EP2414499A1 - Détergents - Google Patents

Détergents

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Publication number
EP2414499A1
EP2414499A1 EP10713611A EP10713611A EP2414499A1 EP 2414499 A1 EP2414499 A1 EP 2414499A1 EP 10713611 A EP10713611 A EP 10713611A EP 10713611 A EP10713611 A EP 10713611A EP 2414499 A1 EP2414499 A1 EP 2414499A1
Authority
EP
European Patent Office
Prior art keywords
washing
detergent
cartridge
cleaning
cleaning agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10713611A
Other languages
German (de)
English (en)
Other versions
EP2414499B1 (fr
Inventor
Arnd Kessler
Christian Nitsch
Thorsten Bastigkeit
Johannes Zipfel
Erik BRÜCKNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL10713611T priority Critical patent/PL2414499T3/pl
Publication of EP2414499A1 publication Critical patent/EP2414499A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the present application describes detergents and cleaners, in particular enzyme-containing detergents and cleaners.
  • the detergents or cleaners contained in these multidose dosing devices are exposed to varying temperatures over a relatively long period of time, these temperatures approximating those used to carry out the washing or cleaning Cleaning method used water temperatures 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 device provided for multiple dosing is repeatedly heated in the course of several washing or cleaning processes to temperatures well above the temperatures customary for transport and storage, with temperature-sensitive active substances in particular being affected. To the group of these temperature-sensitive Washing and cleaning-active substances are primarily the washing and cleaning-active enzymes.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.
  • proteases in particular serine proteases, to which the subtilases according to the invention are also calculated, are used for degrading proteinaceous soils on the items to be cleaned.
  • subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum.
  • ⁇ -amylases are in particular widespread from the enzyme class of the amylases, ⁇ -amylases (E.C. 3.2.1.1) hydrolyze internal ⁇ -1, 4-glycosidic bonds of starch and starch-like polymers.
  • Detergents and cleaning enzymes are formulated in both solid and liquid form.
  • the group of solid enzyme preparations includes, in particular, the enzyme granules consisting of several ingredients, which in turn are preferably incorporated into solid detergents and cleaners.
  • liquid or gel detergents and cleaners often contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.
  • German patent application DE 2 038 103 (Henkel) teaches the stabilization of enzyme-containing dishwashing detergents by saccharides, while in European patent EP 646 170 B1 (Procter & Gamble) propylene glycol is disclosed for enzyme stabilization in liquid detergents.
  • the object of the present application was accordingly in the stabilization of a washing- or cleaning-active enzyme preparation against phase separation / loss of activity at multiple temperature fluctuations, in particular in a temperature range of 10 to 75 0 C.
  • Corresponding enzyme preparations should significant in a located in the interior of the dishwasher or washing machine storage device without Loss of activity storable.
  • the storage and temperature stability and the washing and cleaning performance of a detergent or cleaner composition can be improved by dividing the enzyme-containing formulation into at least two separate formulations, provided that ingredients such as the builders and the complexing agents specifically the separate formulations are distributed.
  • a first subject of the present application is therefore a washing or roundsmittel sosform comprising a) a liquid (2O 0 C) washing or cleaning agent preparation A, containing a1) builder; a2) complexing agent b) a liquid (2O 0 C) of the washing or cleaning agent preparation A different detergent or cleaning composition B having a water content above 1 wt .-%, containing b1) at least 5 wt .-% of at least one washing or cleaning active
  • the subject of this application are detergent and cleaning product forms obtained by the combination of two liquid detergent or cleaner formulations A and B.
  • the liquid detergent and cleaner preparations A and B differ from each other in terms of their composition.
  • the washing or planetsffen sosform further comprises a liquid detergent or cleaning composition C, wherein the washing or Detergent preparation C is preferably different from the detergent or cleaning agent preparations A and B.
  • Detergent preparation A contains as the first essential ingredient one or more builders.
  • the builders include in particular carbonates, phosphates, organic cobuilders and silicates.
  • Detergent or detergent dosage forms according to the invention are preferably characterized in that the builder a1) is selected from the group of the carbonates, the bicarbonates, the citrates, the phosphates, the silicates, the polymeric carboxylates and the polymeric sulfonates.
  • Preferred forms of detergent or cleaning agent comprise a detergent or cleaner composition A which, based on its total weight, contains from 2 to 50% by weight, preferably from 6 to 45% by weight and in particular from 10 to 40% by weight of builder.
  • builders a1) from the group of carbonates and / or bicarbonates, preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of 2 to 30 wt .-%, preferably from 3 to 20 wt .-% and in particular of 4 up to 15% by weight, in each case based on the weight of the detergent or cleaner preparation A.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • washing or cleaning agent preparations A contain citrate as one of their essential builders.
  • Detergent or cleaning agent supply forms characterized in that the washing or cleaning agent preparation A, based on their total weight 2 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 7 to 20 wt .-% citrate, according to the invention prefers.
  • Citrate or citric acid have proven, especially in combination with phosphonate, in particular 1-hydroxyethane-1, 1-diphosphonic acid, and / or the sulfonic acid-containing copolymers as the most effective in terms of cleaning performance as the rinse performance and in particular pad inhibition builders.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • Inventive automatic dishwashing agents crystalline builder layered silicates of general formula NaMSi x O 2x + I ⁇ y H 2 O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • phosphates In addition to citrates, phosphates have proven to be the most effective builders in terms of cleaning performance. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry. Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • HPO 3 metaphosphoric acids
  • phosphates are the pentasodium triphosphate, Na 5 P 3 Oi 0 (sodium tripolyphosphate) and the corresponding potassium salt Pentakaliumtriphosphat, K 5 P 3 Oi 0 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 2 to 40 wt .-%, preferably from 2 to 30 wt .-% and in particular from 3 to 25 wt .-%, particularly preferably from 3 to 15 wt .-%, each based on the Weight of washing or cleaning agent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate
  • 2 to 40 wt .-% preferably from 2 to 30 wt .-% and in particular from 3 to 25 wt .-%, particularly preferably from 3 to
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • the automatic dishwashing compositions according to the invention may contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures of two, three, four or more builders.
  • liquid automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, wherein the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 2 to 50 wt .-%, preferably 5 to 45 wt .-% and in particular 10 to 40 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • the detergent or cleaner composition A contains a complexing agent.
  • the proportion by weight of the complexing agent in the total weight of the washing or cleaning agent preparation A is preferably 2 to 60 wt .-%, preferably 4 to 55 wt .-% and in particular 8 to 50 wt .-%.
  • a first group of preferred complexing agents form the phosphonates.
  • the complex-forming phosphonates include, in addition to the 1-hydroxyethane-1, 1-diphosphonic acid a number of different compounds such as
  • Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • 1-hydroxyethane-1,1-diphosphonate HEDP
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • a preferred washing or cleaning composition A within the scope of this application contains one or more phosphonates (e) from the group a) aminotrimethylenephosphonic acid (ATMP) and / or salts thereof; b) ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and / or salts thereof; c) diethylenetriamine penta (methylenephosphonic 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) hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and / or salts thereof; g) nitrilotri (methylenephosphonic acid) (NTMP) and / or salts thereof.
  • ATMP aminotrimethylenephosphonic acid
  • ETMP ethylenedi
  • washing or cleaning agent compositions A which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylene triamine penta (methylene phosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylene triamine penta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of detergents or cleaning compositions A according to the invention is preferably from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.
  • the complexing agent a2) is selected from the group consisting of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid, hydroxyethane-1, 1-diphosphonic acid or diisobutyric acid.
  • ethylenetriaminepenta methylenephosphonic acid
  • the washing or cleaning agent preparations A according to the invention may comprise ethylenediamine disuccinic acid (EDDS), preferred washing or cleaning agent preparations A being characterized in that, based on their total weight, from 3.0 to 35% by weight, preferably 4.0 to 30 wt .-% and in particular 8.0 to 25 wt .-% ethylenediamine disuccinic acid.
  • EDDS ethylenediamine disuccinic acid
  • ethylenediamine disuccinic acid encompasses not only the free acids but also their salts, for example their sodium or potassium salts
  • EDDS ethylenediamine disuccinic acid
  • the detergent or cleaner composition A further contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants.
  • the surfactants may also be present in a detergent or cleaner preparation which is different from the detergent or cleaner preparations A and B. Surfactants are in a washing or
  • Detergent preparation A if used, preferably in an amount of up to 40 wt .-%, in particular 2 to 40 wt .-% or 4 to 40 wt .-%, particularly preferably in an amount of 5 to 35 wt .-%, in particular 10 to 30 wt .-%, contained.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 mol Ethylene oxide (EO) per mole of alcohol used in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO Ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12 _ 14 - alcohols containing 3 EO, 7 EO or 4 EO, C. 9 ir alcohol containing 7 EO, C. 13 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -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 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Alkyl glycosides are known, mild surfactants.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (I)
  • RCO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C- ⁇ _ 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fraktose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fraktose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of nonionic surfactants in the washing and cleaning preparation A in a preferred embodiment is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, based on the total amount of washing and cleaning preparation A.
  • the washing and cleaning preparation A may also contain anionic surfactants.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C. 9 13- Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12 -i 8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, in consideration.
  • alkanesulfonates which are obtained from C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • esters of .alpha.-sulfo fatty acids esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myrilecyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred.
  • 2,3-alkyl sulfates, which as commercial products of Shell OiI Company under the name DAN ® are suitable anionic surfactants.
  • 2 alcohols such as 2-methyl-branched C ⁇ -alcohols having on average 3.5 moles of ethylene oxide (EO) or C 12 -i 8 -fatty alcohols having 1 to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description see below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Particularly preferred anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of the washing and cleaning preparation A of anionic surfactants in a preferred embodiment is 0.1 to 30 wt .-%, preferably 2 to 20 wt .-%, based on the total amount of the washing or cleaning preparation A.
  • a preferred pH value of washing or cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12. If necessary, the adjustment of the pH can be effected by means of appropriate pH adjusting agents, in particular sodium hydroxide.
  • composition of some exemplary detergent or detergent dosage forms according to the invention comprising detergent and cleaner formulation A and detergent or detergent formulation B, can be found in the following tables:
  • the washing or cleaning agent preparations B according to the invention contain as their first essential constituent at least one washing or cleaning-active enzyme.
  • the weight fraction of the washing or cleaning-active enzymes in the total weight of the washing or cleaning agent preparation is preferably between 5 and 80 wt .-%, preferably between 5 and 60 wt .-%, particularly preferably between 10 and 50 wt .-% and in particular between 10 and 30% by weight.
  • the enzymes used with particular preference include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of from 1 ⁇ 10 -6 to 5% by weight. based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • liquid washing or cleaning agent preparations B according to the invention characterized in that they are a washing or cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or mannanases are preferred.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • preferred liquid washing or cleaning agent preparations B Based on the total weight of the washing or cleaning agent preparation, preferred liquid washing or cleaning agent preparations B according to the invention contain 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations.
  • washing or cleaning agent preparations A which, based on their total weight, contain 15 to 25% by weight of protease preparations.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from ⁇ . agaradherens (DSM 9948).
  • preferred liquid washing or cleaning agent preparations B based on the total weight of the washing or cleaning agent preparation, contain 0.1 to 30% by weight, preferably 1 to 0 to 25% by weight and in particular 2.0 to 20% by weight.
  • % Amylase preparations based on their total weight, of amylase preparations are particularly preferred.
  • Further inventively preferred liquid washing or cleaning preparations B contain, based on the total weight of the washing or cleaning agent preparation, 0.1 to 30% by weight, preferably 1, 0 to 25 wt .-% and in particular 2.0 to 20 wt. -% cellulase preparations. Further inventively preferred liquid washing or cleaning preparations B contain, based on the total weight of the washing or cleaning agent preparation, 0.1 to 30% by weight, preferably 1, 0 to 25 wt .-% and in particular 2.0 to 20 wt. -% mannanase preparations.
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • liquid washing or cleaning preparations B contain, based on the total weight of the washing or cleaning agent preparation, 0.1 to 30% by weight, preferably 1, 0 to 25 wt .-% and in particular 2.0 to 20 wt. -% lipase preparations.
  • enzymes can be used, which are summarized by the term hemicellulases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • Washing or cleaning-active enzymes are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or other auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • a preferred pH of detergents or cleaning compositions B according to the invention is between 6 and 9.
  • composition of some exemplary detergent or detergent dosage forms according to the invention comprising detergent and cleaner formulation A and detergent or detergent formulation B, can be found in the following tables:
  • the washing or cleaning agent preparations B of the washing or cleaning agent supply forms according to the invention contain less than 10% by weight of phosphate and furthermore less than 2.5% by weight of complexing agent.
  • the lowering of the phosphate and complexing agent content below these upper limits has proved to be advantageous for the washing and cleaning performance.
  • By further lowering the content of phosphate and complexing agent well below the upper limits is surprisingly a further increase in the washing and cleaning performance of inventive detergent or makesmittel finesformen feasible.
  • preferred detergent or takesformen characterized in that the detergent or cleaner composition B less than 6 wt .-% phosphate, preferably less than 3 wt .-% phosphate, more preferably less than 1 wt .-% phosphate and especially no phosphate.
  • preferred detergent or takesformen characterized in that the detergent or cleaning composition B less than 2.0 wt .-% complexing agent, preferably less than 1, 0 wt .-% complexing agent, more preferably less than 0.5 wt. % Complexing agents and in particular no complexing agents.
  • the total amount of the phosphate and complexing agent contained in the washing or cleaning agent preparation B is preferably less than 10% by weight, preferably less than 6% by weight, more preferably less than 2% by weight and in particular 0% by weight.
  • composition of some exemplary detergent or detergent dosage forms according to the invention comprising detergent and cleaner formulation A and detergent or detergent formulation B, can be found in the following tables:
  • An optional constituent of the washing or cleaning agent preparations according to the invention, in particular the washing or cleaning agent preparation B, are organic solvents.
  • Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from Ethanol, n- or i-propanol, butanol, glycol, propane- or butanediol, glycerol, monoethanolamine, 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, diethylene glycol ethyl ether, propylene glycol methyl -, - ethyl or - propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof Solvent.
  • a particularly preferred organic solvent which is particularly effective with respect to the stabilization of the detergent or cleaning agent preparation is 1,2-propylene glycol.
  • the proportion by weight of 1,2-propylene glycol in the total weight of the washing or cleaning agent preparations B according to the invention can vary within wide limits, however, such preparations have proved to be particularly stable, which, based on the total weight of the detergent or cleaning preparation B, 5 to 80 wt. %, preferably 10 to 60 wt .-% and in particular 20 to 50 wt .-% 1, 2-propylene glycol. Corresponding preparations are therefore preferred according to the invention.
  • washing or cleaning composition B contains organic solvent, preferably 1, 2-propylene glycol, wherein the weight fraction of 1, 2-propylene glycol, based on the total weight of the detergent or cleaning agent preparation, preferably 5 bis 80 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 50 wt .-%, are preferred because of their increased stability.
  • composition of some exemplary detergent or detergent dosage forms according to the invention comprising detergent and cleaner formulation A and detergent or detergent formulation B, can be found in the following tables:
  • Detergent formulations B is a boric acid or a boric acid derivative.
  • the boronic acids or their salts or esters are preferably used in particular, including, in particular, derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA), or Salts or esters of the compounds mentioned.
  • the proportion by weight of the boric acid or of the boric acid derivatives in the total weight of detergent or cleaner compositions B according to the invention is preferably between 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight.
  • a particularly preferred boric acid derivative which is particularly effective with respect to the stabilization of the detergent or cleaning agent preparation is 4-formylphenylboronic acid.
  • the proportion by weight of 4-formylphenyl-boronic acid in the total weight of the washing or cleaning agent preparations according to the invention can vary within wide limits, but such preparations have proved to be particularly stable, which, based on the total weight of Detergent or detergent formulation B, 0.001 to 10 wt .-%, preferably 0.002 to 6 wt .-% and in particular 0.05 to 3 wt .-%. Corresponding preparations are therefore preferred according to the invention.
  • Detergent formulations is a Ca or Mg ion source.
  • Detergent formulations B is preferably between 0.01 to 10 wt .-%, preferably 0.2 to 8 wt .-% and in particular 0.5 to 5 wt .-%.
  • the organic calcium salts have been found.
  • the proportion by weight of the organic calcium salts in the total weight of the washing or cleaning agent preparations according to the invention can vary within wide limits, but such preparations have proven to be particularly stable, which, based on the total weight of the detergent or cleaning agent preparation, 0.01 to 10 wt .-% , preferably 0.2 to 8 wt .-% and in particular 0.5 to 5 wt .-%. Corresponding preparations are therefore preferred according to the invention.
  • polyols may also be present in detergent or cleaner compositions B according to the invention, in particular sorbitol.
  • the liquid detergent or cleaning compositions B contain, based on their total weight preferably 1, 0 to 35 wt .-%, preferably 1, 5 to 25 wt .-% and in particular 2.0 to 30 wt .-% water.
  • the detergent preparations A and B are used in a preferred embodiment in combination with at least one further detergent preparation C.
  • this detergent composition C is preferably surfactant and / or acid-containing.
  • this detergent composition C preferably contains a textile conditioner and / or a perfume.
  • a surfactant- and / or acid-containing detergent preparation C can improve the rinse performance achieved in the dishwashing processes according to the invention. This applies in particular to those preferred process variants in which the dosage of the Detergent preparations A, B and C takes place with a time delay.
  • Suitable surface-active additives for the detergent preparation C are, in particular, the nonionic surfactants described above.
  • 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 in which
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A, A ', A "and A'” independently represent a group from the group
  • CH (CH 2 -CH 3 ), w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Particularly effective here are the nonionic surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) W -R 2 proved in the
  • R 1 is a linear or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), and w is from 1 to 120, preferably from 10 to 80, in particular from 20 to 40 stands.
  • the group of these nonionic surfactants include, for example, the C 4 . 22 fatty alcohol (EO) 10 - 8 o-2-hydroxyalkyl ethers, in particular the C 8 - I2 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4 . 22 fatty alcohol (EO) 40 - 8 O-2-hydroxyalkyl ether.
  • Detergent preparation C is preferably from 1, 0 to 18 wt .-%, preferably from 2.0 to 15, particularly preferably from 4.0 to 12 wt .-% and in particular from 6.0 to 10 wt .-%.
  • the detergent compositions C according to the invention preferably comprise at least one acidifying agent when used in a dishwashing process.
  • Acidifying agents may be added to the detergent compositions C according to the invention in order to lower the pH of the liquor in the final rinse cycle.
  • inorganic acids and organic acids are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid maximum 33% by weight).
  • Detergent preparations C which, based on the total weight of the detergent preparation C, comprise one or more acidifying agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular acetic acid and / or citric acid Quantities of from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.4 to 8.0% by weight, are preferred embodiments of the present invention.
  • acidifying agents preferably mono-, oligo- and polycarboxylic acids, particularly preferably tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular acetic acid and / or citric acid Quantities of from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.4 to 8.0% by
  • cleaning preparations C When used in a textile washing process, cleaning preparations C according to the invention preferably comprise at least one compound selected from textile conditioners, defoamers, in particular polydimethylsiloxanes, complexing agents and perfuming agents.
  • the textile conditioner here is preferably selected from fabric softeners, in particular esterquats and quaternary silicone compounds, optical brighteners and soil release active ingredients. Particular preference is given to using fabric softeners in the cleaning preparation C.
  • the fabric softening agent is preferably contained in an amount of from 2 to 30% by weight, in particular from 4 to 20% by weight, in cleaning preparations C according to the invention.
  • fabric softeners preferably usable according to the invention
  • the complexing agents used are preferably the compounds already mentioned above.
  • the invention preferably usable perfumes, optical brighteners and soil release agents and their preferred amounts used reference is made to the publication WO 2008/101810.
  • the detergent compositions A, B and C described above differ in their composition, ie they are not identical.
  • composition of some exemplary detergent or detergent dosage forms according to the invention comprising detergent and cleaner preparations A, B and C can be found in the following tables:
  • the packaging of the above-described combination of cleaning agents is carried out by means of a packaging means in which the washing or cleaning agent preparations A and B or A, B and C are present separately.
  • This separation can be achieved for example by separate receiving chambers, each of these receiving chambers containing one of the combined detergent.
  • Examples of such Kon Stammionsformen are cartridges with two, three, four or more separate receiving chambers, for example, two-, three-, four- or multi-chamber bottles.
  • a further subject matter of the present application is a detergent dosage form comprising a) a detergent or cleaner composition A according to the invention in an amount sufficient for the at least twice, preferably at least eight times, carrying out a machine dishwashing or machine textile washing process; b) at least one further washing or cleaning agent preparation B which differs from A in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, the performance of a machine dishwashing process or a machine textile washing process; c) optionally, another washing or cleaning agent other than A and B.
  • Detergent preparation C in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing or machine textile washing process; d) a cartridge for the washing or cleaning preparations A and B or A, B and C, in which the washing or cleaning agent preparations A and B and A, B and C are present in separate receiving chambers.
  • a further subject matter of the present application is a detergent dosing system comprising a) a detergent or cleaner composition A according to the invention in an amount sufficient for at least twice, preferably at least eight times, carrying out a machine dishwashing or machine textile washing process; b) at least one further washing or cleaning agent preparation B which differs from A in an amount sufficient for at least twice, preferably at least four times, and in particular at least eight times, the performance of a machine dishwashing process or a machine textile washing process; c) optionally, another washing or cleaning agent other than A and B.
  • Detergent preparation C in an amount sufficient for at least twice, preferably at least four, and in particular at least eight times, carrying out a machine dishwashing or machine textile washing process; d) a cartridge for the washing or cleaning preparations A and B or A, B and C, in which the washing or cleaning preparations A and B or A, B and C are present in separate receiving chambers; e) a dispenser detachably connected to the cartridge.
  • the previously described cartridges of the detergent product forms are provided with a dispenser detachable from the cartridge.
  • 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.
  • the detachable connection of cartridge and dispenser allows the replacement of 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.
  • a particularly preferred subject matter of this application is a detergent dosing system comprising a) a detergent dosage form according to the invention comprising a sufficient amount of detergent preparations A and B or A for the at least twice, preferably at least four times and in particular at least eight times carrying out a machine dishwashing or machine textile washing process. B and C; b) a releasably connected to the madesstoff insform dosing device.
  • detergent forms are also conceivable in which the cartridge and the dosing device are permanently connected to each other.
  • a subject matter of the present application is furthermore a detergent dosing system comprising a) a detergent dosage form according to the invention comprising a sufficient amount of detergent preparations A and B or A for at least twice, preferably at least four times and in particular at least eight times carrying out a machine dishwashing or machine textile washing process B and C; b) a non-detachably connected to the starsstoff essential part dosing device
  • the vorgenanten starverdosiersysteme comprising the invention starsffen finesform (and optionally one or two further, different from the detergent compositions of the invention A and B cleaning center), 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 metering device are particularly preferably contained separately from each other in the outer packaging.
  • the detergent product form according to the invention in conjunction with a dishwasher or in conjunction with a textile washing machine.
  • Such a combination is particularly advantageous in cases in which the course of the automatic dishwashing process or washing 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.
  • the metering system according to the invention is mobile. Movable in the sense of this application means that the metering system is not inseparably connected to a water-conducting device such as a dishwasher, washing machine, tumble dryer or the like, but for example from a dishwasher by the user removed or positionable in a dishwasher, so is independently handled, is
  • 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.
  • the preparations to be dosed may have a pH between 2 and 14, in particular 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • one of the chambers can be designed for the delivery of volatile preparations, such as a fragrance to the environment.
  • the cartridge is integrally formed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the bottom of the chambers may be funnel-shaped inclined towards the discharge opening.
  • 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.
  • 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.
  • the cartridge preferably has 3 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber an enzymatic preparation
  • the third chamber a rinse aid, wherein the volume ratio of the chambers is approximately 4: 1: 1.
  • a metering chamber may be formed in the flow direction of the preparation in front of the outlet opening.
  • the preparation amount that is to be released in the release of preparation from the chamber to the environment set. This is particularly advantageous when the closure element of the dosing device, which causes the release of preparation from a chamber to the environment, only in a dispensing and a lock state can be offset without controlling the tax amount. 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.
  • 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.
  • 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.
  • the cartridge chambers should not be aerated directly, but via the dosing device or no ventilation, e.g. be provided with the use of flexible containers, such as bags, so this has the advantage that at elevated temperatures in the course of a rinse cycle of a dishwasher by the heating of the chamber contents, a pressure is built up, which presses the preparations to be dosed in the direction of the outlet openings, so that a good residual emptying of the cartridge can be achieved. Furthermore, in the case of such an air-free packaging, there is no risk of oxidation of substances of the preparation, which makes bag packaging or else bag-in-bottle packaging appear expedient, in particular 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.
  • the cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably about 10: 10: 1.
  • 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.
  • 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.
  • the metering unit in cup shape with a substantially circular or square base.
  • 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.
  • 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.
  • 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 a optical or acoustic signal is generated that indicates the user to the present error.
  • 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 recording in each case of different preparations of a detergent or cleaning agent.
  • the cartridge may be designed so that it can be detachably or firmly arranged in or on the dishwasher.
  • control unit e.g., a Bosch Sensortec metering device
  • sensor unit e.g., a Bosch Sensortec metering device
  • actuator necessary for operation are integrated in the dosing device.
  • an energy source is also arranged in the metering device.
  • 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.
  • the dosing device comprises at least one first interface, which interacts with a corresponding interface formed in or on a water-conducting appliance, in particular a water-conducting household appliance, preferably a dishwasher or washing machine, such that a transmission of electrical energy from the water-carrying Device is realized for dosing.
  • a water-conducting appliance in particular a water-conducting household appliance, preferably a dishwasher or washing machine, such that a transmission of electrical energy from the water-carrying Device is realized for dosing.
  • the interfaces are formed by connectors.
  • the interface cells can be designed such that a wireless transmission of electrical energy is effected.
  • a second interface on the dosing device and the water-conducting device, such as a dishwasher, for transmitting electromagnetic signals, in particular Radio Commons-, measuring and / or control information of the dosing and / or the water-bearing device such as Dishwasher represent trained.
  • 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.
  • the adapter 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 run a dosing system for either stand-alone or build-in versions, or it can be used as a charging station for the dosing system, which charges the dosing device's power source, for example, or data be exchanged between 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.
  • 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 of the household appliance in the adapter, wherein the adapter, the dosing device and the household appliance are designed in that a cartridge can be coupled by the user with the dosing device.
  • the detergent dosage forms of the invention are suitable for use in dishwashing as well as for textile cleaning, however, the use of a detergent or makeskar novel novel invention or a detergent dosing system for dishwashing in a dishwasher machine dishwashing process is preferred.
  • 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 suitable exceptionally for the dosage by means of a metering system located in the interior of a washing machine or dishwasher.
  • a dosing system which can be immovably integrated into the interior of the washing machine or dishwasher (machine-integrated dosing), but of course as a movable device in the interior can be introduced (self-sufficient dosing), contains the multiple required to carry out a machine cleaning process amount of 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.
  • Textile washing machine integrated cartridge of a dosing or ii) one for positioning in the interior of a dishwasher or
  • Textile washing provided movable cartridge of a dosing with a for at least twice, preferably at least four times and in particular at least eight times performing a machine dishwashing or machine textile washing sufficient amount of makesstoff insform are also subjects of this application.
  • 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.
  • a movable cartridge is a container which is introduced by the consumer into the interior of the dishwasher and remains there during the entire course of a cleaning cycle.
  • 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 or textile washing machine is carried out as described above, preferably by means of a detachable from the cartridge dosing.
  • a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection.
  • cartridges with a permanently connected metering device can of course also be used.
  • a detergent product form according to the invention as a detergent reservoir for i) an immovable in the interior of a dishwasher or
  • Textile washing machine integrated dosing or ii) one for positioning in the interior of a dishwasher or
  • Textile washing machine provided mobile dosing device.
  • a detergent dosage form comprising a) a washing or cleaning agent preparation A according to the invention for at least twice, preferably at least four times and in particular at least eight times carrying out a machine dishwashing or machine textile washing process; b) at least one further washing or cleaning agent preparation B which differs from A in an amount sufficient for the at least twice, preferably at least four times, and in particular at least eight times, carrying out a machine dishwashing or textile washing process; c) optionally a further detergent or cleaner composition C other than A and B in an amount sufficient for at least two times, preferably at least four times and in particular at least eight times, to carry out a machine dishwashing or textile washing process; d) a cartridge for the detergent or cleaning preparations A and B or A, B and C, in which the washing or cleaning agent preparations A and B or A, B and C in separate receiving chambers are present as a detergent reservoir for i) immovable in the interior of a dishwasher or
  • Textile washing machine integrated dosing device or ii) a for positioning in the interior of a dishwasher or
  • Textile washing machine provided mobile dosing device.
  • the detergents and cleaning agent combinations according to the invention are preferably used as automatic dishwashing detergents or as mechanical laundry detergents.
  • Automatic dishwashing processes and automatic textile washing processes using a detergent dosage form according to the invention or a detergent dosage system according to the invention are characterized in that a subset a of the washing or cleaning agent preparation A in the interior of the cartridge is located in the interior of the cartridge from a cartridge located in the interior of the dishwasher or textile washing machine Dishwasher or textile washing machine is metered, with a residual amount of detergent or in the cartridge remains until the end of dishwashing in the cartridge, characterized in that this residual amount of at least twice, preferably at least four times and in particular at least eight times the amount of Subset a corresponds to; and a subset b of the washing or cleaning agent preparation B present in the cartridge is metered into the interior of the dishwasher or textile washing machine, wherein a residual amount of the washing or cleaning agent preparation in the cartridge remains in the cartridge until the end of the dishwashing process, characterized that this residual amount corresponds to
  • detergent dosage forms according to the invention but also the detergent dosage systems according to the invention can be used in the dishwashing processes and textile washing processes according to the invention.
  • the dosage of the washing or cleaning agent preparation A and of the washing or cleaning agent preparation B and optionally of the washing or cleaning agent preparation C takes place at different times of the cleaning cycle.
  • a further preferred subject matter of this application is therefore a machine dishwashing process or machine textile washing process using 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 or textile washing machine, a subset a of the in located in the cartridge A residual amount of the detergent present in the cartridge remains in the cartridge until the end of the dishwashing process or textile washing process, which of the at least twice, preferably at least four times, and in particular remains in the interior of the dishwashing machine or textile washing machine 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 or textile washing machine, a subset b of the washing or cleaning agent preparation B different from the detergent or cleaning agent preparation B in the second cartridge in the interior of the dishwasher or Textile washing machine is metered, wherein a residual amount of the cleaning agent in this cartridge remains in the cartridge until the end
  • the time t2 is at least 1 minute, preferably at least 2 minutes and especially between 3 and 30 minutes, in particular between 3 and 20 minutes, before or after, preferably before time t1.
  • the time t3 is at least 1 minute longer, preferably at least 2 minutes and especially between 3 and 30 minutes, in particular between 3 and 20 minutes. before or after, preferably after time t1.
  • the cleaning preparation B at a temperature of 20-35 0 C, then the cleaning preparation A at a temperature of 30-60 0 C and then the cleaning preparation C at a temperature below 2O 0 C in the interior preferably added to a textile washing machine.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une forme d'offre d'agents nettoyants ou détergents, comprenant a) une préparation nettoyante ou détergente, liquide (20°C) A, renfermant : a1) un adjuvant; a2) un complexant, b) une préparation nettoyante ou détergente liquide (20°C), différente de la préparation nettoyante ou détergente A, ayant une teneur en eau supérieure à 1 % en poids, renfermant b1) au moins 5% en poids d'au moins une préparation enzymatique nettoyante ou détergente, b2) < 10% en poids de phosphate, b3) < 2,5% en poids de complexant, c) un moyen d'emballage, dans lequel les préparations nettoyantes ou détergentes A et B sont séparées l'une de l'autre. Les détergents précités se caractérisent par une bonne stabilité au stockage et à la température, ainsi que par de bonnes performances nettoyantes et détergentes.
EP10713611.1A 2009-04-01 2010-03-31 Détergents Revoked EP2414499B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL10713611T PL2414499T3 (pl) 2009-04-01 2010-03-31 Środek czyszczący

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009002094A DE102009002094A1 (de) 2009-04-01 2009-04-01 Reinigungsmittel
PCT/EP2010/054306 WO2010112549A1 (fr) 2009-04-01 2010-03-31 Détergents

Publications (2)

Publication Number Publication Date
EP2414499A1 true EP2414499A1 (fr) 2012-02-08
EP2414499B1 EP2414499B1 (fr) 2019-03-13

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EP10713611.1A Revoked EP2414499B1 (fr) 2009-04-01 2010-03-31 Détergents

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US (1) US20120015858A1 (fr)
EP (1) EP2414499B1 (fr)
DE (1) DE102009002094A1 (fr)
PL (1) PL2414499T3 (fr)
WO (1) WO2010112549A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2207822A4 (fr) * 2007-11-09 2012-04-11 Procter & Gamble Compositions de nettoyage contenant des monomères acides monocarboxyliques, monomères dicarboxyliques et monomères comprenant des groupes acides sulfoniques
US9133422B2 (en) 2008-03-31 2015-09-15 Nippon Shokubai Co., Ltd. Sulfonic group-containing, maleic acid-based, water-soluble copolymer aqueous solution and powder obtained by drying the aqueous solution
CN105264559A (zh) * 2013-02-25 2016-01-20 魅股份有限公司 用以接受有价值物品的系统
BR112018075517B1 (pt) 2016-06-09 2022-08-30 Unilever Ip Holdings B.V Aparelho para fornecer produto para lavagem de roupas e dispositivo de distribuição
BR112019002568A2 (pt) 2016-09-07 2019-05-21 Ecolab Usa Inc. composição, e, métodos de limpeza, sanitização e/ou de alvejamento e para estabilizar uma enzima em um detergente sólido
CN110997117B (zh) 2017-06-30 2023-08-01 戴弗西公司 膜清洁溶液和使用其加速膜清洁的方法
US11807974B2 (en) 2017-10-05 2023-11-07 Conopco, Inc. Methods and devices for individualized laundry
GB2571336A (en) 2018-02-26 2019-08-28 Unilever Plc Methods and system for monitoring and replenishing one or more laundry components
US11910982B2 (en) 2019-11-01 2024-02-27 Conopco Inc. Recyclable auto-dosing container

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2038103A1 (de) 1970-07-31 1972-02-10 Henkel & Cie Gmbh Waessrige Reinigungsmittelkonzentrate mit einem Gehalt an stabilisierten Enzymen
WO1994000558A1 (fr) 1992-06-19 1994-01-06 Joslin Diabetes Center, Inc. Rad diabetogene: un gene specifique au diabete de type ii
GB2386129B (en) 2002-03-06 2004-12-01 Reckitt Benckiser Nv Detergent dosing device
DE102005062479A1 (de) 2005-12-27 2007-07-05 BSH Bosch und Siemens Hausgeräte GmbH Dosiervorrichtung für die Zugabe eines Zuschlagmittels in einen Behandlungsraum und Geschirrspülmaschine mit einer Dosiervorrichtung
DE102006004697A1 (de) 2006-01-31 2007-08-02 Henkel Kgaa Wasch- oder Reinigungsmittel mit Farbübertragungsinhibitor
WO2008101810A1 (fr) 2007-02-20 2008-08-28 Henkel Ag & Co. Kgaa Utilisation de dérivés d'urée dans des agents de lavage et de nettoyage
DE102007039655A1 (de) * 2007-08-22 2009-02-26 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007042857A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Verfahren zum maschinellen Reinigen von Geschirr
DE202008001532U1 (de) * 2008-02-01 2008-04-10 Weber, Lothar Ernst Wilhelm Vorrichtung zum Waschen oder Reinigen von Gegenständen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010112549A1 *

Also Published As

Publication number Publication date
PL2414499T3 (pl) 2019-08-30
EP2414499B1 (fr) 2019-03-13
US20120015858A1 (en) 2012-01-19
DE102009002094A1 (de) 2010-10-07
WO2010112549A1 (fr) 2010-10-07

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