinse aid surfactant, preferably an alkoxylated fatty alcohol.

A further preferred subject is therefore a method in which at least one of the surfactants from iii) is a rinse aid surfactant, preferably an alkoxylated fatty alcohol.

In various preferred embodiments, therefore, a fatty alcohol alkoxylate, in particular a fatty alcohol ethoxylate, is used. In particular, non-end-capped fatty alcohol alkoxylates are preferred. In preferred embodiments, the fatty alcohol ethoxylate has the formula R ¹ -0- (E0) _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 unit; and m is 10 to 50, in particular 20 to 30, preferably 22 to 27, in particular 25.

In particularly preferred embodiments, the fatty alcohol ethoxylate has the formula R ¹ -0- (E0) _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 unit; 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 included 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 to be included on the care product. Such amounts are preferred to ensure adequate fat dissolution and removal.

It is preferred that a nonionic surfactant which can be used in the care products described herein for the method according to the invention in an absolute amount of 0.1 to 4 g / job, preferably 1 to 3 g / job, in particular 1.2 to 2.2 g / job, for example 1.5 g / job or 2.0 g / job is contained in the care products.

It is particularly preferred that a fatty alcohol ethoxylate of the formula R ¹ -0- (E0) _m -H, where R ^{1 is} a linear or branched, substituted or unsubstituted alkyl group with 12 to 24, in particular 14 to 20, in particular 16 to 18 C. -Atoms is; EO is an ethylene oxide unit; and m is 10 to 50, in particular 20 to 30, preferably 22 to 27, in particular 25; in an absolute amount of 0.1 to 4 g / job, preferably 1 to 3 g / job, in particular 1.2 to 2.2 g / job, for example 1.5 g / job or 2.0 g / job in the Care products is included.

It is particularly preferred that a fatty alcohol ethoxylate of the formula R ¹ -0- (E0) _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 unit; and m is 20 to 30, preferably 22 to 27, especially 25; in an absolute amount of 0.1 to 4 g / job, preferably 1 to 3 g / job, in particular 1.2 to 2.2 g / job, for example 1.5 g / job or 2.0 g / job in the Care products is included. 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 R ² - (AO) wR ³ , where R ^{2 is} a linear or branched, substituted or unsubstituted alkyl group with 8 to 16 carbon atoms, is also suitable as a nonionic surfactant; R ^{3 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; each A independently represents a radical from the group -CH2CH2- and _{-CH 2} -CH (CH ₃ ) -, CH2-CH2-CH2-, CH2-CH2-CH2-CH2-, -CH2-CH (CH ₂ -CH ₃ ) -, -CH2- C (CH ₃ ) ₂ - or - CH2- CH2-CH (CH ₃ ) -, where at least one A -CH2CH2- and at least one A -CH2-CH (CH ₃ ) -, CH2- CH2-CH2-, CH2- CH2- CH2-CH2-, -CH2- CH (CH ₂ -CH ₃ ) -, -CH2- C (CH ₃ ) ₂ - or-CH ₂ - CH ₂ - 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, in particular 6: 1 to 3: 1. Fatty alcohol alkoxylates of the formula in which R ^{2 is} a linear alkyl group with 12-16 C atoms and R ³ = H and w = 10 to 30 are particularly preferred.

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 aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G that Is a symbol that stands for a glycose 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; x is preferably 1.2 to 1.4.

Another class of usable nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 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 alkanolamides 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 that.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA. It is preferred according to the invention if a care agent is used in the process which contains nonionic surfactant in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 2 to 15% by weight, particularly preferably in an amount from 4 to 10% by weight, based on the total amount of care products.

A further preferred subject is therefore a method in which the care product contains nonionic surfactant in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 2 to 15% by weight, particularly preferably in an amount of 4 to 10% by weight, based on the total amount of care products, is included.

For good fat removal and a gloss effect in the machine and on the dishes, it is preferred according to the invention if a care agent is used in the process in which nonionic surfactant in a proportion of 2 to 50 wt .-%, preferably in a proportion of 5 up to 40% by weight, very particularly preferably in a proportion of 10 to 35% by weight, based on the total amount of nonionic surfactant in the care product, is contained in portion A.

A further preferred subject is therefore a method in which nonionic surfactant is used in a proportion of 2 to 50% by weight, preferably in a proportion of 5 to 40% by weight, very particularly preferably in a proportion of 10 to 35% by weight, based on the total amount of nonionic surfactant in the care product, contained in portion A.

It is preferred according to the invention if a care agent is used in the process which contains nonionic surfactant in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 2 to 15% by weight, particularly preferably in an amount from 4 to 10% by weight, based on the total amount of care agent, the nonionic surfactant being at least partially an alkoxylated, preferably ethoxylated, alcohol.

A further particularly preferred subject is therefore a method in which nonionic surfactant is used in the care product in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 2 to 15% by weight, particularly preferably in an amount of 4 up to 10% by weight, based on the total amount of care agent, is included and the nonionic surfactant is at least partially an alkoxylated, preferably ethoxylated, alcohol.

Furthermore, it is preferred according to the invention if the nonionic surfactant is at least partially a fatty alcohol ethoxylate of the formula R ¹ -0- (E0) _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 unit; and m is 20 to 30, preferably 22 to 27, especially 25.

A further preferred subject is therefore a method in which the care agent contains nonionic surfactant, preferably in an amount of 0.1 to 20% by weight, particularly preferably in an amount of 5 to 17% by weight, particularly preferably in one Amount of 7 to 15% by weight, based on the total amount of care products, the nonionic surfactant being at least partially a fatty alcohol ethoxylate of the formula R ¹ -0- (E0) _m -H, where R ^{1 is} a linear or is branched, substituted or unsubstituted alkyl group having 16 to 18 carbon atoms; EO is an ethylene oxide unit; and m is 20 to 30, preferably 22 to 27, especially 25.

If the care product contains nonionic surfactant, it is preferred that at least 50% by weight of the nonionic surfactant, based on the total mass of nonionic surfactant contained, is at least one alkoxylated alcohol, preferably ethoxylated alcohol and / or ethoxylated, in the care product and otherwise alkoxylated alcohol, particularly preferably at least 60% by weight, in particular at least 75% by weight.

It is preferred according to the invention if the nonionic surfactant is mixtures of different nonionic surfactants. This can be, for example, mixtures of different alkoxylated alcohols and / or mixtures of one or more alkoxylated alcohols with another type of nonionic surfactant.

It is preferred according to the invention if a care agent is used in the process which has at least two different nonionic surfactants, preferably a first nonionic surfactant is contained in part A and in part B and a second nonionic surfactant is in part A and not in part B. contain.

A further preferred subject is therefore a method in which at least two different nonionic surfactants are contained in the care product, preferably a first nonionic surfactant is contained in part A and in part B and / or a second nonionic surfactant is in part A and not in part B. contain.

According to the invention, it is particularly preferred if a care agent is used in the process which has at least two different nonionic surfactants, preferably a first nonionic surfactant is contained in portion A and in portion B and a second nonionic surfactant is in portion A and not in portion B, the second being nonionic The surfactant is a fatty alcohol alkoxylate, preferably a fatty alcohol alkoxylate containing ethoxy and propoxy groups and / or containing ethoxy and butoxy groups. The fatty alcohol alkoxylates mentioned can be end-capped and / or non-end-capped; they are preferably not end-capped.

Another particularly preferred subject is therefore a method in which at least two different nonionic surfactants are contained in the care product, preferably a first nonionic surfactant is contained in part A and in part B and / or a second nonionic surfactant is in part A and not in part B, the second nonionic surfactant being a fatty alcohol alkoxylate, preferably a fatty alcohol alkoxylate containing ethoxy and propoxy groups and / or containing ethoxy and butoxy groups.

It is further preferred according to the invention that the aforementioned at least two different portions A and B are packaged in such a way that they are released into the washing liquor at different times of the cleaning cycle. This enables the ingredients contained in parts A and B to act on the parts to be cleaned or cared for at different times 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 final rinse cycle of the cleaning cycle.

A preferred subject is therefore a method according to the invention in which the care agent used has at least two different proportions A and B, and where B is released into the washing liquor in the pre-wash cycle of the cleaning cycle and / or where A is released into the washing water in the rinse cycle of the cleaning cycle becomes.

Such a time-delayed release can be made possible by different packaging of the parts A and B. There are various conceivable ways in which part A should be designed so that the ingredients are released in the rinse cycle.

It can be preferred according to the invention, for example, if the composition of portion A is in the form of one or more compressed tablets. It can also be preferred according to the invention if the active ingredient composition of portion A is embedded in a wax. It can also be preferred according to the invention if the active ingredient composition of portion A is embedded in a polymer.

There are also various conceivable ways in which part B should be designed so that the ingredients are released in the pre-wash cycle. It can for example be preferred according to the invention if the composition of portion B is not compressed. In the context of this application, non-compressed means that the composition of component 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 portion A is in the form of one or more compressed tablet (s) and / or the active ingredient composition of portion A is embedded in a wax and / or embedded is present in a polymer and / or that the composition of portion B is present in non-compressed form.

A preferred subject is accordingly a method in which the care product is designed in such a way that the composition of portion A is in the form of one or more compressed tablet (s) and / or the active ingredient composition of portion A is embedded in a wax and / or embedded in a polymer is present and / or that the composition of component 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 a hardness at break of at least 150 N, preferably at least 170 N, particularly preferably at least 200 N, after storage for 24 hours at room temperature. It is also preferred according to the invention that such a tablet has a breaking hardness of at least 100 N, preferably at least 110 N, particularly preferably at least 120 N, immediately after production. Hardnesses at break can be determined with special equipment, for example with a "MultiTest 50" from Pharmatron.

It can also be preferred according to the invention if the active ingredient composition of portion A is embedded in a wax, the wax having a melting point of at least 50.degree. C., preferably at least 55.degree. The wax is included in the composition of Part A. This can ensure that the constituents of Part A are not released in the pre-wash cycle and / or the main wash cycle. Naturafin 59/62 ° C from Reseda Binder AG is suitable as an example. If the active ingredient composition of portion A is embedded in such a wax, the wax is contained in the composition of portion A and the proportion of this wax in the overall composition of portion A is preferably 10 to 80% by weight.

It can also be preferred according to the invention if the active ingredient composition of portion A is embedded in a polymer, the polymer being completely soluble in 1L water at a water temperature of 60 ° C. within 1 to 5 minutes. This sure can ensure that the ingredients of Part A are not released during the pre-wash cycle. Solublon EF from Aicello Chemical Europe GmbH is suitable as an example. The solubility of a polymer can be checked with 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 wrinkles nor tears. The film is immersed in the water parallel to the bottom of the beaker so that it is roughly in the middle between the bottom of the beaker and the surface of the water. The water is stirred at 700 rpm with the aid of a magnetic stirrer / magnetic stir bar. 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 ingredient composition of portion A is embedded in such a polymer, the polymer is contained in the composition of portion A and the proportion of this polymer in the total composition of portion 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 portion A is in the form of one or more compressed tablet (s), the tablet having a hardness of at least 150 after storage at room temperature for 24 hours N, preferably at least 170 N, particularly preferably at least 200 N, and / or that the active substance composition of component A is embedded in a wax, the wax having a melting point of at least 50 ° C, preferably at least 55 ° C, and / or that the active ingredient composition of component A is embedded in a polymer, the polymer being completely soluble in 1L water at a water temperature of 60 ° C. within 1 to 5 minutes.

A preferred subject is accordingly a method in which the care product is designed in such a way that the composition of Part A is in the form of one or more compressed tablets, the tablet having a hardness of at least 150 N after storage at room temperature for 24 hours , preferably at least 170 N, particularly preferably at least 200 N, and / or that the active ingredient composition of portion A is embedded in a wax, the wax having a melting point of at least 50 ° C., preferably at least 55 ° C., and / or that the active ingredient composition of component A is embedded in a polymer, the polymer being completely soluble in 1L water at a water temperature of 60 ° C. within 1 to 5 minutes.

The terms composition and active ingredient composition used in this application and in particular in the preceding paragraphs differ in that the active ingredient composition comprises the ingredients which have a direct effect in the context of cleaning and / or maintenance of an automatic dishwasher, including for example and incompletely enumerated acids, bases, enzymes and / or surfactants count. On the other hand, the term active ingredient composition does not include waxes and / or polymers of the type mentioned in the preceding paragraphs and in which the active ingredient compositions can be embedded as described above. The term composition, on the other hand, is more comprehensive and includes all ingredients associated with the respective proportion or the respective agent.

In order to make it easier for the consumer to carry out the process and to ensure 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 possible form of packaging that is in accordance with the stated conditions. Compositions which are present, for example, in the form of a multiphase tablet or a multiphase pouch are preferred. Both in multi-phase tablets and in multi-phase pouches, the different phases can be present both on top of one another and next to one another or at the same time on top of and next to one another.

In the context of the process according to the invention, it is preferred if the care agent 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 agent used in the process is free of phosphate and / or phosphonate. “Phosphate-free” and “phosphonate-free”, as used herein, means that the composition in question is essentially free of phosphates or phosphonates, ie in particular phosphates or phosphonates in quantities of less than 0.1% by weight, preferably less than 0 .01% by weight, based on the total care product. It is preferred that a total amount of phosphorus in the care product of 0.3 g / job, preferably 0.03 g / job, is not exceeded.

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

To make it easier to use, the care product is preferably in a water-soluble cover. It is particularly preferred if the water-soluble packaging is a film containing polyvinyl alcohol. It is preferred that the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility. Suitable water-soluble films for producing the water-soluble envelope 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 .

The production of polyvinyl alcohol is usually done by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are 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 polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope can additionally contain 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 may be added. A preferred additional polymer are polylactic acids. Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

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

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

Suitable water-soluble films for use in the water-soluble envelopes of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray. The care product can be formulated in such a way that the at least one part A and the at least one part B in a weight ratio of 3: 1 to 1:10, preferably in a weight ratio of 1: 1 to 1: 8, in particular 1: 3 to 1: 7, for example from 1: 4 to 1: 6, based on the respective amounts of the parts A and B in the care product.

A preferred subject is accordingly a method in which the care product is such that the at least one part A and the at least one part 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 portions A and B in the care product.

It is preferred that the amount of acid from i and / or ii) is present in an amount that is suitable for reducing or removing lime-containing soiling in the dishwasher. It is therefore preferred that the care agent contains the at least one acid from i) and / or ii) in an amount of 1 to 80% by weight, preferably in an amount of 5 to 60% by weight, particularly preferably in an amount of 20 to 35% by weight or in an amount of 25 to 45% by weight, based on the total amount of care agent, and / or the absolute amount of the at least one acid from i) and / or ii) in the care agent 0.2 to 16 g / job, preferably 3 to 11 g / job, particularly preferably 4 to 10 g / job, for example 7 to 9 g / job.

A preferred subject is therefore a method in which the care product is such that the care product contains the at least one acid from i) and / or ii) in an amount of 1 to 80% by weight, preferably in an amount of 5 to 60 % By weight, particularly preferably in an amount of 20 to 35% by weight or in an amount of 25 to 45% by weight, based on the total amount of care agent, and / or the absolute amount of the at least one acid from i) and / or ii) in the care product is 0.2 to 16 g / job, preferably 3 to 11 g / job, particularly preferably 4 to 10 g / job, for example 7 to 9 g / job.

These quantities are based in each case on the (crystal) anhydrous form.

It is preferred that the active substances of the composition required for the lime dissolving are dissolved as quickly as possible and thus can develop their effect before the automatic dishwashing agent is added.

In the context of the method according to the invention, it is therefore preferred that the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher detergent. A preferred subject is accordingly a method in which the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher detergent.

Dosing or dosing into the interior of the dishwasher means that the care agent or the automatic dishwasher detergent gets into the interior of the dishwasher, for example by inserting it manually, by opening the dosing flap in a program-controlled manner and / or by automatically adding it from an automatic dosing device. It is possible here for the detergent portion or the automatic dishwashing detergent to be completely available in the washing liquor for cleaning and / or care purposes immediately or only after a period of time. This depends on the rate of dissolution 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 coating that may be present, for example a film, is also not part of the metering or metering in of the care product or the automatic dishwashing detergent.

Dosing the care agent at the beginning of the cleaning cycle can enable the care agent to contribute to the cleaning and / or care of the dishwasher in the pre-wash cycle and / or at the start of the main wash cycle. A subsequent dosage of an automatic dishwashing agent can help to maintain the conditions necessary for cleaning and / or caring for the dishwasher.

For the further course of the cleaning cycle and its effect, it is preferred if, as a result of the complete dissolution of the care agent used, a pH value of 3.0 to 7.0, particularly preferably 3.5 to 6.5, very particularly preferably 4 , 0 to 6.0, is achieved in the existing washing liquor.

If the care agent contains at least one buffer system ii), it is preferred that the base corresponding to the acid is used. It goes without saying that the total amounts of acid and base in the buffer system must be chosen so that the desired pH range is achieved. This applies both to the pH range that is achieved by dissolving the acid and the pH range that is achieved by dissolving the buffer system, as well as the pH range that is achieved by dissolving the overall composition of the care product is obtained. For the further course of the cleaning cycle and its effect, it is preferred if, due to the complete dissolution of the claimed composition, a pH value of 3.0 to 7.0, particularly preferably from 3.5 to 6.5, very particularly preferably from 4, 0 to 6.0 is achieved in the existing rinsing solution. A preferred subject is a method in which the rinsing liquor of the cleaning cycle has a pH of 3.0 to 7.0, preferably from 3.5 to 6.5, very particularly preferably 4.0, by at least partially dissolving the care agent to 6.0, preferably before the automatic dishwashing detergent is dosed into the interior of the machine.

It is therefore preferred according to the invention that the acid is released as quickly as possible in order to obtain an acidic washing liquor. It is particularly preferred that the time until the acid is completely released from a pre-portioned care product with a mass of 20 g in 1 L of 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 (blades 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 is accordingly a method in which a care product is used which is designed in such a way that the time until the acid is completely released from 20 g pre-portioned care product 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 (blades of the stirrer 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, particularly 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 min of stirring (in a 3 liter beaker with a diameter of 13 , 5 cm with a propeller stirrer with a diameter of 7 cm (blades of the 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 value of 3.0 to 6, 5, preferably from 4.0 to 6.0, is obtained.

A further preferred subject is accordingly 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, in such a way that after stirring for 1 min A solution (in a 3 liter beaker with a diameter of 13.5 cm with a propeller stirrer with a diameter of 7 cm (blades of the stirrer at a height of 3.5 cm above the bottom of the beaker) at 200 rpm) at room temperature with a pH of 3.0 to 6.5, preferably from 4.0 to 6.0.

It is preferred that the acid from i) or ii) is available as quickly as possible for cleaning and caring for the dishwasher.

It is further preferred that the acid from i) and / or ii) is contained for the most part in portion B. It is therefore preferred that the acid from i) and / or ii) in part B in an amount of 80 to 100% by weight is contained, preferably in an amount of 95 to 100% by weight, particularly preferably in an amount of at least 99% by weight, based on the total amount of acid in the care product.

A preferred subject is accordingly a method in which the care product is such that the acid from i) and / or ii) is contained in portion B in an amount of 80 to 100% by weight, preferably in an amount of 95 Up to 100% by weight, particularly preferably in an amount of at least 99% by weight, based on the total amount of acid in the care product.

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

Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzene 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 with 8 to 18 carbon atoms, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkane sulfonates (ether carboxylic acids), fatty acid carboxylic acids, and fatty acids can also be used in the context of the present invention. 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 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 the sulfonates also in the form of their corresponding acid, for example dodecylbenzenesulfonic acid.

The builders that can additionally be used include, in particular, carbonates, organic cobuilders and silicates. It is possible, for example, to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate. In various embodiments of the invention, alkali carbonates, in particular sodium carbonate, can be contained in the care product in an amount of 1 to 40% by weight, preferably 2 to 30% by weight, based on the total weight of the care product.

Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins. Organic builder substances which can be used are, for example, those in the form of the free acid and / or its sodium salts usable polycarboxylic acids, 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, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.

If the above-mentioned builders are used in the care product, their influence on the buffer system that may be present must be taken into account.

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

Both homopolymers and copolymers as well as terpolymers can be used; more complex types of polymers 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. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 1000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.

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

The unsaturated carboxylic acid (s) used is / are with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ^3, independently of one another, represent -H, -CH3, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -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, a-chloroacrylic acid, a-cyanoacrylic acid, crotonic acid, a-phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, Cinnamic acid or mixtures thereof. The unsaturated dicarboxylic acids can of course also be used.

In the case of monomers containing sulfonic acid ^{groups, preference is given to those of the formula R 5} (R ⁶ ) C =C (R ⁷ ) -X-SC> 3H, in which R ⁵ to R ^7, independently of one another, represent -H, -CH3, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with - NH2, -OH or -COOH or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X stands for an optionally present spacer group which is selected from - (CH2) n- with n = 0 to 4, -COO- (CH2 ) k- with k = 1 to 6, -C (0) -NH-C (CH3) 2-, - C (0) -NH-C (CH ₃ ) 2-CH ₂ - and -C (0) - NH-CH (CH ₃ ) -CH ₂ -.

Those of the formulas H ₂ C = CH-X-S03H, H ₂ C = C (CH3) -X-SO3H or H03S-X- (R ⁶⁾ C = C (R ⁷⁾ -X-S03H Among these monomers, preferably , in which R ⁶ and R ^{7 are} independently selected from -H, -CH3, -CH2CH3, -CH2CH2CH3 and -CH (CH3) 2 and X stands for an optionally present spacer group which is selected from - (CH2) n- with n = 0 to 4, -COO- (CH2) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) 2-, -C (0) -NH-C (CH ₃ ) 2-CH ₂ - and -C (0) -NH-CH (CH ₃ ) -CH ₂ -.

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

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propenl -sulphonic acid, styrenesulphonic acid, methacrylate, 3-sulphopropyl, 3-acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, the sulfonic acid groups can be completely or partially in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized 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 is, in the case of copolymers, the monomers containing only carboxylic acid groups and monomers containing sulfonic acid groups Monomers contain, preferably in each case 5 to 95% by weight, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers here being 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 intended use. 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 agent also comprise, in addition to carboxyl-containing monomer and sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic, monomer.

One embodiment can particularly preferably contain an anionic copolymer, the anionic copolymer used being a copolymer comprising i) monomers containing carboxylic acid groups ii) monomers containing sulfonic acid groups iii) nonionic monomers, in particular hydrophobic monomers.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -Ch or -C2H5, and X represents a optionally present spacer group which is selected from -CH2-, -C (0) 0- and -C (0) -NH-, and R ^{4 represents} a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably an 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, ethylcyclohexyn, 1-octene, α-olefins with 10 or more carbon atoms such as, for example, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, a -Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, methyl acrylate, pentyl acrylate - (Methyl) acrylamide, acrylic acid-2-ethylhexyl ester, methacrylic acid-2-ethylhexyl ester, N- (2-ethylhexyl) acrylamide, acrylic acid octy lester, methacrylic acid octyl ester, N- (octyl) acrylamide, acrylic acid lauryl ester, Methacrylic acid lauryl ester, N- (lauryl) acrylamide, acrylic acid stearyl ester,

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.

The agents can also contain crystalline layered silicates of the general formula NaMSix0 _{2x + i} y H2O as builders, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a module Na2Ü: S1O2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties. In the care agents used in preferred processes, the silicate content, based on the total weight of the care agent, is limited to amounts below 10% by weight, preferably below 7% by weight and in particular below 5% by weight. Care agents used in particularly preferred processes contain silicate as a builder. Care products used in very particularly preferred processes contain silicate in the stated quantity range in portion A, based on the total weight of the care product. It is also preferred that the amount of silicate, based on the mass of component A, is between 5 and 50% by weight, preferably between 10 and 30% by weight, very particularly preferably between 15 and 25% by weight amounts to.

In the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type in the care product can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferably used in the care product, which together produce an appealing fragrance note. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

In possible further embodiments, the care agent in the process according to the invention can contain bleach or contain bleach. It is a preferred embodiment if a bleaching agent is contained in the care product. A preferred bleaching agent is an alkali metal percarbonate, preferably sodium percarbonate. In these preferred embodiments A bleaching agent, preferably sodium percarbonate, can be contained in the care product in an amount of 1 to 15% by weight, preferably 2 to 10% by weight or 3 to 12% by weight, based on the total weight of the care product.

The care product can also contain one or more enzymes. The optionally used enzyme or the used enzymes can 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. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are correspondingly preferred.

Proteases are among the technically most important enzymes of all. They cause the degradation of protein-containing soiling on the items to be cleaned, which can also be parts of the dishwasher itself. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21 .62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned as the most important group within the subtilases.

Examples of the proteases of the subtilisin type preferably used in washing and dishwashing detergents or care products are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense, as well as variants of the proteases mentioned, which have an amino acid sequence that is different from the original protease. Proteases are modified in a targeted or random manner by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. For most of the proteases known from the prior art, correspondingly optimized variants are known.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and those for Further developments of the aforementioned amylases improved their use in dishwashing detergents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.

It is also possible to use lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid substitution D96L.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Among the latter, the licheninases should be mentioned in particular.

To increase the bleaching effect, 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. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

An enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, especially during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Dishwashing detergents or care products for the dishwasher can contain stabilizers for this purpose; the use of such agents in the care agent represents a preferred embodiment of the present invention.

Cleaning-active proteases and amylases and also the other enzymes mentioned are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, Solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by pouring or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

It is also possible to pack 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 used with preference 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% by weight .-% of the enzyme protein.

In particular, those care agents are preferably used in the method according to the invention which, based in each case on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme -Preparations included.

The care products preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method.

It is further preferred that care products are used in the process according to the invention which contain a total amount of active enzyme protein from 0.5 to 500 mg / job, preferably from 10 to 250 mg / job% by weight, particularly preferably from 50 to 150 mg / job.

The compositions described herein can also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Peptide aldehydes, that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose. The peptide 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.

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

If both bleach and enzyme are contained in the care product, it is preferred in the method according to the invention that the bleach and enzyme are present in different phases of the care product.

Claims

Patent claims:

1 . A method for cleaning and / or maintaining an automatic dishwasher, characterized in that in a normal cleaning cycle for cleaning items to be washed, in particular soiled dishes, a pre-portioned care agent for automatic dishwashers formulated separately from the dishwashing detergent is added with an automatic dishwashing detergent, the care agent i. an acid and / or ii. a buffer system composed of at least one acid and at least one base and iii. has at least one nonionic surfactant and wherein the care product has at least two different parts A and B, part B having an acid from i) and / or ii) and at least one nonionic surfactant from iii) and part A at least one nonionic surfactant from iii) and / or has at least one base from ii).

2. The method according to claim 1, characterized in that part B is released into the washing solution in the pre-wash cycle of the cleaning cycle and / or that part A is released into the washing water in the final rinse cycle of the cleaning cycle.

3. The method according to claim 1 or 2, characterized in that the composition of portion A is in the form of one or more compressed tablet (s) and / or the active ingredient composition of portion A is embedded in a wax and / or embedded in a polymer and / or that the composition of portion B is not compressed.

4. The method according to claim 3, characterized in that an optionally present compressed tablet has a hardness at break of at least 150 N, preferably at least 170 N, particularly preferably at least 200 N after storage for 24 hours at room temperature and / or that any wax present in the Composition of Part A is contained and has a melting point of at least 50 ° C, preferably at least 55 ° C, and / or that an optionally present polymer is contained in the composition of Part A and in 1 L of water at a water temperature of 60 ° C is completely soluble within 1 to 5 minutes.

5. The method according to any one of the preceding claims, characterized in that the care agent contains the at least one acid from i) and / or ii) in an amount of 1 to 80% by weight, preferably in an amount of 5 to 60% by weight, particularly preferably in an amount of 20 to 35% by weight or in an amount of 25 to 45% by weight, based on the Total amount of care agent and / or the absolute amount of the at least one acid from i) and / or ii) in the care agent 0.2 to 16 g / job, preferably 3 to 11 g / job, particularly preferably 4 to 10 g / job, for example 7 to 9 g / job.

6. The method according to any one of the preceding claims, characterized in that the acid from i) and / or ii) is contained in portion B in an amount of 80 to 100 wt .-%, preferably in an amount of 95 to 100 wt. %, particularly preferably in an amount of at least 99% by weight, based on the total amount of acid in the care product.

7. The method according to any one of the preceding claims, characterized in that the rinsing liquor of the cleaning cycle by at least partially dissolving the care agent has a pH of 3.0 to 7.0, preferably from 3.5 to 6.5, very particularly preferably from 4.0 to 6.0 is reached, preferably before the automatic dishwashing detergent is dosed into the interior of the machine.

8. The method according to any one of the preceding claims, characterized in that at least two different nonionic surfactants are contained in the care product, preferably a first nonionic surfactant is contained in part A and in part B and / or a second nonionic surfactant is in part A and not included in part B.

9. The method according to any one of the preceding claims, characterized in that at least one of the surfactants from iii) is a rinse aid surfactant, preferably an alkoxylated fatty alcohol.

10. The method according to any one of the preceding claims, characterized in that in the care agent nonionic surfactant in an amount of 0.1 to 20 wt .-%, particularly preferably in an amount of 2 to 15 wt .-%, particularly preferably in an amount from 4 to 10% by weight, based on the total amount of care products.

11. The method according to any one of the preceding claims, characterized in that nonionic surfactant in a proportion of 2 to 50 wt .-%, preferably in a proportion of 5 to 40% by weight, very particularly preferably in a proportion of 10 to 35 wt -%, based on the total amount of nonionic surfactant in the care product, is contained in portion A.

12. The method according to any one of the preceding claims, characterized in that (i) the at least one acid is an organic acid, in particular citric acid, and / or (ii) the buffer system is at least one organic acid, in particular citric acid, and the corresponding base, in particular Contains citrate.

13. The method according to any one of the preceding claims, characterized in that the care agent is dosed into the interior of the automatic dishwasher at the beginning of the cleaning cycle, preferably before the automatic dishwasher detergent.

14. The method according to any 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 portions A and B in the care product.