EP3325591B1 - Produit pour lave-vaisselle multiphase à noyau tensioactif - Google Patents

Produit pour lave-vaisselle multiphase à noyau tensioactif Download PDF

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Publication number
EP3325591B1
EP3325591B1 EP16741024.0A EP16741024A EP3325591B1 EP 3325591 B1 EP3325591 B1 EP 3325591B1 EP 16741024 A EP16741024 A EP 16741024A EP 3325591 B1 EP3325591 B1 EP 3325591B1
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EP
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Prior art keywords
phase
acid
branched
dishwashing detergent
weight
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EP16741024.0A
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German (de)
English (en)
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EP3325591A1 (fr
Inventor
Inga Kerstin Vockenroth
David MATULLA
Oliver Kurth
Volker Blank
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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 present invention relates to a solid, multiphase dishwashing agent comprising at least two phases and the use of such a dishwashing agent and a method for cleaning dishes using such a dishwashing agent.
  • pressed powder phases which in particular consist of dishwasher tablets, do not meet the aesthetic demands of customers.
  • the present invention was based on the object of providing a dishwashing detergent whose composition ensures efficient removal of cooking fat residues from the dishwasher even at low washing temperatures and at the same time has a more appealing aesthetic than current dishwashing detergents, especially tabs made from pressed powder phases.
  • the use of a surfactant melt made of nonionic surfactants can remove the fat from the dishwasher filter more efficiently compared to current formulations.
  • the provision of the surfactant melt in the form of a surfactant core which is inserted into a core recess of a dishwashing tablet made of pressed powder, can lead to a visually appealing tablet.
  • the present invention is therefore directed to a dishwashing detergent comprising at least one first solid, compacted phase and at least one second phase, characterized in that the at least one second phase is a surfactant melt, comprising 10-100% by weight, preferably 20-100%, more preferably 50-100% by weight of surfactant (s), comprising nonionic surfactants, the nonionic surfactants contained in the at least one second phase not end-capped, poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH 2 O] x H, characterized in that R 1 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, and where x stands for values between 1 and 80 , preferably for values between 15 and 50 and in particular for values between 25 and 50 and the at least one second phase in addition to the non-end-capped poly (oxyalkylated) non-ionic surfact
  • s
  • the present invention is directed to the use of a dishwashing detergent according to the invention for machine cleaning of dishes.
  • the present invention is directed to a method for machine cleaning of dishes, characterized in that a dishwashing detergent according to the invention is used in at least one method step.
  • a dishwashing agent is to be understood as meaning all agents which are suitable for washing or cleaning hard surfaces, in particular dishes.
  • Other suitable ingredients are described in detail below.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the dishwashing detergent according to the invention comprises at least two phases, the first phase being solid and compacted and the second phase being a surfactant melt.
  • a "melt” is a composition that liquefies under the action of elevated temperatures (e.g.> 50 ° C or> 60 ° C), which solidifies again when it cools down to room temperature and forms a solid form.
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • One phase is different from another phase by different features, for example ingredients, physical properties, external appearance, etc.
  • Different phases can preferably be distinguished optically.
  • the at least one first phase can be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can also be differentiated from one another with the naked eye, because they differ from one another, for example, in terms of color. The same applies if there are two or more second phases. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a color or transparency difference.
  • Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye.
  • the individual phases can have different properties, such as, for example, the speed with which the phase dissolves in water and thus the speed and the sequence in which the ingredients contained in the respective phase are released.
  • the phases are typically spatially separated from one another. This can take place in various embodiments such that, if one or both of the phases are liquid phases, the liquid phase is present in a separate, closed area, for example the chamber of a pouch, separated from the other phase.
  • Such assembly forms are known in the prior art.
  • the two phases are also packaged spatially separately from one another, for example in the form of a multi-chamber pouch, each of the phases being in a separate chamber.
  • the two phases can be arranged spatially directly adjacent in such a way that the phases are formulated separately and contact each other, but cannot mix.
  • the dishwashing detergent according to the invention comprises at least two different phases. Both the at least one first phase and the at least one second phase are described below. In the event that the dishwashing detergent according to the invention has more than two phases, each further phase corresponds to either the at least one first phase, as defined herein, or the at least one second phase, as defined herein.
  • the compositions of the phases corresponding to one another can differ to the extent that the respective definitions listed below allow both the at least one first phase and the at least one second phase. For example, it can be a three-phase dishwashing detergent that has two phases the first phase, as defined herein, and a phase corresponding to the second phase, as defined herein.
  • the at least one second phase of the dishwashing detergent is a surfactant melt of which 10-100% by weight, preferably 20-100% by weight, more preferably 50-100% by weight, consists of surfactant ( en), in particular nonionic (m) surfactant (s).
  • the second phase is accordingly also referred to below as “surfactant melt” or “surfactant melt phase”.
  • One class of preferably usable nonionic surfactants that can be used in combination with other nonionic surfactants as part of the surfactant melt are alkoxylated (preferably ethoxylated or ethoxylated and propoxylated) fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • R 1 O [CH 2 CH 2 O] x H there are not end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R 1 O [CH 2 CH 2 O] x H, where R 1 stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, and x represents values between 1 and 80, preferably values between 15 and 50 and in particular values between 25 and 50, are used.
  • Fatty alcohol ethoxylates in which R 1 represents a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical are very particularly preferred.
  • the above-described non-end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase are used in amounts of 5-100, preferably 5-50% by weight, preferably 10-30% by weight, based on the surfactant melt Phase used.
  • non-end-capped, poly (oxyalkylated) non-ionic surfactants of the surfactant melt phase described above are combined with another surfactant from the group of end-group-capped, poly (oxyalkylated) non-ionic surfactants, namely those end-group-capped, poly (oxyalkylated) nonionic surfactants which, according to the formula R.
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals R 2 with 1 to 30 carbon atoms, where x is Values between 1 and 80, preferably values between 15 and 50 and in particular values between 25 and 50.
  • End-capped fatty alcohol ethoxylates in which R 1 is a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical, and / or R 2 is a linear or branched C 6-22 alkyl radical, are very particularly preferred. in particular represents a linear or branched C 8-10 alkyl radical.
  • the above-described end-group-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase are used in amounts of 5-60% by weight, preferably 40-60% by weight, based on the surfactant melt phase.
  • the mass ratio between the end-capped non-ionic surfactants described above and the non-end-capped non-ionic surfactants in the surfactant melt phase is from 20: 1 to 1: 5, preferably from 10: 1 to 1: 1. In particularly preferred embodiments, the ratio is 3: 1 to 2: 1.
  • nonionic surfactants used in the surfactant melt phase have a melting point above room temperature.
  • the surfactant melt phase can also contain other ingredients.
  • such ingredients include, for example, polyethylene glycols (PEG).
  • PEG polyethylene glycols
  • the at least one first phase of the dishwasher detergent according to the invention is a solid, compacted phase, typically a pressed powder phase.
  • This at least one first phase of the dishwashing detergent according to the invention usually contains at least one surfactant, preferably at least one nonionic surfactant. Suitable surfactants are described below.
  • Suitable nonionic surfactants in the first phase are, for example, alkyl glycosides of the general formula RO (G) x , in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants in the first phase of the dishwashing detergent, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • low-foaming nonionic surfactants in the first phase preference is given to using low-foaming nonionic surfactants in the first phase, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows.
  • nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each group R 2 or R 3 is independently selected from —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 —CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another stand for whole numbers from 1 to 6.
  • nonionic surfactants which have a C 9-15 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4, are particularly preferred up to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • Especially the C (EO) -2-hydroxyalkyl ether 15-40 8-10 fatty alcohol (PO) 1 - - to the group of these nonionic surfactants include the C 2-26 fatty alcohol, for example (PO) 1 (EO) 22 -2 hydroxydecyl ether.
  • nonionic surfactants are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 are H, -CH 3 or -CH 2 CH 3 particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x 2.
  • the value 3 for x has been chosen as an example and can be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the nonionic surfactants represent statistical mean values which, for a specific product, can be a whole number or a fraction. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different ones of the general formulas mentioned above .
  • the dishwashing detergents described herein which in the at least one first phase comprise at least one surfactant, preferably a nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the agent of at least 2% by weight, preferably at least 5% by weight.
  • the absolute amounts used per application can, for example, be in the range from 0.5-10 g / job, preferably in the range from 0.5-5 g / job.
  • Nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which are solid at room temperature.
  • the first phase can also contain the surfactants described above in connection with the second phase, in particular the optionally described end-group-capped fatty alcohol ethoxylates.
  • the first phase of the dishwashing detergent according to the invention can also contain surfactants from the group of anionic, cationic and amphoteric surfactants.
  • anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such.
  • B a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups, and hydroxyl groups.
  • Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • Cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds, can also be used instead of the surfactants mentioned or in conjunction with them. However, it is preferred that no cationic and / or amphoteric surfactants are used.
  • the dishwashing detergent can contain further ingredients which further improve the application-related and / or aesthetic properties of the dishwashing detergent.
  • the dishwashing detergent contains in various embodiments at least one or preferably more substances from the group of builders, polymers, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives for improvement the drainage and drying behavior, disintegration aids, preservatives, pH adjusters, fragrances and perfume carriers.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.
  • the use of phosphates is largely or completely dispensed with.
  • the agent contains preferably less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates.
  • the proportion by weight of the total builders in the total weight of the compositions according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as, for example, nitro-tetracarboxylic acids diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA)) and their derivatives and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.
  • polymeric polycarboxylates organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule
  • polyacetals polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component and can thus, if desired, also be used to set a lower acidity Serve pH value.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • dishwashing detergents preferably automatic dishwashing detergents
  • these are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.
  • dishwashing detergents preferably automatic dishwashing agents
  • dishwashing detergents are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% 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 cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • one or more other builders can also be included.
  • Preferred cleaning agents in particular dishwashing detergents, preferably machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and / or hydrogen carbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight.
  • one or more other builders can also be included.
  • the cleaning agents according to the invention can in particular contain phosphonates as a further builder.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates.
  • Phosphonates are preferably used in agents according to the invention in amounts from 0.1 to 10% by weight, in particular in amounts from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.
  • citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the abovementioned amounts. In particular, amounts of, based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or hydrogen carbonate), and 2.5 to 7.5% by weight Phosphonate used.
  • dishwashing detergents preferably automatic dishwashing detergents
  • they contain at least one further phosphorus-free builder.
  • this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDSDS) and ethylene diamine disuccinate (preferably from MGDA or GLDA.
  • MGDA methylglycine diacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDSDS iminodisuccinate
  • ethylene diamine disuccinate preferably from MGDA or GLDA.
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granulates which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous.
  • Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.
  • the (homo) polymeric polycarboxylate content of the cleaning agents according to the invention is preferably 0.5 to 20% by weight, more preferably 2 to 15% by weight and in particular 4 to 10% by weight.
  • Cleaning agents according to the invention in particular dishwashing detergents, preferably machine dishwashing detergents, can furthermore contain crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a Na 2 O: SiO 2 module of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which can also be used are preferably delayed in dissolution and have secondary washing properties.
  • the silicate content based on the total weight of the detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight .
  • the washing or cleaning agents according to the invention can also contain alkali metal hydroxides.
  • alkali carriers are used in the detergents or cleaning agents and in particular in the second phases preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the washing or cleaning agent used.
  • Alternative cleaning agents according to the invention are free from alkali metal hydroxides.
  • the at least one first phase of the dishwashing detergents described herein can also contain various polymers.
  • homopolymers of ⁇ , ⁇ ethylenically unsaturated carboxylic acids can be used in various embodiments.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methyl maleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • Acrylic acid is very particularly preferred.
  • the homopolymer is therefore a polyacrylic acid.
  • the carboxylic acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized polymers is preferred according to the invention.
  • the molar mass of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired application.
  • Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M n of 1000 to 20,000 g / mol. Because of their superior solubility can be made from of this group, in turn, the short-chain polyacrylates, which have molar masses from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, are preferred.
  • the agents also contain at least one sulfopolymer.
  • the polymers that can be used in this connection are, in particular, copolymers which can have two, three, four or more different monomer units, at least one monomer unit bearing a sulfonic acid group.
  • Preferred copolymers contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.
  • the unsaturated carboxylic acids described above are / are used with particular preference as the unsaturated carboxylic acid (s).
  • Acrylic acid is very particularly preferred.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) prop1-2-methylsulfonic acid, 2-propenyloxy) propanesulfonic acid sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide
  • the acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers used with preference is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers here being preferably selected from those mentioned above.
  • the copolymers can contain further monomers, in particular unsaturated monomers containing carboxylic acid ester groups.
  • Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl acrylic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • C 1-8 alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate are very particularly preferred.
  • Ethyl acrylate is very particularly preferred.
  • the molar mass of the copolymers used can be varied in order to adapt the properties of the polymers to the intended use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molar masses M n from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.
  • the homopolymers and copolymers described above can each be used in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the agent. Absolute amounts are typically in the range from 0.1 to 2 g / job, preferably in the range from 0.2 to 1.0 g / job.
  • the mass ratio of the polymers to one another, i.e. Homopolymer to copolymer, in various embodiments, is 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
  • the dishwashing detergents can alternatively or additionally contain other polymers.
  • the group of suitable polymers includes in particular the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers that act as softeners.
  • Preferred amphoteric polymers that can be used originate from the group of the alkyl acrylamide / acrylic acid copolymers, the alkyl acrylamide / methacrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid copolymers, the alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth ) acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally
  • zwitterionic polymers that can be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.
  • Cationic polymers that can be used originate from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicate polymers.
  • Dishwashing detergents according to the invention preferably contain one or more enzyme (s) as a further component in the first phase.
  • enzymes 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 accordingly preferred.
  • Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 % by weight 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.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae as well as the improved further developments of the aforementioned amylases for use in cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those with the amino acid exchange in positions D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
  • 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 interacting with the enzymes are added in order to increase the activity of the oxidoreductases concerned (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • Cleansing-active proteases and amylases are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
  • the enzymes for the first and / or second phase can be encapsulated, 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 in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches 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 are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • Particularly preferred cleaning agents are those which, based in each case on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.
  • the dishwashing detergent can also contain one or more enzyme stabilizers.
  • suitable enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, and their salts and esters, polyols such as, for example, glycerol or 1,2-ethylene glycol, sugars, sugar alcohols, lactic acid or antioxidants.
  • dishwashing detergents according to the invention contain at least one zinc salt as a glass corrosion inhibitor as a further component.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C. water temperature).
  • 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 Zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is in cleaning agents according to the invention preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the cleaning agent.
  • Salts especially the zinc salts
  • BASF a polyethyleneimines
  • the at least one first phase of the dishwashing detergent can furthermore contain a bleach, in particular an oxygen bleach and optionally a bleach activator and / or bleach catalyst. If available, these are only included in the first phase.
  • a bleach in particular an oxygen bleach and optionally a bleach activator and / or bleach catalyst. If available, these are only included in the first phase.
  • dishwashing agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaches from the group of organic bleaches can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Sodium percarbonate is particularly preferred because of its good bleaching performance.
  • a particularly preferred oxygen bleach is sodium percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes can also be used as bleach catalysts.
  • Manganese complexes in the II, III, IV or IV oxidation state which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference.
  • Ligands are preferably used which have nitrogen donor functions.
  • bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane Me TACN
  • 2-methyl-1,4,7-triazacyclononane Me TA
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (with OAc
  • the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH being selected depending on the intended use.
  • the pH is in a range from 5.5 to 11, preferably 6 to 10.5, even more preferably 7 to 10.5, in particular greater than 7, especially in the range 8.5 to 10.5.
  • Acids and / or alkalis, preferably alkalis are used as pH adjusting agents.
  • Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulphonic acid.
  • Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof.
  • the dishwashing detergent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Preference is given to buffer substances that are at the same time Complexing agents or even chelating agents (chelators, INCI Chelating Agents) are.
  • buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate ⁇ 2H 2 O and tripotassium citrate ⁇ H 2 O.
  • perfume oils or fragrances individual odoriferous compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. However, it is preferred to use mixtures of different fragrances which together produce an appealing fragrance note.
  • perfume oils can also contain natural odorant mixtures, such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the dishwashing detergent according to the invention can also contain preservatives.
  • preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) -bis- (1-octanamine) -dihydrochloride, N, N'-bis- (4- Chlorophenyl) -3,12-d
  • Particularly preferred preservatives are, however, selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
  • disintegration aids so-called tablet disintegrants
  • Tablet disintegrants or disintegration accelerators are understood as meaning auxiliaries that ensure the rapid disintegration of tablets in water or other media and the rapid release of the active ingredients.
  • Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the agent containing the disintegration aid.
  • the dishwashing detergent according to the invention consists of at least two phases, the first phase being solid and compacted and the second phase consisting of a surfactant melt.
  • the first phase is first produced in the form of a pressed powder phase using methods known in the prior art.
  • the first phase preferably has a depression or the like, into which the second phase can be introduced as a surfactant melt.
  • the components of the surfactant melt are mixed at temperatures at which the components of the surfactant melt are largely, preferably completely, liquefied, for example at temperatures above 50.degree.
  • the melting temperature of the surfactant melt depends on the melting points of the respective components used.
  • the liquid surfactant melt is then poured hot into the trough provided for this purpose in the first solid phase of the dishwashing detergent so that it can harden.
  • the hot, liquid surfactant melt of the second phase can also be pre-formed in any other form provided for this purpose, in order to then be adhered to a suitable place on the surface of the solid first phase provided for this purpose.
  • a suitable location on the surface of the first solid phase can be, for example, a suitable depression or depression.
  • the cured surfactant melt has more appealing optical properties compared to pressed powder phases.
  • the dishwashing detergents described herein are preferably pre-packaged into dosing units. These metering units preferably include the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a total weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial shape are particularly preferably selected so that the pre-assembled units can be metered via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the weight ratio of the first, preferably compacted phase to the second phase (surfactant melt phase) is preferably 20: 1 to 1: 1, preferably 15: 1 to 5: 1, in particular 12: 1 to 7: 1, for example 10: 1 up to 8: 1.
  • the automatic dishwashing detergents in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
  • the water-soluble envelope is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the envelope can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and of the further layers, if any, can be the same or different.
  • Particularly preferred are foils which, for example, can be glued and / or sealed to form packagings such as tubes or pillows after they have been filled with an agent.
  • the water-soluble packaging can have one or more chambers.
  • the agent can be contained in one or more chambers, if present, of the water-soluble envelope.
  • the amount of agent preferably corresponds to the full or half the dose that is required for one wash cycle.
  • the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 5,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are prepared from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope can additionally contain a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added.
  • a preferred additional polymer are polylactic acids.
  • preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-stick agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble envelopes of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the multiphase dishwashing detergent is tightly wrapped in a water-soluble film
  • the water-soluble film which is preferably used for tight wrapping, particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 ⁇ m to 100 ⁇ m, in particular from 12 ⁇ m to 60 ⁇ m, particularly preferably from 15 ⁇ m to 50 ⁇ m ⁇ m, especially from 20 ⁇ m to 40 ⁇ m, in particular from 22 ⁇ m to 35 ⁇ m.
  • a single portion of the detergent or cleaning agent is coated in each case.
  • the coating lies tightly against the surface of the tablets at every point.
  • the envelope is even under tension, but this is not absolutely necessary.
  • This tight fit of the envelope is conducive to disintegration: the first time it comes into contact with water, a small amount of water will let through at some point, whereby it does not need to resolve itself at first. At this point the disintegrant contained in the tablet begins to swell. As a result of the increase in volume of the tablet, the envelope now suddenly tears open and the tablet is released.
  • the mechanism described here does not work if the casing is not tightly fitting, since the tablet can swell without the casing being ruptured as a result.
  • the use of a swellable disintegrant is superior to a gas-generating system, since its disintegrating effect always leads to the covering being torn open.
  • the explosive effect can "fizzle out" as the gas escapes from a leak in the casing.
  • Preferred washing or cleaning agent single portions according to the invention are characterized in that the distance between the single portion and the water-soluble cover over the entire surface is 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 250 ⁇ m and in particular 2.5 to 100 ⁇ m.
  • the film wrapping is first loosely placed around a single portion of detergent or cleaning agent and welded and then shrunk onto it so that there is close contact between the film packaging and the cleaning agent concentrate.
  • one-time washing or cleaning agent portions according to the invention are characterized in that the cover is a film packaging shrunk onto it.
  • this wrapping can take place in that a water-soluble lower film is placed on a transport chain or a mold (s), then one or more detergent or cleaning agent portions are placed on the lower film; then a water-soluble upper film is placed on the detergent or cleaning agent portion (s) on the lower film and this is then fixed on the lower film, including the washing or cleaning agent portion (s),
  • this step can also be carried out using a single-strand film, which is then placed around the disposable portions as a tube. This is followed by sealing and optional cutting of the foils. Then the film can then be shrunk on using hot air or infrared radiation, optionally with pressure applied.
  • Such water-soluble coatings are also in the patent applications WO 2004/031338 A such as WO 2003/099985 A already described.
  • Table 1 Basic formulation of the cleaning agents (basic tablets without surfactant melting core), in particular dishwashing detergents, preferably automatic dishwashing detergents; Unless otherwise stated, the following information relates to% by weight of active substance, based on the total weight of the agent: Wt% preferred weight% Citrate, sodium salt 10-25 15-20 Phosphonate (e.g.
  • HEDP 0-10 2.5-7.5 MGDA, sodium salt 0-40 0-25 Disilicate, sodium salt 0-40 5-35 soda 10-30 10-25 Percarbonate, sodium salt 5.0-20.0 10-15
  • Bleach catalyst preferably Mn-based
  • TAED 0.0-0.8 0.02-0.5
  • Bleach activator e.g. TAED
  • Nonionic surfactant for example fatty alcohol alkoxylate, preferably 20-40 EO, optionally endcapped 1.5-15.0 2.5-10
  • Polycarboxylate 0.5-15 4-10 Cationic copolymer 0.0 -1.0 0-0.75 Disintegrant - (e.g.
  • citric acid 0.0 - 5 0-1.5
  • Process aids 0-10 0-5 Wt% preferred weight% Fatty alcohol ethoxylate (s) without end cap, 10 - 80 EO 5.0 - 100 5 - 50 Fatty alcohol ethoxylate (s) Endcapped 0.0 - 70 5 - 60 PEG 0.0 - 70 10 - 50 Citrate, sodium salt 0.0 - 20 0.0 - 10 Sulfopolymer 0.0 - 15 0.0 - 10 Polyacrylate 0.0 - 15 0.0 - 10 Dyes 0.0 - 5.0 0.0 - 2.0
  • the corresponding use of the dishwashing detergents according to the invention is also an object of the invention.
  • the invention also relates to a method, in particular an automatic dishwashing method, in which a washing or cleaning agent according to the invention is used in at least one step of the method.
  • the present application therefore also relates to a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while a dishwasher program is running before the start of the main wash cycle or during the main wash cycle.
  • the dosing or introduction of the agent according to the invention into the interior of the dishwasher can take place manually, but the agent is preferably dosed into the interior of the dishwasher by means of the dosing chamber.
  • Example 1 Preparation of a tablet with a surfactant melt core
  • the fused body consists, for example, of 10-50% PEG (mean Mr 1000 to 8000 g / mol), 5-60% fatty alcohol ethoxylate endcap, preferably C8-C10 endcap, 5-50% fatty alcohol ethoxylate with 10-80 EO, preferably 25-50 EO.
  • the components are mixed at temperatures> 50 ° C. and poured hot into the recess of a dishwasher tab (preferably according to the basic tablet, Table 3).
  • the crowd is in the Let the well harden. Preforming and then gluing in such a melt is also conceivable.
  • Table 3 raw materials Basic tablet Fusible core Addition g / job % * g / job from to from to Na citrate 12.90 51.61 2.00 8th soda 19.35 32.26 3.00 5 Na percarbonate 12.90 22.58 2.00 3.5
  • Manganese bleach catalyst 0.01 0.32 0.00 1 0.05 TAED 3.23 6.45 0.50 1 Fatty alcohol ethoxylate C10 Endcapped 1.29 3.87 0.20 0.6 0.85 Fatty alcohol ethoxylate C12 Endcapped 0.65 3.23 0.10 0.5 Benzotriazole 0.06 0.65 0.01 0.1 Sulfopolymer 1.94 6.45 0.30 1 Polyethylene glycol medium Mr 4000 g / mol 0.65 3.23 0.10 0.5 0.5 Protease (tq) 0.45 1.42 0.07 0.22 Amylase (tq) 0.13 0.65 0.02 0.1 Perfume 0.06 0.13 0.01 0.02 Dyes 0.65 1.29 0.10 0.2 Zn acetate 0.06 0.26 0.01 0.04 Na sulfate 3.

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Claims (12)

  1. Produit pour lave-vaisselle comprenant au moins une première phase solide compacte et au moins une seconde phase, caractérisé en ce que l'au moins une seconde phase est une matière fondue tensioactive comprenant 10 à 100 % en poids, de préférence 20 à 100 % en poids, plus préférentiellement 50 à 100 % en poids de tensioactifs comprenant des tensioactifs non ioniques, les tensioactifs non ioniques contenus dans l'au moins une seconde phase étant des tensioactifs non ioniques poly(oxyalkylés), non coiffés par des groupes terminaux, de formule R1O[CH2CH2O]xH, où R1 représente des radicaux hydrocarbonés linéaires ou ramifiés, saturés ou insaturés, aliphatiques ou aromatiques comportant 2 à 30 atomes de carbone, de préférence 4 à 22 atomes de carbone, et où x représente des valeurs comprises entre 1 et 80, de préférence des valeurs comprises entre 15 et 50 et en particulier des valeurs comprises entre 25 et 50, et l'au moins une seconde phase contenant, en plus des tensioactifs non ioniques poly(oxyalkylés) non coiffés par des groupes terminaux, au moins un tensioactif non ionique coiffé par des groupes terminaux de formule R1'O[CH2CH2O]xR2, où R1' représente des radicaux hydrocarbonés linéaires ou ramifiés, saturés ou insaturés, aliphatiques ou aromatiques comportant 2 à 30 atomes de carbone, de préférence 4 à 22 atomes de carbone, R2' représente des radicaux hydrocarbonés linéaires ou ramifiés, saturés ou insaturés, aliphatiques ou aromatiques comportant 1 à 30 atomes de carbone, et x représente des valeurs comprises entre 1 et 80, de préférence des valeurs comprises entre 15 et 50 et en particulier des valeurs comprises entre 20 et 50.
  2. Produit pour lave-vaisselle selon la revendication 1, caractérisé en ce que R1 représente un radical alkyle linéaire ou ramifié en C12-20, en particulier un radical alkyle linéaire ou ramifié en C16-18.
  3. Produit pour lave-vaisselle selon l'une des revendications 1 ou 2, caractérisé en ce que l'au moins une seconde phase contient les tensioactifs non ioniques poly(oxyalkylés) non coiffés par des groupes terminaux dans des quantités de 5 à 50 % en poids, de préférence de 10 à 30 % en poids, par rapport à la seconde phase.
  4. Produit pour lave-vaisselle selon les revendications 1 à 3, caractérisé en ce que R1' représente un radical alkyle linéaire ou ramifié en C12-20, en particulier un radical alkyle linéaire ou ramifié en C16-18, et/ou R2' représente un radical alkyle linéaire ou ramifié en C6-22, en particulier un radical alkyle linéaire ou ramifié en C8-12.
  5. Produit pour lave-vaisselle selon l'une des revendications 1 à 4, caractérisé en ce que les tensioactifs non ioniques poly(oxyalkylés) coiffés par des groupes terminaux sont contenus dans des quantités de 5 à 60 % en poids, de préférence 40 à 60 % en poids, par rapport à la seconde phase.
  6. Produit pour lave-vaisselle selon l'une des revendications 1 à 5, caractérisé en ce que le rapport massique entre les tensioactifs non ioniques coiffés par des groupes terminaux et les tensioactifs non ioniques non coiffés par des groupes terminaux dans l'au moins une seconde phase est de 20:1 à 1:5, de préférence de 10:1 à 1:1, en particulier de 3:1 à 2:1.
  7. Produit pour lave-vaisselle selon l'une des revendications 1 à 6, caractérisé en ce que les tensioactifs non ioniques de l'au moins une seconde phase présentent un point de fusion supérieur à 25 °C, de préférence compris entre 25 et 65 °C, plus préférentiellement compris entre 26,6 et 55 °C.
  8. Produit pour lave-vaisselle selon l'une des revendications 1 à 7, caractérisé en ce que l'au moins une seconde phase contient au moins un autre constituant, de préférence des polyéthylène glycols (PEG), préférentiellement de masse molaire moyenne comprise entre 800 et 8000 g/mol, dans une quantité de 10 à 40 % en poids, de préférence 25 à 35 % en poids, par rapport à la seconde phase.
  9. Produit pour lave-vaisselle selon l'une des revendications 1 à 8, caractérisé en ce que l'au moins une première phase contient au moins un tensioactif, de préférence au moins un tensioactif non ionique.
  10. Produit pour lave-vaisselle selon la revendication 9, caractérisé en ce que l'au moins une première phase contient au moins un autre constituant choisi dans le groupe des adjuvants, des polymères, des agents de blanchiment, des activateurs de blanchiment, des catalyseurs de blanchiment, des enzymes, des épaississants, des agents séquestrants, des électrolytes, des inhibiteurs de corrosion, des inhibiteurs de corrosion du verre, des inhibiteurs de mousse, des colorants, des additifs pour améliorer le comportement de drainage et de séchage, des agents auxiliaires de désintégration, des conservateurs, des régulateurs de pH, des parfums et des supports de parfum.
  11. Utilisation d'un produit pour lave-vaisselle selon l'une des revendications 1 à 10 pour le nettoyage automatique de la vaisselle.
  12. Procédé de nettoyage automatique de la vaisselle, caractérisé en ce qu'un produit détergent ou nettoyant selon l'une des revendications 1 à 10 est utilisé dans au moins une étape du procédé.
EP16741024.0A 2015-07-23 2016-07-20 Produit pour lave-vaisselle multiphase à noyau tensioactif Active EP3325591B1 (fr)

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PL16741024T PL3325591T3 (pl) 2015-07-23 2016-07-20 Wielofazowy środek do mycia naczyń obejmujący rdzeń środka powierzchniowo czynnego

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DE102015213939.5A DE102015213939A1 (de) 2015-07-23 2015-07-23 Mehrphasiges Geschirrspülmittel umfassend einen Tensid-Kern
PCT/EP2016/067265 WO2017013161A1 (fr) 2015-07-23 2016-07-20 Produit pour lave-vaisselle multiphase à noyau tensioactif

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JP7091454B2 (ja) 2017-11-14 2022-06-27 エコラボ ユーエスエー インコーポレイティド 固形制御放出苛性洗剤組成物
DE102018212208A1 (de) 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelpouch
EP4007803A1 (fr) 2019-09-27 2022-06-08 Ecolab USA Inc. Détergent et produit de rinçage concentré 2-en-1 pour lave-vaisselle

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877134A (en) 1996-09-11 1999-03-02 The Procter & Gamble Company Low foaming automatic dishwashing compositions
GB2340842A (en) 1998-08-28 2000-03-01 Procter & Gamble Detergent tablet
EP1239029B1 (fr) 2001-03-05 2005-08-31 Unilever Plc Compositions de nettoyage
EP1642961A1 (fr) 2004-10-01 2006-04-05 Unilever N.V. Comprimés détergents
WO2009071311A1 (fr) 2007-12-06 2009-06-11 Dalli-Werke Gmbh & Co. Kg Pastille de détergent comprenant une partie non comprimée

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19961367A1 (de) * 1999-12-17 2001-07-05 Henkel Kgaa Preßverfahren für mehrphasige Formkörper
DE10223266C1 (de) 2002-05-24 2003-11-20 Henkel Kgaa Verwendung Einspülkammer-dosierbare Tabletten-Portionen
DE10245260A1 (de) 2002-09-27 2004-04-15 Henkel Kgaa Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen
EP1669438B1 (fr) * 2004-12-08 2007-10-17 Unilever N.V. Comprimé détergent
EP1746151A1 (fr) * 2005-07-20 2007-01-24 Unilever N.V. Pastilles de composition détergente
EP1845153A1 (fr) * 2006-04-12 2007-10-17 Unilever N.V. Tablettes détergentes
TR201802667T4 (tr) * 2010-06-04 2018-03-21 Dalli Werke Gmbh & Co Kg Otomati̇k bulaşik yikama deterjanlarinin durulama performansini artirmak i̇çi̇n bi̇r yüzey etken maddeni̇n kati bi̇r bi̇leşi̇kle karişimi

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877134A (en) 1996-09-11 1999-03-02 The Procter & Gamble Company Low foaming automatic dishwashing compositions
GB2340842A (en) 1998-08-28 2000-03-01 Procter & Gamble Detergent tablet
EP1239029B1 (fr) 2001-03-05 2005-08-31 Unilever Plc Compositions de nettoyage
EP1642961A1 (fr) 2004-10-01 2006-04-05 Unilever N.V. Comprimés détergents
WO2009071311A1 (fr) 2007-12-06 2009-06-11 Dalli-Werke Gmbh & Co. Kg Pastille de détergent comprenant une partie non comprimée

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EP3325591A1 (fr) 2018-05-30
WO2017013161A1 (fr) 2017-01-26
PL3325591T3 (pl) 2021-03-08
DE102015213939A1 (de) 2017-01-26

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