EP3835397B1 - Produit de nettoyage - Google Patents

Produit de nettoyage Download PDF

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Publication number
EP3835397B1
EP3835397B1 EP20209366.2A EP20209366A EP3835397B1 EP 3835397 B1 EP3835397 B1 EP 3835397B1 EP 20209366 A EP20209366 A EP 20209366A EP 3835397 B1 EP3835397 B1 EP 3835397B1
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EP
European Patent Office
Prior art keywords
weight
cleaning agent
acid
detergent formulation
cartridge
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.)
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Application number
EP20209366.2A
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German (de)
English (en)
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EP3835397A1 (fr
Inventor
Thomas Doering
Brigitte Kempen
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP3835397A1 publication Critical patent/EP3835397A1/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
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to detergents, preferably machine dishwashing detergents, with a pH of 10 to 13, comprising a dye selected from the class of triphenylmethanes and builder(s).
  • those cleaning agents are affected by decoloration of the dye under UV light, which are used in transparent or translucent packaging, e.g. transparent plastic containers, such as e.g. transparent plastic bottles, cartridges or blister packs.
  • DE 10 2009 046240 A1 discloses an automatic dishwashing process using a bleach-free cleaning agent supply form comprising three cleaning agent preparations A, B and C.
  • the object of the present invention is therefore to provide a dye-containing cleaning agent, preferably automatic dishwashing detergent, which, in addition to good cleaning performance, also has good color stability during prolonged storage, especially with changing ambient temperatures, for example during transport in uncooled trucks in summer or when passing through several rinsing cycles in a dishwasher, and/or UV irradiation.
  • a dye-containing cleaning agent preferably automatic dishwashing detergent
  • the cleaning agent A has a pH of from 10 to 13, preferably from 10.5 to 12.5, in particular from 11 to 12.
  • the measurement is carried out at 20 °C using a standard hydrogen pH electrode.
  • the pH can be adjusted using appropriate pH adjusters, in particular sodium hydroxide or potassium hydroxide.
  • the agent is liquid at 20 °C and normal pressure (1.013 bar).
  • the cleaning agent contains at least 10% by weight, in particular at least 20% by weight, preferably from 25 to 85% by weight, of water.
  • the dye which is used according to the invention belongs to the triphenylmethane dyes. It is of course also possible to use two or more dyes selected from the triphenylmethane dyes at the same time. It is also possible to use other dyes in addition to the dye(s) from the group of triphenylmethane dyes. However, preference is given to using only one dye in a detergent preparation.
  • the triphenylmethane dyes have a central carbon trisubstituted with phenyl derivatives.
  • the ligands have at least two amino groups and optionally further substituents, in particular sulfonic acid group(s).
  • Acid Blue 9 also known as Patent Blue IX or Patent Blue AE
  • Acid Blue 7 also Patent Blue A or AF
  • Acid Blue 1 also patent blue VF, disulfine blue VN 150
  • the dye is selected from the group Acid Blue 3, Acid Blue 9, Acid Blue 1, Acid Blue 7, Acid Blue 5, Acid Blue 93, Acid Blue 104, particularly preferably Acid Blue 3 and Acid Blue 9.
  • the dye in particular a dye, is selected from the Acid Blue dyes, preferably selected from the group consisting of Acid Blue 3, Acid Blue 9, Acid Blue 1, Acid Blue 5, Acid Blue 7, Acid Blue 104 and/or Acid Blue 93 , particularly preferably Acid Blue 3, Acid Blue 9, Acid Blue 1, Acid Blue 5 and/or Acid Blue 7, in particular Acid Blue 3 and/or Acid Blue 9, very particularly Acid Blue 3 in an amount of from 0.00001 to 0 9% by weight, preferably in an amount of 0.0001 to 0.5% by weight, in particular in an amount of 0.001 to 0.5% by weight.
  • Acid Blue 3 is contained in an amount of 0.0001 to 0.5% by weight, in particular in an amount of 0.001 to 0.5% by weight, based on the total weight of the composition.
  • the cleaning agent according to the invention contains citrates in an amount of 4 to 40% by weight as a builder.
  • citrates for example, sodium citrate, potassium citrate, lithium citrate, diammonium citrate, magnesium citrate, zinc citrate, bismuth citrate are suitable.
  • Sodium citrate is preferably used. Particular preference is given to using citrates in an amount of from 5 to 25% by weight, preferably from 7.5 to 20% by weight, in particular from 10 to 17% by weight.
  • Sodium citrate is particularly preferred in an amount of 5 to 25% by weight, preferably 7.5 to 20% by weight, in particular 10 to 17% by weight, based on the total weight of the cleaning agent (or cleaning agent A ) contain.
  • the cleaning agent preferably contains at least one further builder.
  • the builders include, in particular, carbonates, organic cobuilders and silicates.
  • Cleaning agents according to the invention are preferably characterized in that the builder, in addition to the citrates, preferably sodium citrate, is selected from the group of carbonates, hydrogen carbonates, silicates and polymeric carboxylates or mixtures thereof.
  • Preferred cleaning agents are those which, based on their total weight, contain 5 to 50% by weight, preferably 6 to 45% by weight and in particular 10 to 40% by weight of builders (including the citrates).
  • Particularly preferred in addition to the preferred citrates is the use of builders from the group of carbonates and/or hydrogen carbonates, 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 from 4 to 15% by weight, based in each case on the weight of the cleaning agent (or cleaning agent A).
  • alkali metal carbonates particularly preferably sodium carbonate
  • Polycarboxylates/polycarboxylic acids polymeric carboxylates, (poly)aspartic acid, polyacetals, dextrins and organic cobuilders can be mentioned in particular as organic cobuilders. These substance classes are described below.
  • Useful organic builder substances 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 as meaning those carboxylic acids which carry more than one acid function. These are, for example, 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 to be understood as meaning non-polymeric polycarboxylates. Such polymeric polycarboxylates have a larger number, preferably 4 or more, carboxylic acid-containing monomers.
  • the free acids typically also have the property of an acidifying component and are therefore also used to adjust a lower and milder pH of cleaning agents.
  • an acidifying component particularly mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.
  • 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 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. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g/mol, and particularly preferably from 3000 to 5000 g/mol, may in turn be preferred from this group.
  • copolymeric polycarboxylates 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 machine dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Dishwashing detergents according to the invention 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, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a modulus NazO:SiO 2 of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which preferably has a delayed dissolution, can also be used and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwashing detergents according to the invention are silicate-free.
  • machine dishwashing detergents according to the invention can contain the abovementioned builders either in the form of individual substances or in the form of substance mixtures of two, three, four or more builders.
  • liquid automatic dishwashing detergents are characterized in that the dishwashing detergent contains at least citrates and carbonates as builders, the proportion by weight of these two builders, based on the total weight of the automatic dishwashing detergent, being preferably 6 to 55% by weight, preferably 8 to 45% by weight. -% and in particular 11 to 35% 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 agents according to the invention.
  • sodium citrate in an amount of 5 to 25% by weight, preferably 7.5 to 20% by weight, in particular 10 to 17% by weight, based on the total weight of the cleaning agent (or cleaning agent A ) and sodium carbonate, in amounts of 2 to 30% by weight, preferably 3 to 20% by weight and in particular 4 to 15% by weight, based in each case on the weight of the cleaning agent (or cleaning agent A).
  • the cleaning agent is characterized in that the cleaning agent preparations are phosphate-free, ie they contain less than 1% by weight phosphate, preferably less than 0.5% by weight phosphate, particularly preferably less than 0.1% by weight phosphate and in particular contain no phosphate.
  • the cleaning agents according to the invention contain aminocarboxylate builders in an amount of less than 4.5% by weight, based in each case on the total weight of the cleaning agent.
  • Aminocarboxylate builders include, in particular, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic acid diacetic acid, in particular L-glutamic acid -N,N -diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, methylglycinediacetic acid, aspartic acid diacetic acid, and salts or mixtures thereof, preferably L-glutamic acid- N , N- diacetic acid and/or methylglycine diacetic acid and salts thereof.
  • the designation methylglycinediacetic acid or L-glutamic acid- N,N -diacetic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • the cleaning agent according to the invention contains aminocarboxylate builders in an amount of less than 3% by weight, preferably less than 1% by weight, in particular less than 0.1% by weight.
  • the cleaning agent according to the invention contains less than 1% by weight, preferably less than 0.1% by weight, in particular less than 0.01% by weight, particularly preferably no polyalkyleneimines.
  • the cleaning agent according to the invention contains less than 1% by weight, preferably less than 0.1% by weight, in particular less than 0.01% by weight, particularly preferably no polyethyleneimines.
  • the cleaning agent according to the invention contains less than 1% by weight of MGDA and less than 0.1% by weight of polyethyleneimines, in particular less than 0.1% by weight of MGDA and less than 0.01% by weight. % polyethylenimines, most preferably less than 0.1% by weight MGDA and less than 0.01% by weight polyalkyleneimines.
  • a further active substance which, according to the invention, is not to be counted among the builders, as described above, are polymers containing sulfonic acid groups.
  • a sulfopolymer preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polymer containing sulfonic acid groups.
  • 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.
  • cleaning agents A which contain at least one polymer containing sulfonic acid groups, preferably in an amount of 1 to 20% by weight, preferably 2 to 15% by weight, in particular 4 to 10% by weight.
  • the unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C ⁇ C(R 3 )COOH, in which R 1 to R 3 independently represent —H, —CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or -COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic 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 contains such a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.
  • Particularly preferred sulfonic acid group-containing monomers 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-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water
  • some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions.
  • metal ions preferably alkali metal ions and in particular sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above.
  • 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 application.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses 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 also comprise at least one nonionic, preferably hydrophobic, monomer in addition to the monomer containing carboxyl groups and the monomer containing sulfonic acid groups.
  • nonionic, preferably hydrophobic, monomer in addition to the monomer containing carboxyl groups and the monomer containing sulfonic acid groups.
  • the nonionic monomers used are preferably monomers of the general formula R 1 (R 2 )C ⁇ C(R 3 )—XR 4 , in which R 1 to R 3 independently represent —H, —CH 3 or —C 2 H 5 , X is an optionally present spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4 is a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or 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 having 10 or more carbon atoms such as 1- Decene, 1-dodecene, 1-hexadecene, 1-octadecene and C 22
  • the cleaning agent according to the invention contains a complexing agent which differs from the builders mentioned above and the aminocarboxylate builders.
  • the phosphonates form a preferred group of complexing agents.
  • the complex-forming phosphonates include a number of different compounds such as, for example, diethylenetriaminepenta-(methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta-(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used 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 from the class of phosphonates is preferably used as the complexing agent.
  • the amino alkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, particularly if the agents also contain bleach, to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • 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 agents according to the invention is preferably 1 to 8% by weight, preferably 1.2 to 6% by weight, preferably 1.3 to 5% by weight; particularly preferably 1.4 to 4.5% by weight and in particular 1.5 to 4% by weight.
  • Citrate or citric acid particularly in combination with phosphonate, particularly 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, rinsing performance and particularly deposit inhibition.
  • cleaning agents A are used as a combination product with other cleaning agents in a cleaning agent supply form.
  • cleaning agents A are then referred to as cleaning agents A or
  • Detergent preparation A denotes. The substance contents given above for the cleaning agent in wt.
  • cleaning agent preparation B contains surfactants, preferably nonionic surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 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 radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of natural 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.
  • 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 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 of this are 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 here, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are distributed randomly rather than in blocks. Such products can be obtained 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-agent preparations B according to the invention contain at least one cleaning-active enzyme as their first component.
  • the proportion by weight 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 0.1 to 40% by weight, preferably 0.2 to 30% by weight and particularly preferably 0.4 to 20% by weight and in particular 0.8 to 10% by weight. -% 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, which are used with preference accordingly. Cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 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 detergent 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 and the further developments of the aforementioned amylases that have been improved for use in detergents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B . agaradherens (DSM 9948).
  • Liquid cleaning agent 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 amylase preparations. Particular preference is given to detergent preparations B which, based on their total weight, contain 4.0 to 16% by weight of amylase preparations.
  • liquid cleaning preparations B 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.
  • liquid cleaning preparations B 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-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus ) or further developed, in particular those with the amino acid substitution D96L. Furthermore, for example, the cutinases can be used which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • liquid cleaning preparations B 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 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) can be used to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (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 preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and the liquid dosage 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 set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
  • Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example due to the application of polymeric film formers, produce little dust and are stable in 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 0.1 to 40% by weight, preferably 0.2 to 30% by weight, particularly preferably 0.4 to 20% by weight and in particular 0 .8 to 10% by weight of the enzyme protein.
  • Liquid cleaning agent preparations B that are particularly preferred according to the invention therefore contain, based on the total weight of the cleaning agent 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 to 16 Wt .-% amylase preparations used, each containing 0.4 to 20 wt .-%, in particular 0.8 to 10 wt .-% 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 of cleaning agent preparations B according to the invention is between 6 and 9.
  • the composition can have a pH of 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1 , 8.2, 8.3, 8.4 or 8.5.
  • organic solvents come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, 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 butoxytriglycol,
  • 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 that is particularly effective with regard to the stabilization of 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 cleaning agent preparations B 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 respective cleaning agent preparation B, 5 to 80% by weight, preferably 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 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, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic 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.
  • 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 from 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 sources of calcium ions, which are 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, based on the total weight of the Cleaning agent preparation containing 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 contain, based on their total weight, preferably 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less water. In a further preferred embodiment, the cleaning agent preparations B contain, based on their total weight, from 0.5 to 30% by weight, preferably from 1.0 to 25% by weight and in particular from 1.5 to 30% by weight, of water.
  • the cleaning agent presentation further comprises a liquid cleaning agent preparation C, wherein the cleaning agent preparation C differs from the cleaning agent preparations A and B.
  • one or more further active substance compositions can be contained separately in the cleaning agent supply form.
  • the detergent preparations A and B and, if appropriate, the optional active ingredient composition described below in combination with at least one further detergent preparation C are used in the machine dishwashing process according to the invention.
  • this cleaning agent preparation C preferably contains surfactants and/or acids, preferably contains surfactants and acids.
  • 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 ether 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% by weight, 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 cleaning-agent preparation B and/or C contains at least one hydrotrope (hereinafter also referred to as solubility promoter).
  • Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea and/or N-methylacetamide, particularly preferably cumene sulfonate and/or xylene sulfonate, especially cumene sulfonate. It has been found that the use of hydrotropes, particularly cumene sulfonate, greatly improves phase stability with respect to temperature variations.
  • At least the cleaning agent preparation C in particular the cleaning agent preparations C and B, contains 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 a quantity from 2 to 25% by weight, in particular from 4 to 20% by weight and particularly preferably in an amount from 6 to 15% by weight, for example from 7 to 12% by weight, based on the total weight of the cleaning agent preparation in question.
  • 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 a quantity from 2 to 25% by weight, in particular from
  • 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 contain at least one acidifying agent when used in a dishwashing process.
  • Acidifiers can the invention
  • Detergent preparations C are added 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. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids can be used in particular. From this group, in turn, preference is given to 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 ( max. 33% by weight).
  • Cleaning agent preparations C which, based on the total weight of the cleaning agent 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 rinsing result, it also has a positive influence on the storage stability of cleaning preparation C, which, as explained above, is subject to severe temperature fluctuations due to storage inside the dishwasher. Furthermore, it has a disinfecting effect, so that when formic acid is used in the 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 sump 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.
  • a composition of active substances in particular comprising fragrances and/or fragrance scavengers
  • formic acid itself has a slightly pungent odor that is unpleasant for sensitive consumers. Due to the separate 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 e.g. zinc ricinoleate, neither arises during the dishwashing process an unpleasant odor inside the dishwasher even in the time between the cleaning cycles.
  • the cleaning agent preparations A, B and C described above differ in terms of their composition and are therefore not identical.
  • the cleaning agent preparation C according to the invention contains at least one glass corrosion inhibitor.
  • the preparation(s) A and/or the 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.
  • 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 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 preferably present in cleaning agent preparations according to the invention 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.
  • composition of some exemplary cleaning agent supply forms according to the invention comprising cleaning agent preparations A, B and C, can be found in the following tables.
  • Ingredients W.-uR preparation A [% by weight] [% by weight] [% by weight] [% by weight] [% by weight]
  • Builder(s) including citrates 5 to 50 6 to 45 10 to 40 12 to 30 Of which citrates 4 to 40 5 to 25 7.5 to 20 10 to 17 amino carboxylate builder ⁇ 2.5 ⁇ 0.1 0 0 Phosphonates where permitted by regulation 0 to 10 1 to 8 1.2 to 6 1.5 to 4
  • Ingredients W.-uR preparation B surfactants 2 to 40 4 to 40 5 to 35 5 to 35
  • Enzyme preparation preferably protease and/or amylase preparation at least 5 at
  • the combination of cleaning agents described above is packaged using a packaging means 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 receiving chambers that are separate from one another, with each of these receiving chambers containing one of the cleaning agents combined with one another.
  • Examples of such packaging forms are cartridges with two, three, four or more receiving chambers that are separate from one another, 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 can be metered out of the packaging means only by opening a valve on the underside of the packaging means (in particular the cartridge) on the basis of gravity, preferably without the involvement of electrical or electronic means such as pumps etc.
  • the chambers are preferably emptied largely completely, ie without large residual amounts of the detergent compositions to be metered. 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 means or the 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 has at least one carrier material, preferably a polymeric carrier material, in particular water-insoluble carrier material, and contains at least one active ingredient D.
  • the polymeric carrier material of the particles consists at least partly of ethylene/vinyl acetate copolymer.
  • a further preferred subject matter 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 designation for copolymers of ethylene and vinyl acetate. This polymer is basically 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 and the hardness of the resulting products are reduced. The vinyl acetate also makes the copolymer more polar, thereby improving 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).
  • Elvax® Duont
  • polyvinyl alcohols that are particularly suitable for the purposes of the present invention are Elvax® 265, Elvax® 240, Elvax® 205 W, Elvax® 200 W and Elvax® 360.
  • Products available under the trademark Evatane® ( Arkema) are also suitable, for example.
  • 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% by weight vinyl acetate, based in each case on the total weight of the copolymer.
  • Suitable carrier materials are the cyclodextrins.
  • inorganic support materials preference is given to using inorganic support materials.
  • Detergent supply forms are particularly preferred, characterized in that at least one of the Support materials is an inorganic support 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 in its substance already contains the active ingredient directly, in particular the glass corrosion inhibitors zinc and/or bismuth) in the carrier material.
  • the cleaning agent supply forms can contain such zinc- or bismuth-containing glasses, particularly preferably zinc phosphate-containing glass, 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.
  • a glass containing zinc phosphate or bismuth phosphate and also contain at least one, preferably two, three, or more 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. Due to the plastic deformation of the carrier materials in the course of one or more applications, a change in the carrier material surface, in particular a change in the size of the carrier material surface, is achieved, which in turn has an advantageous effect on the release profile and the release kinetics of the cleaning 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 of 40 to 125°C, preferably 60 to 100°C, particularly preferably a melting point of 70 to 90°C and in particular 73 to 80°C ( preferred determination method for the melting point according to ISO 11357-3) are preferred according to the invention.
  • the cleaning agent supply forms according to the invention are particularly suitable for multiple dosing of the active ingredients contained in them.
  • it has proven advantageous to use exclusively water-insoluble carrier materials.
  • these water-insoluble carrier materials simplify the production of presentation forms according to the invention.
  • preferred Forms of supply are therefore characterized in that all carrier materials used are water-insoluble.
  • the active substance compositions can assume all states of aggregation and/or three-dimensional shapes that can be realized 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 present as a solid. Active substance compositions are used with particular preference in the form of individual blocks comprising an entire active substance composition.
  • 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 from 1 to 10 mm and in particular from 3 up to 6 mm are particularly preferred.
  • Active substance compositions which comprise at least one colored active substance composition are particularly preferably used. By coloring at least one of the active substance compositions, an optical differentiation of these compositions can be achieved and the multiple benefits of these different compositions can be illustrated in a simple manner. Furthermore, the dyes are also suitable as an indicator, in particular as a consumption indicator for the colored active substance compositions.
  • Preferred dyes the selection of which does not pose any difficulty for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the agent and to light and have no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as glass, ceramics or plastic tableware, to avoid them to color
  • colorant When choosing the colorant, care must be taken to ensure that the colorant has a long shelf life and is insensitive to light and does not have too great an affinity for glass, ceramics or plastic tableware. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities with respect to 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 detergent varies. In the case of colorants which are readily water-soluble, 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 because 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 mixtures thereof, fragrance scavengers such as zinc ricinoleate, cyclodextrins, 2- menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol, especially zinc ricinoleate; Dyes, glass corrosion inhibitors, antimicrobial agents, germicides or fungicides and mixtures thereof, preferably mixtures of at least one scent scavenger, preferably with one, two, three or more scents and/or at least one dye. Further preferred are mixtures of at least one fragrance, preferably two, three or more fragrances, and at least one dye.
  • fragrances preferably linalyl acetate, dihydromyr
  • Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, with the nature of the functional groups and the structure of the chemical compound also having an important role to play in terms of molar mass. Thus, most fragrances have molar masses of up to about 200 daltons, while molar masses of 300 daltons and above tend to be an exception. Due to the different volatility of odoriferous substances, the odor of a perfume or fragrance composed of several odoriferous substances changes during evaporation, with the odor impressions being divided into “top note” (top note), “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 consists for the most part of less volatile, i.e. adherent 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 that ensure a long-lasting fragrance through slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • particularly preferred fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and/or eucalyptol and mixtures thereof.
  • the known ricenoleates in particular the zinc ricenoleates, for example, can be used as fragrance scavengers (or, as hereinafter also used synonymously, odor neutralizers or scent neutralizers, agents against malodour or bad odours).
  • fragrance scavengers 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 more of the fragrances and/or fragrance scavengers mentioned as preferred above 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 fragrance scavengers.
  • fragrances and/or fragrance scavengers can be used as an alternative or in addition to the above-mentioned fragrances and/or fragrance scavengers.
  • bacteriostatics and bactericides fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chloride, alkyl aryl sulfonates, halogenated phenols and phenolmercury acetate, although these compounds can also be dispensed with entirely.
  • the active ingredients can in principle be present in any desired amounts in the active ingredient preparations.
  • the proportion by weight of the active substance(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, in each case based on the total weight of the active ingredient composition(s).
  • active substance compositions can be present separately from one another or alongside one another in the packaging of the detergent presentation.
  • the different active substance compositions can preferably be present next to one another, ie in direct contact with one another, in the packaging means of the cleaning agent supply form.
  • the above-described cartridges of the cleaning agent supply 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.
  • the detachable connection between the cartridge and the dosing device allows the cartridges to be exchanged on the dosing device. Such an exchange can be indicated, for example, when the cleaning program is changed or after the cartridge has been completely emptied.
  • a particularly preferred subject matter of this application is a cleaning agent dosing system, comprising a) a cleaning agent dosage form according to the invention, comprising a quantity of cleaning agent preparations A, B and C or A, B that is sufficient for at least twice, preferably at least four times and in particular at least eight times a machine dishwashing process C and D; b) a dosing device that is detachably connected to the cleaning agent supply form.
  • the subject matter of the present application is also a cleaning agent dosing system, comprising a) a cleaning agent dosage form according to the invention, comprising a sufficient quantity of cleaning agent preparations A, B and C or A, B to carry out an automatic dishwashing process at least twice, preferably at least four times and in particular at least eight times, C and D; b) a dosing device that is inseparably connected to the cleaning agent supply form
  • the aforementioned cleaning agent metering systems comprising the cleaning agent supply form according to the invention (and optionally one or two other compositions different from the cleaning agent preparations A, B and C or A, B, C and D according to the invention, a cartridge and a metering device detachably connected to the cartridge are in one preferred embodiment in a common outer packaging, the filled cartridge and the dosing device are particularly preferably contained separately from each other in the outer packaging.
  • the outer packaging is used for storage, transport and presentation of the cleaning agent supply form according to the invention and protects it from dirt, impact and shock.
  • 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 other assemblies, such as a component carrier, actuator, closure element, sensor, energy source and/or control unit.
  • the dosing system according to the invention is movable. Movable in the context of this application means that the dosing system is not permanently connected to a water-carrying device such as a dishwasher or the like, but can be removed 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 of 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 a corresponding acid and/or alkali resistance. Furthermore, these components should be largely chemically inert, for example to nonionic surfactants, enzymes and/or fragrances, by selecting a suitable material.
  • a cartridge is understood to mean a packaging means which is suitable for enclosing or holding together free-flowing or spreadable preparations and which can be coupled to a dosing device in order to dispense the preparation.
  • a cartridge can also comprise a plurality of chambers which can be filled with compositions that differ from one another. It is also conceivable for a plurality of containers to be arranged in a cartridge unit.
  • the cartridge prefferably has at least one outlet opening which is arranged in such a way that the preparation can be released from the container by gravity when the dosing device is in the position of use.
  • no further means of conveyance are required for releasing preparation from the container, as a result of which the structure of the dosing device can be kept simple and the production costs can be kept low.
  • At least one second chamber is provided for accommodating at least one second free-flowing or spreadable preparation, the second chamber having at least one outlet opening which is arranged in such a way that the product is released from the second chamber by gravity when the dosing device is in the position of use is effected.
  • the arrangement of a second chamber is particularly advantageous when preparations are stored in the separate containers which are usually not stable when stored together, such as bleaches and enzymes.
  • At least one of the chambers is for dispensing active ingredient(s) D, such as a glass corrosion inhibitor, a fragrance or in particular an odor neutralizer to the environment, designed in such a way that it has openings through which the washing liquor and/or the air can flow.
  • active ingredient(s) D such as a glass corrosion inhibitor, a fragrance or in particular an odor neutralizer
  • the cartridge is designed in one piece.
  • the cartridges can be formed cost-effectively 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 produced by injection molding and then joined together. Furthermore, it is conceivable that the cartridge is formed in several pieces in such a way that at least one chamber, preferably all chambers, can be individually removed from the dosing device or inserted into the dosing device. In this way it is possible, when a preparation from one chamber is used to varying degrees, to exchange an already emptied chamber, while the others, which can still be filled with preparation, remain in the dosing device. In this way, the individual chambers or their preparations can be refilled in a targeted and needs-based manner.
  • the chambers of a cartridge can be fixed to one another by suitable connection methods, so that a container unit is formed.
  • the chambers can be fixed to one another in a detachable or non-detachable manner by means of a suitable positive, non-positive or material connection.
  • the fixation can be done by one or more of the connection types 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 snap connections.
  • the fixation can also be formed by a shrink tube (so-called sleeve), which is pulled over the whole 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 inner wall of a chamber can be designed by selecting a suitable material and/or surface design in such a way that the preparation material does not adhere as much to the inner chamber wall. This measure also allows the remaining emptying of a chamber to be further optimized.
  • 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, with 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 one chamber, in the direction of flow of the preparation in front of the outlet opening.
  • the amount of preparation that is to be released into the environment when the preparation is released from the chamber is determined by the dosing chamber. This is particularly advantageous when the closure element of the dosing device, which causes the preparation to be released from a chamber to the environment, can only be put into a release and a closed state without checking the amount released.
  • the dosing chamber then ensures that a predefined amount of preparation is released without immediate feedback of the amount of preparation dispensed.
  • the dosing chambers can be formed in one piece or in several pieces.
  • one or more chambers has, in addition to an outlet opening, a chamber opening that can be closed in a liquid-tight manner.
  • 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 area of the cartridge in order to ensure pressure equalization between the inside of the cartridge chambers and the environment when the filling level of the chambers falls.
  • 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 ventilated directly, but rather via the dosing device or no ventilation, e.g. when using flexible containers such as bags, this has the advantage that at elevated temperatures during a washing cycle of a dishwasher by heating the contents of the chamber, a pressure is built up, which presses the preparations to be dosed in the direction of the outlet openings, so that the cartridge can be easily emptied of residues. Furthermore, with such air-free packaging there is no risk of substances in the preparation oxidizing, which makes pouch packaging or bag-in-bottle packaging appear expedient, particularly for preparations which are sensitive to oxidation.
  • the cartridge usually has a filling volume of ⁇ 5000 ml, in particular ⁇ 1000 ml, preferably ⁇ 500 ml, particularly preferably ⁇ 250 ml, very particularly preferably ⁇ 50 ml.
  • the cartridge can assume any shape. It can, for example, be cube-like, spherical or plate-like.
  • the cartridge and the dosing device can in particular be designed with regard to their three-dimensional shape in such a way that they ensure the lowest possible loss of useful volume, in particular in a dishwasher.
  • the dosing device In order to use the dosing device in dishwashers, it is particularly advantageous to shape the device based on dishes to be cleaned in dishwashers. For example, this can be plate-shaped, approximately the dimensions of a plate. This allows the dosing device to be positioned in a space-saving manner, e.g. in the lower basket of the dishwasher. Furthermore, the correct positioning of the dosing unit is immediately intuitive to the user due to the plate-like shape.
  • the cartridge preferably has a height:width:depth ratio of 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 get 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 this purpose in the lower basket.
  • the width and the height of the dosing system can be selected in particular between 150 mm and 300 mm, particularly preferably between 175 mm and 250 mm.
  • the dosing unit in the form of a cup with an essentially circular or square base.
  • a further 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 polystyrene, which completely or partially enclose the chamber or the cartridge in a suitable manner.
  • the cartridge has an RFID tag that contains at least information about the contents of the cartridge and that can be read by the sensor unit.
  • This information can be used to select a dosing program stored in the control unit. This can ensure that a dosing program that is optimal for a specific preparation is always used. It can also be provided that if an RFID label is not present or if there is an RFID label with an incorrect or faulty identifier, no dosing takes place through the dosing device and instead an optical or acoustic signal is generated that alerts the user to the error present indicates.
  • the cartridges can also have structural elements which interact with corresponding elements of the dispensing device according to the lock and key principle, so that, for example, only cartridges of a specific type can be coupled to the dispensing device. Furthermore, this embodiment makes it possible for information about the cartridge coupled to the dosing device to be transmitted to the control unit, as a result of which the dosing device can be controlled in a way that is tailored to the content of the corresponding container.
  • the cartridge is designed in particular to hold free-flowing cleaning agents.
  • a cartridge particularly preferably has a plurality of chambers for the spatially separated reception of different preparations of a cleaning agent.
  • the cartridge can be designed in such a way that it can be arranged detachably or permanently 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 also preferably arranged in the dosing device.
  • the dosing device preferably consists of a splash-proof housing that prevents splashing water, which can occur, for example, when used in a dishwasher, from penetrating 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-bearing device, in particular a water-bearing household appliance, preferably a dishwasher, in such a way that electrical energy is transmitted from the water-bearing device to the dosing device is realized.
  • a water-bearing device in particular a water-bearing 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 dosing device and the water-bearing device such as a dishwasher, for the transmission of electromagnetic signals, which in particular contain operating status, measurement and/or control information of the dosing device and/or the water-bearing device such as a Represent dishwasher trained.
  • An adapter can be used to easily couple the dosing system to a water-bearing household appliance.
  • the adapter is used to mechanically and/or electrically connect the dosing system to the water-bearing household appliance.
  • the adapter is preferably permanently 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 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 a "build-in" version. It is also possible to design the adapter as a kind 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 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 not positioned in the water-bearing 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 the household appliance being designed in this way that a cartridge can be coupled to the dosing device by the user.
  • the detergent dosage forms according to the invention are suitable for use in dishwashing, although the use of a detergent dosage form according to the invention or a detergent metering system for dishwashing in an automatic dishwashing process is preferred.
  • the cleaning agents according to the invention are distinguished by particular physical and chemical stability, in particular with regard to temperature fluctuations.
  • the cleaning agents according to the invention are therefore exceptionally 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 can of course also be introduced into the interior as a movable device (self-sufficient dosing device), contains many times the amount of cleaning agent required to carry out a mechanical cleaning process.
  • Movable in the sense of this application means that the dispensing and dosing system is not permanently connected to a device such as a dishwasher or the like, but can be removed 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 into the side wall or the inner paneling of the door of a dishwasher.
  • An example of a movable cartridge is a container that is placed in the interior of the dishwasher by the consumer and remains there throughout the course of a 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 again.
  • the cleaning agent or the cleaning agent combination is metered from the cartridge into the interior of the dishwasher, as described above, preferably by means of a metering 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 inseparably connected dosing device can of course also be used.
  • a detergent delivery form according to the invention as a detergent reservoir for i) a dosing device immovably integrated in the interior of a dishwasher or ii) a movable dosing 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 dishwasher detergents.
  • the invention also relates to an automatic dishwashing process in which the active ingredient composition is located in the cartridge and the washing liquor and/or the air flows through openings.
  • the active ingredient composition is located in the cartridge and the washing liquor and/or the air flows through openings.
  • the detergent preparation A and the detergent preparation B as well as the detergent preparation C are metered in at different times of the cleaning cycle.
  • 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-delayed dosing 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 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.
  • the information relates to the respective amount of active ingredient: E V1 v2 V3 MGDA, trisodium salt - 14.2 - - sodium citrate 14 - - 11.2 GLDA, tetrasodium salt - - 14.2 2.7 HEDP 4.5 4.5 4.5 4.5 4.5 KOH 5.6 5.6 5.6 5.6 sodium 8.8 8.8 8.8 8.8 8.8 Acusol ® 588 (38% AS, Dow, sulfonic acid containing polymer) 16 16 16 16 16 16 16 16 16 Acid Blue 3 (JMK 1-0-7, Sensitive) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Water ad 100 ad 100 ad 100 ad 100 ad 100 pH 11.3 11.3 11.3 11.3 11.3 11.3 11.3 11.3 11.3
  • UV stability (1350 W/m2, SOL 500S) >72h ⁇ 3h 5h 5h Cleaning performance at 21°dH* 6.1 6.1 5.8 5.9 Color change after 4 weeks at 50°C stable ultramarine blue green violet violet * determined according to the IKW method, mean value for all soiling
  • an additional 30 mg of active protein/job (corresponding to the content of active enzyme protein/suitable for a cleaning application) protease according to Seq ID No.2 of the WO2013/060621 , 0.3 g of the amylase preparation (Stainzyme ® Plus 12 L from Novozymes) and 0.3 g of nonionic surfactant in the form of a detergent preparation B metered in separately.

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Claims (20)

  1. Forme d'offre de détergent comprenant
    a) une préparation détergente A, liquide à 20°C, comprenant
    i) un colorant choisi dans la classe des triphénylméthanes,
    ii) 4 à 40 % en poids de citrates
    iii) adjuvant aminocarboxylate en une quantité inférieure à 4,5 % en poids, de préférence inférieure à 2,5 % en poids, en particulier inférieure à 0,1 % en poids ;
    l'agent présentant un pH de 10 à 13, de préférence de 10,5 à 12,5, en particulier de 11 à 12, mesuré avec une électrode de pH à hydrogène à 20°C, et en outre encore au moins un polymère contenant des groupes acide sulfonique, de préférence en une quantité de 1 à 20 % en poids, de préférence de 2 à 15 % en poids, en particulier de 4 à 10 % en poids,
    b) une préparation de nettoyage B, liquide à 20°C, différente de la préparation de nettoyage A, contenant
    b1) au moins 5 % en poids d'au moins une préparation d'enzymes actives pour le nettoyage
    et/ou
    b2) au moins un agent tensioactif, de préférence au moins un agent tensioactif non ionique ;
    c) une préparation détergente C, liquide à 20°C, contenant
    c1) un agent acidifiant,
    c2) un inhibiteur de la corrosion du verre,
    c3) éventuellement, un agent de surface non ionique,
    c4) en option, un hydrotrope ; et
    c5) éventuellement moins de 1 % en poids, de préférence moins de 0,5 % en poids, notamment moins de 0,1 % en poids de préparation enzymatique, et
    d) un moyen d'emballage dans lequel les préparations de nettoyage A, B et C sont séparées les unes des autres.
  2. Forme d'offre de détergent selon la revendication 1, caractérisée en ce que la préparation de détergent A contient au moins 10 % en poids, en particulier au moins 20 % en poids, de préférence de 25 à 85 % en poids d'eau.
  3. Forme d'offre de détergent selon la revendication 1 ou 2, caractérisée en ce que le colorant est choisi dans le groupe des colorants de triphénylméthane selon la formule (I),
    Figure imgb0004
     où
    R1 représente H, C2H5, CH2-C6H5, CH2-C6H4-SO3 -
    R2 pour H, OH
    R3 pour H, SO3 -
    est debout.
  4. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que le colorant est choisi parmi le groupe Acid Blue 3, Acid Blue 9, Acid Blue 1, Acid Blue 5, Acid Blue 7, Acid Blue 93, Acid Blue 104, en particulier de préférence Acid Blue 3 et Acid Blue 9.
  5. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que le colorant est utilisé en une quantité de 0,00001 à 0,9 % en poids, de préférence en une quantité de 0,0001 à 0,5 % en poids, en particulier en une quantité de 0,001 à 0,5 % en poids.
  6. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent A contient de l'adjuvant aminocarboxylate en une quantité inférieure à 3 % en poids, de préférence inférieure à 1 % en poids, en particulier inférieure à 0,1 % en poids.
  7. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent A contient moins de 1 % en poids, de préférence moins de 0,1 % en poids, en particulier moins de 0,01 % en poids, de manière particulièrement préférée aucune polyalkylèneimine.
  8. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent A contient moins de 1 % en poids, de préférence moins de 0,1 % en poids, en particulier moins de 0,01 % en poids, de manière particulièrement préférée aucune polyéthylèneimine.
  9. Forme d'offre de détergent selon l'une des revendications précédentes, caractérisée en ce que la préparation de détergent A contient du citrate de sodium en une quantité de 5 à 25 % en poids, de préférence de 7,5 à 20 % en poids, en particulier de 10 à 17 % en poids, ainsi que le cas échéant d'autres adjuvants.
  10. Forme d'offre de détergent selon les revendications 1 à 9, caractérisée en ce que la préparation de détergent B et/ou C contient des tensioactifs respectivement en une quantité de 5 à 35 % en poids, en particulier de 10 à 30 % en poids, par rapport au poids total de la préparation respective.
  11. Forme d'offre de détergent selon l'une des revendications 1 à 10, caractérisée en ce que la préparation de détergent B contient une enzyme active de nettoyage du groupe des amylases et/ou des protéases et/ou des cellulases et/ou des hémicellulases et/ou des lipases, en particulier des amylases et/ou des protéases.
  12. Forme d'offre de détergent selon l'une des revendications 1 à 112, caractérisée en ce que la préparation de détergent B contient, par rapport à son poids total, 30 % en poids et moins, de préférence 25 % en poids et moins, en particulier 15 % en poids et moins d'eau.% et moins d'eau et/ou la préparation détergente B contient un solvant organique, de préférence choisi parmi le glycérol, le 1,2-propylèneglycol, le 1,3-propylèneglycol, le dipropylèneglycol ainsi que les polyéthylèneglycols, en particulier le 1,2-propylèneglycol, la proportion en poids du 1,2-propylèneglycol, par rapport au poids total de la préparation détergente, étant de préférence de 5 à 80 % en poids, de préférence de 10 à 60 % en poids et en particulier de 20 à 50 % en poids.
  13. Forme d'offre de détergent selon la revendication 1 à 12, caractérisée en ce que la préparation de détergent C contient l'agent d'acidification c1) choisi parmi l'acide formique, l'acide tartrique, l'acide succinique, l'acide malonique, l'acide adipique, l'acide maléique, l'acide fumarique, l'acide oxalique et/ou l'acide polyacrylique, en particulier l'acide formique, l'acide acétique et/ou l'acide citrique, et/ou la préparation de détergent C contient l'agent d'acidification c1) de préférence en quantités de 0,1 à 12 % en poids.%, de préférence 0,2 à 10 % en poids et en particulier 0,3 à 8,0 % en poids, à chaque fois par rapport au poids total de la préparation de détergent C.
  14. Forme d'offre de détergent selon l'une des revendications 1 à 13, caractérisée en ce que la préparation de détergent C contient l'inhibiteur de corrosion du verre c2) choisi parmi les sels de zinc solubles dans l'eau, de préférence le chlorure de zinc, le sulfate de zinc et/ou l'acétate de zinc, de manière particulièrement préférée l'acétate de zinc, et/ou la préparation de détergent C contient l'inhibiteur de corrosion du verre c2) de préférence en quantités de 0,01 % en poids à 5 % en poids.% à 5 % en poids, de préférence de 0,05 % en poids à 3 % en poids, en particulier de 0,1 % en poids à 2 % en poids, par rapport au poids total de la préparation de détergent C.
  15. Forme d'offre de détergent selon l'une des revendications 1 à 14, caractérisée en ce que la préparation de détergent C est l'hydrotrope c3) choisi parmi le xylènesulfonate, le cumènesulfonate, l'urée et/ou le N-méthylacétamide, de manière particulièrement préférée le cumènesulfonate et/ou le xylènesulfonate, en particulier le cumènesulfonate, et/ou la préparation de détergent C contient l'hydrotrope c3) en une quantité de 2 à 25 % en poids.%, en particulier de 4 à 20 % en poids et de manière particulièrement préférée en une quantité de 6 à 15, par exemple de 7 à 12 % en poids, par rapport au poids total de la préparation détergente C.
  16. Utilisation d'une forme d'offre de détergent selon l'une des revendications 1 à 15 comme réservoir de détergent pour
    i) un doseur immobile intégré à l'intérieur d'un lave-vaisselle, ou
    ii) un doseur mobile prévu pour être positionné à l'intérieur d'un.
  17. Utilisation d'une forme d'offre de détergent selon l'une des revendications 1 à 15 pour le remplissage
    i) une cartouche d'un système de dosage intégrée de manière immobile dans l'espace intérieur d'un lave-vaisselle, ou
    ii) une cartouche mobile d'un système de dosage destinée à être placée à l'intérieur d'un lave-vaisselle
    avec une quantité de cette forme d'offre de détergent suffisante pour la mise en oeuvre d'un procédé de lavage de la vaisselle en machine ou d'un procédé de lavage des textiles en machine au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois.
  18. Système de dosage de détergent, comprenant
    a) une forme d'offre de détergent selon l'une des revendications 1 à 15, comprenant une quantité de préparations de détergent A, B et C suffisante pour la réalisation d'un procédé de lavage de vaisselle en machine au moins deux fois, de préférence au moins quatre fois et en particulier au moins huit fois ;
    b) un dispositif de dosage relié de manière amovible à la forme d'offre de détergent.
  19. Utilisation d'une forme d'offre de détergent ou d'un système de dosage de détergent selon l'une des revendications précédentes pour le nettoyage de la vaisselle dans un procédé de lavage de la vaisselle en machine.
  20. Procédé de lavage de la vaisselle en machine utilisant une forme d'offre de détergent selon l'une des revendications 1 à 15 ou un système de dosage de détergent selon la revendication 18, au cours duquel, à partir d'une cartouche se trouvant à l'intérieur du lave-vaisselle
    a. une quantité partielle a de la préparation de détergent A se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation de détergent se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins au huitième de la quantité partielle a ; et
    b. une quantité partielle b de la préparation détergente B se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation détergente se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins à l'octuple de la quantité partielle b; et
    c. une quantité partielle c de la préparation de détergent C se trouvant dans la cartouche est dosée dans l'espace intérieur du lave-vaisselle, une quantité résiduelle de la préparation de détergent se trouvant dans la cartouche restant dans la cartouche jusqu'à la fin du processus de lavage de la vaisselle, caractérisé en ce que cette quantité résiduelle correspond au moins au double, de préférence au moins au quadruple et en particulier au moins à huit fois la quantité partielle c.
EP20209366.2A 2019-12-12 2020-11-24 Produit de nettoyage Active EP3835397B1 (fr)

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DE10062045A1 (de) * 2000-12-13 2002-06-27 Henkel Kgaa Verschiedenfarbiges wässriges mehrphasiges Reinigungsmittel
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102009046240A1 (de) * 2009-10-30 2011-05-12 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülverfahren
GB201409632D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved detergent composition
DE102015210828A1 (de) * 2015-06-12 2016-12-15 Henkel Ag & Co. Kgaa Phosphatfreies flüssiges Geschirrspülmittel
DE102018220189A1 (de) * 2018-11-23 2020-05-28 Henkel Ag & Co. Kgaa Reinigungsmittel zur automatischen Dosierung

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