EP3102658B1 - Détergents polyphasiques préportionnés - Google Patents

Détergents polyphasiques préportionnés Download PDF

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Publication number
EP3102658B1
EP3102658B1 EP15704269.8A EP15704269A EP3102658B1 EP 3102658 B1 EP3102658 B1 EP 3102658B1 EP 15704269 A EP15704269 A EP 15704269A EP 3102658 B1 EP3102658 B1 EP 3102658B1
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EP
European Patent Office
Prior art keywords
cleaning agent
liquid phase
alkyl
branched
acid
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EP15704269.8A
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German (de)
English (en)
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EP3102658A1 (fr
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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Priority to PL15704269T priority Critical patent/PL3102658T3/pl
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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 cleaners, especially automatic dishwashing detergents, and their use.
  • Hard surface cleaners such as dishwashing detergents
  • dishwashing detergents are available to the consumer in a variety of forms.
  • traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
  • the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
  • compositions in which in particular the water content is reduced compared to conventional compositions, increases.
  • compositions whose water content is as low as possible are particularly desirable.
  • Disposable portions in particular water-soluble bags or multi-chamber tablets made of water-soluble material, enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. For the consumer, it is therefore a nuisance if the bags lose their attractive appearance.
  • the liquid phase loses volume in the mentioned migration processes, even if the pre-portioned detergents are stored in a sealed outer packaging. This volume loss is visually so clearly visible for longer storage times that the consumer can perceive this. Often, the consumer concludes from such observed loss of volume on a leakage of the bag or detergent molding or at least on a deterioration in the function of the detergent itself.
  • the object of the present invention was therefore to provide a pre-portioned multiphase cleaning agent which is dimensionally stable and storage-stable, and in which there is no appreciable migration of components between the various chambers.
  • 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, more preferably less than 1% by weight. Contains% water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • the liquid phase according to c) is "substantially free of water", this means that the liquid phase is less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, particularly preferred contains less than 1% by weight of water.
  • the water content refers to the water content determined by Karl Fischer titration.
  • all liquid phases and all solid phases of the detergent of the invention are "substantially free of water", i. each of the individual phases contains in each case 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 reference to the cleaning agent of the present invention includes all flowable compositions and more particularly includes gels and pastes Compositions. In particular, the term also includes non-Newtonian fluids having a yield point.
  • At least one means 1 or more, for example, 1, 2, 3, 4, 5, or more.
  • solid as used herein with respect to the cleaning composition of the invention includes all solid compositions, and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tabletted compositions. In addition to powdery constituents, powdery compositions may also partially contain granules.
  • the cleaning agent according to the invention is present in a water-soluble packaging.
  • the water-soluble packaging allows a portioning of the detergent.
  • the amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
  • the cleaning agent is preferably present in a sufficient amount for performing the cleaning, in machine dishwashing detergents in particular a cycle or a complete program cycle of a dishwasher before.
  • the water-soluble packaging in this case has at least two or more spatially separated compartments (chambers), in which spatially separated at least one solid, preferably pulverulent, and at least one liquid phase are filled.
  • two-chamber bags or two-chamber tablets which contain a solid and a liquid phase in separate compartments.
  • multi-chamber packages multi-chamber bags or multi-chamber shaped bodies
  • a phase is understood here to mean a detergent (partial) composition which, in combination with the other phase or phases, results in a cleaning agent, in particular a machine dishwashing detergent.
  • the cleaning agent according to the invention in particular machine dishwashing detergent, can also be present in a water-soluble packaging, which in particular contains more than two, so for example, three, four, five or six compartments.
  • the package contains three or more chambers (compartments), wherein one, two or more of these chambers are filled with liquid phases, which are preferably different from each other, and in particular one or more mutually different ingredients.
  • pre-portioned detergents in which the water-soluble package contains one, two or more solid phase chambers (compartments) in addition to one, two or more liquid phases.
  • solid phase chambers components
  • two or more solid phases it is preferred that they be of different composition and / or have a different solid form.
  • pre-portioned detergents which have at least one solid, preferably at least one pulverulent phase and at least one liquid phase in separate compartments.
  • pre-portioned detergents which have at least one solid, preferably at least one compressed phase and one liquid phase, in separate compartments.
  • the pre-portioned cleaning agent may also be preferable for the pre-portioned cleaning agent to have two or more solid phases, of which at least one powdery and at least one compressed and at least one, also two, three or more liquid phases are in each case separate compartments.
  • the pre-portioned detergent in particular the multi-chamber bag, contains a solid, one of which is different powdery and two liquid phases in each separate compartments.
  • the at least one liquid phase in the cleaning agent according to the invention is essentially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol; Substantially free of organic components which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, means that in the liquid phase (in the case of several liquid phases in each individual liquid phase) less than 5 Wt .-%, preferably less than 3 wt .-% of such organic compounds are contained, 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 having 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 be avoided, which are particularly prone to migration between the compartments.
  • said organic components preferably organic solvents, which have an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol, in each case only to a proportion of less be contained as 5 wt .-%, preferably of less than 3 wt .-% (each based on the composition of the individual liquid phase).
  • the pre-portioned cleaning agent in particular machine dishwashing detergent, comprises a plurality of liquid phases in separate compartments
  • each of the liquid phases is essentially free of organic components having an average molecular weight of less than 175 g / mol, preferably less than 150 g / mol (other than the components mentioned under a)), since otherwise there is a migration of the components between the individual liquid phases in the separate compartments.
  • the liquid phase or the liquid phases of the cleaning agents according to the invention contain at least one component according to a).
  • Formula (I) are also a large part of the nonionic surfactants to grasp.
  • Low-foaming alkoxylated nonionic surfactants in particular ethoxylated, low-foaming nonionic surfactants, are preferably used with preference.
  • the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated 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 used are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants having a C 9-15 alkyl group having 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.
  • the rinse performance of the preparations according to the invention can be significantly improved, both compared to surfactant-free system and compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain.
  • nonionic surfactants include, 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 ether.
  • R 1 is -O- (CH 2 -CH (R 2 ) -O) w - (CH 2 -CH (R 3 ) -O) x - (CH 2 -CH (R 4 ) -O) y - (CH 2 -CH (R 5 ) -O) z -R 6
  • R 6 a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and w for values of 1 and 2 (for mixtures of such products also between 1 and 2, eg 1 , 5) and x stands for a value of at least 15.
  • non-ionic surfactants include, 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 -hydroxydecylether.
  • 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 the liquid phase, in particular ⁇ 20 ° C on.
  • the cleaning agent in particular machine dishwashing detergent in the liquid phase, as one of the components according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, especially at least one polyethylene glycol, with an average molecular weight between 180 and 6000, is preferred 200 to 5000, in particular between 300 and 4000 is included.
  • 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 is a medium Molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular about 4000, (INCI: PEG 4000).
  • PEG polyethylene glycol
  • the liquid phase has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 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 comprise at least one nonionic surfactant, preferably one which likewise represents a component according to a) according to formula I.
  • components according to a) are particularly advantageous, since they may optionally in addition to the liquid polyalkylene glycols, provide a basis for the liquid phase, without causing organic components, in particular organic solvents having an average molecular weight of less than 175 g / mol preferred of less than 150 g / mol, must be used.
  • At least one polyalkylene glycol preferably at least one polyethylene glycol having an average molecular weight between about 300 and about 5000, in particular approx 4000 g / mol is used.
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) additionally 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 having an average molecular weight between 3500 to 4500, in particular about 4000 has.
  • PEG polyethylene glycol
  • the liquid phase has a PEG having an average molecular weight of about 400 (INCI: PEG 400) and a PEG having an average molecular weight of about 4000 (INCI: PEG 4000).
  • the amount of all components mentioned according to a) in the liquid phase is 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 of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 15 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • the amount of all of the components referred to as preferred according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (each based on the total weight of the liquid phase) ,
  • a 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 , 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, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, h for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand.
  • 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 may 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 carbon 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 may be different if h ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for h has been chosen here by way of example and may well be greater, with the variation range increasing with increasing h values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 8 , R 10 and R 9 are as defined above and x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 8 and R 10 have 9 to 14 C atoms, R 9 is H and h assumes values of 6 to 15.
  • the amount of all components according to a) in the liquid phase is between 10 to 80 wt .-%, preferably between 20 to 70 wt .-% (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 / powder phases the total weight of all solid and powder phases) to the weight of one or more liquid phases (in the case of several liquid phases 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
  • substantially free of anionic surfactants means that a composition is less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, most preferably less than 1% by weight. -%, particularly preferably less than 0.1 wt .-% anionic surfactant (based on the total weight of the composition). This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
  • the water-soluble coating of the cleaning agent, the packaging is preferably made of a water-soluble film material selected from the group consisting of Polymers or polymer mixtures formed.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably 20,000 to 500,000 gmol -1 , more preferably 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group consisting of (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above may be additionally used in a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating Be added polymers.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, 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 include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such Polyvinyl alcohol copolymers in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents according to the invention can be used as dishwashing agents, in particular automatic dishwasher detergents.
  • the corresponding use is also the subject of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a cleaning agent according to the invention is used.
  • the particular embodiments described above also apply to the use or the method.
  • the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
  • the pre-portioned detergent according to the invention in particular machine dishwashing detergent, is substantially free of phosphates. This preferably applies to all, in particular also the combinations according to the invention explicitly mentioned as preferred above.
  • Substantially free of phosphates means that the total cleaning agent resulting from the addition of all phases (or all ingredients of all compartments) is preferably substantially free of phosphate-containing components.
  • Phosphates or else phosphate-containing components in the context of the present invention are in particular phosphates, polyphosphates and pyrophosphates. However, phosphonates or hexafluorophosphate are not covered by this term.
  • the total detergent thus contains less than 1 wt .-%, preferably 0.5% by weight of phosphates, based on the total weight of the cleaning agent (ie the total weight of all phases (ie all liquid and solid phases).
  • the detergents according to the invention in particular machine dishwashing detergents, comprise builders, such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • builders such as, for example, zeolites, silicates, carbonates, in particular the alkali metal carbonates, for example sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, and organic cobuilders.
  • Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where 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 are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, into consideration. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 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 preferably delayed release and have secondary washing properties.
  • the content of silicates based on the total weight of the cleaning agent, to amounts below 10 wt .-%, preferably below 5 wt .-%.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the automatic dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • aminocarboxylic acids and / or their salts are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or their salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • IDA iminodiacetic acid
  • Aminocarboxylic acids and their salts can be used together with the abovementioned builders, in particular also with the phosphate-free builders.
  • MGDA MGDA
  • GLDA GLDA
  • salts thereof MGDA
  • MGDA MGDA
  • MGDA can be used preferably as granules, and particularly preferably in the solid phase. Particular preference is given to those MGDA granules which contain as little water as possible and / or have low hygroscopicity.
  • MGDA or salts thereof in a total amount of 3 to 50 wt .-% based on the total weight of the cleaning agent.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the polyacrylate or the polyacrylates are used here in particular in a dried, particularly preferably in a dried and granulated (solid) form, which may optionally additionally be ground.
  • Suitable polymers are in particular polyacrylates which preferably have a molecular weight of about 1000 to 20,000, in particular 2,000 to 10,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the detergents may contain, in particular, phosphonates as builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonate-containing components are in the Agents preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
  • the compositions according to the invention contain from 0.01 to 25% by weight, preferably from 5 to 20% by weight, from 8 to 15% by weight. % Phosphonate (in each case based on the total weight of the composition).
  • the phosphonates are preferably contained in the solid phase (s).
  • the cleaning agents of the invention may further contain a sulfopolymer.
  • the proportion by weight 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 1.0 to 15 wt .-%, most preferably 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 additionally be 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.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • 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) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing the sulfonic acid group, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-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 in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • compositions according to the invention preferably comprise at least one further constituent, 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, bitter substances , and antimicrobial agents.
  • bleaching agents can also be used.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. It is also possible to use all other inorganic or organic peroxy bleaches known to the person skilled in the art.
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • detergents preferably dishwashing agents, in particular automatic dishwasher detergents, 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 wt .-% and in particular 5 to 18 wt .-% (based on the total weight of the cleaning agent) bleach, preferably sodium percarbonate.
  • the cleaning agents may contain bleach catalysts.
  • Useful 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, more preferably from the group of manganese and / or cobalt salts and / or or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate and the 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).
  • detergents preferably dishwashing agents, in particular automatic dishwasher detergents, which contain from 0.001 to 1% by weight, preferably from 0.01 to 0.1% by weight (based in each case on the total weight of the cleaning agent) of bleach catalyst, preferably a Mn complex.
  • 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-tri-azacyclononane (Mn 4 -TACN).
  • the cleaning agents preferably dishwashing agents, in particular automatic dishwasher detergents, additionally comprise at least one bleach activator.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) is particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU Tetraacetylglycoluri
  • 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 from 0.1% by weight to 8% by weight, especially from 2 to 8% by weight and more preferably from 2 to 6% by weight, based in each case on the total weight of the detergents used.
  • the bleaching agent and also 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 hetero atoms 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 -Alkyldimethylcarboxymethylbetain and C 11 -C 17 -Alkylamidopropyl-dimethylcarboxymethylbetain.
  • 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 are four identical or different, in particular two long and two short-chain, alkyl radicals and X - are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect 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 basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisins those of the subtilisin type are preferable.
  • examples include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which are attributed to the subtilases, but not the subtilisins in the narrower sense.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from, or further developed, Humicola lanuginosa ( Thermomyces lanuginosus ), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, most 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 according to the invention to increase the bleaching effect.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents can use stabilizers for this purpose contain; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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 wt .-% of the enzyme protein.
  • detergents which, based in each case 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 preferably present in (one) of the solid phase (s), preferably as granules or granules.
  • Glass corrosion inhibitors used are metal salts, in particular zinc salts or bismuth salts, preferably zinc salts, in particular zinc acetate.
  • Polyethyleneimines and polyvinylamines which are obtainable for example under the name Lupasol® or Lupamin® from BASF, in particular non-alkoxylated polyethyleneimines, are also preferably used as glass corrosion inhibitors.
  • Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
  • the cleaning agents according to the invention are characterized in that they are stable on storage and even after a prolonged period, no phase separation occurs.
  • a further subject of the present invention is also a machine dishwashing process 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 automatic dishwashing detergent.
  • liquid phase E1
  • closed outer packaging glass container
  • the chamber containing the solid phase was significantly more filled, gravimetric weight gain equivalent to weight loss of the fluid chamber was observed.

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Claims (13)

  1. Agent de nettoyage pré-dosé, de préférence agent de lavage pour lave-vaiselle, dans un emballage hydrosoluble comportant au moins deux compartiments, comprenant au moins une phase solide, de préférence pulvérulente, et au moins une phase liquide,
    caractérisé en ce que la phase liquide (ou les phases liquides)
    a) contien(nen)t au moins un, et de préférence deux, trois, quatre constituant(s) alcoxylé(s) ou plus, répondant à la formule I ci-après

            R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6     (formule I)

    où
    R1 est choisi parmi -H, -CH3 ou représente un radical alkyle ou alcényle en C2 à C24 linéaire ou ramifié, saturé ou mono- ou poly-insaturé ;
    R2, R3, R4, R5 sont, dans chaque cas indépendamment les uns des autres, choisis parmi -H, -CH3, -CH2CH3, -CH2CH2CH3, CH(CH3)2, et de préférence -H ou -CH3 ;
    R6 est choisi parmi -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, - CH2CH(CH3)2, -C(CH3)3, un radical alkyle ou alcényle en C5 à C24, ainsi que - CH2CH(OH)R7,
    R7 représente un radical alkyle ou alcényle en C6 à C26 linéaire ou ramifié, saturé ou mono- ou poly-insaturé ; et
    w, x, y et z peuvent, dans chaque cas indépendamment les uns des autres, prendre des valeurs allant de 1 à 120, avec x, y et/ou z = 0,
    b) contien(nen)t moins de 5 % en poids des composés organiques, qui ont un poids moléculaire moyen inférieur à 175 g/mol, de préférence inférieur à 150 g/mol ; et
    c) contien(nen)t moins de 7 % en poids d'eau.
  2. Agent de nettoyage selon la revendication 1, caractérisé en ce que, dans la phase liquide, au moins l'un, de préférence plusieurs, en particulier la totalité des constituants selon a) ont un point de fusion (à 1 bar) ≤ 30 °C, de préférence ≤ 25 °C, et en particulier ≤ 20 °C.
  3. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'au moins un polyalkylèneglycol, de préférence au moins un polyéthylèneglycol ou au moins un polypropylèneglycol, et en particulier au moins un polyéthylèneglycol ayant un poids moléculaire moyen compris entre 160 et 6 000, de préférence entre 200 et 5 000, et en particulier entre 300 et 4 000, est présent dans la phase liquide en tant que l'un des constituants selon a).
  4. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'un constituant de formule (I)

            R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6

    où
    R1 est choisi parmi les radicaux alkyle en C8 à C16 linéaires ou ramifiés, et saturés ;
    R2 et R4 correspondent à -H, et R3 et R5 correspondent à -CH3,
    R6 est choisi parmi -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2-CH2-CH2CH3, - CH2CH(CH3)2, -C(CH3)3, un radical alkyle en C5 à C20 (linéaire ou ramifié), et, choisis indépendamment les uns des autres,
    w = 1 à 6, de préférence 1,5 à 4,5, et en particulier 2 à 3 ;
    x = 1 à 6, de préférence 1,5 à 4,5, et en particulier 2 à 3 ;
    y = 0 à 6, de préférence 1,5 à 4,5, 2 à 3 ;
    z = 0 à 6, de préférence 1,5 à 4,5, 2 à 3,
    est présent dans la phase liquide en tant que l'un des constituants selon a).
  5. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'au moins un tensioactif non ionique fermé par des groupes terminaux selon la formule (I)

            R1-O-(CH2-CH(R2)-O)w-(CH2-CH(R3)-O)x-(CH2-CH(R4)-O)y-(CH2-CH(R5)-O)z-R6

    Où
    - R1 représente un radical hydrocarboné linéaire ou ramifié ayant de 2 à 26 atomes de carbone ;
    - R2 = H,
    - R6 est choisi parmi -CH2CH(OH)R7, R7 représentant un radical alkyle ou alcényle en C6 à C26 linéaire ou ramifié, saturé ou mono- ou poly-insaturé ; et
    - w = 1 à 120, de préférence 10 à 80, et en particulier 20 à 40 ; et x, y, z = 0,
    est présent dans la phase liquide en tant que l'un des constituants selon a).
  6. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que la quantité de tous les constituants selon a) dans la phase liquide représente entre 10 et 80 % en poids, de préférence entre 20 et 70 % en poids (dans chaque cas par rapport au poids total de la phase liquide).
  7. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que les constituants organiques selon b) sont liquides à 20 °C et 1 bar.
  8. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que l'agent de nettoyage contient de préférence moins de 1 % en poids de phosphates, par rapport au poids total de l'agent de nettoyage.
  9. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce que l'agent de nettoyage contient de préférence du phosphonate (par rapport au pourcentage du groupe phosphonate) en des quantités allant de 0,01 à 25 % en poids, de préférence de 5 à 20 % en poids, de 8 à 15 % en poids de phosphonate (dans chaque cas par rapport au poids total de l'agent).
  10. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'il s'agit d'un emballage multi-compartiments, de préférence d'un sachet multi-compartiments, comportant en particulier deux, trois, quatre compartiments ou plus.
  11. Agent de nettoyage selon l'une des revendications précédentes, caractérisé en ce qu'il s'agit d'un emballage hydrosoluble constitué d'un film à base d'alcool polyvinylique ou de copolymère d'alcool polyvinylique.
  12. Utilisation d'un agent de nettoyage selon l'une des revendications précédentes 1 à 11 dans un procédé de nettoyage en lave-vaisselle.
  13. Procédé de nettoyage de la vaisselle, de préférence en lave-vaisselle, caractérisé en ce que l'on utilise un agent de nettoyage selon l'une des revendications 1 à 11.
EP15704269.8A 2014-02-06 2015-02-04 Détergents polyphasiques préportionnés Active EP3102658B1 (fr)

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EP3275986B1 (fr) 2016-07-26 2020-07-08 The Procter and Gamble Company Composition de détergent de lave-vaisselle automatique
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
WO2018138119A1 (fr) 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
DE102019219812A1 (de) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Mittel für das maschinelle Geschirrspülen mit verbesserter Reinigungsleistung für bleichbare Anschmutzungen

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US20100216683A1 (en) 2007-08-22 2010-08-26 Arnd Kessler Cleaning Product

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ES2729654T3 (es) * 2010-01-29 2019-11-05 Monosol Llc Película soluble en agua que tiene propiedades de disolución y sobrecarga mejoradas, así como envases fabricados a partir de la misma
EP2821474A1 (fr) * 2011-01-12 2015-01-07 The Procter and Gamble Company Procédé de contrôle de la plastification d'un film hydrosoluble
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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