WO2010031605A1

WO2010031605A1 - Bleach-containing cleaning agent

Info

Publication number: WO2010031605A1
Application number: PCT/EP2009/056991
Authority: WO
Inventors: Arnd Kessler; Indra BÖHM; Johannes Zipfel
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-09-18
Filing date: 2009-06-08
Publication date: 2010-03-25
Also published as: EP2328457A1; DE102008047943A1; ES2432193T3; EP2328457B1; PL2328457T3

Abstract

The invention relates to cleaning agents with a water content of less than 5 wt. %, comprising a) 10 to 45 wt. % oxygenated bleaching agent, b) 15 to 60 wt..-% organic solvent, c) 15 to 60 wt..-% non-ionic surfactant of general formula R¹-CH(OH)CH₂O-(AO)_w-(A'O)_x-(A"O)_y-(A"'O)_z-R², in which R¹ and R² independently = straight chain, or branched, saturated or mono- or multi-unsaturated C_2-40alkyl or alkenyl, A, A', A" and A'" independently = -CH₂CH₂, -CH₂CH₂-CH₂, - CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, or -CH₂-CH(CH₂-CH₃) and w, x, y and z = 0.5 to 90 where x, y and/or z can also be 0, d) 0.1 to 5 wt..-% suspension agent and dishwasher powder method using said cleaning agent.

Description

Bleach-containing cleaning agent

The present application describes bleach-containing detergents.

The make-up and supply forms of detergents and cleaners are subject to continuously changing requirements. For some time now, the main focus has been on the convenient dosing of detergents and cleaners by the consumer and the simplification of the work steps necessary to carry out a washing or cleaning process.

In this context, in particular dosing systems for the multiple dosing of detergents and cleaners have recently come into the field of vision of the product developers. In these devices, it is possible to distinguish between dosing systems integrated in the dishwasher or textile washing machine on the one hand and independent and mobile dosing systems independent of the dishwasher or textile washing machine on the other hand. By means of these metering systems, which contain the multiple of the amount of detergent necessary for carrying out a single cleaning process, detergent or cleaning agent portions are metered into the interior of the cleaning machine by means of a metering device from a cartridge in an automatic or semi-automatic manner in the course of several successive cleaning processes. For the consumer eliminates the need for repeated manual dosing of detergents and cleaners. Examples of such devices are described in European patent application EP 1 759 624 A2 (Reckitt Benckiser) or in German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausgeräte GmbH).

Regardless of the exact type of dosing used in the interior of dishwashers or textile washing machines contained in these devices for multi-dosing detergents or cleaning agents are exposed over a longer period of time in particular changing temperatures, these temperatures in about the water temperatures used to carry out the washing or cleaning process same. These temperatures can be up to 95 ⁰ C, wherein in the range of machine dishwashing usually only temperatures between 50 and 75 ⁰ C are reached. Accordingly, a washing or cleaning agent contained in a dosing system provided for multiple dosing is repeatedly heated to temperatures well above the temperatures customary for transport and storage in the course of several washing or cleaning processes, temperature-sensitive active substances in particular being able to be affected. to Group of these temperature-sensitive washing and cleaning-active substances include the

Bleach.

The use of bleaching agents to increase the washing and cleaning performance of washing and cleaning

Detergents has been established in the art for decades, and in the field of machine textile and dishwashing in particular oxygen bleach with perborates and

Percarbonate find application.

The decisive for the end user cleaning effect of bleach used in detergents and cleaners is determined except by the bleach itself to a considerable extent by the nature of the preparation of these bleaches and their stabilization against environmental influences.

Bleaching agents are offered in both solid and liquid, for example dispersed, formulated.

The object of the present application was to provide a chemically and physically stable bleach dispersion, wherein in particular a stabilization of the bleach dispersion against phase separation / loss of activity in multiple

Temperature fluctuations (10 to 75 ⁰ C) should be achieved. Corresponding bleach preparations should be storable in a storage device located in the interior of a dishwasher or textile washing machine without significant loss of activity and be usable over a plurality of rinse cycles.

It has been found that low-water or anhydrous bleach preparations can be stabilized in a matrix of organic solvents, nonionic surfactants and suspending agents. A first subject of the present application is therefore a cleaning agent with a water content below 5 wt .-%, comprising a) 10 to 45 wt .-% oxygen bleaching agent b) 15 to 60 wt .-% organic solvent c) 15 to 60 wt. % nonionic surfactant of the general formula R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C ₂ - ₄ o-alkyl or - alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.1 to 5% by weight of suspending agent. The water content of cleaning agents according to the invention is preferably less than 4% by weight, preferably less than 2% by weight and in particular less than 0.5% by weight. Particularly preferred cleaning agents according to the invention are anhydrous.

Bleaching agent preparations according to the invention contain as the first essential constituent one or more oxygen bleaching agents a). Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

Preferred bleach preparations are characterized in that the oxygen bleach a) is sodium percarbonate.

The weight fraction of bleach a), based on the total weight of the bleach preparation, in preferred embodiments is between 15 and 40% by weight, preferably between 18 and 35% by weight and in particular between 21 and 30% by weight.

The cleaning agents according to the invention, hereinafter also referred to as bleach preparations, are in dispersed form. For the desired physical stability of the bleach preparation, it has proven to be advantageous to control the particle size of the solid oxygen bleach present in the dispersion and to limit it to particle sizes below 1, 0 mm.

Particularly preferred bleach formulations of the invention are characterized in that the particle size of the bleach is less than 100 microns, preferably less than 50 microns and more preferably less than 20 microns, with particle sizes between 0.1 and 100 .mu.m, preferably 0.1 and 80 .mu.m and in particular 0.1 and 50 microns are preferred.

Some exemplary and advantageous in their chemical and physical stability bleach preparations are listed in Table 1 below:

* nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ - ₄ o-alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0

As a second essential ingredient, bleach compositions according to the invention contain one or more organic solvents b).

Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di -ethylenglykolethylether,

Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures this solvent.

Be particularly advantageous for the chemical and physical stability of the bleaching compositions when stored at temperatures above 2O ⁰ C, the 1, 3 propandiol has been found. Detergents according to the invention, which contain propanediol as organic solvent 1, 3, are particularly preferred for this reason. The proportion by weight of the organic solvent used in the bleach compositions according to the invention, in particular of 1, 3 propanediol, based on the total weight of the cleaning agent, preferably b) between 20 and 50 wt .-%, preferably between 23 and 47 wt .-% and in particular between 25 and 45 wt .-% is.

Some exemplary and advantageous in their chemical and physical stability bleach preparations are listed in Table 2 below:

* nonionic surfactant of the general formula

As third essential ingredient, the invention

Bleaching compositions Nonionic surfactant of the general formula R ¹ O- (AO) _W - (A'O) _X - (A "O) _y - (A '" O) _z -H, where R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C ₂ . ₄₀ alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ - CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0.

Nonionic surfactants c) which have alternating ethylene oxide and alkylene oxide units have proven particularly suitable for stabilizing the bleach preparation. Among these are in turn surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

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

In summary, especially nonionic surfactants c) are preferred, which have a C. _9-i ₅ alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Further preferred nonionic surfactants of the general formula R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -H are selected from the group of alkoxylated alcohols, especially fatty alcohol ethoxylates , In particular, alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol used. The preferred ethoxylated alcohols include, for example, Ci ₂ _i ₄ -alcohols with 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C-ms alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ , _18- alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . -i ₄ -alcohol with 3 EO and C ₁₂ . _18- alcohol with 5 EO. In addition or as an alternative to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include C ₆ - ₂ o- alcohols, preferably tallow fatty alcohol containing 12 to 40 EO, preferably up to at least 12 EO, more preferably at least 14 EO, in particular preferably at least 16 EO, but also nonionic surfactants with 25 EO, 30 EO or 40 EO can be realized.

Particular preference is given to ethoxylated nonionic surfactants which are selected from C ₆ . ₂ o-monohydroxyalkanols or C ₆ . _20- alkylphenols or Ci ₆ - ₂ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C-ι ₆ - ₂ o alcohol), preferably obtained a d ₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide. Of these, the alcohol alkoxylates with concentrated homolegen distribution ("narrow-ranked ethoxylates") are particularly preferred.

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 60 EO.

Bleach compositions according to the invention, which as non-ionic surfactant c) a surfactant of the formula R ¹ - contain (AO) _W, where R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C _{_2-4} o alkyl or - Alkenyl radical; A is a radical from the group - CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w is values between 0.5 and 90 are preferred.

Bleach compositions according to the invention are particularly preferred in particular, characterized in that it is the non-ionic surfactant c) is a surfactant of the general formula R ¹ - is (AO) _W, in which R ¹ is a linear, saturated C. ₂ ₂₀ alkyl radical; A is a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH ₂ -CH (CH ₂ -CH ₃ ); and w is between 15 and 90, preferably between 20 and 60 and especially 25, 30 or 40.

The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).

Preferred nonionic surfactants c) have a melting point above room temperature. Nonionic surfactant (s) (e) with a melting point above 2O ⁰ C, preferably above 25 ⁰ C, more preferably between 25 and 6O ⁰ C and in particular from 26.6 to 43.3 ⁰ C, is / are particularly preferred ,

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

The proportion by weight of the nonionic surfactant c) used in the bleach compositions according to the invention is preferably between 20 and 50% by weight, preferably between 23 and 47% by weight and in particular between 25 and 45% by weight. Some exemplary and advantageous in their chemical and physical stability bleach preparations are listed in the following Tables 3a and 3b:

* nonionic surfactant of the general formula

nonionic surfactant of the general formula Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) -H

R2 R3

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

As a fourth essential ingredient included in the invention

Bleaching compositions Suspending agents. The suspended agent used not only enables the adjustment of the viscosity of bleach preparations according to the invention but surprisingly additionally contributes to the chemical stability of the preparations, wherein an increase in the bleach stability was observed, in particular at suspension levels of 1, 1 wt .-% and above.

The weight fraction of the suspending agent c) in the total weight of the cleaning agent is preferably between 0.2 and 4% by weight, preferably between 0.4 and 3% by weight, preferably between 0.5 and 2.5% by weight and in particular 1 , 1 to 2.5 wt .-%.

Some exemplary and advantageous in their chemical and physical stability bleach preparations are listed in Table 4 below:

* nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ . ₄₀ alkyl or alkenyl radical; A, A ', A "and A'" independently of one another from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH ₂ -CH ₂ -CH ₂ , -CH ₂ - CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0

Particularly suitable as suspending agents c) are phyllosilicates (for example montmorillonites), castor oil derivatives, soya lecithin, ethylcellulose, low molecular weight polyamides, silicic acid (for example hydrophobicized and / or amorphous silica), polyacrylates, polyvinylpyrrolidone, cellulose derivatives, polyureas, polyurethanes and polysaccharides.

Preferred cleaning agents are characterized in that the suspending agent c) is a saccharide suspending agent or a silicic acid suspending agent or a mixture of a saccharidic suspending agent with a suspending agent of silicic acid.

Particularly preferred cleaning agents comprise a) 15 to 40 wt .-% sodium percarbonate b) 20 to 50 wt .-% 1, 3-propanediol c) 20 to 50 wt .-% of nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ . ₄₀ alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.4 to 3 wt .-% suspended matter from the group of saccharidic suspending agents and Silica suspended matter, wherein

Cleaning agent comprising a) 15 to 40 wt .-% sodium percarbonate b) 20 to 50 wt .-% 1, 3-propanediol c) 20 to 50 wt .-% of nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ . ₄₀ alkyl or alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.4 to 3% by weight of hydroxyethylcellulose

respectively. Cleaning agent comprising a) 15 to 40 wt .-% sodium percarbonate b) 20 to 50 wt .-% 1, 3-propanediol c) 20 to 50 wt .-% of nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ - ₄ o-alkyl or - alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.4 to 3% by weight of silica

are very particularly preferred.

Some other exemplary bleaching agent formulations which are advantageous in terms of their chemical and physical stability are listed in Tables 5a and 5b below:

* nonionic surfactant of the general formula

* nonionic surfactant of the general formula

R2 R3

Despite their high physical and chemical stability, the detergents according to the invention are distinguished by a low formulation complexity. This low level of complexity simplifies the preparation of the detergents and thus reduces the costs involved in providing these detergents. For this reason, preferred cleaners according to the invention are characterized in that, in addition to the essential constituents a), b), c) and d)), they have at most three, preferably the highest two, more preferably at most one and in particular no further constituents. The proportion by weight of further constituents is preferably less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight and most preferably less than 0.1% by weight. Very particularly preferred cleaning agents according to the invention consist of the constituents listed in Tables 1 to 6.

A further subject matter of the present application is a detergent dosage form comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, to carry out a machine dishwashing process; b) a cartridge for the cleaning agent A.

The cleaning agents according to the invention are combined in another embodiment with one or more further cleaning agents. A detergent combination comprising a) a cleaning agent A according to the invention; b) at least one, preferably at least two further cleaning agents other than A. The further cleaning agents combined with the cleaning agent according to the invention are preferably detergents containing enzyme and / or surfactants and / or builders.

Tables 1 to 5b have described some cleaning agents of the invention which are advantageous in terms of their chemical and physical stability. preferred

Detergent combinations of two or three different detergents, which have proven to be particularly advantageous in terms of their performance, are shown in Tables 6a and 6b below:

In a preferred embodiment, the cleaning agents A and B shown in the above Table 6a are flowable (2O ⁰ C).

In a preferred embodiment, the cleaning agents listed in the above table 6b A, B and C flowable (2O ⁰ C).

The preparation of the above-described combination of cleaning agents takes place in the form of separate receiving chambers, each of these receiving chambers containing one of the combined detergents. Examples of such Konfektionsformen are cartridges with two, three, four or more separate receiving chambers, for example, two-, three-, four- or multi-chamber bottles. By separating the detergent of different composition unwanted reactions due to chemical incompatibility can be excluded.

A subject matter of the present application is furthermore a detergent dosage form comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, to carry out a machine dishwashing process; b) a cartridge for the cleaning agent A.

Preferred detergent combinations for such detergent dosage forms can be found in Tables 1 to 6 above.

Another object of the present application is a Reinigungsmittelangebotsform comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) a cartridge for the cleaning agents A and B, in which the cleaning agents A and B are present in separate receiving chambers.

Preferred detergent combinations for such detergent dosage forms can be found in Table 6a above.

Also claimed is a detergent dosage form comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, to carry out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) at least one further cleaning agent C other than A and B in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; d) a cartridge for the cleaning agents A, B and C, in which the cleaning agents A, B and C are present in separate receiving chambers.

Preferred detergent combinations for use in such

Detergent offer forms are shown in Table 6b above.

A further subject matter of the present application is a detergent dosing system comprising a) a cleaning agent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) a cartridge for the cleaning agent A; c) a metering device connected or connectable to the cartridge.

In a preferred embodiment, the previously described cartridges of the detergent product forms are provided with a dispenser detachable from the cartridge. Such a dosing device can be connected to the cartridge, for example by means of an adhesive, latching, snap or plug connection. The separation of the cartridge and dosing device, for example, the filling of the cartridge is simplified. Alternatively, allows the detachable connection The cartridge and dispenser change the cartridges on the dispenser. Such an exchange may be indicated, for example, in the event of a change in the cleaning program or after the cartridge has been completely emptied.

An object of the present application is further a Reinigungsmitteldosiersystem, comprising a) a detergent A according to the invention in an at least twice, preferably at least four times, and in particular at least eight times performing a machine dishwashing sufficient amount; b) a cartridge for the cleaning agent A; c) a dispenser detachably connected to the cartridge.

A further subject matter of the present application is a detergent dosing system comprising a) a cleaning agent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) a cartridge for the cleaning agents A and B, in which the cleaning agents A and B are present in separate receiving chambers; d) a releasably connected to the cartridge dosing device.

A particularly preferred subject of this application is a Reinigungsmitteldosiersystem comprising a) a detergent A according to the invention in an at least twice, preferably at least four times, and in particular at least eight times performing a machine dishwashing sufficient amount; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) at least one further cleaning agent C other than A and B in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; d) a cartridge for the cleaning agents A, B and C, in which the cleaning agents A, B and C are present in separate receiving chambers; e) a dispenser detachably connected to the cartridge.

Preferred detergent combinations for use in such detergent dosage forms can be found in Table 6b above.

Of course, detergent forms are also conceivable in which the cartridge and the dosing device are permanently connected to each other.

An object of the present application is further a Reinigungsmitteldosiersystem, comprising a) a detergent A according to the invention in an at least twice, preferably at least four times, and in particular at least eight times performing a machine dishwashing sufficient amount; b) a cartridge for the cleaning agent A; c) a metering device undetachably connected to the cartridge.

A further subject matter of the present application is a detergent dosing system comprising a) a cleaning agent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) a cartridge for the cleaning agents A and B, in which the cleaning agents A and B are present in separate receiving chambers; d) a non-releasably connected to the cartridge dosing device.

A particularly preferred subject matter of this application is a detergent dosing system, comprising a) a detergent A according to the invention in an at least twice, preferably at least four times, and in particular at least eight times, carrying out a machine

Dishwashing process sufficient amount; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) at least one further cleaning agent C other than A and B in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; d) a cartridge for the cleaning agents A, B and C, in which the cleaning agents A, B and C are present in separate receiving chambers; e) a metering device undetachably connected to the cartridge.

The vorgenanten Reinigungsmitteldosiersysteme, comprising a cleaning agent according to the invention (and optionally one or two further, different from the cleaning agent according to the invention cleaning), a cartridge and a releasably connected to the cartridge dosing device are in a preferred embodiment in a common outer packaging, wherein the filled cartridge and the dosing device are particularly preferably contained separately from one another in the outer packaging. The outer packaging is used for storage, transport and presentation of the invention Reinigungsmitteangebotsform and protect them from dirt, shock and shock. In particular for the purpose of presentation, the outer packaging should at least partially be made transparent.

As an alternative or in addition to an outer packaging, it is of course possible to use the detergents, detergent combinations or

Marketing detergent forms in conjunction with a dishwasher. Such a combination is particularly advantageous in cases in which the course of the automatic dishwashing process (for example duration, temperature profile, water supply) and the detergent formulation or the control electronics of the dosing device are matched to one another.

The dosing system according to the invention consists of the basic components of a cartridge filled with the detergent according to the invention and a metering device which can be coupled to the cartridge, which in turn is formed from further assemblies such as component carrier, actuator, closure element, sensor, energy source and / or control unit.

It is preferred that the metering system according to the invention is mobile. Movable in the sense of this application means that the metering system is not insoluble with a water-bearing device such as a dishwasher, washing machine, clothes dryer or the like is connected, but can be removed, for example, from a dishwasher by the user or positioned in a dishwasher, so is independently handled, is

According to an alternative embodiment of the invention, it is also conceivable that the dosing device for the user is not detachably connected to a water-carrying device such as a dishwasher, washing machine, tumble dryer or the like and only the cartridge is movable.

Since the preparations to be dosed may have a pH between 2 and 12, depending on the intended use, all components of the dosing system which come into contact with the preparations should have a corresponding acid and / or alkali resistance. Furthermore, these components should be largely chemically inert by a suitable choice of material, for example against nonionic surfactants, enzymes and / or fragrances.

cartridge

For the purposes of this application, a cartridge is understood as meaning a packaging material which is suitable for enveloping or holding together flowable or spreadable preparations and which can be coupled to a dosing device for dispensing the preparation.

In particular, a cartridge can also comprise a plurality of chambers which can be filled with mutually different compositions. It is also conceivable that a plurality of containers is arranged to form a cartridge unit.

It is advantageous that the cartridge has at least one outlet opening, which is arranged such that a gravity-induced release of preparation from the container in the position of use of the dosing device can be effected. As a result, no further funding for the release of preparation from the container is required, whereby the structure of the metering device can be kept simple and the production costs low.

In a preferred embodiment of the invention, at least one second chamber is provided for receiving at least one second flowable preparation, the second chamber having at least one outlet opening arranged such that a gravity-induced product release from the second chamber in the use position of the dosing is effected. The arrangement of a second chamber is particularly advantageous if in the separate containers preparations are stored, which are usually not stable to each other, such as bleaching agents and enzymes. Furthermore, it is conceivable that more than two, in particular three to four chambers are provided in or on a cartridge. In particular, one of the chambers can be designed for the delivery of volatile preparations, such as a fragrance to the environment.

In a further embodiment of the invention, the cartridge is integrally formed. In this way, the cartridges, in particular by suitable blow molding, cost-effectively trained in a manufacturing step. The chambers of a cartridge can in this case be separated from one another, for example, by webs or material bridges.

The cartridge can also be formed in several pieces by injection molded and then assembled components.

Further, it is conceivable that the cartridge is formed in such a multi-piece, that at least one chamber, preferably all chambers, can be removed individually from the metering device or inserted into the metering device. This makes it possible, with a different consumption of a preparation from a chamber to exchange an already empty chamber, while the rest, which may still be filled with preparation, remain in the metering device. Thus, a targeted and needs-based refilling the individual chambers or their preparations can be achieved.

The chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed. The chambers can be fixed by a suitable form-fitting, non-positive or cohesive connection releasably or permanently against each other. In particular, the fixation by one or more of the types of compounds from the group of snap-in compounds, Velcro, press joints, fusions, glued joints, welded joints, solder joints, screw, wedge, clamp or bounce joints can be done. In particular, the fixation can also be formed by a shrink sleeve (so-called sleeve), which is pulled in a heated state over the entire or sections of the cartridge and firmly encloses the chambers or the cartridge in the cooled state.

To provide advantageous residual emptying characteristics of the chambers, the bottom of the chambers may be funnel-shaped inclined towards the discharge opening. Furthermore, the inner wall of a chamber can be formed by suitable choice of material and / or surface design in such a way that a low material adhesion of the preparation to the inner chamber wall is realized. Also by this measure, the residual emptiness of a chamber can be further optimized. The chambers of a cartridge may have the same or different filling volumes. In a two-chamber configuration, the ratio of container volumes is preferably 5: 1, with a three-chamber configuration it is preferably 4: 1: 1, and these configurations are particularly suitable for use in dishwashers.

As mentioned above, the cartridge preferably has 3 chambers. For the use of such a cartridge in a dishwasher, it is particularly preferred that the first chamber contains an alkaline cleaning preparation, the second chamber an enzymatic preparation and the third chamber a rinse aid, wherein the volume ratio of the chambers is approximately 4: 1: 1.

In or on a chamber, a metering chamber may be formed in the flow direction of the preparation in front of the outlet opening. Through the metering chamber, the preparation amount that is to be released in the release of preparation from the chamber to the environment, set. This is particularly advantageous if the closure element of the dosing device, which causes the preparation discharge from a chamber to the environment, can only be put into a dispensing and a closure state without controlling the dispensing quantity. It is then ensured by the metering chamber that a predefined amount of preparation is released without an immediate feedback of the delivered preparation amount. The metering chambers can be formed in one piece or in several pieces.

According to a further advantageous development of the invention, one or more chambers in addition to an outlet opening each have a liquid-tight sealable chamber opening. Through this chamber opening, it is possible, for example, to refill stored in this chamber preparation.

For ventilation of the cartridge chambers ventilation possibilities can be provided in particular in the head region of the cartridge in order to ensure a pressure equalization with decreasing filling level of the chambers between the interior of the cartridge chambers and the environment. These ventilation options can be designed, for example, as a valve, in particular silicone valve, micro-openings in the cartridge wall or the like.

If, according to another embodiment, the cartridge chambers are not ventilated directly but are provided via the metering device or no ventilation, for example when using flexible containers such as bags, this has the advantage that at elevated temperatures during a dishwashing cycle of a dishwasher by the heating of the chamber contents, a pressure is built up, which presses the preparations to be metered in the direction of the outlet openings, so that a good emptying of the cartridge can be achieved. Furthermore, there is no risk of oxidation of substances of the preparation in such an air-free packaging, which makes a pouch packaging or bag-in-bottle packaging appear appropriate especially for oxidation-sensitive preparations.

The cartridge usually has a filling volume of <5,000 ml, in particular <1,000 ml, preferably <500 ml, more preferably <250 ml, most preferably <50 ml.

The cartridge can take on any spatial form. It can for example be cube-shaped, spherical or plate-like.

The cartridge and the dosing device can in particular be configured with respect to their spatial form such that they ensure the least possible loss of useful volume, in particular in a dishwasher.

To use the dispenser in dishwashers, it is particularly advantageous to mold the device based on dishes to be cleaned in dishwashers. So this example, plate-shaped, be formed in approximately the dimensions of a plate. As a result, the metering device can save space, e.g. be positioned in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit opens up to the user intuitively through the plate-like shape. The cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1. Due to the "slim" design of the dosing device and the cartridge, it is in particular possible to position the device in the lower cutlery basket of a dishwashing machine in the receptacles provided for plates This has the advantage that the preparations discharged from the dosing device pass directly into the wash liquor and can not adhere to other items to be washed.

Usually, commercial household dishwashers are designed in such a way that the arrangement of larger items to be washed, such as pans or large plates, is provided in the lower basket of the dishwasher. In order to avoid a non-optimal positioning of the metering by the user in the upper basket, the metering system is dimensioned in an advantageous embodiment of the invention such that a positioning of the metering system is only possible in the receptacles provided for the lower basket. For this purpose, the width and the height of the metering system can be selected in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.

However, it is also conceivable to form the metering unit in cup shape with a substantially circular or square base. In order to protect heat-sensitive components of a preparation in a cartridge from heat, it is advantageous to produce the cartridge from a material with a low thermal conductivity.

Another way to reduce the effect of heat on a preparation in a chamber of the cartridge is to isolate the chamber by suitable means, e.g. by the use of thermal insulation materials such as styrofoam, which enclose the chamber or the cartridge in a suitable manner, in whole or in part.

In a preferred embodiment of the invention, the cartridge has an RFID tag that contains at least information about the contents of the cartridge and that can be read by the sensor unit.

This information can be used to select a dosing program stored in the control unit. In this way it can be ensured that an optimal dosing program is always used for a particular preparation. It can also be provided that in the absence of an RFID label or an RFID label with a false or faulty identifier, no dosage is done by the dosing and instead an optical or acoustic signal is generated that the user on the present Error indicates. To preclude misuse of the cartridge, the cartridges may also have structural elements which cooperate with corresponding elements of the metering device according to the key-lock principle, so that, for example, only cartridges of a particular type can be coupled to the metering device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which control of the dosing device coordinated with the contents of the corresponding container can take place.

The cartridge is designed in particular for receiving flowable detergents or cleaning agents. Particularly preferably, such a cartridge has a plurality of chambers for the spatially separated receiving in each case of different preparations of a washing or cleaning agent. By way of example, but not exclusively, some possible combinations of the filling of the chambers with different preparations are listed in Tables 1 to 8 above in the description.

The cartridge may be designed so that it can be detachably or firmly arranged in or on the dishwasher. dosing

The control unit, sensor unit and at least one actuator necessary for operation are integrated in the dosing device. Preferably, an energy source is also arranged in the metering device.

Preferably, the metering device consists of a splash-proof housing, which prevents the penetration of spray water, as may occur, for example, when used in a dishwasher, into the interior of the metering device.

It is particularly preferred that the dosing device comprises at least a first interface, which in or on a water-conducting device such as in particular a water-conducting household appliance, preferably a dishwashing or washing machine formed corresponding interface cooperates in such a way that a transfer of electrical energy from the water-bearing device realized for dosing.

In one embodiment of the invention, the interfaces are formed by connectors. In a further embodiment, the interface cells can be designed in such a way that a wireless transmission of electrical energy is effected.

In an advantageous further development of the invention, in each case a second interface on the dosing device and the water-conducting device, such as a dishwasher, for transmitting electromagnetic signals, which in particular Betriebszustandands-, measuring and / or control information of the dosing and / or the water-bearing device such as Dishwasher represent trained.

adapter

By means of an adapter, a simple coupling of the dosing system with a water-conducting domestic appliance can be realized. The adapter serves for the mechanical and / or electrical connection of the metering system with the water-conducting household appliance.

The adapter is, preferably fixed, connected to a water-carrying pipe of the household appliance. However, it is also conceivable to provide the adapter for positioning in or on the household appliance, in which the adapter is detected by the water flow and / or spray of the household appliance.

The adapter makes it possible to carry out a dosing system both for a stand-alone version and a build-in version, and it is also possible to design the adapter as a charging station for the dosing system in which, for example, the dosing device's energy source is charged or data is transferred be exchanged with the dosing device and the adapter. The adapter can be arranged in a dishwasher on one of the inner walls of the washing chamber, in particular on the inner side of the dishwasher door. However, it is also conceivable that the adapter is positioned as such inaccessible to the user in the water-conducting household appliance, so that the dosing device is used for example during assembly with the household appliance in the adapter, wherein the adapter, the dosing device and the household appliance in such are formed so that a cartridge can be coupled by the user with the dosing device.

Figure 1 Self-sufficient dosing device with two-chamber cartridge in the separated and assembled state

Figure 2 Autarkes dosing with two-chamber cartridge arranged in a drawer of a dishwasher

Figure 3 two-chamber cartridge in the separated state to a self-sufficient and internal machine-integrated dosing

Figure 4 two-chamber cartridge in the assembled state with an internal machine-integrated dosing

Figure 5 two-chamber cartridge in the separated state to a self-sufficient and external machine-integrated dosing

Figure 6 Two-chamber cartridge in the assembled state with an external machine-integrated dosing

Figure 7 two-chamber cartridge in the separated and assembled state to a self-sufficient, machine-integrated dosing

Figure 8 Two-chamber cartridge in the assembled state to a self-sufficient, machine-integrated dosing device Figure 9 Autarkes dosing device with refillable two-chamber cartridge and refill unit

FIG. 1 shows a self-sufficient dosing device 2 with a two-chamber cartridge 1 in the separated and assembled state.

The metering device 2 has two metering chamber inlets 21a, 21b for repeatedly releasably receiving the corresponding outlet openings 5a, 5b of the chambers 3a, 3b of the cartridge 1. On the front are display and controls 37, which indicate the operating state of the dosing device 2 and act on this.

The metering chamber inlets 21a, 21b furthermore have means which, when the cartridge 1 is pushed onto the metering device 2, effect the opening of the outlet openings 5a, 5b of the chambers 3a, 3b, so that the interior of the chambers 3a, 3b communicating with the metering chamber inlets 21a, 21 b is connected. The cartridge 1 may consist of one or more chambers 3a, 3b. The cartridge 1 may be integrally formed with a plurality of chambers 3a, 3b or more pieces, in which case the individual chambers 3a, 3b are joined together to form a cartridge 1, in particular by cohesive, positive or non-positive connection methods.

In particular, the fixation by one or more of the types of compounds from the group of snap-in compounds, press joints, fusions, glued joints, welded joints, solder joints, screw, wedge,

Clamping or bouncing done. In particular, the fixation can also be formed by a shrink sleeve (so-called sleeve), which is pulled in a heated state at least in sections over the cartridge and firmly encloses the cartridge in the cooled state.

In order to provide advantageous residual emptying properties of the cartridge 1, the bottom of the cartridge 1 may be funnel-shaped inclined to the discharge opening 5a, 5b. Furthermore, the inner wall of the cartridge 1 can be formed by suitable choice of material and / or surface design in such a way that a low material adhesion of the product to the inner cartridge wall is realized. Also by this measure, the residual emptying of the cartridge 1 can be further optimized.

The chambers 3a, 3b of the cartridge 1 may have the same or different filling volumes. In a two-chambered configuration 3a, 3b, the chamber volume ratio is preferably 5: 1, in a 3-chamber configuration it is preferably 4: 1: 1, which configurations are particularly suitable for use in dishwashers. A connection method can also be that the chambers 3a, 3b are inserted into one of the corresponding metering chamber inlets 21a, 21b of the metering device 2 and thus fixed against each other.

The connection between the chambers 3a, 3b may in particular be made detachable in order to allow a separate exchange of a chamber.

The chambers 3a, 3b each contain a preparation 40a, 40b. The preparation 40a, 40b may have the same or different composition.

Advantageously, the chambers 3a, 3b are made of a transparent material, so that the filling level of the preparations 40a, 40b is visible from the outside by the user. However, it may also be advantageous to manufacture at least one of the chambers from an opaque material, in particular if the preparation contained in this chamber contains light-sensitive ingredients.

The outlet openings 5a, 5b are designed such that they form a positive and / or non-positive, in particular liquid-tight, connection with the corresponding metering chamber inlets 21a, 21b.

It is particularly advantageous that each of the outlet openings 5a, 5b is formed so that it fits only one of the Dosierkammereinlässe 21a, 21b, thereby preventing a chamber is accidentally plugged onto a wrong Dosierkammereinlass.

The cartridge 1 usually has a filling volume of <5,000 ml, in particular <1,000 ml, preferably <500 ml, more preferably <250 ml, most preferably <50 ml.

The metering unit 2 and the cartridge 1 can be adapted in the assembled state in particular to the geometries of the devices or in which they are applied in order to ensure the least possible loss of useful volume. To use the dosing unit 2 and the cartridge 1 in dishwashers, it is particularly advantageous to mold the dosing unit 2 and the cartridge 1 on the basis of dishes to be cleaned in dishwashers. Thus, the dosing unit 2 and the cartridge 1, for example, plate-shaped, be formed in approximately the dimensions of a plate. As a result, the dosing unit can be positioned to save space in the lower basket.

To provide an immediate optical level control, it is advantageous to form the cartridge 1 at least in sections of a transparent material.

In order to protect heat-sensitive components of a product contained in a cartridge from heat, it is advantageous to produce the cartridge 1 from a material with a low thermal conductivity.

The outlet openings 5a, 5b of the cartridge 1 are preferably arranged on a line or in alignment, whereby a slender, plate-shaped design of the dosing dispenser is made possible.

FIG. 2 shows a self-sufficient dosing device with a two-chamber cartridge 1 in the dish drawer 11 with the dishwasher door 39 of a dishwasher 38 open.

Figure 3 shows a two-chamber cartridge 1 in the separated state to a self-sufficient dosing device 2 and an internal, machine-integrated dosing. Here, the cartridge 1 is in such a way designed so that it (not shown) can be coupled with both the self-sufficient dosing device 2 and with the machine-integrated dosing device, which is indicated by the dargstellten in Figure 3 arrows.

A recess 43 into which the cartridge 1 can be inserted is formed on the side of the dishwasher door 39 directed inside the dishwasher 38, the outlet openings 5a, 5b of the cartridge 1 communicating with the adapter pieces 42a, 42b being connected by insertion. The adapter pieces 42a, 42b are in turn coupled to the machine-integrated dosing device.

For fixing the cartridge 1 in the recess 43 holding elements 44a, 44b may be provided on the recess 43, which ensure a positive and / or positive fixing of the cartridge in the recess 43. Of course, it is also conceivable that corresponding retaining elements are provided on the cartridge 1. The holding elements 44a, 44b may preferably be selected from the group of snap connections, latching connections, snap-lock connections, clamping connections or plug-in connections.

During operation of the dishwasher 38, preparation 40a, 40b from the cartridge 1 through the adapter elements 42a, 42b is added to the corresponding rinsing cycle by the machine-integrated dosing device.

Figure 4 shows the error! Reference source could not be found, known cartridge 1 in the installed state in the door 39 of a dishwasher 38th

Another embodiment of the invention is shown in FIG. FIG. 5 shows the cartridge 1 known from FIG. 3 with a chamber 45 arranged at the head of the cartridge 1, which chamber has a plurality of openings 46 in its lateral surface. Preferably, the chamber 45 is filled with an air freshener formulation which is delivered through the openings 46 to the environment. The air-conditioning preparation may in particular comprise at least one fragrance and / or an odor-controlling substance.

Unlike the arrangement of the cartridge 1 in the interior of a dishwasher 38 known from FIGS. 3 and 4, it is also possible to provide a recess 43 with adapter elements 42a, 42b for coupling to the cartridge 1 on an outer surface of a dishwasher 38. This is shown by way of example in FIG. 5 and FIG.

Of course, the cartridge 1 depicted in FIG. 5 and FIG. 6 can also be arranged with a chamber 45 containing an air-improving substance in a correspondingly formed receptacle in the interior of a dishwasher 38. A further embodiment of the invention is shown in FIG. The dosing device 2 can in this case be coupled to the cartridge 1, which is indicated by the first, left arrow in the drawing accordingly. Subsequently, cartridge 1 and dosing device 2 are coupled as an assembly via the interface 47, 48 to the dishwasher, which is indicated by the right arrow. The dosing device 2 has an interface 47, via which data and / or energy are transferred to and / or from the dosing device 2. In the door 39 of the dishwasher 38, a recess 43 for receiving the dosing device 2 is provided. In the depression 43, a second interface 48 is provided, which transmits data and / or energy to and / or from the dosing device 2.

Preferably, data and / or energy are exchanged wirelessly between the first interface 47 on the dosing device 2 and the second interface 48 on the dishwasher 38. It is particularly preferred that energy from the interface 48 of the dishwasher 38 is transmitted wirelessly via the interface 47 to the dosing device 2. This can be done, for example, inductively and / or capacitively.

It is also advantageous to form the interface for transmitting data wirelessly. This can be realized by the methods known in the prior art for the wireless transmission of data, such as by means of radio transmission or IR transmission.

Alternatively, the interfaces 47, 48 may be formed by integrated connectors. Advantageously, the connectors are formed in such a way that they are protected from the entry of water or moisture.

FIG. 9 shows a cartridge 1 whose chambers 3a, 3b can be filled via the head-side openings 49a, 49b, for example by means of a refill cartridge 51. The openings 49a, 49b of the cartridge 1 may be formed, for example, as silicone valves, which open when piercing through the adapter 50a, 50b and close again upon removal of the adapter 50a, 50b, so that an inadvertent leakage of preparation from the cartridge is prevented.

The adapters 50a, 50b are formed in such a way that they can pierce the openings 49a, 49b of the cartridge 1. Advantageously, the openings 49a, 49b of the cartridge 1 and the adapters 50a, 50b are configured with regard to their position and size in such a way that the adapter can engage in the openings 49a, 49b only in a predefined position. In this way, in particular, incorrect filling of the cartridge chambers 3a, 3b can be prevented and it is ensured that the respectively identical or compatible preparation passes from a chamber 52a, 52b of the refill cartridge 51 into the corresponding chamber 3a, 3b of the cartridge 1. The inventive cleaning agents, detergent combinations or

Detergent supply forms are suitable for use in dishwashing as well as for textile cleaning, however, the use of a detergent according to the invention, a detergent combination according to the invention or a novel detergent

Detergent supply form for dishwashing in a dishwasher machine preferred.

As stated at the outset, the cleaning agents according to the invention are distinguished by a particular physical and chemical stability, in particular with respect to temperature fluctuations. The cleaning agents according to the invention are thus exceptionally suitable for the metering by means of a metering system located in the interior of a washing or dishwashing machine. Such a metering system, which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated metering device) but of course also as a movable device in the interior can be introduced (self-sufficient dosing device), contains the multiple required to carry out a machine cleaning process amount of the detergent.

Movable in the sense of this application means that the dispensing and metering system is not inseparably connected to a device such as a dishwasher, washing machine, tumble dryer or the like, but can be removed, for example, from a dishwasher or positioned in a dishwasher.

The use of a detergent according to the invention or of a detergent combination according to the invention for filling i) a cartridge of a dosing system immovably integrated in the interior of a dishwasher or ii) a movable cartridge of a dosing system provided with at least twice, preferably at least twice, for positioning in the interior of a dishwasher four times and in particular at least eight times carrying out a machine dishwashing sufficient amount of this detergent or this detergent combination are also objects of this application.

Preferred cleaning agents or cleaning agent combinations for such uses can be found in Tables 1 to 8 above.

An example of a stationary cartridge is a container immovably integrated into the interior, for example in the side wall or the inner lining of the door of a dishwasher.

An example of a movable cartridge is a container that is introduced by the consumer in the interior of the dishwasher and there throughout the course of a Cleaning course remains. Such a cartridge is, for example, by simply setting in the cutlery or crockery basket, integrated into the interior but can be removed from the consumer again from the interior of the dishwasher.

The dosage of the cleaning agent or the detergent combination from the cartridge into the interior of the dishwasher is carried out as described above, preferably by means of a detachable from the cartridge dosing. Such a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection. However, cartridges with a permanently connected metering device can of course also be used.

The use of a detergent dosage form according to the invention, comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) a cartridge for the cleaning agent A as a cleaning agent reservoir for i) a metering device immovably integrated into the interior of a dishwasher, or ii) a movable metering device provided for positioning in the interior of a dishwasher are also objects of this application. Preferred cleaning agents A for such uses are given in Tables 1 to 6 above.

The use of a detergent dosing system according to the invention as a detergent reservoir for a dishwasher is a further subject of the present application.

Two further subjects of this application are the use of a detergent dosage form according to the invention, comprising a) a detergent A according to the invention in an amount sufficient for the at least twice, preferably at least four and in particular at least eight times carrying out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) a cartridge for the cleaning agents A and B, in which the cleaning agents A and B in separate receiving chambers are present as a detergent reservoir for i) a metering device that is immovably integrated into the interior of a dishwashing machine or ii) a movable metering device provided for positioning in the interior of a dishwashing machine.

Preferred detergent combinations A and B for such uses are shown in Table 6a above.

Also claimed is the use of a detergent dosage form according to the invention, comprising a) a detergent A according to the invention in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; b) at least one further cleaning agent B other than A in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; c) at least one further cleaning agent C other than A and B in an amount sufficient for the at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing process; d) a cartridge for the cleaning agents A, B and C, in which the cleaning agents A, B and C are present in separate receiving chambers as a cleaning agent reservoir for i) an immovably integrated into the interior of a dishwasher metering device or ii) one for positioning in the interior a dishwasher provided mobile dosing

Preferred detergent combinations A, B and C for such uses are shown in Table 6b above.

The detergents and cleaning agent combinations according to the invention are, as stated above, preferably used as automatic dishwasher detergents.

Automatic dishwashing processes according to the invention using a cleaning agent A according to the invention are characterized in that a subset a of the cleaning agent A in the cartridge is metered into the interior of the dishwasher in the course of this process from a cartridge located in the interior of the dishwasher Cartridge cleaning agent remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount at least twice, preferably at least four times and in particular at least eight times the amount of subset a corresponds.

Of course, not only the detergents according to the invention but also the detergent combinations or detergent dosage forms or detergent dosage systems according to the invention described above can be used in the dishwashing processes according to the invention.

An object of this application is therefore furthermore a machine dishwashing process using a detergent combination according to the invention comprising a cleaning agent A according to the invention and another cleaning agent B other than A, in the course of which a cartridge located in the interior of the dishwasher contains a subset a of the cleaning agent contained in the cartridge A as well as a subset b of the present in the cartridge detergent B is dosed into the interior of the dishwasher, with residual amounts of the detergent A and B remain until the end of dishwashing in the cartridge and the residual amount of the detergent A at least twice, preferably at least the four times and in particular at least eight times the amount of subset a and the residual amount of the cleaning agent B at least twice, preferably at least four times, and in particular at least eight times the amount of subset b.

Preferred detergent combinations for such automatic dishwashing processes can be found in Table 6a above.

A subject of this application is further a machine dishwashing process using a detergent combination according to the invention, comprising a detergent A according to the invention and another detergent B different from A and a third detergent A different from A and B, in the course of which a cartridge located in the interior of the dishwasher a subset a of the cleaning agent A present in the cartridge as well as a subset b of the cleaning agent B present in the cartridge and additionally a subset c of the cleaning agent C present in the cartridge are metered into the interior of the dishwasher, remaining amounts of the cleaning agents A, B and C remain in the cartridge until the end of the dishwashing process and the residual amount of the detergent A at least twice, preferably at least four times and in particular at least eight times the amount of Te ilmenge a, the residual amount of the detergent B at least twice, preferably at least four times and in particular at least eight times the amount of subset b corresponds and the residual amount of the detergent C at least twice, preferably at least four times and in particular at least eight times the amount of subset c equivalent. Preferred detergent combinations for such automatic dishwashing processes can be found in Table 6b above.

Be in the machine dishwashing process according to the invention

Used detergent combinations with two, three or more different detergents, the dosage of the different detergents is preferably carried out at different times of the cleaning cycle.

A further subject of this application is therefore a machine dishwashing process using a cleaning agent according to the invention or a detergent dosage form according to the invention or a detergent dosing system according to the invention, in the course of which a) at a time t1 from a cartridge located in the interior of the dishwasher, a subset a of The cleaning agent A according to the invention located in the cartridge is metered into the interior of the dishwasher, wherein a residual amount of the cleaning agent contained in the cartridge remains in the cartridge until the end of the dishwashing process, which of the at least twice, preferably at least four times, and in particular at least eight times, amount of the subset a corresponds; b) at least one further time t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset b of located in the second cartridge of the inventive detergent A different detergent B in the interior of the dishwasher, with a residual amount of in this cartridge remaining detergent in the cartridge remains until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset b.

This application further claims a machine dishwashing process using a detergent according to the invention or a detergent dosage form according to the invention or a detergent dosing system according to the invention, in the course of which a) at a time t1 from a cartridge located in the interior of the dishwasher, a subset a of the located in the cartridge Cleaning agent A according to the invention is metered into the interior of the dishwasher, wherein a residual amount of the cleaning agent A in the cartridge remains in the cartridge until the end of dishwashing, which corresponds to at least twice, preferably at least four times and in particular at least eight times the amount of subset a ; b) at least one further time t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset b of located in the second cartridge of the inventive detergent A different detergent B in the interior of the dishwasher, with a residual amount of in this cartridge remaining cleaning agent B remains in the cartridge until the end of dishwashing, which at least twice, preferably at least four times, and in particular at least eight times the amount of subset b corresponds; c) at least one further time t3 ≠ t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset c of located in the third cartridge of the inventive detergent A and the detergent B different detergent C in the interior of the dishwasher, wherein a residual amount of the cleaning agent C present in this cartridge remains in the cartridge until the end of the dishwashing process, which corresponds to at least twice, preferably at least four times, and in particular at least eight times, the quantity of the subset c.

Preferred detergent combinations for such automatic dishwashing processes can be found in Table 6b above.

In preferred embodiments of the above-described automatic dishwashing processes with time-delayed metering of the cleaning agents A and B or A, B and C, the time t2 is at least 1 minute, preferably at least 2 minutes and in particular between 3 and 20 minutes before or after the time t1 ,

Examples

To demonstrate the improved physical and chemical stability of detergents according to the invention, the following five detergent formulations were provided (data in [% by weight]):

* nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 is} a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C ₂ - ₄ o-alkyl or alkenyl radical; A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -

CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0

** Hydroxymix ether: iso-do fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether

These five detergents were stored in sealed, water-tight containers with pressure equalizing a) for a period of 24 hours at room temperature (2O ⁰ C) and b) for a period of twenty cleaning cycles (intensive 65 ⁰ C) (in a continuously operating a domestic dishwasher Miele G 1220 Konti) spent.

Subsequently, the bleach-containing formulations were assessed for their sedimentation stability (yes = stable to sedimentation, no = not sedimentation-stable):

This series of tests shows that the combination according to the invention of an oxygen bleaching agent, organic solvent, a specific nonionic surfactant and a suspending agent has a sedimentation-stable property at room temperature

Detergent composition can be obtained. The test series can also be seen that a stabilization of the bleaching agent at temperatures above room temperature is achieved in particular by a matrix based on 1, 3 propanediol.

Claims

claims

1. detergent having a water content below 5 wt .-%, comprising a) 10 to 45 wt .-% oxygen bleach b) 15 to 60 wt .-% organic solvent c) 15 to 60 wt .-% nonionic surfactant of the general formula R. ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated one C ₂ - alkenyl - ₄ o-alkyl or; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) - CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.1 to 5% by weight of suspending agent.

2. Cleaning agent according to claim 1, characterized in that it is the oxygen bleaching agent is sodium percarbonate.

3. Cleaning agent according to one of the preceding claims, characterized in that the weight fraction of the oxygen bleaching agent a) is between 15 and 40 wt .-%, preferably between 18 and 35 wt .-% and in particular between 21 and 30 wt .-%.

4. Cleaning agent according to one of the preceding claims, characterized in that is used as the organic solvent 1, 3 propanediol.

5. Cleaning agent according to one of the preceding claims, characterized in that the weight fraction of the organic solvent b) is between 20 and 50 wt .-%, preferably between 23 and 47 wt .-% and in particular between 25 and 45 wt .-%.

6. Cleaning agent according to one of the preceding claims, characterized in that the weight fraction of the nonionic surfactant c) is between 20 and 50 wt .-%, preferably between 23 and 47 wt .-% and in particular between 25 and 45 wt .-%.

7. Cleaning agent according to one of the preceding claims, characterized in that it is the suspending agent c) is a saccharidic suspending agent or a silicic acid suspending agent or a mixture of a saccharidic suspending agent and a silicic acid suspending agent.

8. Cleaning agent according to one of the preceding claims, characterized in that the weight proportion of the suspending agent c) between 0.2 and 4 wt .-%, preferably between 0.4 and 3 wt .-%, preferably 0.5 to 2.5 and in particular between 1, 1 and 2.5 wt .-% is.

9. Cleaning agent according to one of the preceding claims, characterized in comprising a) 15 to 40 wt .-% sodium percarbonate b) 20 to 50 wt .-% 1, 3-propanediol c) 20 to 50 wt .-% of nonionic surfactant of the general formula

R ¹ O- (AO) _w - (A'O) _x - (A "O) _y - (A '" O) _z -H, in which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C ₂ - ₄ o-alkyl or alkenyl; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), - CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 d) 0.4 to 3 wt .-% suspended matter from the group of saccharidic suspending agents and silica-settling agent

10. A detergent combination comprising a) a cleaning agent A according to one of the preceding claims; b) at least one, preferably at least two further cleaning agents other than A.

11. Use of a cleaning agent or a detergent combination according to one of the preceding claims for filling i) an immovable integrated into the interior of a dishwasher cartridge of a dosing or ii) provided for positioning in the interior of a dishwasher movable cartridge of a dosing with one for the at least twice , Preferably at least four times, and in particular at least eight times performing a machine dishwashing sufficient amount of this detergent or this detergent combination.

12. detergent dosage form, comprising a) a cleaning agent A according to one of the preceding claims in a sufficient for at least twice, preferably at least four times, and in particular at least eight times performing a machine dishwashing process sufficient amount; b) a cartridge for the cleaning agent A.

13. Use of a detergent product form according to claim 12 as a detergent reservoir for i) an immovable integrated into the interior of a dishwasher

Dosing device or ii) a provided for positioning in the interior of a dishwasher movable dosing device.

14. Reinigungsmitteldosiersystem, comprising a) an inventive cleaning agent A according to one of the preceding claims in a sufficient for the at least twice, preferably at least four times and in particular at least eight times performing a machine dishwashing process sufficient amount; b) a cartridge for the cleaning agent A; c) a metering device connected or connectable to the cartridge.

15. Use of a cleaning agent, a detergent combination, a detergent dosage form or a detergent dosing system according to one of the preceding claims for dishwashing in a dishwasher machine.

16. Machine dishwashing process using a cleaning agent or a detergent combination or a Reinigungsmittelangebotsform or a Reinigungsmitteldosiersystems according to any one of the preceding claims, in the course of a cartridge located in the interior of the dishwasher a subset a of the cleaning agent located in the cartridge is dosed into the interior of the dishwasher , wherein a residual amount of the detergent present in the cartridge remains in the cartridge until the end of the dishwashing process, characterized in that this residual amount corresponds to at least twice, preferably at least four times, and in particular at least eight times, the amount of subset a.

17. A machine dishwashing process using a cleaning agent or a detergent combination or a detergent dosage form or a detergent dosing system according to one of the preceding claims, in the course of which a) at a time t1 from a cartridge located in the interior of the dishwasher, a subset a of the cleaning agent A present in the cartridge according to one of the preceding claims is metered into the interior of the dishwasher, wherein a residual amount of the cleaning agent A in the cartridge remains in the cartridge until the end of the dishwashing process, which at least the double, preferably at least four times and in particular at least eight times the amount of subset a corresponds; at least one further time t2 ≠ t1 from a cartridge located in the interior of the dishwasher is dosed a subset b of the present in the second cartridge of the detergent A different detergent B in the interior of the dishwasher, with a residual amount of the present in this cartridge detergent until remains at the end of the dishwashing process in the cartridge, which at least twice, preferably at least four times and in particular at least eight times the amount of subset b corresponds.