KR20120101641A - Dishwasher detergent - Google Patents

Abstract

The present invention relates to a detergent formulation for washing dishes in a dishwasher, which comprises the following and is characterized by excellent film inhibition and good cleaning and rinsing performance:
a1) 1.0 to 20% by weight of ethylenediamine isuccinic acid, a2) 1.0 to 20% by weight of phosphonate, b) 2.0 to 30% by weight of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid Copolymer.

Description

Dishwasher detergent {DISHWASHER DETERGENT}

The present application describes a cleaning agent for automatic cleaning of tableware. Cleaning processes comprising these cleaners are additional subject matter herein.

Today, stricter standards are required for washing utensils with a machine than with human hands. Thus, after automatic dishwashing, the dishes should not only be free of food residues, but also have no white stains caused by other mineral salts or water hardness (which originate from water droplets drying in the absence of wetting agents).

Modern automatic dishwasher detergents meet these requirements by incorporating cleaning, care, water-softening and rinsing active substances and are known to consumers as, for example, "2 in 1" or "3 in 1" dishwasher detergents. have. Automatic dishwasher detergents provided to the end individual user include builders as essential ingredients for successful cleaning and rinsing. Preferentially, these builders increase the alkalinity of the cleaning solution, whereby the increase in alkalinity causes the fats and oils to be emulsified and saponified, and secondly to reduce the water hardness of the cleaning solution by complexation of calcium ions contained in the aqueous solution. . Alkali metal phosphates have proved to be particularly effective builders and for this reason form the majority of the major components of commercial dishwasher detergents.

Although phosphate is a very valuable component that has a beneficial effect as a component of automatic dishwasher detergents, their use is problematic in terms of environmental protection, because large amounts of phosphate are introduced into natural water through household wastewater, especially where This is because it plays an important role when it is fertilized in places (lakes, dams). As a result of this phenomenon (known as eutrophication), in some countries (e.g. USA, Canada, Italy, Sweden, Norway), the use of pentasodium triphosphate in textile cleaners has been substantially reduced by law and is completely banned in Switzerland. It became. Since 1984, cleaning agents in Germany have been allowed to contain up to 20% of these builders.

In addition to nitrilotriacetic acid, sodium aluminosilicate (zeolite) is mainly used as phosphate substitute or replacement in fabric cleaners. However, these materials are not suitable for use in automatic dishwasher detergents for a variety of reasons. Thus, several alternatives are discussed in the literature as an alternative to alkali metal phosphates in automatic dishwasher detergents, with citrate in particular being emphasized.

In addition to citrate, phosphate-free automatic dishwasher detergents which also include carbonates, bleaches and enzymes are described, for example, in European patent EP 662 117 117 B1 (Henkel) and European patent EP 690 2020 020 B1 (Henkel).

Another alternative to alkali metal phosphates used as the only builder (preferably used in combination with citrate) is methylglycine diacetic acid (MGDA). Automatic dishwasher detergents containing MGDA are described, for example, in European patent application EP # 906-407-B1 (Reckitt Benckiser) and European patent application EP-1-113-070-A2 (Reckitt Benckiser).

Despite prior efforts, manufacturers of automatic dishwasher detergents provide phosphate-free automatic dishwasher detergents comparable to or exceeding phosphate-containing detergents in terms of their cleaning and rinsing power, as well as their sediment-lowering power. It was not successful. However, equivalence in these performances is an essential prerequisite for successful entry into the market for phosphate-containing cleaners, with the vast majority of end-users noticing that their products are price and / or performance despite a wide range of social discussions. If they do not meet the standard, they will not choose products with ecologically sustainable benefits.

Therefore, starting from such a situation, it is an object of the present invention to provide a phosphate-free automatic dishwasher detergent comparable to or exceeding conventional phosphate containing detergents in terms of rinsing results and precipitation inhibiting performance as well as cleaning power.

Automatic dishwasher detergents comprising mixtures of certain organic builders and sulfonic acid-containing polymers have been found to exhibit excellent precipitation inhibition and cleaning and rinsing power, even in the absence of alkali metal phosphates.

Accordingly, a first subject matter of this application is detergent formulation A for automatic dishwashing, comprising:

a1) 1.0 to 20 wt% ethylenediamine isuccinic acid;

a2) 1.0 to 20 weight percent phosphonate;

b) from 2.0 to 30% by weight of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid.

The first essential ingredient included in the detergent formulation of the present invention is 1.0 to 20% by weight of ethylenediamine isuccinic acid (EDDS), wherein preferred detergent formulations are based on their total weight, preferably from 2.0 to 15% by weight, preferably Comprises 2.5 to 12% by weight, in particular 3.0 to 10% by weight of ethylenediamine isuccinic acid.

The term "ethylenediamine isuccinic acid (EDDS)" also includes salts thereof, for example sodium or potassium salts thereof, in addition to the free acid. For the weight fraction of ethylenediamine isuccinic acid used in the agents of the invention, the acid salt must be added to the weight fraction of the free acid, ie the weight fraction of the salt must be converted to the weight fraction of the acid.

The second essential ingredient included in the detergent formulation A of the present invention is phosphonate (s). The weight fraction of phosphonate is preferably 2.0 to 15% by weight, preferably 2.5 to 12% by weight, in particular 3.0 to 10% by weight, based on the total weight of the cleaning formulation of the invention.

Phosphonate complexes comprise a series of different compounds, such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylene phosphonic acid) (DTPMP). Particular preference is given here to hydroxyalkane phosphonates or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a cobuilder. It is usually added as sodium salt, disodium salt reacts neutral and tetrasodium salt reacts with alkali (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferably selected as aminoalkane phosphonates. They are preferably added in the form of neutral-reacted sodium salts, for example as hexasodium salt of EDTMP or as hepta and octasodium salts of DTPMP. HEDP is preferably used from the group of phosphonates.

In the context of the present application, preferred automatic dishwasher detergents comprise one or more phosphonate (s) from the following group:

a) aminotrimethylene phosphonic acid (ATMP) and / or salts thereof;

b) ethylenediamine tetra (methylene phosphonic acid) (EDTMP) and / or salts thereof;

c) diethylenetriamine penta (methylene phosphonic acid) (DTPMP) and / or salts thereof;

d) 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or salts thereof;

e) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or salts thereof;

f) hexamethylenediamine tetra (methylene phosphonic acid) (HDTMP) and / or salts thereof;

g) nitrilotri (methylene phosphonic acid) (NTMP) and / or salts thereof.

Particularly preferred detergent formulations include 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylene phosphonic acid) (DTPMP) as phosphonates.

A third feature of detergent formulation A of the present invention is a sulfonic acid group-containing copolymer. Preferred detergent formulations of the invention have a weight fraction of the copolymer of (meth) acrylic acid and 2-acrylicamino-2-propane sulfonic acid in the range of 3.0 to 26% by weight, preferably 5.0 to 22% by weight, based on the total weight of the detergent formulation, In particular from 7.0 to 18% by weight of detergent formulations.

The sulfonic acid group-containing copolymer comprises acrylic acid and / or methacrylic acid, preferably acrylic acid or a water soluble salt thereof as the unsaturated carboxylic acid (s). Sulphonic acid group-containing monomers relate to 2-acrylamido-2-propane sulfonic acid or water soluble salts thereof.

The sulfonic acid groups may be present in fully or partially neutralized form, ie the acidified hydrogen atoms of the sulfonic acid groups may be replaced by metal ions, preferably alkali metal ions, more particularly sodium ions, in some or all of the sulfonic acid groups. The addition of copolymers containing partially or completely neutralized sulfonic acid groups is preferred according to the invention.

The copolymer may comprise two, three, four or a plurality of different monomer units. In another preferred embodiment, the sulfonic acid group-containing copolymer contains at least one nonionic, preferably hydrophobic monomer. In particular, the rinsing performance of the detergent formulations of the invention can be improved by the addition of these hydrophobically modified polymers.

Monomers of the general formula R ¹ (R ² ) C═C (R ³ ) -XR ⁴ are preferably added as nonionic monomers, wherein R ¹ to R ³ are independently of each other —H, —CH ₃ or -C ₂ H ₅ , X represents any existing spacer group selected from -CH _2- , -C (O) O- and -C (O) -NH-, and R ⁴ is straight or branched saturated alkyl Group (C2-C22), or unsaturated, preferably aromatic group (C6-C22).

Particularly preferred nonionic monomers are: butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclo Hexene, 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-dimethylhexene-1, ethylcyclohexine, 1-octene, α-olefin (10 or more carbon atoms) such as, for example 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ -α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, Methyl methacrylate Hite, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) Acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl Methacrylate and N- (behenyl) acrylamide or mixtures thereof.

The molecular weight of the preferred sulfo-copolymers of the present invention used can be varied to adapt the properties of the polymer to the desired application requirements. Preferred automatic dishwasher detergents are characterized in that the copolymer has a molecular weight of 2000 to 200 000 gmol ^-1 , preferably 4000 to 25 000 gmol ^-1 , in particular 5000 to 15 000 gmol ^{- 1} .

Detergent preparation A preferably comprises an additional alkali source. Here, the group of alkali sources includes carbonates and / or hydrogen carbonates and alkali metal hydroxides. In the context of the present application, the group of carbonates and hydrogen carbonates is summarized by the term (hydrogen) carbonate.

Preferred detergent formulations A of the present invention are builder (s) from the group of alkali sources, based on their total weight of 1.0 to 30% by weight, preferably 2.0 to 25% by weight, in particular 5.0 to 20% by weight. It includes.

The addition of the (hydrogen) carbonate (s) is preferably in an amount of 1.0 to 40% by weight, preferably 2.0 to 30% by weight, in particular 4.0 to 15% by weight, based on the total weight of the detergent formulation A Is particularly preferred alkali metal (hydrogen) carbonate (s), particularly preferably sodium (hydrogen) carbonate or potassium (hydrogen) carbonate.

Preferred detergent formulations A of the present invention comprise alkali metal hydroxide (s) for increasing or adjusting the alkalinity. Alkali metal hydroxides are preferably added to the detergent in amounts of 2.0 to 22% by weight, preferably 4.0 to 20% by weight, in particular 8.0 to 18% by weight, based on the total weight of the detergent.

The detergent formulation A of the present invention is preferably a liquid. These are aqueous preparations each having a water content of 25 to 75% by weight, preferably 30 to 70% by weight, in particular 35 to 65% by weight, based on the total weight of detergent preparation A.

The detergent formulation of the present invention is slightly alkaline. Preferred detergent formulations of the invention are those having a pH (10% solution; 20 ° C.) of 9 to 11.5, preferably 9.5 to 11.5.

The compositions of some liquid detergent formulations preferred according to the invention can be shown in Table 1 below.

[Table 1]

* Copolymers of (meth) acrylic acid and 2-acrylamido-2-propane-sulfonic acid

In order to improve the cleaning results, detergent formulation A of the present invention can be combined with additional detergent formulations. Further detergents which are combined with the detergents according to the invention preferably relate to detergents comprising surfactants and / or enzymes and / or builders.

Thus, another subject matter of this application is a detergent formulation containing:

a) detergent formulation A of the present invention;

b) detergent formulation B comprising:

  b1) one or more cleaning active enzymes.

Preferred detergent formulation B comprises one or more detergent active enzymes. The weight fraction of the cleaning active enzyme preparation (s) in the total weight of detergent preparation B is advantageously from 10 to 60% by weight, preferably from 20 to 55% by weight, in particular from 30 to 55% by weight. In particular, cleaning active enzyme preparations from preparations of the amylase, protease and lipase groups are added as cleaning active enzyme preparations.

Particularly preferably added enzymes include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Improved variants based on natural molecules can be used in the detergents or cleaners, and therefore they are preferably used. The detergent or detergent preferably comprises enzymes in a total amount of 1 × 10 ⁻⁶ to 5% by weight based on the active protein. Protein concentration can be measured by known methods, such as the BCA method or the burette method.

Preferred proteases are of the subtilisin type. Examples are subtilisin BPN Shin 'and Carlsberg (Carlsberg) and these additional gaebalhyeong, protease PB92, subtilisin 147, and Shin-309, Bacillus alkylene tooth (Bacillus lentus ), subtilase enzymes of subtilisin DY, and the termitase, protease K and proteases TW3 and TW7 (which are no longer classified as subtilisin in the strict sense).

Preferred liquid detergent formulations B according to the invention comprise 5 to 50% by weight, preferably 7 to 40% by weight, in particular 10 to 30% by weight, of the protease formulation, relative to the total weight of the detergent formulation B. Particular preference is given to detergent formulation B comprising from 15 to 25% by weight of the protease formulation relative to the total weight.

Examples of amylases that can be used according to the invention are from Bacillus licheniformis , from B. amyloliquefaciens , from Bacillus stearotermophilus, Aspergillus niger ), α-amylase from Aspergillus duckbill ( A. oryzae ), and further developments of the above-mentioned amylases, which have been improved for use in cleaners and cleaners. Further, the species of Bacillus (Bacillus sp . ) Α-amylase from A 7-7 (DSM 12368) and cyclodextrin glucotransferase (CGTase) from B. agaradherens (DSM 9948) are noted for this purpose.

Preferred liquid detergent formulation B of the present invention comprises 0.1 to 30% by weight, preferably 1.0 to 25% by weight, in particular 2.0 to 20% by weight of amylase formulation, relative to the total weight of detergent formulation B. Especially preferred are detergents or detergent formulations A comprising from 4.0 to 16% by weight amylase formulation, relative to the total weight.

Active washing proteases and amylases are generally made available in the form of stabilized, hypotonic and mobile agents rather than pure protein forms. These prefabricated preparations are stabilizers, for example, as solid preparations obtained by extrusion, granulation of lyophilization or as low water content enzyme solutions (advantageously at the highest possible concentrations), especially in the case of liquid or gelatinous agents. Or in admixture with other adjuvants.

As shown in the above examples, enzyme proteins form only a fraction of the total weight of conventional enzyme preparations. Preferred added protease and amylase formulations of the invention comprise 0.1 to 40% by weight, preferably 0.2 to 30% by weight, particularly preferably 0.4 to 20% by weight, in particular 0.8 to 10% by weight of enzyme protein.

In addition, lipases or cutinases can be used according to the invention, in particular because of their triglyceride-degrading activity, also to generate in-situ ferrasides from suitable precursors. These are, for example hyumi furnace coke La leak OSU (Humicola lanuginose (Mrs. La Terre leak furnace Seuss (Thermomyces lanuginosus ))) and / or further developed lipases, especially those having amino acid exchange D96L. Moreover, suitable cutinases, for example Fusarium solani fish ( Fusarium solani pis i) and Humicola insolens . Further suitable is that its starting enzyme is Pseudomonas mendocina ) and lipase or cutinase originally isolated from Fusarium solanii .

In addition, enzymes which are summarized by the term hemicellulase may be added. These include, for example, mannase, xanthanase, pectinase (= pectinase), pectin esterase, pectatease, xyloglucanase (= xylanase), pullulanase and β-glucanase do.

To increase the bleaching effect, oxidoreductases such as oxadaase, oxygenase, catalase, peroxidase such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidase, deoxygenase or Lacase (phenol oxidase, polyphenol oxidase) can be used according to the invention to increase the bleaching effect. Furthermore, preferably organic, particularly preferably aromatic compounds (which interact with enzymes) are added to increase the activity of each oxidoreductase (enhancer) or redox between the oxidase and contaminants (mediators) If there is a much greater difference in potential, it is advantageous to add it to ensure electron flow.

Plural enzyme and / or enzyme preparations, preferably liquid protease preparations and / or amylase preparations and / or lipase preparations, are preferably added.

The second key component of detergent formulation B according to the invention is cumene sulfonate. For cumene sulfonate, para-isopropyl benzene sulfonate is the preferred compound.

Surprisingly, cumene sulfonate has proven to be superior in its stabilizing properties to solvents such as glycerin, triacetin or diethylene glycol, as well as to hydrotropes such as xylene sulfonates.

Preferred detergent formulations B of the present invention each contain 0.5 to 60% by weight, advantageously 1.0 to 50% by weight, preferably 2.0 to 40% by weight, in particular 5.0 to 30, based on the total weight of the detergent formulation. Cumene sulfonate in an amount by weight. The weight fraction of cumene sulfonate in the total amount of detergent formulation B is particularly preferably 2.0 to 20% by weight, preferably 3.0 to 18% by weight, in particular 4.0 to 15% by weight.

Another preferred component of the added detergent formulation B of the present invention is an organic solvent. Preferred organic solvents are from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvent is ethanol, n- or i -propanol, butanol, glycol, propane diol or butane diol, glycerin, diglycol, propyl diglycol or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono- n -butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl-, -ethyl- or -propyl ether, dipropylene glycol methyl-, or From ethyl ether, methoxy-, ethoxy- or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t -butyl ether and mixtures of these solvents Is selected. The weight fraction of these organic solvents in the total weight of cleaning formulation B of the invention is advantageously from 5 to 80% by weight, preferably from 8 to 60% by weight, in particular from 10 to 50% by weight.

Organic solvents which are particularly preferred and particularly effective in terms of stabilization of the cleaning formulation are 1,2-propylene glycol. The weight fraction of 1,2-propylene glycol relative to the total weight of detergent formulation B according to the present invention may vary to a wide extent, but these formulations comprise an organic solvent, preferably 1,2-propylene glycol. Proved to be particularly stable, wherein the weight fraction of 1,2-propylene glycol is advantageously from 5 to 80% by weight, preferably from 8 to 60% by weight and in particular from 10 to 50% by weight relative to the total weight of the detergent formulation, respectively. .

Compositions of some preferred liquid detergent formulations according to the invention can be shown in Table 2 below.

[Table 2]

* Copolymers of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid

** 1,2-propylene glycol

Thus, another subject matter of this application is a detergent formulation containing:

a) detergent formulation A of the present invention;

c) detergent formulation C comprising:

  c1) at least one nonionic surfactant,

  c2) water.

The rinsing performance achieved can be improved by adding surfactant-containing detergent formulation C. This is particularly true for preferred process variants, where detergent formulations A, B and C are administered at different time points.

Further preferred components of the detergent formulation C of the present invention are finally nonionic surfactants of the general formula:

R ¹ -CH (OH) CH ₂ O- (AO) _w- (A'O) _x- (A "O) _y- (A '" O) _z -R ² ,

[Wherein,

R ¹ represents a straight or branched, saturated or mono or polyunsaturated C _{6 -24} alkyl or alkenyl group;

R ² represents a linear or branched hydrocarbon group (2-26 carbon atoms);

-A, A ', A "and A'" are independently of each other the groups -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ Group from —CH ₂ , —CH ₂ —CH (CH ₃ ) —CH ₂ —, —CH ₂ —CH (CH ₂ —CH ₃ );

w, x, y and z represent values from 0.5 to 120, wherein x, y and / or z may be zero.

The above-mentioned nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w- (A'O) _x- (A "O) _y- (A '" O) _z -R ² By addition of (also referred to hereinafter as "hydroxy mixed ether"), the cleaning power of the enzyme-containing formulation is compared to a system comprising a surfactant-free system and an alternative nonionic surfactant (e.g., For example from the group of polyalkoxylated fatty alcohols).

The stability of the enzymes contained in the detergents or detergent formulations according to the invention can be significantly improved by using these nonionic surfactants having at least one free hydroxyl group on one or both terminal alkyl groups.

Especially preferred are end-capped polyalkoxylated nonionic surfactants according to formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , which are linear or branched, saturated or unsaturated, aliphatic or In addition to having residues R ¹ representing an aromatic hydrocarbon group (2 to 30 carbon atoms, preferably 4 to 22 carbon atoms), it is also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R ² (1 to 30 carbon atoms). ), Wherein x has a value from 1 to 90, preferably a value from 30 to 80, in particular a value from 30 to 60.

Especially preferred are surfactants of the formula:

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ²

[Wherein,

R ¹ represents a linear or branched aliphatic hydrocarbon residue (4-18 carbon atoms) or mixtures thereof,

R ² represents a linear or branched hydrocarbon residue (2-26 carbon atoms) or a mixture thereof,

x represents a value of 0.5 to 1.5,

y represents a value of at least 15].

Group of non-ionic surfactants, for example, C _{2 -26} fatty alcohols _{(PO) 1 - (EO)} 15-40 -2- hydroxyalkyl ether, in particular, also C _{8 -10} fatty alcohols (PO) ₁ - (EO ) and a _{22-hydroxy-2-decyl} ether.

Also particularly preferred are end-capped poly (alkoxylated) nonionic surfactants of the formula:

R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ²

[Wherein,

R ¹ and R ² independently of one another represent a linear or branched, saturated or mono- and / or polyunsaturated hydrocarbon residue (2 to 26 carbon atoms),

R ³ is independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , preferably -CH ₃ ,

x and y represent a value from 1 to 32 independently of each other.

Most particularly preferred are nonionic surfactants wherein R ³ = -CH ₃ , the value for x is 15 to 32, and the y value is 0.5 to 1.5.

Also preferred and suitable nonionic surfactants are end-shielded poly (alkoxylated) nonionic surfactants of the formula:

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² ,

[Wherein,

R ¹ and R ² represent a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue (1 to 30 carbon atoms),

R ³ represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue,

x represents a value from 1 to 30,

k and j represent values of 1 to 12, preferably 1 to 5;

When the x value is 2 or more, any of R ³ in the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues (from 6 to 22 carbon atoms), with groups having from 8 to 18 carbon atoms being particularly preferred. With respect to the residue R ³ , H, —CH ₃ or —CH ₂ CH ₃ are particularly preferred. Particularly preferred values for x are 1-20, in particular 6-15.

As described above, each R ³ in the formula given above may be different (when x is 2 or more). The alkylene oxide units in parentheses may vary in this way. For example, when x represents 3, the R ³ residues may be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units, which are in sequence to each other (E.g., (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO ) (PO) (EO) and (PO) (PO) (PO)). A value 3 for x has been chosen as an example and a larger number can be easier, with increasing range of variables as the value of x increases and, for example, multiple (EO) groups or inverses thereof combined with a small number of (PO) groups. It includes.

Particularly preferred end-capped poly (alkoxylated) alcohols of the formula given above have values of k = 1 and j = 1 where the formula R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH Simplified to CH ₂ OR ² . In this formula, R ¹ , R ² and R ³ are as defined above and x represents a number from 1 to 30, preferably from 1 to 20, in particular from 6 to 18. Particularly preferred surfactants are those in which the residues R ¹ and R ² have 9 to 14 carbon atoms, R ³ represents H and x is a value from 6 to 15.

Finally, nonionic surfactants of the general formula below proved to be particularly effective:

R ¹ -CH (OH) CH ₂ O- (AO) _w -R ²

[Wherein,

R ¹ represents a linear or branched, saturated or mono- and / or polyunsaturated C _{6 -24} alkyl or alkenyl group;

R ² represents a linear or branched hydrocarbon group (2-20 carbon atoms);

A represents a residue from the group CH ₂ CH ₂ , —CH ₂ CH ₂ —CH ₂ , —CH ₂ —CH (CH ₃ ) group;

w represents a value from 10 to 120, preferably from 10 to 80, in particular from 20 to 40;

For example, C _{4 -22} fatty alcohols (EO) _10-80 -2- hydroxyalkyl ether, in particular, also C _{8 -12} fatty alcohol (EO) ₂₂ -2- _{hydroxy-4-decyl} ether, and C _-22 fatty alcohols -(EO) _40-80-2 -hydroxyalkyl ether belongs to this group of nonionic surfactants.

The weight fraction of the nonionic surfactant in the total weight of detergent formulation C is advantageously from 2.0 to 25% by weight, preferably from 5.0 to 20% by weight, in particular from 7.0 to 15% by weight.

In addition to or alternatively to nonionic surfactants, the detergent formulation C of the present invention preferably comprises one or more acidifying agents.

Acidifying agents may be added to the detergent formulation C of the present invention to lower the pH of the wash liquor in the rinse cycle. Inorganic acids and organic acids are available as acidifying agents as long as they are compatible with the other components. For reasons of consumer protection and handling safety, solid mono, oligo and polycarboxylic acids are particularly suitable. Within this group, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are also preferred. Organic sulfonic acids such as amidosulfonic acid may also be used. A mixture of Sokalan® DCS (trade name: BASF), succinic acid (up to 31 wt.%), Glutaric acid (up to 50 wt.%) And adipic acid (up to 33 wt.%) Are commercially available and acidic in the context of the present invention. It can be advantageously used as a topical agent. Based on the total weight of the detergent formulation C, at least one acidifying agent, preferably mono, oligo and polycarboxylic acids, particularly preferably tartaric acid, succinic acid malonic acid, adipic acid, maleic acid, particularly preferably tartaric acid , From 0.1 to 8% by weight, preferably from 0.2 to 6.0% by weight, in particular from 0.4 to 5.0% by weight of succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid, in particular acetic acid and / or citric acid Detergent preparation C comprising a is a preferred embodiment of the present invention.

Some preferred compositions of liquid detergent formulations according to the present invention can be shown in Table 3 below.

[Table 3]

* Copolymers of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid

Detergent formulations comprising: are additional subject matter of the present invention:

a) detergent formulation A of the present invention;

d) detergent formulation D comprising:

  d1) one or more oxygen bleaches,

  d2) water.

Cleanser Formulation D includes at least one oxygen bleach as an essential ingredient. Of the compounds that act as bleach and generate H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Examples of further bleaches that can be used are peroxypyrophosphate, citrate perhydrate and H ₂ O ₂ -generating peracid salts or peracids such as perbenzoate, peroxyphthalate, diperoxyazelaic acid, phthaloimino peracid or Diperoxydodecanedioic acid. In a preferred embodiment, imido peroxycarboxylic acids, in particular phthalimido peroxycarboxylic acids, and above all phthalimido peroxyhexanoic acid (PAP), are used as peracids. Furthermore, bleaches from the group of organic bleaches can be used. Typical organic bleaches are diacyl peroxides such as for example dibenzoyl peroxide. Further typical organic bleaches are peroxy acids, with alkylperoxy acids and arylperoxy acids as examples. Further preferred bleaches are the salts of peroxy monosulfate and peroxy disulfate, in particular the sodium, potassium and ammonium salts of these anions.

Bleach is selected from hydrogen peroxide, peroxy monosulfate salt, peroxy disulfate salt and PAP is particularly preferred. Very particularly preferred bleach is hydrogen peroxide. The weight fraction of the bleach, in particular hydrogen peroxide, the peroxy monosulfate salt, the peroxy disulfate salt and / or the weight fraction of PAP, is from 0.1 to 50% by weight, preferably from 0.2 to 35% by weight, relative to the total weight of the detergent formulation D. Particularly preferred according to the invention are automatic dishwashing processes and automatic fabric washing processes which are particularly preferably 0.5 to 20% by weight, in particular 1.0 to 10% by weight. Very particular preference is given to the use of an aqueous hydrogen peroxide solution as detergent preparation D.

In a preferred embodiment, the oxygen bleach-containing detergent preparation D is stabilized by adding tin compounds, phosphates, di or triphosphates, phosphonates or radical scavengers.

Preferred detergent formulations D, based on their total weight, comprise from 10 ppm to 1.0 wt%, preferably from 20 ppm to 1000 ppm (0.1 wt%), in particular from 50 ppm to 500 ppm of stabilizer (from stannate group) do. Such stannates can be prepared in situ by hydrolyzing tin compounds, for example tin sulphate, sodium stannate (Na ₂ SnO ₃ 3H ₂ O), tin dichloride or tin tetrachloride. Stanate stabilizers are referred to as colloidal sodium stannate or sodium stannate, but are accepted as colloidal tin oxide.

In addition to or alternatively to stannates, the preferred detergent formulation D comprises one or more stabilizers from the phosphonate group. In this regard, complex phosphonates of the following additional list are particularly suitable, wherein 1-hydroxyethane-1,1-diphosphonate (HEDP), aminotrimethylene phosphonic acid (ATMP) and diethylenetriamine pentamethylene phosphate Phonates (DTPMP) are preferred.

In addition to or alternatively to stannates and phosphonates, preferred detergent formulations D comprise one or more stabilizers from the phosphate group, preferably pyrophosphates such as Na ₄ P ₂ O ₇ , Na ₃ HP ₂ O ₇ , Na ₂ H ₂ P ₂ O ₇ And K ₂ H ₂ P ₂ O ₇ .

Some preferred compositions of liquid detergent formulations according to the invention can be shown in Table 4:

[Table 4]

* Copolymers of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid

The detergent formulations A, B, C and D described above are different in terms of their composition and are therefore not identical.

Preferred detergent formulations A, B, C and D of the present invention comprise less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 2% by weight of phosphate. Phosphate-free detergent formulations A, B, C and D are very particularly preferred in the present invention. Also preferred are detergent formulations A, B, C and D of the invention comprising less than 2% by weight, preferably less than 1% by weight, in particular less than 0.5% by weight of silicates. Lowering both the phosphate content and the silicate content has proven advantageous for the stability of the automatic dishwasher detergent of the present invention.

As mentioned in the introduction, the detergent formulations described above are particularly suitable for automatic dishwashing. Thus, an automatic dishwashing process comprising the detergent formulation A of the present invention is another subject matter herein.

Surprisingly, detergent formulation A of the present invention exhibits high temperature stability. This is especially true for liquid detergent formulation A. Thus, the detergent formulations of the present invention and the detergent combinations of the present invention are particularly suitable for multi-administration from the dosing vessel located inside the automatic dishwasher to the cleaning liquid. These dosing containers can be located inside the automatic dishwasher without any mechanical connection to the automatic dishwasher or can be integrated into the automatic dishwasher. In the course of a plurality of sequential cleaning steps, the detergent portions are metered automatically or semi-automatically into the interior of the automatic dishwasher by these devices containing multiple doses of detergent required to carry out the cleaning process.

Independently of the precise design of the metering device incorporated into the automatic dishwasher, the cleaners included in these multi-dose devices are treated at various temperatures over an extended time point, where these temperatures are used to perform the cleaning process. Approximately equal to the water temperature. These temperatures can be up to 95 ° C, with automatic dishwashing temperatures usually maintained at 50 to 75 ° C. During the multiple cleaning process, the detergents included in the device intended for multiple administration will thus be heated repeatedly at temperatures significantly above those typical for transport and storage.

Preferred processes for dish washing include metering the liquid detergent formulation into the automatic dishwasher from a reservoir located in the automatic dishwasher, which includes multiple amounts of detergent or detergent formulation needed to perform the cleaning process.

As described in the introduction, the reservoir used for weighing may be a reservoir which is integrated into an automatic dishwasher, i.e. a reservoir permanently fixed (built-in) in the automatic dishwasher, but which is to be inserted into an independent storage, ie the interior of the automatic dishwasher. It can be an independent repository.

An example of an integrated reservoir is a receptacle that is integrated into the door of an automatic dishwasher and is connected to the inside of the automatic dishwasher by a supply line.

An example of a self-contained reservoir is a so-called "top-down bottle" with a basic outlet valve, which can be placed in the cutlery basket of an automatic dishwasher.

The reservoir comprises at least one chamber for containing a liquid detergent or detergent formulation according to the invention. In a preferred embodiment, the reservoir treats more than one, preferably two, three, four or more, separate chambers, one or more of which comprise a liquid detergent formulation according to the invention, whereas one or more, preferably Preferably at least two further chambers comprise a liquid formulation having a composition different from the liquid detergent formulation according to the invention.

In particular, these processes according to the invention particularly preferably use a reservoir having two separate chambers separated from one another, one of which comprises a liquid detergent formulation according to the invention, while the second chamber Liquid formulations of different compositions.

In a preferred cleaning process, the liquid detergent according to the invention in an amount of 1.0 to 15 ml, preferably 2.0 to 12 ml, in particular 4.0 to 10 ml, is metered into the automatic dishwasher per wash cycle.

The volume of the preferred reservoir having one or more chambers is 10 to 1000 ml, preferably 20 to 800 ml, in particular 50 to 500 ml.

As described above, the detergent formulations according to the invention are particularly characterized by temperature stability and are especially used in the process according to the invention for the repeated metering of these formulations from reservoirs located inside the automatic dishwasher. Preferred processes according to the invention are two or more, preferably four or more, particularly preferably eight or more separate cleaning processes in a reservoir located in an automatic dishwasher, prior to being metered into the interior of the automatic dishwasher. One or more, in particular 12 or more times.

In the context of the present application, a "separated cleaning process" is a so-called completed cleaning process that preferably includes a preliminary rinse cycle and / or a final rinse cycle in addition to the main cleaning cycle, which can be operated and selected in the program conversion manner of an automatic dishwasher. These separation cleaning process durations are advantageously at least 15 minutes, advantageously 20 to 360 minutes, preferably 30 to 240 minutes.

The length of time between the two separate cleaning processes, in which the liquid detergent or detergent formulation is metered into the interior of the automatic dishwasher, is at least 20 minutes, preferably at least 60 minutes, particularly preferably at least 120 minutes.

The exposure of the liquid detergent or detergent formulation according to the invention to a high temperature can vary widely during the process according to the invention, wherein the liquid detergent or detergent formulation comprises at least two liquid detergents or detergent formulations A in the reservoir, It is particularly suitable for these processes which are preferably heated to a temperature of at least 4 times, particularly preferably at least 8 times, in particular at least 12 times above 30 ° C., preferably above 40 ° C., particularly preferably above 50 ° C. Naturally, heating the liquid detergent or detergent formulation A to a temperature above 60 ° C. or above 70 ° C. or heating it 20 or 30 times can be realized according to the invention.

That is, the liquid detergent formulation A in the reservoir is heated by the washing liquid surrounding this reservoir in each subsequent separate cleaning process. In a preferred process, the liquid detergent formulation A in the reservoir is cooled to a temperature below 30 ° C., preferably below 26 ° C., in particular below 22 ° C. between the separate cleaning processes.

The above-described combination of detergents is configured in the form of a receiving chamber separate from each other, each of which contains one of the formulated cleaning agents. Examples of such configurations are cartridges having two, three, four or more separate receiving chambers, for example two, three, four or multi-chamber bottles. Unwanted reactions due to chemical incompatibility can be ruled out by separating detergents of different composition.

In addition, the subject matter of the present application is a detergent presenting form comprising:

a) an amount of at least two, preferably four or more, in particular eight or more, amounts of sufficient amount to carry out the automatic dishwasher process, preferably liquid detergent formulation A of the present invention;

b) Cartridge for Cleanser Formula A.

A further subject matter herein is a detergent presenting form comprising:

a) an amount of the detergent formulation A of the present invention sufficient to carry out the automatic dishwasher process at least twice, preferably at least four times, in particular at least eight times;

b) at least one further cleaning agent or detergent formulation B different from A, in an amount sufficient to carry out the automatic dishwasher process at least twice, preferably at least four, in particular at least eight;

c) Cartridge for detergent or detergent formulations A and B, A and C or A and D, wherein the detergent formulations A and B, A and C or A and D are in separate receiving chambers.

Also claimed is a detergent presentation form comprising:

a) an amount of the detergent formulation A of the present invention sufficient to carry out the automatic dishwasher process at least twice, preferably at least four times, in particular at least eight times;

b) at least one additional detergent or detergent formulation B different from A, in an amount sufficient to carry out the automatic dishwasher process at least twice, preferably at least four, in particular at least eight;

c) one or more additional detergent formulations C or D, different from A and B, in an amount sufficient to carry out the automatic dishwasher process at least two times, preferably at least four times, in particular at least eight times;

d) Cartridges for detergent formulations A, B and C or A, B and D, wherein cartridge detergent or detergent formulations A, B and C or A, B and D are present in a separate receiving chamber.

The detergent formulation of the present invention is metered by a special metering system. In a preferred embodiment, the cartridge described above in the form of a detergent present is provided as a metering device which can be detached from the cartridge. This type of metering device can be connected to the cartridge by, for example, an attachment engagement, a lock connection, a snap-in connection or a push-fit connection. The cartridge can be easily filled, for example by separating the cartridge from the metering device.

Alternatively, the removable connection of the cartridge from the metering device allows the cartridge to be exchanged on the metering device. Such an exchange can be indicated, for example, when the cleaning process is changed or when the cartridge is completely empty.

Another subject matter of the present application is a detergent metering system comprising:

a) an amount of at least two, preferably four or more, in particular eight or more, amounts of sufficient amount to carry out the automatic dishwasher process, preferably liquid detergent formulation A of the present invention;

b) cartridge for detergent formulation A;

c) a weighing unit that can be connected or connectable to a cartridge.

The cartridge and metering device are preferably detachably connected to one another, but can also be permanently connected to one another.

Of course, the corresponding detergent metering system may include additional detergent formulations in addition to detergent formulation A.

Another subject matter of the present application is a detergent metering system comprising:

a) an amount of at least two, preferably four or more, in particular eight or more, amounts of sufficient amount to carry out the automatic dishwasher process, preferably liquid detergent formulation A of the present invention;

b) at least one further preferably liquid detergent formulation B, C or D, different from A, in an amount sufficient to carry out the automatic dishwasher process at least twice, preferably at least four, in particular at least eight;

c) Cartridge for detergent formulations A and B, A and C or A and D, wherein the detergent formulations A and B, A and C or A and D are present in a separate receiving chamber.

d) a metering unit releasably or non-releasably connected to the cartridge.

A particularly preferred subject of the present application is a detergent metering system comprising:

a) an amount of at least two, preferably four or more, in particular eight or more, amounts of sufficient amount to carry out the automatic dishwasher process, preferably liquid detergent formulation A of the present invention;

b) at least one further preferably liquid detergent formulation B different from A in an amount sufficient to carry out the automatic dishwasher process at least twice, preferably at least four, in particular at least eight;

c) at least one further preferably liquid detergent formulation C or D, different from A and B, in an amount sufficient to carry out the automatic dishwasher process at least twice, preferably at least four times, in particular at least eight times;

d) cartridges for detergent formulations A, B and C or A, B and D, wherein the detergent formulations A, B and C or A, B and D cartridges are present in a separate receiving chamber;

e) metering unit releasably or non-releasably connected to the cartridge.

In a preferred embodiment, the above-mentioned comprises a cleaning agent of the invention (and optionally one or two further cleaning agents different from the cleaning agent of the invention), a cartridge and a metering device releasably or non-releasably connected to the cartridge. The detergent metering system is particularly preferably included separately in the packaging unit. Packaging units are used for storage, transportation, and the detergent presenting form of the present invention and protect it from stains, impacts and debris.

The packaging unit must in particular be designed to be at least partially transparent in order to be presented.

Alternatively or in addition to the packaging unit, there is naturally a possibility to commercialize the detergent, detergent formulation or detergent presentation form of the present invention with an automatic dishwasher. This type of formulation is particularly advantageous in these cases, where the cycle of the automatic dishwasher (eg, persistence, temperature cycle, water supply) and the control electronics of the detergent formulation or dosing device are matched with each other.

 The metering system of the present invention consists of a basic component of a cartridge which is filled with a detergent of the present invention and a dosage device connectable to the cartridge, the metering device comprising a group of additional components, for example a component support, an actuator, a closing element, a sensor, It is formed again from the energy source and / or the control unit.

The metering system of the present invention is preferably movable. In the present context, “movable” means that the dosing system is not detachably-connected with a water-conducting device such as, for example, an automatic dishwasher, a washing machine, a washer dryer, etc., but rather can be removed from the automatic dishwasher by the consumer. Or automatic dishwasher, that is, independently manageable.

According to an alternative development of the invention, it is also contemplated that for the consumer the dosing device can be releasably connected with water-conducting devices such as, for example, automatic dishwashers, washing machines, washer dryers and the like and only the cartridge can be removed. Can be.

Since the pH of the formulation to be administered may be between 2 and 12 depending on the intended use, all components of the administration system in contact with the formulation must be approximately resistant to acids and alkalis. Moreover, by selecting suitable materials, these components should be as chemically inert as possible, for example to nonionic surfactants, enzymes and / or flavors.

cartridge

In the context of the present application, the term "cartridge" is understood to mean a package suitable for enclosing or holding with a free-flowing or dispersible formulation, which may be coupled with an administration device for dispersing the formulation.

In particular, the cartridge may also comprise a plurality of chambers which may be filled independently of the different agents and from one another. Also, a plurality of containers assembled into one cartridge unit may be considered.

Advantageously the cartridge comprises one or more outlets arranged to allow the product to be released by gravity from the container in the operating state of the administration system. This ensures a further mode of transport without the need for product to be released from the container, as a result of which the dosing device can be simplified and the cost of production can be lowered.

In a preferred development of the invention, there is provided at least a second chamber containing at least one second free-flowing or dispersible product, wherein the second chamber is gravity released from the second chamber by the product during the operating state of the dosing device. And at least one outlet arranged so that it can be arranged. The design of the second container is then particularly advantageous when the formulations stored in independent containers are usually stored in unstable, for example with bleach and enzymes.

Moreover, it can be contemplated that more than two, in particular three to four chambers, are provided on or in one cartridge. In particular, one of the chambers can be designed to disperse volatile agents, for example perfumes.

In a further development of the invention, the cartridge is essentially formed. In this way, the cartridge can be produced in a cost-effective manner by one manufacturing step, in particular by a suitable blow molding process. In this regard, the chambers of the cartridge may be separated from each other by cross-linking of partition walls or materials.

The cartridge may also be formed sequentially from the assembled components and produced in a multipiece design by injection molding.

In addition, a cartridge may be considered that is formed in a multi-piece design such that one or more chambers, preferably all chambers, may be individually removed from or inserted into the administration device. In this way, when consuming differently high levels of preparation from one chamber, it is possible to exchange an already empty chamber, while those which still contain the preparation remain in the administration device. Thus, individual chambers or their formulations may be selected and refilled as needed.

잠금장치, 압력-붙박이 조립물, 융합된 조인트, 접착 조인트, 용접 이음, 납땜 이음, 나사 연결, 키 조인트, 클램프 조인트 또는 압력 스터드 연결의 군으로부터 선택되는 연결형 하나 이상에 의해 제조될 수 있다. 특히, 연결은 또한 가열된 상태 일부 이상이 카트리지에 걸쳐 당겨져 줄어든 쉬링크 슬리브 방식으로 형성될 수 있고 강하게 냉각될 때 챔버 또는 카트리지를 둘러쌀 수 있다.The chambers of the cartridges can be bundled together in a suitable connection manner, thereby forming a container unit. The chambers may be detachably or non-removably fixed to one another in the manner of occlusal, occlusal friction and / or material mating connections. Especially the connection, snap-in connection, Velcro

It can be produced by one or more connected types selected from the group of locks, pressure-built assemblies, fused joints, adhesive joints, weld joints, solder joints, screw connections, key joints, clamp joints or pressure stud connections. In particular, the connection may also be formed in a shrink sleeve manner in which at least a portion of the heated state is pulled over the cartridge and may surround the chamber or cartridge when strongly cooled.

Advantageously, the bottom of the chamber may be in the form of a funnel that is inclined toward the outlet to provide a feature that the residue of the chamber is empty. In addition, by selecting suitable material and / or surface features, the inner wall of the chamber can be made such that the product exhibits low material adhesion into the chamber wall. This technique also optimizes emptying of remaining product from the chamber.

The chambers can have the same or different filling volumes. The ratio of container volumes in the two container arrangements is preferably 5: 1 and in the three container arrangements is preferably 4: 1: 1, these arrangements being particularly suitable for use in automatic dishwashers.

As mentioned above, the cartridge preferably has three chambers. When this type of cartridge is used in an automatic dishwasher, the first chamber containing the alkaline detergent formulation is particularly preferred, the second chamber contains the enzyme formulation and the third chamber contains the rinse aid, wherein the volume of the chamber The ratio is for example 4: 1: 1.

The metering chamber may be designed on or in one chamber in the direction of flow of the formulation prior to the outlet. Chamber metering is defined as the amount of agent intended to be released from the chamber to the environment. This is particularly advantageous if the closed part of the metering device, which affects the discharge of the formulation from the chamber to the surroundings, can be moved to the discharge and closing point without control of the discharge. The metering chamber then provides the desired amount of formulation to be released without direct feedback of the desired amount of dispersed formulation. The dosing chamber may be formed completely or in a plurality of parts.

According to another advantageous further development of the invention, the one or more chambers each have a liquid-dense, closeable chamber opening in addition to the outlet port. Such chamber openings allow the formulation to be filled, for example, in such chambers.

Ventilation schemes may be provided for cartridge chamber ventilation to ensure pressure equilibrium between the interior and the surroundings of the cartridge chamber, particularly as the level of filling in the chamber at the top of the cartridge is reduced. These ventilation schemes can be designed with micro-openings, for example in valves, in particular silicone valves, cartridge walls and the like.

According to another development, the contents of the chamber are not intended to be directly ventilated in the cartridge chamber and to provide ventilation through the dosing device or to provide no ventilation at all, for example by using a fluid container such as a pouch. While pressure will be generated at increased temperatures during the cleaning cycle of the automatic dishwasher, the pressure has the advantage of applying pressure to the formulation administered directly to the outlet opening, so that the cartridge can in this way Can be easily emptied. In addition, with this type of air-free packaging, there is no risk of any oxidation of the material in the formulation, thereby providing a pouch packaging or advantageously removing the bag from a suitable, particularly oxidizing, bottle packaging of the formulation. To manufacture.

The cartridge usually has a filling volume (dose) of less than 5000 ml, in particular less than 1000 ml, preferably less than 500 ml, particularly preferably less than 250 ml, quite particularly preferably less than 50 ml.

The cartridge may be in any form. For example, it may be in the form of a cube, sphere or disc.

Cartridge forms and dosing devices can be designed, in particular, in automatic dishwashers so that they take as little useful volume as possible.

For use of the dosing device in an automatic dishwasher, it is particularly advantageous to shape the dosing device with the function that the dishes are cleaned in the automatic dishwasher. Thus, the metering device can be designed, for example, in the form of a disc on an approximate plate. In this way, the dosing device can be located in a space-saving manner, for example on the lowest shelf of the dishwasher. Moreover, due to the plate-like form, the consumer can intuitively know the position of the weighing unit correctly. The dimensions of the cartridge are preferably in the ratio of height: width: depth 5: 5: 1 to 50: 50: 1, particularly preferably 10: 10: 1. In particular, the "slim" design of the cartridge and the dispensing device allows it to be positioned lower in the tray basket of the automatic dishwasher to maintain the fixation provided for the plates. This has the advantage that the formulation dispersed from the administration device cannot reach the wash liquid directly and attach to other articles to be washed.

Commercially available domestic automatic dishwashers are designed so that larger items to be cleaned, such as pans or dishes, are placed on the lower shelves of the dishwasher. In order to avoid placing the dosing system on the upper shelf rather than the optimal position, the weighing system is sized so that it can only be placed on the retaining fixture provided on the lower shelf. With this in mind, the width and height of the administration system can be chosen in particular from 150 mm to 300 mm, particularly preferably from 175 mm to 250 mm.

However, it is also conceivable to design the weighing unit in the form of a ball having essentially a circular or rectangular base.

In order to protect the thermally sensitive formulation of the formulation in the cartridge against heat, the cartridge is advantageously made from a material having low thermal conductivity.

Another possibility to reduce the heat acting on the formulation in the chamber of the cartridge is to insulate the chamber in a suitable manner by using an insulating material such as, for example, Styropor, which completely or partially suitably surrounds the cartridge or chamber. It is to let.

In a preferred embodiment of the invention, the cartridge has at least an RFID tag with information about the contents of the cartridge, which can be read by the sensing unit.

This information can be used to select the dosing program stored in the control unit. This ensures that a dosing program optimized for a particular formulation is always used. In the absence of an RFID-label or in the presence of an RFID-label where false or inaccurate is perceived, the dosing device is not administered but instead emits an optical or acoustic signal informing the consumer of the error.

To rule out any misuse of the cartridges, they may also comprise structural elements which cooperate in accordance with the lock-key principle with the corresponding elements of the metering device, for example so that only certain types of cartridges can be coupled with the metering device. . Moreover, this design ensures that information about the cartridge is coupled with the metering device and the dosing device in communication with the control unit, thereby enabling cooperative control of the dosing device according to the contents of the corresponding container.

The cartridge is especially designed to contain a freely moving detergent or detergent. It is particularly preferred that this type of cartridge comprises a plurality of chambers for the spatial separation of each of the detergents or different formulations of detergents.

The cartridge may be designed to be fixedly or releasably arranged on or in the automatic dishwasher.

Weighing device

The control unit, the sensing unit and one or more actuators required for operation are integrated in the weighing station. Likewise, the energy source is preferably located in the metering device.

The metering device is preferably composed of a housing which prevents water drops from entering the interior of the metering device and which is impervious to the water drops, which can occur, for example, which may occur when the metering device according to the invention is used in an automatic dishwasher. .

The metering device interacts with a corresponding connector located on or in the water supply device, in particular a household appliance, preferably an automatic dishwasher or washing machine, to which water is supplied, so that the movement of electrical energy from the water supply device to the dosing unit is recognized. It is particularly preferred to include at least one of the first connectors that act.

In one development of the invention, the connector is formed by a plug-in connector. In another development, the connector can be designed to allow electrical energy to move wirelessly.

In a further advantageous development of the invention, the second connector is especially for the movement of electromagnetic signals which display information on the operating state, metering and / or control of water-supply devices and / or dispensing devices, such as automatic dishwashers, For example, in a water-supply device such as an automatic dishwasher and in a dispensing device.

adapter

Simple coupling of the household device to the dosing device, which is supplied with water, can be achieved by means of an adapter. The adapter provides the mechanical and / or electrical connection of the dosing system to the household appliance supplied with the water.

The adapter is preferably fixedly connected to the water supply pipe of the household appliance. However, it is also conceivable to provide an adapter located on or within the household appliance, wherein the adapter is protected from water jets and / or spray jets of the household appliance.

The adapter enables the administration system to be designed in a self-containing version and a "built-in" version. It is also possible to design the adapter as a filling station type for the metering system, for example where the energy source of the metering device is recharged or data is exchanged between the dosing device and the adapter.

The adapter may be located in an automatic dishwasher, on one of the inner walls of the cleaning chamber, in particular on the inner side of the automatic washer door. However, it may be contemplated to place the adapter in a place that is inaccessible to the consumer in a household device that is supplied with water so that the dosing device is inserted into the adapter, for example during assembly of the household appliance, where the adapter, dosing device and household The device is designed to enable the consumer to couple the cartridge to the dosing device.

The detergent, detergent formulation or detergent presentation form of the invention is suitable for use in dish washing, because the detergent formulation of the invention, the detergent formulation of the invention or the detergent presentation form of the invention is used for washing dishes in an automatic dishwasher process. Because it is used.

As mentioned in the introduction, the cleaning agents of the invention are characterized by physical and chemical stability, in particular against temperature fluctuations. Thus, the cleaning agents of the present invention are exceptionally suitable for weighing by means of a metering system located inside a washing machine or automatic dishwasher. Such a metering system can be fixedly integrated inside a washing machine or automatic dishwasher (injection device integrated into the machine) but can also be inserted internally as a movable device (self-containing dosing device) and to carry out an automatic cleaning process. Multiple amounts of detergent required.

In the context of the present application, “movable” is not inseparably connected to devices such as, for example, automatic dishwashers, washing machines, washing machine dryers, etc. but can be removed from the automatic dishwasher or located in the automatic dishwasher, for example. Decentralized system and weighing system.

In order to carry out the automatic dishwasher process two or more times, preferably four or more times, in particular eight or more times,

i) a cartridge of the weighing system fixedly integrated inside the automatic dishwasher, or

ii) a removable cartridge of a dispensing system that can be placed inside an automatic dishwasher

The use of a detergent or detergent formulation of the invention or a detergent formulation of the invention for filling in a sufficient amount of such detergent or detergent formulation is likewise a subject matter herein.

An example of a removable cartridge is a container that is movably integrated into the interior of an automatic dishwasher, for example into the inner packaging of a door or into a side wall.

An example of a removable cartridge is a container that remains there and completes the cycle of the cleaning step and is inserted into the interior of the automatic dishwasher by the consumer. For example, such a cartridge can be integrated inside by simply placing it on a cutlery shelf or a dishware shelf and can also be removed from the interior of the automatic dishwasher again by the consumer.

The detergent or detergent formulation is administered from the cartridge into the interior of the automatic dishwasher, as described above, and preferably in the manner of a metering device that can be detached from the cartridge. This type of metering device can be connected to the cartridge by an adhesive bond, a lock connection, a snap-in connection or a push-fit connection. Of course, cartridges having a detachably connected dosing device may also be used.

Also,

i) a metering device fixedly integrated within the automatic dishwasher, or

ii) a movable dispensing device designed to be located inside an automatic dishwasher

As a detergent reservoir for

a) a sufficient amount of the detergent or detergent formulation A of the present invention for carrying out two or more, preferably four or more, in particular eight or more, automatic dishwasher processes;

b) cartridge for cleaner or detergent formulation A;

Use of the detergent presenting form of the present invention including the subject matter of the present application.

The use of the detergent metering system of the present invention as a detergent reservoir for an automatic dishwasher is another subject matter herein.

With additional subject matter 2 of the present application,

i) a weighing unit fixedly integrated into the interior of an automatic dishwasher, or

ii) a mobile weighing unit that can be located inside the automatic dishwasher

As a detergent reservoir for

a) an amount of liquid detergent formulation A of the present invention sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes;

b) at least one further preferably liquid detergent formulation B, C or D, different from A, in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes; And

c) cartridge for detergent or detergent formulations A and B, A and C, or A and D, wherein the detergent or detergent formulations A and B are present in a separate receiving chamber

It is the use of the detergent presenting form of this invention containing a.

Also, what is charged

i) a weighing unit fixedly integrated into the interior of an automatic dishwasher, or

ii) a mobile weighing device that can be located inside the automatic dishwasher

As a detergent reservoir for

a) in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes of the present invention, preferably liquid detergent formulation A;

b) at least one further preferably liquid detergent formulation B, different from wh, in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes;

c) at least one further preferably liquid detergent formulation C or D, different from A and B, in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes; And

d) cartridges for detergent formulations A, B and C, or A, B and D, wherein cartridge detergent formulations A, B and C, or A, B and D are present in a separate receiving chamber

It is the use of the detergent presenting form of this invention containing a.

The detergents and detergent combinations, detergent presentation forms and detergent metering systems of the present invention are preferably used as automatic dishwasher detergents as already mentioned.

The automatic dishwasher process of the present invention using detergent formulation A or detergent formulation or detergent presentation form or detergent metering system, in these processes, a portion of detergent or detergent A present in the cartridge present inside the automatic dishwasher. characterized in that a is metered from the cartridge into the interior of the automatic dishwasher, wherein the residual amount of detergent present in the cartridge remains at the end of the dishwashing process in the cartridge, wherein the residual amount is at least twice the amount of the portion a , Preferably at least 4 times, in particular at least 8 times.

Thus another subject matter of the present application is an automatic dishwasher process using a detergent formulation or detergent presentation form or detergent metering system of the present invention comprising detergents A, and detergents B, C or D different from A, wherein In the process, the portion a of the cleaner or cleaner A present in the cartridge located inside the automatic dishwasher and the portion b, c or d of the cleaner or cleaner B, C or D present in the cartridge are And the residual amounts of detergents A and B, C or D present in the cartridge remain until the end of the dishwashing process in the cartridge and the residual amount of detergent A is at least two times the amount of partial a, preferably Preferably at least 4 times, in particular at least 8 times, the residual amount of the detergents B, C or D is at least 2 times, preferably at least the partial amount b, c or d Crab corresponds at least 4 times, in particular at least 8 times.

Accordingly, another subject matter of this application is detergent A of the present invention; Additional cleaner B different from A; And an automatic dishwasher process using a detergent formulation of the present invention comprising a third detergent formulation C or D different from A and B, in which the detergent or cleaner A present in the cartridge located inside the automatic dishwasher. Partial amount of a; The amount b of detergent or detergent B present in the cartridge; And the portion c or d of detergent C or D in the cartridge is metered from the cartridge into the interior of the automatic dishwasher, wherein the residual amount of detergent A, B and C or D present in the cartridge is determined at the end of the dishwashing process in the cartridge. And the residual amount of detergent A corresponds to at least two times, preferably at least four times, in particular at least eight times, the amount of the portion a, and the residual amount of the cleaner B is at least two times the amount of the portion b, preferably Is at least 4 times, in particular at least 8 times, and the residual amount of detergent C or D corresponds to at least 2 times, preferably at least 4 times, in particular at least 8 times, the partial amount c or d.

When detergent formulations having two, three or more different detergents are used in the automatic dishwasher process of the present invention, different detergents are preferably administered at different times in the cleaning process.

Thus, another subject matter of this application is an automatic dishwasher process using the detergent of the invention or the detergent formulation of the invention or the detergent presentation form of the invention or the detergent metering system of the invention, wherein

a) time t1 is the time at which a portion a of the detergent or detergent formulation A of the present invention is administered into the automatic dishwasher from the cartridge present in the interior of the automatic dishwasher, wherein the residual amount of detergent A present in the cartridge is It remains in the cartridge until the end of the cleaning process and corresponds to at least 2 times, preferably at least 4 times, in particular at least 8 times, the amount of partial amount a;

b) Another time t2 (t1 ≠ t2) different from at least t1 is determined from the second cartridge in which the partial amount b of the detergent or detergent B of the present invention different from the detergent or detergent A of the present invention is present inside the automatic dishwasher. The amount of detergent present in such a cartridge will remain in the cartridge until the end of the dishwashing process, at least 2 times, preferably at least 4 times, in particular 8 Corresponds to more than twice.

Accordingly, the present application further claims an automatic dishwasher process using a detergent of the invention or a detergent formulation of the invention or a detergent presentation form of the invention or a detergent metering system of the invention, wherein

a) time t1 is the time at which a portion a of the detergent or detergent formulation A of the present invention is administered into the automatic dishwasher from the cartridge present in the interior of the automatic dishwasher, wherein the residual amount of detergent A present in the cartridge is It remains in the cartridge until the end of the cleaning process and corresponds to at least 2 times, preferably at least 4 times, in particular at least 8 times, the amount of partial amount a;

b) Another time t2 (t1 ≠ t2) different from at least t1 is determined from the second cartridge in which the partial amount b of the detergent or detergent B of the present invention different from the detergent or detergent A of the present invention is present inside the automatic dishwasher. The amount of detergent present in such a cartridge will remain in the cartridge until the end of the dishwashing process, at least 2 times, preferably at least 4 times, in particular 8 Corresponds to at least two times;

c) Another time t3 different from at least t1 and t2 (t1 ≠ t2 ≠ t3) is such that a partial amount c of the cleaning agent or cleaner C of the invention different from the cleaning agent or cleaner A of the invention and the cleaning agent or Is the time to be dispensed into the automatic dishwasher from the third cartridge present in the dishwasher, wherein the residual amount of detergent C present in the cartridge remains in the cartridge until the dishwashing process is terminated and the portion c amount of 2 At least 4 times, preferably at least 4 times, in particular at least 8 times.

In a preferred embodiment of the automated dishwasher process described above in which the time of administration of the cleaning agent and detergent formulations A and B or A, B and C is delayed, time t2 is at least 1 minute, preferably at least 2 minutes before or after time t1. , Especially 3 to 20 minutes.

Claims (10)

Detergent formulation A for automatic dishwashing comprising:
a1) 1.0 to 20 wt% ethylenediamine isuccinic acid;
a2) 1.0 to 20 weight percent phosphonate;
b) from 2.0 to 30% by weight of (meth) acrylic acid and 2-acrylamido-2-propane sulfonic acid. The detergent preparation according to claim 1, wherein the weight fraction of ethylenediamine isuccinic acid is from 2.0 to 15% by weight, preferably from 2.5 to 12% by weight, in particular from 3.0 to 10% by weight, relative to the total weight of the detergent formulation. 3. The detergent preparation according to claim 1, wherein the weight fraction of phosphonate is from 2.0 to 15% by weight, preferably from 2.5 to 12% by weight, in particular from 3.0 to 10% by weight, relative to the total weight of the detergent formulation. The weight fraction of the copolymer of (meth) acrylic acid and 2-acrylamino-2-propane sulfonic acid is from 3.0 to 26% by weight, preferably with respect to the total weight of the detergent formulation. Is 5.0 to 22% by weight, in particular 7.0 to 18% by weight. Detergent formulations comprising:
a) detergent formulation A according to any one of claims 1 to 4;
b) detergent formulation B comprising:
b1) one or more enzymes having washing and washing activity. Detergent formulations comprising:
a) detergent formulation A according to any one of claims 1 to 5;
c) detergent formulation C comprising:
c1) at least one nonionic surfactant,
c2) water. Detergent formulations comprising:
a) detergent formulation A according to any one of claims 1 to 6;
d) detergent formulation D comprising:
d1) one or more oxygen bleaches,
d2) water. Detergent presentation forms comprising:
a) a liquid detergent formulation A according to any one of claims 1 to 7 in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight, automatic dishwasher processes;
b) cartridge for detergent or detergent formulation A. Detergent dosing systems comprising:
a) liquid detergent formulation A according to any one of claims 1 to 8 in an amount sufficient to carry out at least two, preferably at least four, in particular at least eight automatic dishwasher processes;
b) a cartridge for detergent formulation A;
c) a dispensing unit releasably connected to the cartridge. An automatic dishwashing process using an automatic detergent formulation, detergent formulation, detergent presentation form or detergent administration system according to any of claims 1 to 9.