EP3102658B2 - Mehrphasiges vorportioniertes reinigungsmittel - Google Patents

Mehrphasiges vorportioniertes reinigungsmittel Download PDF

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Publication number
EP3102658B2
EP3102658B2 EP15704269.8A EP15704269A EP3102658B2 EP 3102658 B2 EP3102658 B2 EP 3102658B2 EP 15704269 A EP15704269 A EP 15704269A EP 3102658 B2 EP3102658 B2 EP 3102658B2
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EP
European Patent Office
Prior art keywords
cleaning agent
liquid phase
weight
alkyl
acid
Prior art date
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EP15704269.8A
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German (de)
English (en)
French (fr)
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EP3102658B1 (de
EP3102658A1 (de
Inventor
Ulrich Pegelow
Noelle Wrubbel
Martina Hutmacher
Matthias Sunder
Volker Blank
Britta Strauss
Oliver Kurth
von den Karl-Josef DRIESCH
Friedhelm Siepmann
Mario Sturm
Klaus Dorra
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL15704269.8T priority Critical patent/PL3102658T5/pl
Publication of EP3102658A1 publication Critical patent/EP3102658A1/de
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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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the present invention relates to pre-portioned multi-phase cleaning agents, in particular automatic dishwashing detergents, and their use.
  • Cleaning agents for hard surfaces such as dishwashing detergents
  • dishwashing detergents are available to consumers in a wide variety of forms.
  • free-flowing and especially liquid to gel-like cleaning agents have recently gained increasing importance. Consumers particularly value the rapid solubility and the associated rapid availability of the ingredients in the cleaning solution, especially in short dishwashing programs and at low temperatures.
  • the liquid phase loses volume during the aforementioned migration processes, even when the pre-portioned cleaning agents are stored in a sealed outer package. This volume loss is so noticeable over longer storage periods that it can be perceived by the consumer. Consumers often conclude from such an observed volume loss that the bag or detergent tablet is leaking, or at least that the cleaning agent itself is deteriorating in function.
  • the object of the present invention was therefore to provide a pre-portioned multi-phase cleaning agent which is dimensionally and storage-stable and in which no significant migration of components between the different chambers occurs.
  • substantially free of water means that a composition contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, and most preferably less than 1% by weight of water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • the liquid phase according to c) is "essentially free of water,” which means that the liquid phase contains less than 7 wt.%, in particular less than 5 wt.%, preferably less than 3 wt.%, particularly preferably less than 1 wt.% water.
  • the water content refers to the water content determined by Karl Fischer titration.
  • all liquid phases and all solid phases of the cleaning agent according to the invention are "essentially free of water", i.e. each of the individual phases contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight of water (in each case based on the total weight of the respective phase).
  • Liquid as used herein in relation to the cleaning agent according to the invention, includes all flowable compositions and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a yield point.
  • At least one means 1 or more, for example 1, 2, 3, 4, 5, or more.
  • Solid as used herein in relation to the cleaning agent according to the invention, includes all solid compositions and particularly encompasses powdered, granulated, amorphous, compressed, especially pressed, tabletted compositions. Powdered compositions may also contain granules in addition to powdered components.
  • the cleaning agent according to the invention is present in a water-soluble package.
  • the water-soluble packaging allows for portioning of the cleaning agent.
  • the amount of cleaning agent in the portion pack is preferably 5 to 50 g, particularly preferably 10 to 30 g, and especially 15 to 25 g.
  • the cleaning agent is preferably present in a sufficient quantity to carry out the cleaning, in the case of machine dishwashing detergents in particular one cycle or one complete program run of a dishwasher.
  • the water-soluble packaging has at least two or more spatially separated compartments (chambers) into which at least one solid, preferably powdery, and at least one liquid phase are filled in a spatially separated manner.
  • two-chamber bags or two-chamber molded bodies that contain a solid and a liquid phase in separate compartments.
  • multi-chamber packaging multi-chamber bags or multi-chamber molded bodies
  • phase is understood here to mean a cleaning agent (partial) composition, which, in combination with the other phase(s), results in a cleaning agent, in particular a dishwasher detergent.
  • the cleaning agent according to the invention in particular automatic dishwashing detergent, can also be present in a water-soluble package which contains in particular more than two, for example three, four, five or six compartments.
  • the packaging preferably contains three or more chambers (compartments), one, two or more of these chambers being filled with liquid phases which are preferably different from one another and in particular have one or more ingredients which are different from one another.
  • pre-portioned cleaning agents in which the water-soluble package contains, in addition to one, two, or more liquid phases, one, two, or more chambers (compartments) with solid phases. If two or more solid phases are provided, it is preferred that they be of different composition and/or have a different solid form.
  • pre-portioned cleaning agents which contain at least one solid, preferably at least have a powdered phase and at least one liquid phase in separate compartments.
  • pre-portioned cleaning agents have at least one solid phase, preferably at least one compressed phase, and a liquid phase in separate compartments.
  • the pre-portioned cleaning agent has two or more solid phases, of which at least one is powdery and at least one is compressed and at least one, also two, three or more liquid phases in separate compartments.
  • the pre-portioned cleaning agent in particular the multi-chamber bag, contains a solid phase, a different powder phase and two liquid phases in separate compartments.
  • the at least one liquid phase in the cleaning agent according to the invention is substantially free of organic components which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol; Essentially free of organic components which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol, means that the liquid phase (in the case of several liquid phases, in each individual liquid phase) contains less than 5% by weight, preferably less than 3% by weight, of such organic compounds which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol.
  • the presence of usually short-chain organic solvents which have an average molecular weight of less than 175 g/mol, such as dipropylene glycol dimethyl ether, preferably less than 150 g/mol, such as decane, octane, dipropylene glycols, glycerol, propanediols, monoethanolamine, diethanolamine, which have a particularly strong tendency to migrate between the compartments, should be avoided.
  • each of the liquid phases is substantially free of organic components which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol (except for the components mentioned under a), since otherwise migration of the components between the individual liquid phases in the separate compartments occurs.
  • the liquid phase (are the liquid phases) of the cleaning agent according to the invention in particular machine dishwashing detergent, is substantially free of organic components which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol and are liquid at 20 °C and 1 bar.
  • the liquid phase or the liquid phases of the cleaning agents according to the invention contain at least a component according to a).
  • a which is selected from the polyalkylene glycols according to formula (I) with R 1 -O-(CH 2 -CH(R 2 )-O) w -(CH 2 -CH(R 3 )-O) x -(CH 2 -CH(
  • nonionic surfactants are also included in the above-mentioned formula (I).
  • Low-foaming alkoxylated nonionic surfactants especially ethoxylated low-foaming nonionic surfactants, are preferred.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of alkoxylated alcohols.
  • Preferred surfactants come from the group of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants are low-foaming nonionic surfactants containing alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups bonded to one another before a block of the other groups follows.
  • 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 are particularly preferred.
  • the rinse performance of the preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • the group of these non-ionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the group of these non-ionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15 - 40 -2-hydroxyalkyl ethers, in particular the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2-hydroxydecyl ethers.
  • At least one, preferably at least two, in particular at least three of the components according to a) have a melting point (at 1 bar) of ⁇ 30 °C, preferably ⁇ 25 °C, in particular ⁇ 20 °C in the liquid phase.
  • a component according to a) is at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between 300 and 600 g/mol.
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) is a component according to a) at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g/mol, preferably an average molecular weight between 3500 and 4500, in particular about 4000, (INCI: PEG 4000).
  • PEG polyethylene glycol
  • liquid phase(s) comprise a PEG with an average molecular weight of approximately 400 (INCI: PEG 400) and a PEG with an average molecular weight of approximately 4000 (INCI: PEG 4000).
  • the liquid phase or the at least one liquid phase or the liquid phases of the cleaning agent according to the invention preferably additionally contain at least one non-ionic surfactant, preferably one which is also a component according to a) according to formula I.
  • components according to a) are particularly advantageous since they can optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols, without having to use organic components, in particular organic solvents, which have an average molecular weight of less than 175 g/mol, preferably less than 150 g/mol.
  • At least one polyalkylene glycol preferably at least one polyethylene glycol, which has an average molecular weight between approximately 300 and approximately 5000, in particular approximately 4000 g/mol, is used as a further preferred component according to a).
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) additionally comprises, as a further component according to a), at least one further polyalkylene glycol, preferably at least one polyethylene glycol (PEG), which has an average molecular weight between 2000 and 6000 g/mol, in particular a PEG with an average molecular weight between 3500 and 4500, in particular approximately 4000.
  • PEG polyethylene glycol
  • liquid phase(s) comprise a PEG with an average molecular weight of approximately 400 (INCI: PEG 400) and a PEG with an average molecular weight of approximately 4000 (INCI: PEG 4000).
  • C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the amount of all components mentioned according to a) in the liquid phase between 10 to 80 wt.%, preferably between 20 to 70 wt.% (in each case based on the total weight of the liquid phase).
  • the amount of all the components mentioned as preferred according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • the amount of all the components mentioned as preferred according to a) in the liquid phase is between 15 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • the amount of all the components mentioned as preferred according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • an end-capped nonionic surfactant according to formula II R 8 O[CH 2 CH(R 9 )O] h [CH 2 ] k CH(OH)[CH 2 ] j OR 10 , may be present, in particular poly(oxyalkylated) nonionic surfactants of the formula II in which R 8 and R 10 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 9 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, h are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 9 in the above formula R 8 O[CH 2 CH(R 9 )O] h [CH 2 ] k CH(OH)[CH 2 ] j OR 10 can be different.
  • R 8 and R 10 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 C atoms being particularly preferred.
  • R 9 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for h are in the range from 1 to 20, in particular from 6 to 15.
  • each R 9 in the above formula can be different if h ⁇ 2. This allows the alkylene oxide unit in the square brackets to be varied.
  • the value 3 for h has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing h values and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.
  • R 8 , R 10 and R 9 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 amount of all components according to a) in the liquid phase is between 10 and 80% by weight, preferably between 20 and 70% by weight (in each case based on the total weight of the liquid phase).
  • the ratio of the weight of one or more solid phases (of which preferably at least one solid phase is powdery, (in the case of several solid/powdery phases the total weight of all solid and powdery phases) to the weight of one or more liquid phases (in the case of several liquid phases) is preferably 1:10 to 10:1, particularly preferably 1:5 to 5:1, very particularly preferably 4:1 to 1:2.
  • the cleaning agent in particular machine dishwashing detergent, is substantially free of anionic surfactants.
  • Essentially free of anionic surfactants, as used herein, means that a composition contains less than 7% by weight, preferably less than 5% by weight, in particular less than 3% by weight, very particularly preferably less than 1% by weight, especially preferably less than 0.1% by weight of anionic surfactant (based on the total weight of the composition). This preferably applies to all combinations according to the invention, in particular also to the combinations explicitly mentioned above as preferred.
  • the water-soluble wrapping of the cleaning agent, the packaging is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapping can be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and/or sealed, for example, to form packages such as tubes or pillows after they have been filled with an agent are particularly preferred.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly cold water solubility.
  • Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 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 typically produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced 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 especially 82 to 88 mol%.
  • a polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble wrapping.
  • a preferred additional polymer is polylactic acid.
  • Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, 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 comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester.
  • polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof.
  • the film material may contain further additives.
  • the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400, or M8900.
  • Other suitable films include films designated Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL by Aicello Chemical Europe GmbH, or VF-HP films by Kuraray.
  • the cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwashing agents.
  • the corresponding use is also the subject of the invention.
  • the invention also relates to a dishwashing process, in particular an automatic dishwashing process, in which a cleaning agent according to the invention is used.
  • the particular embodiments described above also apply to the use and the process.
  • the cleaning agents according to the invention are preferably a dishwashing detergent, in particular an automatic dishwashing detergent.
  • the pre-portioned cleaning agent according to the invention in particular automatic dishwashing detergent, is essentially free of phosphates. This preferably applies to all combinations according to the invention, in particular also to the combinations explicitly mentioned above as preferred.
  • Essentially free of phosphates means that the entire cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably essentially free of phosphate-containing components.
  • Phosphates or phosphate-containing components within the meaning of the present invention include, in particular, phosphates, polyphosphates, and pyrophosphates. However, phosphonates or hexafluorophosphate are not encompassed by this term.
  • the entire cleaning agent thus contains less than 1% by weight, preferably 0.5% by weight, of phosphates based on the total weight of the cleaning agent (i.e., the total weight of all phases (i.e., all liquid and solid phases).
  • the cleaning agents according to the invention in particular automatic dishwashing agents, contain builders such as zeolites, silicates, carbonates, in particular the alkali carbonates, for example sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, and organic cobuilders.
  • builders such as zeolites, silicates, carbonates, in particular the alkali carbonates, for example sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, and organic cobuilders.
  • silicates are crystalline layered silicates of the general formula NaMSi x O 2x+1 y H 2 O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight.
  • Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders, and phosphonates. These substance classes are described below.
  • Useful organic framework substances are, for example, those in the form of the free acid and/or its Polycarboxylic acids that can be used as sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function.
  • Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable on ecological grounds, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of the automatic dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof should be mentioned here.
  • aminocarboxylic acids and/or their salts are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts, glutamic diacetic acid (GLDA) or its salts, or ethylenediamine diacetic acid or its salts (EDDS). Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable. Aminocarboxylic acids and their salts can be used together with the aforementioned builders, especially with phosphate-free builders.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • EDDS ethylenediamine diacetic acid or its salts
  • Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable.
  • Aminocarboxylic acids and their salts can be used together with the aforementioned builders, especially with phosphate-free builders.
  • MGDA MGDA
  • GLDA GLDA
  • salts MGDA
  • MGDA MGDA
  • MGDA can preferably be used as granules, and especially preferably in the solid phase.
  • Particularly preferred are MGDA granules that contain as little water as possible and/or have low hygroscopicity.
  • MGDA or its salts in a total amount of 3 to 50 wt.% based on the total weight of the cleaning agent.
  • Polymeric polycarboxylates are also suitable as builders. These include, 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.
  • the polyacrylate or polyacrylates are used here in particular in a dried, particularly preferably dried and granulated (solid) form, which may optionally be additionally ground.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of approximately 1000 to 20,000, in particular 2000 to 10,000 g/mol. Due to their superior solubility, short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably 3000 to 5000 g/mol, may be preferred from this group.
  • copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.% acrylic acid and 50 to 10 wt.% maleic acid, have proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol, and especially 30,000 to 40,000 g/mol.
  • the cleaning agents can also contain phosphonates, in particular, as builders.
  • a hydroxyalkane and/or aminoalkanephosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues are preferred as aminoalkanephosphonates.
  • Phosphonate-containing components are preferably present in the agents in amounts of 0.1 to 10 wt. %, in particular in amounts of 0.5 to 8 wt. %, based in each case on the total weight of the cleaning agent.
  • the agents according to the invention contain from 0.01 to 25 wt. %, preferably 5 to 20 wt. %, 8 to 15 wt. % phosphonate (in each case based on the total weight of the agent).
  • the phosphonates are preferably contained in the solid phase(s).
  • the cleaning agents according to the invention may further contain a sulfopolymer.
  • the weight fraction of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt. %, in particular from 0.5 to 18 wt. %, particularly preferably from 1.0 to 15 wt. %, very particularly preferably from 2.0 to 14 wt. %, in particular from 4 to 14 wt. %, especially from 4.5 to 12 wt. %.
  • the sulfopolymer is used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally be additionally ground.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, b a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • the molecular weight of the sulfo-copolymers preferably used according to the invention can be varied to adapt the properties of the polymers to the desired application.
  • Preferred cleaning agents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably of 4000 to 25,000 gmol -1 , and in particular of 5000 to 15,000 gmol -1 .
  • Anionic copolymers comprising carboxylic acid group-containing monomers, sulfonic acid group-containing monomers and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • non-ionic 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-dimehtylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-Octadecene and
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably 5 to 80% by weight in relation to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, particularly preferably the proportion of the sulfonic acid group-containing monomer and the hydrophobic monomer is each 5 to 30% by weight and the proportion of the carboxylic acid group-containing monomer is 60 to 80% by weight, the monomers are preferably selected from those mentioned above.
  • the agents according to the invention preferably contain at least one further component, preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents.
  • at least one further component preferably selected from the group consisting of cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bittering agents, and antimicrobial agents.
  • Bleaching agents can also be used in cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents.
  • cleaning agents preferably dishwashing detergents, in particular automatic dishwashing detergents.
  • compounds used as bleaching agents that yield H2O2 in water sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are particularly important.
  • Other useful bleaching agents include peroxypyrophosphates, citrate perhydrates, and H2O2 - yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid , phthaloiminoperic acid, or diperdodecanedioic acid. All other inorganic or organic peroxy bleaching agents known to those skilled in the art from the prior art can also be used.
  • Chlorine- or bromine-releasing substances can also be used as bleaching agents.
  • Suitable chlorine- or bromine-releasing materials include heterocyclic N-bromo- and N-chloroamides, such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid, and/or dichloroisocyanuric acid (DICA), and/or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Cleaning agents preferably dishwashing agents, in particular automatic dishwashing agents, are preferred which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 25% by weight, very particularly preferably 4.0 to 20% by weight and in particular 5 to 18% by weight (based on the total weight of the cleaning agent) of bleaching agent, preferably sodium percarbonate.
  • the cleaning agents can contain bleach catalysts.
  • the usable bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru, or Mo complexes, particularly preferably from the group of manganese and/or cobalt salts and/or complexes, in particular cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, cobalt or manganese chlorides, manganese sulfate, and complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn 4 -TACN).
  • Cleaning agents preferably dishwashing agents, in particular automatic dishwashing agents, are preferred which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight (in each case based on the total weight of the cleaning agent) of bleaching catalyst, preferably a Mn complex, in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn 4 -TACN).
  • Mn complex in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn 3 -TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn 4 -TACN).
  • the cleaning agents preferably dishwashing detergents, in particular automatic dishwashing detergents, additionally contain at least one bleach activator.
  • Compounds which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU acylated glycolur
  • Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the cleaning agents.
  • the bleaching agent as well as bleach catalysts and/or bleach activators are preferably contained in the solid phase(s).
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii )(R iv )(R v )N + CH 2 COO - , in which R iii is an alkyl radical optionally interrupted by heteroatoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyldimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyldimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi )(R vii )(R viii )(R ix )N + X - , in which R vi to R ix represent four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X - represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary surface-active compounds, in particular those containing a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be given an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.
  • the enzymes include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably used.
  • Cleaning agents according to the invention preferably contain enzymes in total amounts of 1 x 10 -6 to 5 wt.% based on active protein.
  • the protein concentration can be determined using known methods, for example, the BCA method or the biuret method.
  • subtilisins those of the subtilisin type are preferred.
  • subtilisins BPN' and Carlsberg and their more advanced forms protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.
  • amylases that can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger , and A. oryzae , as well as the improved versions of the aforementioned amylases for use in cleaning agents. Also particularly suitable for this purpose are the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • DSM 12368 Bacillus sp. A 7-7
  • CTTase cyclodextrin glucanotransferase
  • Lipases or cutinases can also be used according to the invention, particularly because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with one or more of the following amino acid substitutions starting from the aforementioned lipase at positions D96L, T213R, and/or N233R, particularly preferably all of the substitutions 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 according to the invention.
  • organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators).
  • a protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation due to physical influences, oxidation, or proteolytic cleavage.
  • damage such as inactivation, denaturation, or degradation due to physical influences, oxidation, or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Cleaning agents can be used for this purpose. Contain stabilizers; the provision of such agents represents a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations.
  • These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and/or containing stabilizers or other additives.
  • the enzymes can be encapsulated for both solid and liquid dosage forms, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in core-shell capsules in which an enzyme-containing core is coated with a water-, air-, and/or chemical-impermeable protective layer.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film formers, are low in dust and, due to the coating, are stable in storage.
  • the enzyme protein constitutes 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 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and in particular between 0.8 and 10 wt.% of the enzyme protein.
  • Particularly preferred cleaning agents are those which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations.
  • the enzymes in particular the amylase(s) and/or protease(s), are contained in (one of) the solid phase(s), preferably as granules.
  • Metal salts especially zinc or bismuth salts, preferably zinc salts, especially zinc acetate, are used as glass corrosion inhibitors.
  • Polyethyleneimines and polyvinylamines such as those available from BASF under the name Lupasol® or Lupamin® , are also preferably used as glass corrosion inhibitors, especially non-alkoxylated polyethyleneimines.
  • Glass corrosion inhibitors are preferably present in the compositions according to the invention in an amount of 0.05 to 5 wt. %, in particular in an amount of 0.1 to 2 wt. %.
  • the cleaning agents according to the invention are characterized by the fact that they are storage-stable and no phase separation occurs even after a longer period of time.
  • the present invention also relates to a machine dishwashing method in which a cleaning agent according to the invention is used.
  • the invention also relates to the use of the cleaning agent according to the invention as a dishwashing detergent, in particular an automatic dishwashing detergent.
  • the cleaning agent formulation according to the invention with a solid phase according to Table 1 and a liquid phase according to Table 2, E1, as well as a comparative formulation V1 with a solid phase according to Table 1 and a liquid phase according to Table 2, V1, were prepared.
  • the amounts stated in the tables are in wt. % active ingredient. 15 g of the solid phase were sealed into a first polyvinyl alcohol bag, and 5 g of the liquid phase (E1 or V1) were sealed into a second polyvinyl alcohol bag.
  • liquid phase E1
  • the pre-portioned cleaning agent according to the invention showed good stability and a weight loss of less than 5 wt.% of the liquid phase (based on the initial weight of the liquid phase) after a storage time of 2 weeks at 25 °C when the outer packaging (glass container) was closed.
  • the compartment containing the solid phase was significantly more densely filled, and a weight gain equivalent to the weight loss in the liquid compartment was determined gravimetrically.

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EP15704269.8A 2014-02-06 2015-02-04 Mehrphasiges vorportioniertes reinigungsmittel Active EP3102658B2 (de)

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EP3275986B1 (en) 2016-07-26 2020-07-08 The Procter and Gamble Company Automatic dishwashing detergent composition
DE102016223472A1 (de) * 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Mehrkammer-Portionsbeutel mit Bleichaktivator/Komplexbildner-Compound
DE102017201097A1 (de) 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
EP3574074A1 (de) * 2017-01-24 2019-12-04 Henkel AG & Co. KGaA Wasch- oder reinigungsmittelportion umfassend wenigstens zwei phasen
DE102019219812A1 (de) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Mittel für das maschinelle Geschirrspülen mit verbesserter Reinigungsleistung für bleichbare Anschmutzungen
USD1088343S1 (en) 2022-05-11 2025-08-12 People Against Dirty Holdings Limited Packet

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WO2006086109A1 (en) † 2005-01-10 2006-08-17 The Procter & Gamble Company Machine cleaner
US20100216683A1 (en) † 2007-08-22 2010-08-26 Arnd Kessler Cleaning Product

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RU2575930C2 (ru) * 2010-01-29 2016-02-27 МОНОСОЛ, ЭлЭлСи Улучшенные водорастворимые пленки на основе смеси пвс-полимеров и пакеты из них
EP2476744A1 (en) * 2011-01-12 2012-07-18 The Procter & Gamble Company Method for controlling the plasticization of a water soluble film
GB201101547D0 (en) * 2011-01-31 2011-03-16 Reckitt Benckiser Nv Container for use in a washing process
DE102012208286A1 (de) * 2012-05-16 2013-11-21 Henkel Ag & Co. Kgaa Wasserarmes, flüssiges Waschmittel mit aus nachwachsenden Rohstoffen gewonnenen Tensiden

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WO2006086109A1 (en) † 2005-01-10 2006-08-17 The Procter & Gamble Company Machine cleaner
US20100216683A1 (en) † 2007-08-22 2010-08-26 Arnd Kessler Cleaning Product

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