EP3656839B1 - Reinigungsmittel zur automatischen dosierung - Google Patents

Reinigungsmittel zur automatischen dosierung Download PDF

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Publication number
EP3656839B1
EP3656839B1 EP19209989.3A EP19209989A EP3656839B1 EP 3656839 B1 EP3656839 B1 EP 3656839B1 EP 19209989 A EP19209989 A EP 19209989A EP 3656839 B1 EP3656839 B1 EP 3656839B1
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EP
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Prior art keywords
weight
cleaning agent
acid
preparation
detergent
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EP19209989.3A
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German (de)
English (en)
French (fr)
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EP3656839A1 (de
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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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

  • devices for multiple dosing of cleaning agents are desired by consumers.
  • Devices can be differentiated between dosing containers integrated into the dishwasher on the one hand and independent devices independent of the dishwasher on the other.
  • cleaning agent 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. This eliminates the need for the consumer to dose the cleaning agent before starting each individual cleaning cycle.
  • Examples of such devices are given 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).
  • Cleaning agent offerings with separate compositions are in DE102013225920 A1 and DE102009027164 A1 disclosed.
  • the cleaning agents contained in these devices for multiple dosing are also exposed to changing temperatures over a longer period of time, with these temperatures being, to a first approximation, the same as the water temperatures used to carry out the cleaning processes. These temperatures can be up to 95°C, although in the area of automatic dishwashing only temperatures between 50 and 75°C are usually achieved.
  • a cleaning agent contained in a device intended for multiple dosing is therefore repeatedly heated to temperatures well above those for transport and delivery over the course of several cleaning processes Storage is heated to usual temperatures, with temperature-sensitive active substances in particular being affected.
  • the object of the present application was therefore to provide a cleaning agent offering which delivers good cleaning performance, especially on dried food residues, in particular minced meat, oatmeal and/or tea, even if there are several days between the individual usage cycles.
  • This system should be less complicated, especially 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 replaces the combination together and does not have to worry about replacing individual products separately.
  • the cleaning agent form according to the invention has a good cleaning performance, preferably for stubborn, especially dried-up food residues on the items to be washed, for example oatmeal or tea. It is therefore no longer necessary to rinse food residues before putting them in the dishwasher, which is particularly advantageous for ecological and time-related reasons as well as in terms of additional water costs.
  • the subject of this application are corresponding cleaning agent offerings that are obtained by combining two liquid cleaning agent preparations A and B.
  • the liquid cleaning agent preparations A and B and the active ingredient composition differ from each other in terms of their composition.
  • the cleaning agent supply form is characterized in that the cleaning agent 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 do not contain phosphate.
  • the cleaning composition A contains, as complexing agents, from 8.0 to 30% by weight of L-glutamic acid- N , N -diacetic acid and/or the corresponding alkali metal salt (GLDA), preferably the tetrasodium salt, and/or methylglycinediacetic acid and/or the corresponding alkali metal salt, preferably the trisodium salt.
  • the trisodium salt of methylglycinediacetic acid (MGDA) or the corresponding sodium salts is particularly preferably included.
  • methylglycinediacetic acid or L-glutamic acid- N , N -diacetic acid includes, in addition to the free acids, also 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 contain 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 polymer containing sulfone groups is preferably a sulfopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain 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, methylenemalonic 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, acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic 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-propene1-sulfonic acid, styrenesulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfo propyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned
  • the sulfonic acid groups can be present entirely or partially in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group is present in some or all of the sulfonic acid groups
  • Metal ions preferably alkali metal ions and in particular sodium ions, can be exchanged.
  • 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 for copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, and particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the monomer containing carboxylic acid groups 10 to 50% by weight, the monomers are preferably selected from those mentioned above.
  • the molecular weight 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 molecular weights of from 2000 to 200,000 g mol -1 , preferably from 4000 to 25,000 g mol -1 and in particular from 5000 to 15,000 g mol -1 .
  • the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to the carboxyl group-containing monomer and the sulfonic acid group-containing monomer.
  • nonionic, preferably hydrophobic monomer in addition to the carboxyl group-containing monomer and the sulfonic acid group-containing monomer.
  • 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 cleaning agent forms include a cleaning agent 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 bicarbonates, preferably alkali metal 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, each based on the weight of the cleaning agent preparation A.
  • alkali metal carbonates particularly preferably sodium carbonate
  • Organic cobuilders that should be mentioned in particular are polycarboxylates/polycarboxylic acids, polymeric carboxylates, (poly)aspartic acid, polyacetals, dextrins and organic cobuilders. These substance classes are described below.
  • Useful organic builders are, for example, the polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to mean those carboxylic acids that 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 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 or more, monomers containing carboxylic acid.
  • the free acids typically also have the properties of an acidifying component and are therefore also used to set a lower and milder pH value of cleaning agents.
  • an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.
  • Particularly preferred cleaning agent preparations A according to the invention contain citrate as one of their essential builders.
  • Cleaning agent supply forms characterized in that the cleaning agent preparation A contains 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight of citrate, based on its total weight, are preferred according to the invention.
  • Citrate or citric acid have proven to be the most effective builders, particularly in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and/or the polymers containing sulfonic acid groups, in terms of cleaning performance such as rinse performance and, in particular, deposit inhibition.
  • cleaning agent preparation A based on its total weight, contains 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% by weight.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred from this group.
  • Copolymeric polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and 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 mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
  • the content of (co-)polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Machine dishwashing detergents can use crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O as a builder, in which M represents sodium or hydrogen, particularly preferred values for x are 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 detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwashing detergents according to the invention are silicate-free.
  • the automatic dishwashing detergents according to the invention can contain the aforementioned builders both in the form of individual substances and in the form of mixtures of two, three, four or more builders.
  • the dishwashing detergent contains at least two builders from the group of carbonates and citrates and the polymers containing sulfonic acid groups, the proportion by weight of these builders, based on its total weight of the automatic dishwashing detergent, preferably being 2 to 50 wt .-%, preferably 5 to 45% by weight and in particular 10 to 40% by weight.
  • 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 detergents according to the invention.
  • the cleaning agent preparation A contains a complexing agent which is different from the builders mentioned above.
  • the proportion by weight 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.
  • Phosphonates form another group of preferred complexing agents, provided they can be used for regulatory reasons.
  • the complex-forming phosphonates include a number of different compounds such as diethylenetriaminepenta-(methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • DTPMP diethylenetriaminepenta-(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as a sodium salt, with the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9).
  • the preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP from the phosphonate class is preferably used as the builder.
  • the aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, particularly if the agents also contain bleach, it may be preferred to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • cleaning agent preparations A which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • the automatic dishwashing detergents according to the invention can 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% by weight and in particular 1.5 to 4% by weight.
  • Particularly preferred cleaning agent forms 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 aciddiacetic acid, hydroxyethane-1,1-diphosphonic acid or diethylenetriaminepenta(methylenephosphonic acid) and their salts or mixtures thereof .
  • further complexing agents selected from the group of hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, aspartic aciddiacetic acid, hydroxyethane-1,1-diphosphonic acid or diethylenetriaminepenta(methylenephosphonic acid) and their salts or mixtures thereof .
  • 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 bicarbonate and optionally at least one polymer containing sulfonic acid groups.
  • the cleaning agent preparation A contains, based on its total weight, 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 from 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 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 from 4 to 15% by weight, and carbonate in amounts of 5 to 30% by weight, in particular 7 to 20% by weight.
  • phosphonate and/or its salt in amounts of 1.2 to 6% by weight, preferably 1.3 to 5% by weight, particularly preferably 1 .4 to 4.5% by weight, in particular 1.5 to 4% by weight.
  • one of the cleaning agent preparations preferably cleaning agent preparation B, further 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 cleaning agent preparations A and B.
  • Surfactants are in a cleaning agent preparation B according to the invention, if used, preferably 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% by weight.
  • Cleaning agent 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 the cleaning agent preparation A.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are 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 of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 7 EO.
  • the ethoxylation levels reported represent statistical averages, which may be a whole or a fractional number 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants that 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 here, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but rather randomly. Such products are obtainable by 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.
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate types.
  • Sulfonate-type surfactants are preferably C 9-13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is taken into consideration.
  • Alkane sulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
  • 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 soaps, can be in the form of their sodium, potassium or ammonium salts as well 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 the cleaning preparation B is 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of the cleaning preparation A.
  • a preferred pH value for cleaning preparations A according to the invention is between 9 and 14, in particular 9 and 12.
  • the pH value can be adjusted, if necessary, using 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 component, the proportion by weight of the cleaning-active enzyme preparation in the total weight of the cleaning agent preparation B being at least 5% by weight, preferably 5 to 80% by weight, preferably 5 to 60% by weight. , particularly preferably 10 to 50% by weight and in particular 10 to 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, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferred.
  • Cleaning agents contain enzymes preferably in total amounts of 1 x 10 -6 to 5% by weight 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 contain at least one cleaning-active enzyme from the group of amylases and / or proteases and / or cellulases and / or Mannanases, in particular from the group of amylases and/or proteases, are preferred.
  • subtilisin type those of the subtilisin type are preferred.
  • 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 be assigned to the subtilases but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • Liquid cleaning agent preparations B preferred according to the invention contain, based on the total weight of the cleaning agent preparation, 5 to 50% by weight, preferably 7 to 40% by weight and in particular 10 to 30% by weight of protease preparations. Particular preference is given to cleaning agent preparations B which, based on their total weight, contain 15 to 25% by weight of protease preparations.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis , from B. amyloliquefaciens , from B. stearothermophilus , from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • 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 also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available or further developed from Humicola lanuginosa ( Thermomyces lanuginosus ), especially those with the amino acid exchange D96L. Furthermore, for example, the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. 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.
  • Cleaning-active enzymes in particular proteases and amylases, are generally not provided in the form of 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, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
  • the enzyme protein only forms a fraction of the total weight of common 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.
  • a preferred pH value for cleaning agent preparations B according to the invention is between 6 and 9.
  • the cleaning agent preparations B of the cleaning agent forms according to the invention contain 2.5% by weight or less of complexing agents. They preferably contain less than 2.5% by weight of complexing agents and/or builders. Reducing the complexing agent content below these upper limits has proven to be advantageous for cleaning performance. By further reducing the content of complexing agent well below the upper limits, a further increase in the cleaning performance of cleaning agent forms according to the invention can surprisingly be achieved.
  • cleaning agent forms preferred according to the invention are characterized in that the cleaning agent 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 cleaning agent 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, propanediol 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 glycol methyl ether , diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy-, ethoxy- or butoxytrig
  • a particularly preferred organic solvent that 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 the 1,2-propylene glycol in the total weight of the cleaning agent preparations B according to the invention can vary within wide limits, but those preparations which, based on the total weight of the respective cleaning agent preparation B, have proven to be particularly stable are 5 to 80% by weight, preferably Contain 10 to 60% by weight and in particular 20 to 50% by weight of 1,2-propylene glycol. Corresponding preparations are therefore preferred according to the invention.
  • a further optional component of the cleaning agent preparations according to the invention is boric acid or a boric acid derivative.
  • boronic acids or their salts or esters are preferably used, including, in particular, derivatives with aromatic groups, such as 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 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 that is particularly effective in terms of stabilizing the cleaning agent preparation is 4-formylphenyl boronic acid.
  • the proportion by weight of the 4-formylphenyl boronic acid in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparation B, are 0.001 to 10% by weight, preferably 0.002 to 6% by weight and in particular 0.05 to 3% by weight. 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 proportion by weight 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 calcium ion sources with regard to the stabilization of the cleaning agent preparation B.
  • the proportion by weight of the organic calcium salts in the total weight of the cleaning agent preparations according to the invention can vary within wide limits, but those preparations which, based on the total weight of the cleaning agent preparation, are 0.01 to 10% by weight, preferably 0.2 to 8% by weight and in particular 0.5 to 5% by weight. Corresponding preparations are therefore preferred according to the invention.
  • cleaning agent preparations B according to the invention can 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 of water. In a further preferred embodiment, the cleaning agent preparations B 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, based on their total weight.
  • the cleaning agent supply form further comprises a liquid cleaning agent preparation C, wherein the cleaning agent preparation C is different from the cleaning agent preparations A and B.
  • the cleaning agent preparations A and B and the active ingredient composition D are used in a preferred embodiment in combination with at least one further cleaning agent preparation C.
  • this cleaning agent preparation C preferably contains surfactant and/or acid, preferably contains surfactant and acid.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent preparation C is preferably from 1.0 to 20% by weight, preferably from 2.0 to 18, particularly preferably from 4.0 to 15% by weight and in particular from 6.0 to 12% by weight.
  • At least one cleaning agent preparation in particular at least one cleaning agent preparation further comprising a nonionic surfactant, particularly preferably at least the cleaning agent preparation B and/or D contains at least one hydrotrope (hereinafter also referred to as a solubilizer).
  • a solubilizer contains at least one hydrotrope (hereinafter also referred to as a solubilizer).
  • Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and/or N-methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, especially cumene sulfonate. It was found that the use of hydrotropes, especially cumene sulfonate, enormously improves the phase stability with regard to temperature fluctuations.
  • At least the cleaning agent preparation C in particular the cleaning agent preparations C and B, has 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, 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 from 6 to 15, for example from 7 to 12% by weight, based on the total weight of the respective cleaning agent preparation.
  • hydrotrope preferably xylene sulfonate, cumene sulfonate, urea and/or N-methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, in particular cumene sulfonate, preferably in an amount from 2 to 25% by weight, in particular from 4 to 20% by weight
  • the weight ratio of the at least one nonionic surfactant to the at least one hydrotrope is preferably xylene sulfonate, cumene sulfonate, urea and/or N-methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, in particular cumene sulfonate. 2:1 to 1:2, especially 1.6:1 to 1:1.
  • 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 final rinse cycle.
  • Both inorganic acids and organic acids are suitable here, as long as they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular. 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.
  • Commercially available and also preferably used as an acidification agent in the context of the present invention is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid ( max. 33% by weight.
  • Cleaning agent preparations C which, based on the total weight of the cleaning agent preparation C, contain one or more acidification 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.
  • acidification 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
  • formic acid is preferred because, in addition to the acid function to improve the final rinse result, it also has a positive influence on the storage stability of the cleaning preparation C, which is subject to strong temperature fluctuations due to storage in the interior of the dishwasher, as explained above. It also has a disinfectant effect, so that when formic acid is used in the final rinse cycle, the number of bacteria is reduced. This applies both to those bacteria that are in the rinsing liquor of the final rinse cycle and to those that are in the rinsing liquor remaining in the bottom of the dishwasher and the interior of the dishwasher during and after the rinsing process. This can also reduce the number of residual germs on the washed dishes.
  • an active ingredient composition D in particular comprising fragrances and/or scent catchers, and at the same time formic acid as an acidifying agent in the Preparation C is used.
  • Formic acid itself has a slightly pungent odor, which is unpleasant for sensitive consumers.
  • the cleaning agent preparations A, B and C described above differ in terms of their composition and are therefore not identical.
  • the cleaning agent 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 as a further component at least one zinc salt, 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 consisting 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 is in cleaning agent preparations according to the invention 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 cleaning agent preparation, in particular the respective cleaning agent preparation A or C.
  • Polyethyleneimines such as those available 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 can be used.
  • composition of some exemplary cleaning agent forms according to the invention comprising cleaning agent preparations A, B and C, can be found in the following tables.
  • the previously described combination of cleaning agents is packaged using a packaging material 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 cleaning agents.
  • Examples of such packaging 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 cleaning agent preparations can be dosed from the packaging only by opening a valve on the underside of the packaging (in particular the cartridge) based on gravity, preferably without the involvement of electrical or electronic means, such as pumps etc.
  • the chambers preferably empty largely completely, i.e. without any large residual amounts of the cleaning agent preparations to be dosed. This is advantageous for the consumer and for the environment because only small amounts of the cleaning agent preparations remain unused in the chambers of the packaging or cartridge.
  • the packaging means also contains at least one active ingredient 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.
  • at least one active ingredient 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. This is preferably:
  • the polymeric carrier material of the particles consists at least partially of ethylene/vinyl acetate copolymer.
  • a further preferred subject of the present application is therefore a cleaning agent supply form as described above, characterized in that a polymeric carrier material contains 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 made entirely of ethylene/vinyl acetate copolymer.
  • Ethylene/vinyl acetate copolymers is the name for copoylmers made from ethylene and vinyl acetate.
  • the production of this polymer is basically carried out in a process comparable to the production of low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • vinyl acetate With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is interrupted and thus 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.
  • active ingredient 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% by weight of vinyl acetate, based on the total weight of the copolymer.
  • suitable carrier materials are cyclodextrins.
  • inorganic carrier materials are preferably used.
  • Particularly preferred cleaning agent forms are 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 zinc phosphate.
  • the carrier material is water-soluble and its substance already contains the active ingredient, in particular the glass corrosion inhibitors zinc and/or bismuth) in the carrier material.
  • the cleaning agent delivery forms can contain such zinc or bismuth-containing glasses, particularly preferably zinc phosphate-containing glass, in addition to a further active ingredient composition comprising a carrier material, preferably a water-insoluble carrier material, and at least one active ingredient D.
  • a further active ingredient composition comprising a carrier material, preferably a water-insoluble carrier material, and at least one active ingredient 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 rinsing liquor and/or the air can flow through them.
  • cleaning agent forms that contain a glass containing zinc phosphate or bismuth phosphate and also at least one, preferably two, three or more Contain active ingredient compositions which comprise one or more fragrances and/or one or more scent catchers as active ingredients.
  • thermoplastic carrier materials or carrier materials that deform plastically under the influence of the ambient temperatures that occur 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 cleaning-active active ingredients contained in the active ingredient 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 cleaning agent forms according to the invention are particularly suitable for multiple dosing of the active ingredients they contain.
  • water-insoluble carrier materials In order to ensure such multiple dosing across a variety of cleaning processes, it has proven to be advantageous to only use water-insoluble carrier materials.
  • These water-insoluble carrier materials also simplify the production of forms according to the invention. Preferred forms of offer are therefore characterized in that all carrier materials used are water-insoluble.
  • the active ingredient compositions can in principle assume all physical states and/or spatial forms that can be realized depending on the chemical and physical properties of the carrier materials.
  • at least one of the active ingredient compositions is in the form of a gel.
  • At least one of the active ingredient compositions is present as a solid.
  • Active ingredient compositions are particularly preferably used in the form of individual blocks comprising an entire active ingredient composition.
  • the active ingredient compositions can preferably be in particulate form, the active ingredient compositions in which the carrier material of at least one of the active ingredient compositions is in particle form, these particles preferably having an average diameter of 0.5 to 20 mm, preferably of 1 to 10 mm and in particular of 3 up to 6 mm are particularly preferred.
  • active ingredient compositions which comprise at least one colored active ingredient composition.
  • 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 poses no difficulty for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light as well as no pronounced substantivity compared to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware to color.
  • the cleaning agent form is characterized in that the at least one active ingredient D is selected from the group of fragrances, preferably linalyl acetate, dihydromyrcenol, citronellonitriles, menthyl acetate, methylphenylbutanol, eucalyptol and mixtures thereof, scent catchers, such as zinc ricinoleate, cyclodextrins, 2- menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol, especially zinc ricinoleate; Dyes, glass corrosion inhibitors, antimicrobial active ingredients, germicides or fungicides and mixtures thereof, preferably mixtures of at least one scent catcher, preferably with one, two, three or more fragrances and / or at least one dye. Mixtures of at least one fragrance, preferably two, three or more fragrances and at least one dye are further preferred.
  • fragrances preferably linalyl acetate, dihydromyrcenol,
  • fragrance compounds for example synthetic products of the ester, ether, aldehyde type
  • perfume oils or fragrances Ketones, alcohols and hydrocarbons are used.
  • mixtures of different fragrances are preferably used, which together produce an appealing scent.
  • perfume oils can also contain natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • a fragrance In order to be perceivable, a fragrance must be volatile; in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Most fragrances have molecular weights of up to around 200 Daltons, while molecular weights of 300 Daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, with the odor impressions being divided into “top note” and “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 consists largely of less volatile, i.e. more adhesive, odorants.
  • more volatile fragrances can, for example, be bound to certain fixatives, which prevents them from evaporating too quickly.
  • the following classification of fragrances into "more volatile” or “firm” fragrances says nothing about the olfactory impression and whether the corresponding fragrance is perceived as a top or middle note.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting scent through a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliary substances.
  • particularly preferred fragrances are linalyl acetate, dihydromyrcenol, citronellonitriles, menthyl acetate, methylphenylbutanol and/or eucalyptol and mixtures thereof.
  • the well-known ricenolates in particular the zinc ricenolates, can be used as scent catchers (or, as used synonymously below, odor neutralizers or scent neutralizers, agents against malodour or bad smells).
  • scent catchers 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 catchers is particularly preferred since it also has a positive effect on inhibiting glass corrosion during the rinsing process.
  • antimicrobial active ingredients can be used as an alternative or in addition to the above-mentioned fragrances and/or scent traps.
  • fragrances and/or scent traps can be used as an alternative or in addition to the above-mentioned fragrances and/or scent traps.
  • bacteriostatics and bactericides fungistatics and fungicides, etc.
  • Important substances from these groups include benzalkonium chlorides, alkylarlylsulfonates, halogenphenols and phenol mercuriacetate, although these compounds can also be dispensed with entirely.
  • the active ingredients can in principle be contained in any desired amounts in the active ingredient preparations.
  • dosing devices in which the weight proportion 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, are particularly preferred. each based 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 of the cleaning agent presentation form.
  • the different active ingredient compositions can preferably be present next to one another, that is to say in direct contact with one another, in the packaging of the cleaning agent supply form.
  • the previously described cartridges of the cleaning agent forms are provided with a dosing device that can be detached from the cartridge.
  • a dosing device can be connected to the cartridge, for example by means of an adhesive, snap-in, snap-in or plug-in connection.
  • filling the cartridge is simplified, for example.
  • the detachable connection between the cartridge and the dosing device makes it possible to exchange the cartridges on the dosing device. Such a replacement can be indicated, for example, when changing the cleaning program or after the cartridge has been completely emptied.
  • the aforementioned cleaning agent dosing systems comprising the cleaning agent dosage form according to the invention (and optionally one or two further compositions different from the cleaning agent 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
  • the connected dosing device is present in a common outer packaging, with the filled cartridge and the dosing device particularly preferably being contained separately from one another in the outer packaging.
  • the outer packaging is used for the storage, transport and presentation of the cleaning agent supply form according to the invention and protects it from contamination, Impact and impact: Particularly for the purpose of presentation, the outer packaging should be at least partially 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 component carriers, actuators, closure elements, sensors, energy sources and / or control units.
  • the dosing system according to the invention is movable. Movable in the sense of this application means that the dosing system is not inseparably connected to a water-carrying device such as a dishwasher or the like, but can be removed, for example, from a dishwasher by the user or positioned in a dishwasher, i.e. can be handled independently
  • the dosing device is not detachably 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 value 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 appropriate acid and/or alkali resistance. Furthermore, through a suitable selection of materials, these components should be largely chemically inert, for example against nonionic surfactants, enzymes and/or fragrances.
  • a cartridge is understood to mean a packaging material which is suitable for enveloping or holding together flowable or spreadable preparations and which can be coupled to a dosing device in order to dispense the preparation.
  • a cartridge can also include several chambers that can be filled with different compositions. It is also conceivable that a plurality of containers are arranged to form a cartridge unit.
  • the cartridge has at least one outlet opening, which is arranged such that a gravity-induced release of the preparation from the container can be effected in the use position of the dosing device.
  • At least one second chamber is provided for receiving at least one second flowable or spreadable preparation, the second chamber having at least one outlet opening which is arranged in such a way that gravity-induced product release from the second chamber in the use position of the dosing device is effected.
  • the arrangement of a second chamber is particularly advantageous if the separate containers contain preparations that are usually not stable in storage, such as bleach and enzymes.
  • the chambers for releasing active ingredient(s) D such as a glass corrosion inhibitor, a fragrance or, in particular, an odor neutralizer, into the environment is designed in such a way that it has openings through which the rinsing liquor and/or air can flow .
  • the cartridge is formed in one piece.
  • the cartridges can be formed cost-effectively in one manufacturing step, in particular using suitable blow molding processes.
  • the chambers of a cartridge can be separated from one another, for example, by webs or material bridges.
  • the chambers of a cartridge can be fixed to one another using suitable connection methods, so that a container unit is formed.
  • the chambers can be releasably or permanently fixed to one another by a suitable positive, non-positive or cohesive connection.
  • the fixation can be carried out using one or more of the connection types from the group of snap-in connections, Velcro connections, press connections, fused connections, adhesive connections, welded connections, soldered connections, screw connections, wedge connections, clamp connections or bounce 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 tightly 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 inner wall of a chamber can be designed by suitable choice of material and/or surface design in such a way that the preparation has little material adhesion to the inner chamber wall. This measure can also be used to further optimize the residual emptying capacity 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 it is 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 ingredient composition, comprising the at least one active ingredient D and a carrier material, preferably a water-insoluble carrier material.
  • a dosing chamber can be formed in or on a chamber in front of the outlet opening in the direction of flow of the preparation.
  • the dosage 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 dosing device, which causes the preparation to be dispensed from a chamber to the environment, can only be placed in a dispensing and a closure state without controlling the dispensed quantity.
  • the dosing chamber then ensures that a predefined amount of preparation is released without immediate feedback on the amount of preparation dispensed.
  • the dosing 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 preparations stored in this chamber.
  • the cartridge chambers are not ventilated directly, but rather via the dosing 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 dishwasher cycle by the heating of the Chamber contents build up a pressure that pushes the preparations to be dosed towards the outlet openings, so that the cartridge can be easily emptied. Furthermore, with such air-free packaging there is no risk of oxidation of substances in the preparation, which makes bag packaging or bag-in-bottle packaging particularly useful for oxidation-sensitive preparations.
  • 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 spatial shape. It can, for example, be cube-shaped, spherical or plate-shaped.
  • the cartridge and the dosing device can in particular be designed in such a way with regard to their spatial shape that they ensure the lowest possible loss of useful volume, especially in a dishwasher.
  • the dosing device based on dishes to be cleaned in dishwashers.
  • this can be plate-shaped, approximately 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 about 10:10:1.
  • the "slim" design of the dosing device and the cartridge makes 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 liquid and cannot stick to other items to be washed.
  • the dosing system is dimensioned such that positioning of the dosing system is only possible in the receptacles provided for this purpose in the lower basket.
  • the width and height of the dosing system can be chosen in particular between 150mm and 300mm, particularly preferably between 175mm and 250mm.
  • the dosing unit in the form of a cup with a substantially circular or square base area.
  • Another possibility for reducing the influence of heat on a preparation in a chamber of the cartridge is to insulate the chamber by suitable measures, for example by using thermal insulation materials such as Styrofoam, which fully or partially enclose the chamber or the cartridge in a suitable manner.
  • suitable measures for example by using thermal insulation materials such as Styrofoam, which fully or partially enclose the chamber or the cartridge in a suitable manner.
  • the cartridge has an RFID label 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. This can ensure that an optimal dosing program is always used for a specific preparation. It can also be provided that if an RFID label is not present or if an RFID label has an incorrect or faulty identifier, no dosing is carried out by the dosing device and instead an optical or acoustic signal is generated that alerts the user to the error present points out.
  • the cartridges can also have structural elements that interact with corresponding elements of the dosing device according to the key-lock principle, so that, for example, only cartridges of a certain type can be coupled to the dosing device. Furthermore, this configuration makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, whereby the dosing device can be controlled in a manner tailored to the contents of the corresponding container.
  • the cartridge is designed in particular to hold flowable cleaning agents. Particularly preferably, such a cartridge has a plurality of chambers for spatially separated accommodation of different preparations of a cleaning agent.
  • the cartridge can be designed so that it can be detachably or permanently arranged in or on the dishwasher.
  • control unit The control unit, sensor unit and at least one actuator required for operation are integrated into the dosing device.
  • An energy source is also preferably arranged in the dosing device.
  • the dosing device preferably consists of a splash-proof housing that prevents the penetration of splash water, such as can occur when used in a dishwasher, into the interior of the dosing device.
  • the dosing device comprises at least one first interface, which interacts with a corresponding interface formed 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 a wireless transmission of electrical energy is effected.
  • a second interface on the dosing device and the water-carrying device for transmitting electromagnetic signals, which in particular contain operating status, measurement and/or control information of the dosing device and/or the water-carrying device such as one Represent dishwasher.
  • An adapter can be used to easily connect the dosing system to a water-conducting household appliance.
  • the adapter is used to mechanically and/or electrically connect the dosing system to the water-carrying household appliance.
  • the adapter is, preferably firmly, connected to a water-carrying pipe of the household appliance.
  • the adapter for positioning in or on the household appliance, in which the adapter is caught 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 "build-in” version. It is also possible to design the adapter as a type of charging station for the dosing system, in which, for example, the energy source of the dosing device is charged or data is 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 as such is positioned in the water-carrying household appliance so that it is not accessible to the user, so that the dosing device is inserted into the adapter, for example during assembly of the household appliance, with the adapter, the dosing device and that Household appliance are designed such that a cartridge can be coupled to the dosing device by the user.
  • the cleaning agent dosage forms according to the invention are suitable for use in dishwashing, although the use of a cleaning agent dosage form according to the invention or a cleaning agent dosing system for cleaning dishes in a machine dishwashing process is preferred.
  • the cleaning agents according to the invention are characterized by a particular physical and chemical stability, in particular against temperature fluctuations.
  • the cleaning agents according to the invention are therefore particularly suitable for dosing by means of a dosing 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 of course can also be introduced into the interior as a movable device (self-sufficient dosing device), contains several times the amount of cleaning agent required to carry out a machine cleaning process .
  • Movable in the sense of this application means that the dispensing and dosing system is not inextricably connected to a device such as a dishwasher or the like, but can be removed, for example, from a dishwasher or positioned in a dishwasher.
  • An example of an immovable cartridge is a container that is immovably integrated into the interior, for example in the side wall or the inner lining of the door of a dishwasher.
  • An example of a movable cartridge is a container that is placed by the consumer into the interior of the dishwasher and remains there throughout the entire cleaning cycle. Such a cartridge can be integrated into the interior, for example by simply placing it in the cutlery or crockery basket, but the consumer can also remove it from the interior of the dishwasher.
  • the cleaning agent or combination of cleaning agents 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, snap-in, snap-in or plug-in connection.
  • cartridges with an inextricably connected dosing device can of course also be used.
  • a cleaning agent supply form according to the invention as a cleaning agent reservoir for i) a dosing device that is immovably integrated into the interior of a dishwasher or ii) a movable dosing device intended for positioning in the interior of a dishwasher is preferred.
  • the cleaning agents and cleaning agent combinations according to the invention are, as stated above, preferably used as automatic dishwashing agents.
  • the invention also relates to an automatic dishwashing process in which the active ingredient composition is located in the cartridge and the washing liquid and/or air flows through openings.
  • the active ingredient composition is located in the cartridge and the washing liquid and/or air flows through openings.
  • fragrance(s) are released into the air in the interior of the dishwasher and, in addition to scenting the washing liquor, also results in the dishwashing process between the individual wash cycles creates a pleasant odor situation for the consumer when opening and loading the dishwasher.
  • the cleaning agent preparation A and the cleaning agent preparation B and, if appropriate, the cleaning agent preparation C are metered at different times during the cleaning cycle.
  • the time t2 is at least 1 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 before time t1.
  • time-shifted dosage 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 Reinigungsmittel zur automatischen dosierung Active EP3656839B1 (de)

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)

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EP3656839A1 EP3656839A1 (de) 2020-05-27
EP3656839B1 true EP3656839B1 (de) 2024-01-03

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DE (1) DE102018220189A1 (es)
ES (1) ES2970752T3 (es)
PL (1) PL3656839T3 (es)

Families Citing this family (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 (en) * 2022-11-30 2024-06-05 Henkel AG & Co. KGaA Builder system for effect on boosting protein soil removal

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994934A1 (en) 1997-06-30 2000-04-26 The Procter & Gamble Company LIGHT-DUTY LIQUID OR GEL DISHWASHING DETERGENT COMPOSITIONS HAVING CONTROLLED pH AND DESIRABLE FOOD SOIL REMOVAL, RHEOLOGICAL AND SUDSING CHARACTERISTICS
US6281181B1 (en) 1997-10-14 2001-08-28 The Procter & Gamble Company Light-duty liquid or gel dishwashing detergent compositions comprising mid-chain branched surfactants
EP1262539A1 (en) 2001-05-22 2002-12-04 The Procter & Gamble Company Pouched compositions
US20070054828A1 (en) 2005-09-02 2007-03-08 Henkel Kgaa Detergents
US20120015858A1 (en) 2009-04-01 2012-01-19 Henkel Ag & Co. Kgaa Cleaning agent
EP2652108A1 (en) 2010-12-13 2013-10-23 Colgate-Palmolive Company Dilutable concentrated cleaning composition
WO2015086761A1 (de) 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
WO2015132279A1 (de) 2014-03-06 2015-09-11 Henkel Ag & Co. Kgaa Vorportionierte reinigungsmittel umfassend mindestens zwei getrennte flüssige zubereitungen
EP3008159A2 (en) 2013-06-12 2016-04-20 Unilever N.V. Pourable detergent composition comprising suspended particles
WO2016198446A1 (de) 2015-06-12 2016-12-15 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
WO2018169421A1 (en) 2017-03-14 2018-09-20 Octagon International Trade Zbigniew Bąbelek Complex capsule-in-capsule detergent

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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
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0994934A1 (en) 1997-06-30 2000-04-26 The Procter & Gamble Company LIGHT-DUTY LIQUID OR GEL DISHWASHING DETERGENT COMPOSITIONS HAVING CONTROLLED pH AND DESIRABLE FOOD SOIL REMOVAL, RHEOLOGICAL AND SUDSING CHARACTERISTICS
US6281181B1 (en) 1997-10-14 2001-08-28 The Procter & Gamble Company Light-duty liquid or gel dishwashing detergent compositions comprising mid-chain branched surfactants
EP1262539A1 (en) 2001-05-22 2002-12-04 The Procter & Gamble Company Pouched compositions
US20070054828A1 (en) 2005-09-02 2007-03-08 Henkel Kgaa Detergents
US20120015858A1 (en) 2009-04-01 2012-01-19 Henkel Ag & Co. Kgaa Cleaning agent
EP2652108A1 (en) 2010-12-13 2013-10-23 Colgate-Palmolive Company Dilutable concentrated cleaning composition
EP3008159A2 (en) 2013-06-12 2016-04-20 Unilever N.V. Pourable detergent composition comprising suspended particles
WO2015086761A1 (de) 2013-12-13 2015-06-18 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
WO2015132279A1 (de) 2014-03-06 2015-09-11 Henkel Ag & Co. Kgaa Vorportionierte reinigungsmittel umfassend mindestens zwei getrennte flüssige zubereitungen
WO2016198446A1 (de) 2015-06-12 2016-12-15 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges geschirrspülmittel
WO2018169421A1 (en) 2017-03-14 2018-09-20 Octagon International Trade Zbigniew Bąbelek Complex capsule-in-capsule detergent

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DE102018220189A1 (de) 2020-05-28
PL3656839T3 (pl) 2024-05-20
EP3656839A1 (de) 2020-05-27
ES2970752T3 (es) 2024-05-30

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