EP3102659B1 - Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau - Google Patents

Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau Download PDF

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Publication number
EP3102659B1
EP3102659B1 EP15704267.2A EP15704267A EP3102659B1 EP 3102659 B1 EP3102659 B1 EP 3102659B1 EP 15704267 A EP15704267 A EP 15704267A EP 3102659 B1 EP3102659 B1 EP 3102659B1
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weight
acid
bis
water
cleaning agent
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German (de)
English (en)
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EP3102659A1 (fr
Inventor
Ulrich Pegelow
Noelle Wrubbel
Martina Hutmacher
Matthias Sunder
Volker Blank
Klaus Dorra
Britta Strauss
Oliver Kurth
von den Karl-Josef DRIESCH
Friedhelm Siepmann
Mario Sturm
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles

Definitions

  • the invention relates to the use of at least one aminocarboxylic acid for stabilizing low-water, preferably essentially water-free, liquid detergent or cleaning agent components.
  • Detergents or cleaning agents for hard surfaces such as dishwashing detergents
  • dishwashing detergents are available to the consumer in a large number of forms.
  • flowable and especially liquid to gel-like cleaning agents have recently become increasingly important.
  • the consumer 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, are increasing.
  • compositions with as low a water content as possible are therefore particularly desirable.
  • phase separation can be caused, for example, by the fact that, in particular in low-water or essentially water-free compositions, the different components, for example dispersed solids or not completely miscible non-aqueous liquids, disintegrate and a phase separation takes place. The consumer perceives this phase separation as not aesthetic and, in the worst case, doubts the usability of the product, which no longer appears flawless.
  • the WO9900478 describes the use of iminiodisuccinate (IDS) to stabilize enzymes or enzyme granules, the enzyme-stabilizing effect being explicitly attributed to the complexation of divalent metal ions.
  • the FR 2818150 also discloses IDS for stabilizing enzymes.
  • the DE102008034231 relates to compositions with a high water content in which very small amounts of IDS are used in order to complex Mn catalysts and thereby stabilize them.
  • the post-published WO2014198557 discloses phase-stable, liquid compositions which have aminocarboxylic acids and a water content of> 37% by weight. It is therefore the object of the present invention to provide a method which counteracts the phase separation in low-water, in particular in substantially anhydrous detergent or cleaning agent compositions, and increases the stability, in particular the storage stability, of such compositions.
  • the object was achieved through the use of at least one aminocarboxylic acid and / or its salt for phase stabilization of liquid detergent or cleaning agent compositions that contain less than 20% by weight, preferably less than 15% by weight, particularly preferably less than 10% by weight. -% water, the detergents or cleaning agents containing no water-soluble surfactant selected from aryl sulfonate, alkyl sulfate and mixtures thereof.
  • aminocarboxylic acids the aminocarboxylic acids themselves and / or their salts are to be understood, for example also nitrilotriacetic acid, in particular methylglycinediacetic acid (MGDA) or its salts and glutamine diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS).
  • MGDA methylglycinediacetic acid
  • GLDA glutamine diacetic acid
  • EDDS ethylenediamine diacetic acid or its salts
  • Iminodisuccinic acid (IDS) and iminodiacetic acid (IDA) are also suitable.
  • the aminodicarboxylic acids are preferably used. Particularly preferred representatives of this class are amino diacetic acids,
  • the aminocarboxylic acid is selected from the group GLDA and MGDA, preferably MGDA.
  • the aminocarboxylic acid is contained in amounts from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid detergent or cleaning agent component) .
  • Aminodicarboxylic acids can preferably be used, preferably in amounts from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid detergent or cleaning agent component) contain.
  • aminocarboxylic acids are exclusively aminodicarboxylic acids, in particular in an amount from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid detergent or Detergent component) used.
  • MGDA or its salt is preferably used, in particular in an amount from 2 to 25% by weight, in particular from 3 to 15% by weight, preferably from 4 to 10% by weight (based on the weight of the liquid detergent or detergent component).
  • low-water means that a composition contains less than 20% by weight, in particular less than 15% by weight, preferably less than 13% by weight, particularly preferably less than 10% by weight, of water.
  • Essentially free of water means that a composition has 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.
  • % Contains water.
  • the water content as defined herein relates to the water content determined by means of Karl Fischer titration.
  • the detergent or cleaning agent is pre-portioned.
  • the single-use portion it is possible for the single-use portion to have one or more liquid phases located in several separate compartments.
  • an aminocarboxylic acid in particular an aminodicarboxylic acid, in particular GLDA or MGDA, in particular MGDA, is then preferably used for phase stabilization in at least one, preferably in several, in particular in all liquid phases.
  • the liquid phase is preferably "essentially 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 preferably less than Contains 1% by weight of water.
  • the water content as defined herein relates to the water content determined by means of Karl Fischer titration.
  • all liquid phases and all solid phases of the cleaning agent used according to the invention are "essentially free of water", ie 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 used according to the invention, includes all flowable compositions and in particular also includes gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a flow limit.
  • 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 used according to the invention, includes all solid compositions and includes in particular powdered, granulated, amorphous, compressed, in particular pressed, tableted compositions. Powdery compositions can also contain granules in addition to powdery constituents.
  • the cleaning agent is preferably in a water-soluble package.
  • the water-soluble packaging allows the cleaning agent to be portioned.
  • the amount of cleaning agent in the portion pack is preferably 5 to 50 g, particularly preferably 10 to 30 g, especially 15 to 25 g.
  • the cleaning agent is preferably present in a sufficient amount to carry out the cleaning, in the case of machine dishwashing agents in particular one cycle or a 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 spatially separated.
  • Two-chamber bags or two-chamber shaped bodies which contain a solid and a liquid phase in separate compartments are particularly suitable.
  • multi-chamber packagings are particularly suitable which contain a powdery phase in at least one of the separated compartments and a liquid phase in at least one other compartment.
  • a phase is understood here to be a (partial) composition of detergent which, in combination with the other phase or phases, results in a detergent, in particular a machine dishwashing detergent.
  • the cleaning agent used 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, for example three, four, five or six compartments.
  • the packaging preferably contains two, 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 different ingredients.
  • Pre-portioned cleaning agents are preferred in which the water-soluble packaging 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 these are of different composition and / or have a different solid form.
  • Pre-portioned cleaning agents are particularly preferred which have at least one solid phase, preferably at least one pulverulent phase, and at least one liquid phase in separate compartments.
  • Pre-portioned cleaning agents are also preferred which have at least one solid phase, of which preferably at least one compressed phase, and one liquid phase in separate compartments.
  • the pre-portioned cleaning agent has 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 in each case in 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).
  • the above formula (I) also includes a large number of nonionic surfactants.
  • Low-foaming alkoxylated nonionic surfactants especially ethoxylated, low-foaming nonionic surfactants, are preferably used.
  • the automatic dishwashing agents contain nonionic surfactants from the group of alkoxylated alcohols.
  • the low-water, preferably essentially water-free, liquid detergent or cleaning agent components contain one or more nonionic surfactants in an amount of 15 to 60% by weight, preferably 20 to 50% by weight, in particular 30 to 40% by weight. % (based on the weight of the liquid detergent or cleaning agent component).
  • Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.
  • Low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units are used as particularly preferred nonionic surfactants.
  • surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows.
  • nonionic surfactants 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.
  • the cleaning performance of the preparations according to the invention can be significantly improved, both in comparison to surfactant-free systems and in comparison to systems that use alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols contain
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the C 40 2-hydroxyalkyl ether 8-10 fatty alcohol (PO) 1 - - to the group of these nonionic surfactants include the C 2-26 fatty alcohol, for example (PO) 1 - (EO) 15 (EO) 22 -2 hydroxydecyl ether.
  • End-capped poly (oxyalkylated) nonionic surfactants of the formula are also preferred R 1 -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 -CH 2 CH (OH)
  • R 7 with R 7 for a straight-chain or branched, saturated or single or polyunsaturated C 6-26 alkyl or alkenyl radical in which R 1, independently of R 7, is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 —CH 3 , —CH (CH 3 ) 2
  • the cleaning agent in particular machine dishwashing detergent, has 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.
  • the cleaning agent in particular machine dishwashing detergent in the liquid phase, preferably has at least one polyalkylene glycol, preferably at least one polyethylene glycol or at least one polypropylene glycol, in particular at least one polyethylene glycol, with an average molecular weight between 180 and 6000 as one of the components according to a) 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 has an average molecular weight between 2000 and 6000 g / mol, preferably an average molecular weight between 3500 to 4500, in particular approx. 4000, (INCI: PEG 4000).
  • PEG polyethylene glycol
  • the liquid phase (the liquid phases) have a PEG with an average molecular weight of approx. 400 (INCI: PEG 400) and a PEG with an average molecular weight of approx. 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 nonionic surfactant, preferably one which is also a component according to a) according to formula I.
  • components according to a) are particularly advantageous because they can optionally provide a basis for the liquid phase in addition to the liquid polyalkylene glycols without the need for organic components, in particular organic solvents, which have an average molecular weight of less than 175 g / mol, preferably of less than 150 g / mol must be used. It is particularly preferred here if in addition to one of the components preferred here according to a) as a further preferred component according to a) at least one polyalkylene glycol, preferably at least one polyethylene glycol, which has an average molecular weight between approx. 300 and approx. 5000, in particular approx 4000 g / mol is used.
  • the liquid phase (at least one of the liquid phases, preferably the liquid phases) is 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 with an average molecular weight between 3500 and 4500, in particular approx. 4000.
  • PEG polyethylene glycol
  • the liquid phase (the liquid phases) have a PEG with an average molecular weight of approx. 400 (INCI: PEG 400) and a PEG with an average molecular weight of approx. 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-C 4-22 hydroxydecylether and the fatty alcohol (EO ) 40-80 -2-hydroxyalkyl ethers.
  • the amount of all components mentioned in accordance with a) in the liquid phase is between 10 to 80% by weight, preferably between 20 to 70% by weight (in each case based on the total weight of the liquid phase).
  • the amount of all of the components mentioned as preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 to 70% by weight (in each case based on the total weight of the liquid phase) .
  • the amount of all of the components mentioned as preferred according to a) in the liquid phase is between 15 to 80% by weight, preferably between 20 to 70% by weight (in each case based on the total weight of the liquid phase) .
  • the amount of all of the components mentioned as preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 to 70% by weight (in each case based on the total weight of the liquid phase) .
  • the amount of all components mentioned as preferred according to a) in the liquid phase is between 10 to 80% by weight, preferably between 20 to 70% by weight (each 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 , be included, in particular poly (oxyalkylated) nonionic surfactants of the formula II in which R 8 and R 10 stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 9 for H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, h stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R 9 in the above formula can be 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, 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 value 3 for h has been chosen as an example and can certainly be larger, the range of variation increasing with increasing h-values and including, 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.
  • Particularly preferred are surfactants in which the radicals R 8 and R 10 have 9 to 14 carbon atoms, R 9 stands for 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% by weight, preferably between 20 to 70% by weight (based in each case on the total weight of the liquid phase).
  • the cleaning agent in particular machine dishwashing detergent, is essentially free of anionic surfactants
  • substantially free of anionic surfactants means that a composition has 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. -%, particularly preferably less than 0.1% by weight of anionic surfactant (based on the total weight of the agent). This preferably applies to all, in particular also to the combinations according to the invention explicitly mentioned above as preferred.
  • the water-soluble envelope of the cleaning agent, the packaging is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the envelope can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different.
  • Particularly preferred are foils which, for example, can be glued and / or sealed to form packaging such as tubes or pillows after they have been filled with an agent.
  • the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 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 usually 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 in particular 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope can additionally contain a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added.
  • a preferred additional polymer are polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, 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 vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.
  • the film material contains further additives.
  • the film material can for example contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or mixtures thereof.
  • Further Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-stick agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the cleaning agents used 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 a machine dishwashing process, in which a cleaning agent according to the invention is used.
  • the particular embodiments described above apply to the use as well as the method.
  • the cleaning agents used according to the invention are preferably a dishwashing agent, in particular an automatic dishwashing agent.
  • the pre-portioned cleaning agent used according to the invention in particular machine dishwashing agent, is essentially free of phosphates. This preferably applies to all, in particular also to the combinations according to the invention explicitly mentioned above as preferred.
  • Essentially free of phosphates means that the entire cleaning agent, which results from the addition of all phases (or all ingredients of all compartments), is preferably essentially free of phosphate-containing components.
  • Phosphates, polyphosphates and pyrophosphates are to be regarded as phosphates or also phosphate-containing components in the context of the present invention. Phosphonates or hexafluorophosphate are not included in this term.
  • the total 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 used according to the invention in particular machine dishwashing detergents, 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.
  • Particularly suitable silicates are crystalline layered silicates of the general formula NaMSi x O 2x +1 ⁇ y H 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred ones 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 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties.
  • the content of silicates is below 10% by weight, preferably below 5% by weight.
  • Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.
  • Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as 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), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in automatic dishwashing detergents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the polyacrylate or the polyacrylates are used here in particular in a dried form, particularly preferably in a dried and granulated (solid) form, which can optionally also be milled.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of approx. 1000 to 20,000, in particular 2000 to 20,000 g / mol. Because of their superior solubility, short-chain polyacrylates, the molecular weights of 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the cleaning agents can in particular also contain phosphonates as builders.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates.
  • Phosphonate-containing components are contained in the agents preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, based in each case on the total weight of the cleaning agent.
  • the agents used according to the invention contain from 0.01 to 25% by weight, preferably 5 to 20% by weight, 8 to 15% by weight. -% phosphonate (each based on the total weight of the agent). According to the invention, the phosphonates are preferably contained in the solid phase or phases.
  • the cleaning agents used according to the invention can also contain a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the cleaning agent used according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably 1.0 to 15% by weight, very particularly preferably 2.0 to 14% by weight, in particular from 4 to 14% by weight, especially from 4.5 to 12% by weight.
  • the sulfopolymer is used here in particular in a dried form, particularly preferably in a dried and granulated (solid) form, which can optionally also be milled.
  • a copolymeric polysulfonate preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.
  • the copolymers can have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group 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.
  • the unsaturated dicarboxylic acids can of course also be used.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups can be wholly or partly in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulphonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50% by weight, the monomers here are preferably selected from those mentioned above.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred cleaning agents are characterized in that the copolymers have molecular weights from 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 also comprise, in addition to carboxyl-containing monomer and sulfonic acid-containing monomer, at least one nonionic, preferably hydrophobic, monomer.
  • these hydrophobically modified polymers made it possible, in particular, to improve the rinsing performance of automatic dishwashing agents 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, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, alpha-olefins with 10 or more carbon atoms such as, for example, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is, in relation to the monomer containing sulfonic acid groups, the hydrophobic monomer and the monomer containing carboxylic acid groups, preferably in each case 5 to 80% by weight, particularly preferably the proportion of the monomer and the sulfonic acid group hydrophobic monomer in each case 5 to 30% by weight and the proportion of the carboxylic acid group-containing monomer 60 to 80% by weight, the monomers here are preferably selected from those mentioned above.
  • the pH of an aqueous solution at 20 °, containing 10% by weight of the total cleaning agent is in a range from 7 to 14, in particular greater than 7, in particular in a range from 8 to 13, preferably 9 to 12 .
  • the agents used according to the invention preferably contain at least one further component, preferably selected from the group consisting of cationic and amphoteric Surfactants, bleaches, 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.
  • at least one further component preferably selected from the group consisting of cationic and amphoteric Surfactants, bleaches, 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.
  • Bleaches can also be used in the cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
  • Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaches known to the person skilled in the art from the prior art can also be used.
  • Substances releasing chlorine or bromine can also be used as bleaching agents.
  • Suitable materials releasing chlorine or bromine are, for example, heterocyclic N-bromo- and N-chloramides, 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 detergents, in particular automatic dishwashing detergents, 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 up to 20% by weight and in particular 5 to 18% by weight (based on the total weight of the cleaning agent) of bleach, preferably sodium percarbonate.
  • the cleaning agents can also contain bleach catalysts.
  • the bleach catalysts that can be used include, but are not limited to, the group of the bleach-enhancing transition metal salts and transition metal complexes, preferably the Mn, Fe, Co, Ru or Mo complexes, particularly preferably from the group of the manganese and / or cobalt salts and / or complexes, in particular the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of 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 detergents, in particular automatic dishwashing detergents, are preferred which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight (each based on the total weight of the detergent) of a bleach catalyst, preferably an 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).
  • a bleach catalyst preferably an 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 detergents, in particular machine dishwashing detergents, additionally contain at least one bleach activator.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon 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, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferred.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU tetraacetylgly
  • 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, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight, each based on the total weight of the cleaning agent 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 with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and iv and R v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetaine.
  • 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 types, in particular two long and two short-chain, alkyl radicals and X - stand for 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 with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • 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 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 of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are correspondingly preferred.
  • Cleaning agents used according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein.
  • the protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method.
  • subtilisins those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilase enzymes, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the improved further developments of the aforementioned amylases for use in cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtained or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those with one or more of the following amino acid exchanges starting from the lipase mentioned in positions D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and, owing to the coating, are stable in storage.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • Particularly preferred cleaning agents are those which, based in each case on their total weight, 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 contained in (one) of the solid phase (s), preferably as granules or granules.
  • Metal salts in particular zinc or bismuth salts, preferably zinc salts, in particular zinc acetate, are used as glass corrosion inhibitors.
  • Polyethyleneimines and polyvinylamines such as those available, 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 contained in the agents according to the invention preferably in an amount of 0.05 to 5% by weight, in particular in an amount of 0.1 to 2% by weight.
  • the cleaning agents used according to the invention are distinguished by the fact that they are stable in storage and that no phase separation occurs even after a long period of time.
  • the present invention also relates to an automatic dishwashing process in which a cleaning agent according to the invention is used.
  • the invention also relates to the use of the cleaning agent used according to the invention as a dishwashing agent, in particular an automatic dishwashing agent.
  • Comparative formulation V1 shows a visible phase separation within 4 weeks when stored at 40 ° C., 1 bar, whereas example E1 according to the invention showed no visible phase separation under these conditions.
  • liquid formulation according to Tab. 2 is also suitable.

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Claims (6)

  1. Utilisation d'au moins un acide aminocarboxylique et/ou de son sel pour la stabilisation de phase de compositions liquides de lessive ou de détergent contenant moins de 20 % en poids, de préférence moins de 15 % en poids, de manière particulièrement préférée moins de 10 % en poids d'eau, caractérisée en ce que les lessives ou détergents ne contiennent pas de tensioactif hydrosoluble choisi parmi l'arylsulfonate, l'alkylsulfate et leurs mélanges.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'acide aminocarboxylique est choisi dans le groupe de l'acide nitrilotriacétique, l'acide méthylglycine diacétique (MGDA), l'acide glutamine diacétique (GLDA), l'acide éthylènediamine diacétique (EDDS), l'acide iminodisuccinique (IDS), l'acide iminodiacétique (IDA) ou les sels des acides mentionnés, de préférence le GLDA et MGDA, de manière particulièrement préférée le MGDA.
  3. Utilisation selon l'une des revendications précédentes, caractérisée en ce que l'acide aminocarboxylique et/ou son sel sont contenus en des quantités de 2 à 25 % en poids, en particulier de 3 à 15 % en poids, de préférence de 4 à 10 % en poids (par rapport au poids du composant liquide de lessive ou de détergent).
  4. Utilisation selon l'une des revendications précédentes, caractérisée en ce que la composition liquide de lessive ou de détergent contient moins de 1 % en poids de phosphates, par rapport au poids total de la composition.
  5. Utilisation selon l'une des revendications précédentes, caractérisée en ce que la composition liquide de lessive ou de détergent contient un ou plusieurs tensioactifs non ioniques en une quantité de 15 à 60 % en poids, de préférence de 20 à 50 % en poids, en particulier de 30 à 40 % en poids (par rapport au poids de la composition liquide de lessive ou de détergent).
  6. Utilisation selon l'une des revendications précédentes, caractérisée en ce que la composition liquide de lessive ou de détergent contient moins de 7 % en poids, de préférence moins de 5 % en poids, plus préférentiellement moins de 3 % en poids, en particulier moins de 1 % en poids d'eau.
EP15704267.2A 2014-02-06 2015-02-04 Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau Active EP3102659B1 (fr)

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DE102014202223.1A DE102014202223A1 (de) 2014-02-06 2014-02-06 Verwendung von Aminocarbonsäuren zur Stabilisierung von wasserarmen flüssigen Wasch- oder Reinigungsmittelkomponenten
PCT/EP2015/052295 WO2015118008A1 (fr) 2014-02-06 2015-02-04 Utilisation d'acides aminocarboxyliques pour la stabilisation des lessives ou détergents pauvres en eau

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Citations (7)

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GB1270040A (en) 1967-01-27 1972-04-12 Unilever Ltd Liquid detergent compositions
GB1292352A (en) 1969-01-17 1972-10-11 Unilever Ltd Liquid detergent compositions
GB2178754A (en) 1985-08-05 1987-02-18 Colgate Palmolive Co Phosphate free or low phosphate laundry detergent
GB2197339A (en) 1986-10-30 1988-05-18 Unilever Plc Non-aqueous liquid cleaning products
WO2009125335A2 (fr) 2008-04-07 2009-10-15 Ecolab Inc. Composition de dégraissage liquide ultra-concentrée
WO2010024470A1 (fr) 2008-09-01 2010-03-04 The Procter & Gamble Company Composition comprenant une composition polymère à base de polyoxyalkylène
US20120053107A1 (en) 2010-09-01 2012-03-01 Regine Labeque Detergent composition comprising mixture of chelants

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CA2295233A1 (fr) * 1997-06-27 1999-01-07 Lorenzo Matteo Pierre Gualco Compositions detergentes liquides non aqueuses contenant des particules enzymatiques
FR2818150B1 (fr) * 2000-12-15 2004-04-30 Anios Lab Sarl Composition pour le traitement d'objets destines a etre desinfectes
DE10153553A1 (de) * 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
DE102008034231A1 (de) * 2008-07-23 2010-01-28 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
GB201216028D0 (en) * 2012-09-07 2012-10-24 Reckitt Benckiser Nv Detergent formulation
PT3008159T (pt) * 2013-06-12 2017-02-10 Unilever Nv Composição detergente passível de ser vertida compreendendo partículas suspensas

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1270040A (en) 1967-01-27 1972-04-12 Unilever Ltd Liquid detergent compositions
GB1292352A (en) 1969-01-17 1972-10-11 Unilever Ltd Liquid detergent compositions
GB2178754A (en) 1985-08-05 1987-02-18 Colgate Palmolive Co Phosphate free or low phosphate laundry detergent
GB2197339A (en) 1986-10-30 1988-05-18 Unilever Plc Non-aqueous liquid cleaning products
WO2009125335A2 (fr) 2008-04-07 2009-10-15 Ecolab Inc. Composition de dégraissage liquide ultra-concentrée
WO2010024470A1 (fr) 2008-09-01 2010-03-04 The Procter & Gamble Company Composition comprenant une composition polymère à base de polyoxyalkylène
US20120053107A1 (en) 2010-09-01 2012-03-01 Regine Labeque Detergent composition comprising mixture of chelants

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