EP3656839A1 - Détergent destiné au dosage automatique - Google Patents

Détergent destiné au dosage automatique Download PDF

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Publication number
EP3656839A1
EP3656839A1 EP19209989.3A EP19209989A EP3656839A1 EP 3656839 A1 EP3656839 A1 EP 3656839A1 EP 19209989 A EP19209989 A EP 19209989A EP 3656839 A1 EP3656839 A1 EP 3656839A1
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EP
European Patent Office
Prior art keywords
weight
detergent
preparation
cleaning agent
acid
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
EP19209989.3A
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German (de)
English (en)
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EP3656839B1 (fr
Inventor
Thomas Doering
Carola ULBRICH
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP3656839A1 publication Critical patent/EP3656839A1/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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • 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
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • 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

Definitions

  • the invention relates to a cleaning agent combination which, in a packaging means, separate from one another, at least one builder-containing preparation which contains 8 to 30% by weight of at least one complexing agent selected from glutamic acid- N , N -diacetic acid and / or methylglycinediacetic acid and / or salts thereof, and at least one contains an enzyme-containing preparation.
  • Devices for multiple dosing of detergents in particular are desired by the consumer.
  • Devices can be differentiated between metering containers integrated in the dishwasher on the one hand and independent devices independent of the dishwasher on the other.
  • Using these devices which contain several times the amount of detergent required to carry out a cleaning process, detergent portions are metered into the interior of the cleaning machine in an automatic or semi-automatic manner in the course of several successive cleaning processes. For the consumer, this eliminates the need to dose the detergent before the start of each individual cleaning cycle. Examples of such devices are found in the European patent application EP 1 759 624 A2 (Reckitt Benckiser ) or in the German patent application DE 10 2005 062 479 A1 (BSH Bosch and Siemens Hausmaschine GmbH).
  • the cleaning agents contained in these devices for multiple dosing are also exposed to changing temperatures over a longer period of time, these temperatures being approximately the same as the water temperatures used to carry out the cleaning processes. These temperatures can be up to 95 ° C, with usually only temperatures between 50 and 75 ° C being achieved in the area of machine dishwashing.
  • a cleaning agent contained in a device provided for multiple dosing is accordingly repeated in the course of several cleaning processes to temperatures significantly above those for transport and for Storage heated temperatures, in particular temperature-sensitive active substances are affected.
  • the object of the present application was accordingly to provide a form of cleaning agent which provides good cleaning performance, in particular on dried-on food residues, in particular minced meat, oatmeal and / or tea, even if there are several days between the individual usage cycles.
  • This system is said to be particularly inexpensive for the consumer.
  • the combination of such a composition with the cleaning agent preparations according to the invention has the advantage for the consumer that he does not have to worry much about renewing or replacing the active ingredient composition and the cleaning agent preparations. He exchanges the combination together and does not have to worry about replacing individual products separately.
  • the form of the detergent according to the invention has good cleaning performance, preferably in the case of stubborn, in particular dried-on food residues on the dishes, for example oatmeal or tea. Rinsing off food residues before sorting them into the dishwasher can therefore be dispensed with, which is particularly advantageous for ecological and time reasons and with regard to the additional water costs.
  • the subject of this application are corresponding forms of detergent that are obtained by combining two liquid detergent preparations A and B.
  • the liquid cleaning agent preparations A and B and the active ingredient composition differ from one another in terms of their composition.
  • the form of the detergent is characterized in that the detergent preparations are phosphate-free, i.e. that they contain less than 1% by weight of phosphate, preferably less than 0.5% by weight of phosphate, particularly preferably less than 0.1% by weight of phosphate and in particular no phosphate.
  • the cleaning composition A contains as a complexing agent from 8.0 to 30% by weight of L-glutamic acid- N , N -diacetic acid and / or the corresponding alkali salt (GLDA), preferably the tetrasodium salt, and / or methylglycinediacetic acid and / or the corresponding alkali salt, preferably the trisodium salt.
  • GLDA alkali salt
  • the trisodium salt of methylglycinediacetic acid (MGDA) or the corresponding sodium salts are very particularly preferably present.
  • the term methylglycinediacetic acid or L-glutamic acid- N , N -diacetic acid also includes their salts, for example their sodium or potassium salts.
  • Preferred cleaning agent preparations A are characterized in that, based on the total weight of the cleaning agent preparations A, they are 10 to 20% by weight, preferably 11 to 18% by weight and in particular 12 to 15.5% by weight, very particularly preferably 13 up to 15% by weight of glutamic acid, N , N -diacetic acid and / or methylglycinediacetic acid and / or salts thereof, preferably 10 to 20% by weight, preferably 11 to 18% by weight and in particular 12 to 15.5% by weight %, very particularly preferably 13 to 15% by weight of methylglycinediacetic acid and / or its salts, in particular its trisodium salt.
  • the cleaning agent preparation A contains one or more builders as the first essential component.
  • the builders include in particular carbonates, organic cobuilders and silicates.
  • Forms of cleaning agent 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 silicates, the polymeric carboxylates and the sulfonic acid group-containing polymers or mixtures thereof.
  • a sulfopolymer preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfone group-containing polymer.
  • the copolymers can have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • H 2 C CH-X-SO 3 H
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH (CH 3 ) 2
  • a cleaning agent preparation preferably cleaning agent preparation A, contains such a polymer comprising, as a monomer containing sulfonic acid groups, acrylamidopropane sulfonic acids, methacrylamidomethyl propane sulfonic acids or acrylamidomethyl propane sulfonic acid.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups can be wholly or partly in neutralized form, that is to say that the acidic hydrogen atom of the sulfonic acid group can be present in some or all of the sulfonic acid groups
  • Metal ions preferably alkali metal ions and especially sodium ions, can be replaced.
  • the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the monomer containing carboxyl groups and the monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • Monomers of the general formula R 1 (R 2 ) C C (R 3 ) -XR 4 , in which R 1 to R 3 independently of one another are -H, -CH 3 or - C 2 H 5 , are preferably used as nonionic monomers , X represents an optionally available spacer group which is selected from -CH 2 -, - C (O) O- and -C (O) -NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22
  • Preferred forms of detergent supply comprise a detergent preparation A which, based on its total weight, contains 2 to 50% by weight, preferably 6 to 45% by weight and in particular 10 to 40% by weight of builder.
  • builders a1) from the group of carbonates and / or hydrogen carbonates, preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 up to 15% by weight, based on the weight of the detergent preparation A.
  • Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, (poly) aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Usable 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 being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Polycarboxylic acids are preferably understood to mean non-polymeric polycarboxylates. Such polymeric polycarboxylates have a larger number, preferably 4 and more carboxylic acid-containing monomers.
  • the free acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH value of cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Particularly preferred cleaning agent preparations A according to the invention contain citrate as one of their essential builders.
  • Forms of detergent characterized in that the detergent preparation A, based on their total weight, contains 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight of citrate, are preferred according to the invention.
  • Citrate or citric acid in particular in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and / or the polymers containing sulfonic acid groups have proven to be the most effective builders in terms of cleaning performance, such as rinse aid performance and in particular scale inhibition.
  • detergent in which the detergent preparation A, based in each case on its total weight, citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular Contains 7 to 20 wt .-%.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • 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 with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the amount of (co) polymeric polycarboxylates in the dishwasher detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Automatic dishwashing agents according to the invention can contain crystalline layered silicates of the general formula NaMSi x O 2x + 1 .y H 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where are particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the silicate content based on the total weight of the automatic dishwashing agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwashing agents according to the invention are silicate-free.
  • the automatic dishwashing agents according to the invention can 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.
  • the dishwashing agent contains at least two builders from the group of the carbonates and citrates, and the polymers containing sulfonic acid groups, the weight fraction of these builders, based on its total weight of the machine dishwashing agent, preferably 2 to 50% by weight .-%, preferably 5 to 45 wt .-% and in particular 10 to 40 wt .-%.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • the cleaning agent preparation A contains a complexing agent which is different from the builders mentioned above.
  • the weight fraction of the complexing agent in the total weight of the cleaning agent preparation A is preferably 2 to 60% by weight, preferably 3 to 55% by weight, preferably 4 to 55% by weight and in particular 8 to 50% by weight.
  • the phosphonates form a further group of preferred complexing agents, provided that they can be used for regulatory reasons.
  • the complex-forming phosphonates comprise a number of different compounds, such as, for example, diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Detergent preparations A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • phosphonates are particularly preferred.
  • the automatic dishwashing agents according to the invention can of course contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of cleaning agent preparations A according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight, preferably 1.3 to 4.5% by weight, particularly preferably 1.4 to 4 , 5 wt .-% and in particular 1.5 to 4 wt .-%.
  • cleaning agent are characterized in that they additionally contain further complexing agents selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, aspartic acid diacetic acid, hydroxyethane-1,1-diphosphonic acid or mixtures thereof (1,1-methylenediphosphonic acid) or their ethylenediophosphonic acid or mixtures of these (methanediol-1-diphosphonic acid) or mixtures of them (methane-1,1-diphosphonic acid) or diethyl-diphosphonic acid or mixtures thereof (1,1-methylenediphosphonic acid or diethyl-diphosphonic acid or mixtures thereof) .
  • further complexing agents selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepent
  • the cleaning agent preparation A contains the complexing agents selected from phosphonates, in particular HEDP, if permitted for regulatory reasons, and / or MGDA and their respective salts.
  • the builders then include citrate and carbonate and / or hydrogen carbonate and optionally at least one polymer containing sulfonic acid groups.
  • the detergent preparation A based on its total weight, contains MGDA and / or its salts in amounts of 5 to 30% by weight, in particular 8 to 25% by weight, for example 10 to 15% by weight .-%, citrate in amounts of 3 to 20% by weight, in particular 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight.
  • MGDA and / or its salt is also preferred in amounts of 1.2 to 6% by weight, preferably 1.3 to 5% by weight, particularly preferably 1 , 4 to 4.5 wt .-% contain in particular 1.5 to 4 wt .-%.
  • one of the cleaning agent preparation preferably cleaning agent preparation B, furthermore contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants.
  • the surfactants can also be contained in a cleaning agent preparation different from the cleaning agent preparations A and B. If used in a cleaning agent preparation B according to the invention, surfactants are preferably used in an amount of up to 40% by weight, in particular 2 to 40% by weight or 4 to 40% by weight, particularly preferably in an amount of 5 to 35% by weight .-%, in particular 10 to 30 wt .-%, contain.
  • Detergent preparation A preferably contains less than 2% by weight of surfactant, preferably less than 1% by weight of surfactant, particularly preferably less than 1% by weight of surfactant, in particular no surfactant, in each case based on the total weight of detergent preparation A.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain 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.
  • mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained from the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • the content of nonionic surfactants in the cleaning preparation B 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 the cleaning preparation B.
  • the cleaning preparation B can also contain anionic surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • the anionic surfactants, including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of cleaning preparation A.
  • a preferred pH value of cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12.
  • the pH can, if necessary, be adjusted by means of appropriate pH adjusting agents, in particular sodium or potassium hydroxide.
  • the cleaning agent preparations B according to the invention contain at least one cleaning-active enzyme as their first essential constituent.
  • the weight fraction of the cleaning-active enzyme preparation in the total weight of the cleaning agent preparation B is preferably 5 and 80% by weight, preferably 5 and 60% by weight, particularly preferably 10 and 50% by weight and in particular 10 and 30% by weight.
  • the enzyme preparations used in this way each contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight and particularly preferably from 0.4 to 20% by weight and in particular from 0.8 up to 10% by weight of active enzyme protein.
  • the enzymes used with particular preference include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred.
  • Detergents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • liquid cleaning agent preparations B according to the invention characterized in that they have at least one cleaning-active enzyme from the group of the amylases and / or proteases and / or cellulases and / or Mannanases, in particular from the group of amylases and / or proteases, are included.
  • subtilisin type those of the subtilisin type are preferred. Examples of this 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.
  • Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the improved for use in cleaning agents aforementioned amylases. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Liquid detergent preparations B preferred according to the invention contain, based on the total weight of the detergent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of amylase preparations.
  • Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of cellulase preparations.
  • Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of mannanase preparations.
  • Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors.
  • suitable precursors 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, for example, which were originally isolated from Fusarium solani pisi and Humicola insolens . Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • Further liquid cleaning preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 0.1 to 30% by weight, preferably 1.0 to 25% by weight and in particular 2.0 to 20% by weight of lipase preparations.
  • enzymes can be used, which are summarized under 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)
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose- or manganese peroxidases, dioxygenases or laccases
  • organic, particularly preferably aromatic, compounds which interact with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons to the oxidizing enzymes and the soiling in the case of very different redox potentials (mediators).
  • Cleaning-active enzymes in particular proteases and amylases, 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, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Enzyme preparations preferably used according to the invention in particular the protease and amylase preparations, contain from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.4 to 20% by weight and in particular from 0.8 to 10% by weight of the enzyme protein.
  • Liquid detergent preparations B which are particularly preferred according to the invention therefore contain, based on the total weight of the detergent preparation, 7 to 40% by weight, in particular 10 to 30% by weight of protease preparations and 2 to 20% by weight, in particular 4.0 up to 16% by weight of amylase preparations, each containing 0.4 to 20% by weight, in particular 0.8 to 10% by weight, of active protein.
  • a plurality of enzymes and / or enzyme preparations preferably liquid protease preparations and / or amylase preparations, and optionally cellulase preparations and / or mannanase preparations are preferably used.
  • a preferred pH value of detergent preparations B according to the invention is between 6 and 9.
  • the cleaning agent preparations B of the cleaning agent dosage forms according to the invention preferably contain less than 2.5% by weight of complexing agents. They preferably contain less than 2.5% by weight of complexing agents and / or builders. Lowering the complexing agent content below these upper limits has proven to be advantageous for the cleaning performance. A further reduction in the content of complexing agent clearly below the upper limits can surprisingly result in a further increase in the cleaning performance of the forms of cleaning agent according to the invention.
  • detergent preparation B contains less than 2.0% by weight of complexing agent, preferably less than 1.0% by weight of complexing agent, particularly preferably less than 0.5% by weight of complexing agent and in particular none Contains complexing agents.
  • the total amount of complexing agent and / or builders contained in the detergent preparation B is preferably less than 10% by weight, preferably less than 6% by weight, particularly preferably less than 2% by weight and in particular 0% by weight.
  • organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, monoethanolamine, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2
  • Preferred solvents are preferably selected from glycerol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular those polyethylene glycols which have an average molecular weight between 100 and 800, preferably 200 and 600 g / mol.
  • the proportion by weight of these organic solvents in the total weight of the respective cleaning agent preparations according to the invention is preferably 5 to 80% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight.
  • a particularly preferred organic solvent which is particularly effective in terms of stabilizing the cleaning agent preparation, in particular cleaning agent preparation B, is 1,2-propylene glycol.
  • the proportion by weight of 1,2-propylene glycol in the total weight of the detergent preparations B according to the invention can vary within wide limits, but those preparations which, based on the total weight of the respective detergent preparation B, are preferably 5 to 80% by weight have proven to be particularly stable Contain 10 to 60 wt .-% and in particular 20 to 50 wt .-% 1,2-propylene glycol. Corresponding preparations are therefore preferred according to the invention.
  • Another optional component of the cleaning agent preparations B according to the invention is a boric acid or a boric acid derivative.
  • the boronic acids or their salts or esters are preferably used, in particular derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid (4-FPBA), or the Salts or esters of the compounds mentioned.
  • the proportion by weight of boric acid or of the boric acid derivatives in the total weight of cleaning agent preparations B according to the invention is preferably 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 in terms of stabilizing the cleaning agent preparation is 4-formylphenyl-boronic acid.
  • the proportion by weight of 4-formylphenyl boronic acid in the total weight of the detergent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the detergent preparation B, preferably 0.001 to 10% by weight have proven to be particularly stable Contain 0.002 to 6 wt .-% and in particular 0.05 to 3 wt .-%. Corresponding preparations are therefore preferred according to the invention.
  • Another optional component of the cleaning agent preparations according to the invention is a Ca or Mg ion source.
  • the weight fraction of the Ca or Mg ion source in the total weight of cleaning agent preparations B according to the invention is preferably 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight.
  • the organic calcium salts have proven to be particularly preferred and particularly effective in terms of stabilizing the cleaning agent preparation B.
  • the proportion by weight of the organic calcium salts in the total weight of the detergent 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 preparation, 0.01 to 10 wt .-%, preferably 0.2 to Contain 8 wt .-% and in particular 0.5 to 5 wt .-%. Corresponding preparations are therefore preferred according to the invention.
  • detergent preparations B according to the invention may also contain polyols, in particular sorbitol.
  • the liquid cleaning agent preparations B preferably contain 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less.
  • the detergent preparations B based on their total weight, contain 0.5 to 30% by weight, preferably 1.0 to 25% by weight and in particular 1.5 to 30% by weight of water.
  • the form of detergent supply further comprises a liquid detergent preparation C, the detergent preparation C being different from the detergent preparations A and B.
  • the detergent preparations A and B and the active compound composition D are used in a preferred embodiment in combination with at least one further detergent preparation C.
  • this detergent preparation C is preferably surfactant and / or acidic, preferably surfactant and acidic.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyatkytether.
  • the weight fraction of the nonionic surfactant in the total weight of the detergent preparation C is preferably from 1.0 to 20% by weight, preferably from 2.0 to 18% by weight, particularly preferably from 4.0 to 15% by weight and in particular from 6.0 to 12% by weight.
  • At least one detergent preparation in particular at least one detergent preparation further comprising a nonionic surfactant, particularly preferably at least detergent preparation B and / or D contains at least one hydrotrope (hereinafter also referred to as a solubilizer).
  • Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and / or N- methyl acetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate. It was found that the use of hydrotropes, in particular cumene sulfonate, enormously improves the phase stability with regard to the temperature fluctuations.
  • At least the detergent preparation C in particular the detergent preparations C and B, have at least one hydrotrope, preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly preferably in an amount of 6 to 15, for example from 7 to 12% by weight, based on the total weight of the respective detergent preparation.
  • hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, especially cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly
  • the weight ratio of the at least one nonionic surfactant to the at least one hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and / or N-methylacetamide, particularly preferably cumene sulfonate and / or xylene sulfonate, in particular cumene sulfonate, is preferred.
  • the cleaning agent preparations C according to the invention preferably contain at least one acidifying agent when used in a dishwashing process.
  • Acidifying agents can be added to the cleaning agent preparations C according to the invention in order to lower the pH of the liquor in the rinse cycle.
  • Both inorganic acids and organic acids are suitable here, provided they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. Preferred from this group are formic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • Detergent preparations C which, based on the total weight of the detergent preparation C, contain one or more acidifying agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular formic acid, acetic acid and / or citric acid in amounts of 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.3 to 8.0% by weight are preferred embodiments of the present invention.
  • acidifying agents preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and in particular formic acid, acetic acid and / or citric acid in amounts of 0.1 to 12% by weight, preferably 0.2 to 10% by weight
  • the use of formic acid is preferred because, in addition to the acid function to improve the rinse aid result, it also has a positive influence on the storage stability of the cleaning preparation C, which, as explained above, is subject to severe temperature fluctuations due to storage in the interior of the dishwasher. Furthermore, it has a disinfectant effect, so that when using formic acid in the rinse cycle, both the number of bacteria is reduced. This applies both to those bacteria that are in the rinse liquor of the rinse cycle and to those that remain in the sump of the dishwasher during and after the rinse cycle as well as the interior of the dishwasher. The number of residual germs on the washed dishes can also be reduced as a result.
  • an active ingredient composition D in particular comprising fragrances and / or scent scavengers, and at the same time formic acid as an acidifying agent in the Preparation C is used.
  • the formic acid itself has a slightly pungent smell, which is noticeable to sensitive consumers.
  • the separated storage of the active ingredient composition and the release of the at least one active ingredient D in particular if it is one or more fragrances, in particular those preferred above, and / or one or more fragrance scavengers, in particular, for example, zinc ricinoleate, does not occur during the dishwashing process an unpleasant smell inside the dishwasher even between cleaning cycles.
  • the cleaning agent preparations A, B and C described above differ in their composition and are therefore not identical.
  • the detergent preparations A, B and / or C according to the invention preferably contain at least one glass corrosion inhibitor when used in a dishwashing process.
  • Preparation (s) A and / or preparation (s) C, preferably at least preparation (s) C particularly preferably contain a corresponding amount of glass corrosion inhibitor (s).
  • These glass corrosion inhibitors are preferably selected from water-soluble zinc salts, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines.
  • the preparations according to the invention contain at least one zinc salt as a further constituent, in particular inorganic or organic, as a glass corrosion inhibitor.
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt in cleaning agent preparations according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the respective detergent preparation, in particular the respective detergent preparation A or C.
  • Polyethyleneimines as are available, for example, under the name Lupasol® (BASF), are preferably used in an amount of 0 to 5% by weight, in particular 0.01 to 2% by weight, based on the total weight of the respective preparation Glass corrosion inhibitors are used.
  • composition of some exemplary cleaning agent forms according to the invention comprising the cleaning agent preparations A, B and C, can be found in the following tables.
  • Recipe 1 Recipe 2 Recipe 3 Recipe 4 Ingredients W.-uR preparation A [% By weight] [% By weight] [% By weight] [% By weight] [% By weight] Builders 2 to 50 2 to 50 2 to 30 4 to 30 MGDA 2 to 60 8 to 30 10 to 20 12 to 15 Phosphonates, if permitted by regulation 0 to 10 1 to 8 1.2 to 6 1.5 to 4 Misc ad 100 ad 100 ad 100 ad 100
  • the combination of cleaning agents described above is packaged using a packaging agent in which the cleaning agent preparations A and B or A, B and C are present separately from one another.
  • This separation can be achieved, for example, by separate receiving chambers, each of these receiving chambers being one of the other combined detergent.
  • Examples of such assembly forms are cartridges with two, three, four or more separate receiving chambers, for example two, three, four or multi-chamber bottles.
  • the viscosity of all cleaning agent preparations A and B or A, B and C is preferably less than 120 mPas, in particular from 1 to 100 mPas, in particular 10 to 80 mPas, preferably 20 to 60 mPas (measured at 20 ° C. with a Brookfield Instrument LVDV II +, spindle 31, 100 rpm).
  • This has the advantage that the detergent preparations from the packaging material can only be opened by opening a valve on the underside of the packaging material (in particular the cartridge) on the basis of gravity, preferably without the involvement of electrical or electronic means, e.g. Pumps etc. can be dosed.
  • the chambers are preferably largely completely emptied, i.e. without large residual amounts of the detergent preparations to be dosed. This is advantageous for the consumer and for the environment because only small amounts of the detergent preparations remain unused in the chambers of the packaging means or the cartridge.
  • the packaging means additionally contains at least one active substance composition, preferably separate from the cleaning agent preparations, in particular from the cleaning agent preparations A and B, which contains at least one carrier material, preferably a water-insoluble carrier material. and contains at least one active ingredient D.
  • active substance composition preferably separate from the cleaning agent preparations, in particular from the cleaning agent preparations A and B, which contains at least one carrier material, preferably a water-insoluble carrier material. and contains at least one active ingredient D.
  • the polymeric carrier material of the particles consists at least in part of ethylene / vinyl acetate copolymer.
  • Another preferred subject of the present application is therefore a cleaning agent supply form as described above, characterized in that a polymeric carrier material has at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 70% by weight, of ethylene / vinyl acetate copolymer contains, preferably is made entirely of ethylene / vinyl acetate copolymer.
  • Ethylene / vinyl acetate copolymers is the name for copolymers of ethylene and vinyl acetate. This polymer is generally produced in a process comparable to the production of low density polyethylene (LDPE). With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is interrupted and in this way the melting and softening points or the hardness of the resulting products reduced. The vinyl acetate also makes the copolymer more polar and thus improves its adhesion to polar substrates.
  • LDPE low density polyethylene
  • ethylene / vinyl acetate copolymers described above are widely available commercially, for example under the trademark Elvax® (Dupont).
  • Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Elvax® 265, Elvax® 240, Elvax® 205 W, Elvax® 200 W and Elvax® 360. Products which are available under the trademark Evatane® (Arkema) are also suitable.
  • active substance compositions are particularly preferred in which ethylene / vinyl acetate copolymer is used as the polymeric carrier material and this copolymer contains 5 to 50% by weight of vinyl acetate, preferably 10 to 40% by weight .-% vinyl acetate and in particular 20 to 30 wt .-% vinyl acetate, each based on the total weight of the copolymer contains.
  • suitable carrier materials are the cyclodextrins.
  • inorganic carrier materials are preferably also used.
  • Forms of cleaning agent are particularly preferred, characterized in that at least one of the carrier materials is an inorganic carrier material, preferably a silicate, phosphate or borate.
  • the silicates, phosphates or borates are preferably in the form of a glass, particularly preferably in the form of a water-soluble glass.
  • Particularly preferred glasses are glasses containing zinc and / or bismuth, in particular glasses containing bismuth phosphate and / or glasses containing zinc phosphate.
  • the carrier material is water-soluble and already contains in its substance the active ingredient, in particular the glass corrosion inhibitors (zinc and / or bismuth) in the carrier material.
  • the cleaning agent supply forms can contain such glasses containing zinc or bismuth, particularly preferably glass containing zinc phosphate, in addition to a further active substance composition comprising a carrier material, preferably a water-insoluble carrier material and at least one active substance D. These can then be contained in a common chamber or in separate chambers, in particular in one or more chambers which have openings, in particular openings such that the washing liquor and / or the air can flow through them.
  • Preferred forms of cleaning agents are those which contain a glass containing zinc phosphate or bismuth phosphate and furthermore at least one, preferably two, three or more Contain active ingredient compositions which comprise one or more fragrances and / or one or more fragrance scavengers as active ingredients.
  • thermoplastic carrier materials or carrier materials which deform plastically under the influence of the ambient temperatures occurring during use are particularly preferred.
  • the plastic deformation of the carrier materials in the course of one or more applications results in a change in the carrier material surface, in particular a change in the size of the carrier material surface, which in turn has an advantageous effect on the release profile and the release kinetics of the active cleaning compositions contained in the active substance compositions.
  • Dosing devices characterized in that at least one polymeric carrier material has a melting or softening point between 40 and 125 ° C, preferably between 60 and 100 ° C, particularly preferably a melting point of 70 to 90 ° C and in particular between 73 and 80 ° C ( preferred determination method for the melting point according to ISO 11357-3) are preferred according to the invention.
  • the forms of cleaning agent according to the invention are particularly suitable for multiple dosing of the active substances contained in them.
  • water-insoluble carrier materials In order to ensure such multiple dosing via a large number of cleaning processes, it has proven to be advantageous to use only water-insoluble carrier materials.
  • These water-insoluble carrier materials also simplify the manufacture of the forms according to the invention. Preferred forms of offer are therefore characterized in that all the carrier materials used are water-insoluble.
  • the active substance compositions can in principle assume all physical states and / or spatial forms that can be achieved depending on the chemical and physical properties of the carrier materials.
  • at least one of the active substance compositions is in the form of a gel.
  • At least one of the active substance compositions is in the form of a solid. Active ingredient compositions in the form of individual blocks comprising an entire active ingredient composition are used with particular preference.
  • the active substance compositions can preferably be in particulate form, the active substance compositions in which the carrier material of at least one of the active substance compositions is in particle form, these particles preferably having an average diameter of 0.5 to 20 mm, preferably 1 to 10 mm and in particular 3 have up to 6 mm, are particularly preferred.
  • Active ingredient compositions which comprise at least one colored active ingredient composition are particularly preferably used.
  • the coloring of at least one of the active ingredient compositions enables an optical differentiation of these compositions to be achieved and the multiple use of these different compositions can be clarified in a simple manner.
  • the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active ingredient compositions.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware, to be precise stain.
  • the colorants When choosing the colorant, it must be noted that the colorants have a high storage stability and insensitivity to light and do not have too strong an affinity for glass, ceramics or plastic dishes. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the cleaning agents varies. In the case of readily water-soluble colorants, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically chosen. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance but are less readily water-soluble, the suitable concentration of the colorant in cleaning agents is typically a few 10 -3 to 10 -4 % by weight.
  • the cleaning agent supply form is characterized in that the at least one active ingredient D is selected from the group of fragrances, preferably linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol, eucalyptol and their mixtures, fragrance scavengers, e.g.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons can be used.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described as “top note”, “heart or middle note” (middle note or body ) and “base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, i.e. non-stick fragrances.
  • more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
  • fixatives for example, which prevents them from evaporating too quickly.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and / or eucalyptol and mixtures thereof.
  • the known ricenolates in particular the zinc ricenoleates, can be used, for example, as scent catchers (or odor neutralizers or scent neutralizers, agents against malodour or bad odors). Also preferred are 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol. Activated carbon and / or cyclodextrins and / or zeolites, preferably acid-modified zeolites, can also be used with particular preference.
  • Zinc ricinoleate alone or in combination with one or several of the above-mentioned fragrances and / or scent scavengers is particularly preferred, since it also has a positive effect on the inhibition of glass corrosion during the rinsing process.
  • Fragrances and / or fragrance scavengers antimicrobial agents are used.
  • bacteriostatics and bactericides fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuriacetate, although these compounds can be dispensed with entirely.
  • the active substances can be contained in the active substance preparations in any amounts.
  • dosing devices are particularly preferred in which the proportion by weight of the active ingredient (s) is 1 to 70% by weight, preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight, in particular 30 to 40% by weight, is based in each case on the total weight of the active ingredient composition (s).
  • active ingredient compositions can be present separately from one another or next to one another in the packaging means of the detergent form.
  • the different active substance compositions can preferably be present next to one another, that is to say in direct contact with one another, in the packaging means of the detergent form.
  • the cartridges of the cleaning agent forms described above are provided with a metering device that can be detached from the cartridge.
  • a metering device can be connected to the cartridge, for example, by means of an adhesive, snap-in, snap or plug connection. Filling the cartridge is simplified, for example, by separating the cartridge and the metering device.
  • the detachable connection of the cartridge and metering device enables the cartridges on the metering device to be replaced. Such an exchange can be indicated, for example, when the cleaning program is changed or after the cartridge has been completely emptied.
  • the aforementioned detergent dosing systems comprising the detergent supply form according to the invention (and optionally one or two further compositions different from the detergent preparations A and B or A, B and C or A, B, C and D according to the invention, a cartridge and a detachable with the cartridge in a preferred embodiment, the connected dosing device is present in a common outer packaging, the filled cartridge and the dosing device being particularly preferably contained separately from one another in the outer packaging.
  • the outer packaging serves for storage, transport and presentation of the cleaning agent form according to the invention and protects it from contamination, Strike and shock, especially for the purpose of presentation, the outer packaging should at least partially be made transparent.
  • the dosing system according to the invention consists of the basic components of a cartridge filled with the cleaning agent according to the invention and a dosing device that can be coupled to the cartridge, which in turn is formed from further assemblies, such as, for example, component carrier, actuator, closure element, sensor, energy source and / or control unit.
  • the metering system according to the invention is movable. Movable in the sense of this application means that the metering system is not inextricably linked to a water-carrying device such as a dishwasher or the like, but rather can be removed from a dishwasher by the user or positioned in a dishwasher, i.e. can be handled independently
  • the metering device is not releasably connected to a water-carrying device such as a dishwasher or the like for the user and only the cartridge is movable.
  • the preparations to be dosed can have a pH between 2 and 14, in particular 2 and 12, depending on the intended use, all components of the dosing system that come into contact with the preparations should have an appropriate acid and / or alkali resistance. Furthermore, these components should be largely chemically inert, for example against nonionic surfactants, enzymes and / or fragrances, through a suitable choice of material.
  • a cartridge in the sense of this application is understood to mean a packaging material which is suitable for enveloping or holding together flowable or scatterable preparations and which can be coupled to a metering device for dispensing the preparation.
  • a cartridge can also comprise a plurality of chambers which can be filled with compositions which differ from one another. It is also conceivable for a plurality of containers to be arranged to form a cartridge unit.
  • the cartridge has at least one outlet opening, which is arranged in such a way that the preparation can be released from the container under the force of gravity in the use position of the metering device.
  • At least one second chamber is provided for receiving at least one second flowable or scatterable preparation, the second chamber having at least one outlet opening which is arranged in such a way that product release caused by gravity from the second chamber in the use position of the metering device is effected.
  • the arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers, which are usually not stable with one another, such as bleaches and enzymes.
  • At least one of the chambers for dispensing active substance (s) D is designed such that it has openings through which the washing liquor and / or the air can flow .
  • the cartridge is formed in one piece.
  • the cartridges can be formed inexpensively in one production step, in particular by means of suitable blow molding processes.
  • the chambers of a cartridge can be separated from one another, for example, by webs or material bridges.
  • the cartridge can also be formed in several pieces by components that are injection molded and then joined together. Furthermore, it is conceivable that the cartridge is formed in such a way that at least one chamber, preferably all chambers, can be removed individually from the dosing device or inserted into the dosing device. This makes it possible to replace a chamber that has already been emptied if the consumption of a preparation from one chamber varies, while the others, which may still be filled with preparation, remain in the metering device. In this way, a targeted and needs-based refilling of 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 detachably or non-releasably fixed to one another by a suitable positive, non-positive or material connection.
  • the fixation can be carried out by one or more of the types of connections from the group of snap-in connections, Velcro connections, press connections, fusion connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or bump connections.
  • the fixation can also be formed by a shrink tube (so-called sleeve), which is pulled over the entire or sections of the cartridge in a heated state and firmly encloses the chambers or the cartridge in the cooled state.
  • the bottom of the chambers can be inclined in a funnel shape towards the discharge opening.
  • the interior wall of a chamber can be designed in such a way by a suitable choice of material and / or surface design that the preparation adheres little to the interior wall of the chamber. This measure can also further optimize the residual emptiness of a chamber.
  • the chambers of a cartridge can have the same or different filling volumes.
  • the ratio of the container volumes is preferably 5: 1, in a configuration with three chambers preferably 4: 1: 1, these configurations being particularly suitable for use in dishwashers.
  • the cartridge preferably has 3, 4, 5 or 6 chambers.
  • the first chamber contains an alkaline cleaning preparation
  • the second chamber contains an enzymatic preparation
  • the third chamber contains a rinse aid, the volume ratio of the chambers being approximately 4: 1: 1.
  • the fourth chamber contains the at least one active substance composition, comprising the at least one active substance D and a carrier material, preferably a water-insoluble carrier material.
  • a dosing chamber can be formed in or on a chamber in the direction of flow of the preparation in front of the outlet opening.
  • the metering chamber determines the amount of preparation that is to be released into the environment when preparation is released from the chamber. This is particularly advantageous if the closure element of the metering device, which causes the preparation to be dispensed from a chamber into the environment, can only be put into a dispensing and a closure state without checking the dispensing quantity.
  • the dosing chamber then ensures that a predefined amount of preparation is released without an immediate feedback of the dispensed preparation amount.
  • the metering chambers can be formed in one piece or in several pieces.
  • one or more chambers each have a chamber opening that can be closed in a liquid-tight manner in addition to an outlet opening.
  • This chamber opening makes it possible, for example, to refill the preparation stored in this chamber.
  • ventilation options can be provided in particular in the head region of the cartridge, in order to ensure pressure compensation when the filling level of the chambers falls between the interior of the cartridge chambers and the surroundings.
  • These ventilation options can be designed, for example, as a valve, in particular a silicone valve, micro-openings in the cartridge wall or the like.
  • the cartridge chambers are not to be ventilated directly, but rather to be provided via the metering device or no ventilation, for example when using flexible containers such as bags, this has the advantage that at elevated temperatures in the course of a dishwashing cycle of a dishwasher by warming the A pressure is built up in the chamber contents, which presses the preparations to be metered in the direction of the outlet openings, so that the cartridge can be easily emptied. Furthermore, with such an air-free packaging there is no risk of oxidation of substances in the preparation, which makes bag packaging or bag-in-bottle packaging appear expedient, in particular for preparations sensitive to oxidation.
  • the cartridge usually has a filling volume of ⁇ 5,000 ml, in particular ⁇ 1,000 ml, preferably ⁇ 500 ml, particularly preferably ⁇ 250 ml, very particularly preferably ⁇ 50 ml.
  • the cartridge can take any shape. For example, it can be cube-shaped, spherical or plate-like.
  • the shape of the cartridge and the metering device can in particular be designed in such a way that they ensure as little loss of useful volume as possible, in particular in a dishwasher.
  • the dosing device based on the dishes to be cleaned in dishwashers.
  • this can be plate-shaped, approximately in the dimensions of a plate.
  • the cartridge preferably has a ratio of height: width: depth between 5: 5: 1 and 50: 50: 1, particularly preferably of about 10: 10: 1.
  • the "slim" design of the dosing device and the cartridge make it possible in particular to position the device in the lower cutlery basket of a dishwasher in the receptacles provided for plates. This has the advantage that the preparations dispensed from the dosing device go directly into the washing liquor and cannot adhere to other items to be washed.
  • the dosing system is dimensioned such that the dosing system can only be positioned in the receptacles provided for the lower basket.
  • the width and the height of the metering system can be chosen in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the dosing unit in a cup shape with an essentially circular or square base area.
  • the cartridge In order to protect heat-sensitive components of a preparation in a cartridge from exposure to heat, it is advantageous to manufacture the cartridge from a material with a low thermal conductivity.
  • a further possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to isolate the chamber by means of suitable measures, e.g. through the use of thermal insulation materials such as styrofoam, which completely or partially enclose the chamber or the cartridge in a suitable manner.
  • the cartridge has an RFID label that at least contains information about the contents of the cartridge and that can be read out by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. This can ensure that an optimal dosing program is always used for a specific preparation. It can also be provided that, in the absence of an RFID label or in the case of an RFID label with an incorrect or incorrect identification, no dosing is carried out by the dosing device and instead an optical or acoustic signal is generated that the user is aware of the error points out.
  • the cartridges can also have structural elements which interact with corresponding elements of the metering device according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the metering device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the metering device to be transmitted to the control unit, as a result of which the metering device can be controlled in a manner which is coordinated with the content of the corresponding container.
  • the cartridge is designed in particular for receiving flowable cleaning agents.
  • a cartridge particularly preferably has a plurality of chambers for spatially separated accommodation of preparations of a cleaning agent which are in each case different from one another.
  • the cartridge can be designed such that it can be detachably or firmly arranged in or on the dishwasher.
  • control unit The control unit, sensor unit and at least one actuator required for operation are integrated in the dosing device.
  • An energy source is preferably also arranged in the metering device.
  • the metering device preferably consists of a splash-proof housing that prevents the penetration of splashing water, as can 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 designed in or on a water-carrying device, in particular a water-carrying household appliance, preferably a dishwasher, such that a transmission of electrical energy from the water-carrying device to the dosing device is realized.
  • a water-carrying device in particular a water-carrying household appliance, preferably a dishwasher
  • the interfaces are formed by plug connectors.
  • the interfaces can be designed in such a way that wireless transmission of electrical energy is effected.
  • a second interface on the metering device and the water-carrying device for the transmission of electromagnetic signals, which, in particular, indicate the operating status, measurement and / or control information of the metering device and / or the water-carrying device such as one Represent dishwasher, trained.
  • An adapter can be used to easily couple the dosing system to a water-bearing household appliance.
  • the adapter is used for the mechanical and / or electrical connection of the dosing system to the water-bearing household appliance.
  • the adapter is, preferably fixed, connected to a water-carrying line 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 captured by the water flow and / or spray jet of the household appliance.
  • the adapter makes it possible to run a dosing system for both a self-sufficient and a "build-in" version. It is also possible to design the adapter as a type of charging station for the metering system, in which, for example, the energy source of the metering device is charged or data is exchanged between the metering 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 as such is positioned inaccessible to the user in the water-carrying household appliance, so that the metering device is inserted into the adapter, for example during assembly of the household device, the adapter, the metering device and the like Household appliance are designed such that a cartridge can be coupled by the user to the dosing device.
  • the forms of detergent according to the invention are suitable for use in dishwashing, but the use of a form of detergent according to the invention or a detergent dosing system for washing dishes in a machine dishwashing method is preferred.
  • the cleaning agents according to the invention are notable for special physical and chemical stability, in particular with respect to temperature fluctuations.
  • the cleaning agents according to the invention are therefore particularly suitable for metering by means of a metering system located in the interior of a dishwasher.
  • a dosing system which can be immovably integrated into the interior of the dishwasher (machine-integrated dosing device), but can of course also be introduced into the interior as a mobile device (self-sufficient dosing device), contains the multiple amounts of detergent required to carry out a mechanical cleaning process .
  • Movable in the sense of this application means that the dispensing and metering system is not inextricably linked to a device such as a dishwasher or the like, but rather can be removed from a dishwasher or positioned in a dishwasher, for example.
  • An example of an immovable cartridge is a container integrated immovably into the interior, for example into the side wall or the interior lining of the door of a dishwasher.
  • An example of a movable cartridge is a container that the consumer places in the interior of the dishwasher and remains there throughout the course of a cleaning cycle.
  • Such a cartridge can be integrated into the interior, for example by simply inserting it into the cutlery or crockery basket, but can also be removed from the interior of the dishwasher by the consumer.
  • the detergent or the detergent combination is dosed from the cartridge into the interior of the dishwasher, as described above, preferably by means of a dosing device that can be detached from the cartridge.
  • a dosing device can be connected to the cartridge by means of an adhesive, latching, snap or plug connection. Cartridges with an inseparably connected dosing device can of course also be used.
  • a form of detergent according to the invention as a detergent reservoir for i) a metering device immovably integrated into the interior of a dishwasher or ii) a movable metering device provided for positioning in the interior of a dishwasher is preferred.
  • the cleaning agents and cleaning agent combinations according to the invention are preferably used as automatic dishwashing agents.
  • the invention also relates to an automatic dishwashing process in which the active substance composition is in the cartridge and the washing liquor and / or air flows through openings.
  • the fragrance (s) are released into the air in the interior of the dishwasher, and in addition to scenting the washing liquor during the dishwashing process between the individual rinse cycles to create a pleasant smell situation for the consumer when opening and loading the dishwasher.
  • the dosage of the cleaning agent preparation A and the cleaning agent preparation B and optionally the cleaning agent preparation C is carried out at different times in the cleaning cycle.
  • the time t2 is at least 1 minute in time, preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes , before or after, preferably before time t1.
  • a delayed metering of the minute preferably at least 2 minutes and in particular between 3 and 30 minutes, in particular between 3 and 20 minutes, before or after, preferably after the time t1.
  • the cleaning preparation B is metered into the interior at a temperature of 20-35 ° C., then the cleaning preparation A at a temperature of 30-60 ° C. and then the cleaning preparation C at a temperature below 20 ° C.

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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)
EP19209989.3A 2018-11-23 2019-11-19 Détergent destiné au dosage automatique Active EP3656839B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102018220189.7A DE102018220189A1 (de) 2018-11-23 2018-11-23 Reinigungsmittel zur automatischen Dosierung

Publications (2)

Publication Number Publication Date
EP3656839A1 true EP3656839A1 (fr) 2020-05-27
EP3656839B1 EP3656839B1 (fr) 2024-01-03

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EP19209989.3A Active EP3656839B1 (fr) 2018-11-23 2019-11-19 Détergent destiné au dosage automatique

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Country Link
EP (1) EP3656839B1 (fr)
DE (1) DE102018220189A1 (fr)
ES (1) ES2970752T3 (fr)
PL (1) PL3656839T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019219448A1 (de) * 2019-12-12 2021-06-17 Henkel Ag & Co. Kgaa Reinigungsmittel
EP4379028A1 (fr) * 2022-11-30 2024-06-05 Henkel AG & Co. KGaA Systeme de builder pour l'élimination des taches de protéines

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EP1759624A2 (fr) 2002-03-06 2007-03-07 Reckitt Benckiser N.V. Améliorations d'un récipient ou relative à un récipient
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
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102013225920A1 (de) * 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel

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AU9181698A (en) 1997-10-14 1999-05-03 Procter & Gamble Company, The Light-duty liquid or gel dishwashing detergent compositions comprising mid-chainbranched surfactants
ES2266150T3 (es) 2001-05-22 2007-03-01 THE PROCTER & GAMBLE COMPANY Composiciones embolsadas.
DE102005041708A1 (de) 2005-09-02 2007-03-08 Henkel Kgaa Reinigungsmittel
DE102009002094A1 (de) 2009-04-01 2010-10-07 Henkel Ag & Co. Kgaa Reinigungsmittel
CA2818719C (fr) 2010-12-13 2015-11-24 Colgate-Palmolive Company Composition de nettoyage concentree a diluer
PT3008159T (pt) 2013-06-12 2017-02-10 Unilever Nv Composição detergente passível de ser vertida compreendendo partículas suspensas
DE102014204144A1 (de) 2014-03-06 2015-09-10 Henkel Ag & Co. Kgaa Vorportionierte Reinigungsmittel umfassend mindestens zwei getrennte flüssige Zubereitungen
DE102015210828A1 (de) 2015-06-12 2016-12-15 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel
PL420843A1 (pl) 2017-03-14 2018-09-24 Bąbelek Zbigniew Octagon International Trade Złożony środek detergentowy typu kapsułka w kapsułce

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EP1759624A2 (fr) 2002-03-06 2007-03-07 Reckitt Benckiser N.V. Améliorations d'un récipient ou relative à un récipient
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
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102013225920A1 (de) * 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019219448A1 (de) * 2019-12-12 2021-06-17 Henkel Ag & Co. Kgaa Reinigungsmittel
EP4379028A1 (fr) * 2022-11-30 2024-06-05 Henkel AG & Co. KGaA Systeme de builder pour l'élimination des taches de protéines

Also Published As

Publication number Publication date
PL3656839T3 (pl) 2024-05-20
DE102018220189A1 (de) 2020-05-28
ES2970752T3 (es) 2024-05-30
EP3656839B1 (fr) 2024-01-03

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