EP3430112B1 - Granulat umfassend einen anorganischen, festen träger, auf dem mindestens ein biotensid enthalten ist - Google Patents

Granulat umfassend einen anorganischen, festen träger, auf dem mindestens ein biotensid enthalten ist Download PDF

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Publication number
EP3430112B1
EP3430112B1 EP17707570.2A EP17707570A EP3430112B1 EP 3430112 B1 EP3430112 B1 EP 3430112B1 EP 17707570 A EP17707570 A EP 17707570A EP 3430112 B1 EP3430112 B1 EP 3430112B1
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EP
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Prior art keywords
weight
formulation
granular material
acid
biosurfactant
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EP17707570.2A
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German (de)
English (en)
French (fr)
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EP3430112A1 (de
Inventor
Dirk Kuppert
Rudolf Egner
Jürgen LATTICH
Jens Hildebrand
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Evonik Operations GmbH
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Evonik Operations GmbH
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether 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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to granules comprising an inorganic, solid carrier on which at least one biosurfactant is present, formulations comprising these granules and their use.
  • WO2010063689 discloses single or multi-phase, phosphate-free detergent or cleaning agent tablets.
  • DE102014212642 and WO015189370 disclose cleaning agents which use enzymes, in particular amylases, to remove starchy soiling.
  • EP1411111 discloses biodegradable low-foaming compositions comprising sophorolipids.
  • the JP2009091534 discloses mixing sophorolipid with a powder of sodium hydrogen carbonate and citric acid to produce a medicament.
  • the JP2009052006 discloses an enzyme-containing composition with high cleaning power against soiling that is otherwise difficult to adhere, in particular starch stains, which also contains an amylase in addition to sophorolipid.
  • the JP 2006274233 discloses a composition containing sophorolipid, oxygen-containing bleach and bleach activator for use in automatic dishwashers.
  • the object of the present invention is now to provide a cleaning agent for hard surfaces which removes stubborn stains, in particular starchy stains.
  • the object is to provide a cleaning agent for dishes, in particular to provide a cleaning agent for machine washing dishes.
  • the present invention therefore relates to granules comprising an inorganic, solid carrier on which at least one biosurfactant selected from the group comprising, preferably consisting of, sophorolipids and rhamnolipids, in particular sophorolipids, is present, characterized in that the carrier selected at least one solid from the group comprising carbonates, sesquicarbonates, percarbonates, perborates, sulfates, silicates, aluminosilicates, zeolites, precipitated silicas and pyrogenic silicas.
  • the carrier selected at least one solid from the group comprising carbonates, sesquicarbonates, percarbonates, perborates, sulfates, silicates, aluminosilicates, zeolites, precipitated silicas and pyrogenic silicas.
  • Another object of the invention is a process for the production of granules comprising an inorganic carrier on which at least one biosurfactant is contained, formulations containing the granules according to the invention and the use of the formulations.
  • An advantage of the present invention is that stubborn, dried-on stains are removed very well at low ambient temperatures. Another advantage of the present invention is that the formulations remove starchy contaminants without the need to use enzymes. Another advantage of the present invention is that granules can be defoamed excellently with small amounts of defoamers.
  • sophorolipids in the context of the present invention is understood to mean sophorolipids, as in the general formulas (Ia) and (Ib) EP2501813 played.
  • rhamnolipids in the context of the present invention means rhamnolipids, as in the general formula (I) EP2598646 played.
  • the carbonates, sesquicarbonates, percarbonates, perborates and sulfates are salts of the alkali or alkaline earth metals, in particular the alkali metals.
  • the granulate is characterized in that the at least one solid is selected from sodium carbonate, sodium percarbonate, pyrogenic and precipitated silicas, in particular in combination with a sophorolipid as the biosurfactant contained on the carrier.
  • the granulate is characterized in that the at least one solid is selected from pyrogenic and precipitated silicas in combination with a sophorolipid as the biosurfactant contained on the carrier.
  • Suitable precipitated silicas are sold, for example, by Evonik Industries as Sipernat®, for example Sipernat 22, and suitable pyrogenic silicas as Aerosil®.
  • the granules according to the invention comprise an inorganic, solid carrier which contains the abovementioned solids in an amount from 40% by weight to 100% by weight, preferably from 50% by weight to 90% by weight, particularly preferably from 60% by weight to 80% by weight, the percentages by weight relating to the total carrier.
  • sophorolipids can be contained in the granules according to the invention in their acid form or in their lactone form.
  • the term "acid form” of sophorolipids is based on the general formula (Ia) EP2501813 referred to the term “lactone form” of sophorolipids on the general formula (Ib) of EP2501813 directed.
  • Granules preferred according to the invention are characterized in that the biosurfactant contained on the carrier is a sophorolipid in which the weight ratio of lactone form to acid form is in a range from 20 to 80 to 80 to 20, preferably from 30 to 70 to 40 to 60.
  • the biosurfactant contained on the carrier is preferably present in the granules according to the invention in an amount of from 0.01% by weight to 70% by weight, preferably from 0.25% by weight to 60% by weight, particularly preferably from 1 , 5 wt .-% to 50 wt .-%, contain, the weight percentages refer to the sum of the weights of biosurfactant and carrier.
  • the granulate according to the invention advantageously has a half-value particle size d50 [ ⁇ m] in the range from 100 to 2000 ⁇ m, in particular in the range from 200 to 1500 ⁇ m and especially in the range from 700 to 1300 ⁇ m.
  • d50 [ ⁇ m] value marks the point at which half the examined particle quantity is larger or smaller.
  • d10 and d90 value indicate the range in which 10% and 90% are less than or equal to this Are particle size.
  • the half-value particle size d50 [ ⁇ m], as well as the d10 [ ⁇ m] and the d90 [ ⁇ m] value of the particle collective are determined with the help of a Camsizer® from Retsch (Haan, Germany) using the dynamic image analysis method with the choice of standard settings (ISO 13322-2: 2006).
  • the measurement method used provides a detailed particle size analysis of the entire particle collective, which is shown as a distribution density function.
  • the d50 value is taken as the abscissa value of the largest maximum.
  • Particle collectives with a narrow particle size distribution should preferably be selected. These are characterized in that the d10 [ ⁇ m] value of the particle collective is not less than 50% and the d90 [ ⁇ m] is not greater than 150% of the half-value particle size d50 [ ⁇ m].
  • the granules additionally contain at least one defoamer.
  • Defoamers include, for example, a wide variety of oils, such as organopolysiloxanes, for example in the form of silicone oils or polyoxyalkylene-polysiloxane block copolymers, polyethers, vegetable or animal oils, paraffins or mineral oils.
  • the oils may contain finely divided solids, which further enhance the defoaming effect.
  • An example of such a suitable finely divided solid is highly disperse, pyrolytically or wet-chemically obtained silica, which is commercially available as Aerosil or Sipernat and can be rendered hydrophobic by treatment with organosilicon compounds.
  • Suitable solids are metal soaps such as magnesium, aluminum and calcium soaps as well as polyethylene and amide waxes
  • Defoamers preferably contained according to the invention are selected from the group consisting of vegetable oils, in particular rape oil and rapeseed oil, silicone oils, hydrophobized silica, paraffins, paraffin-alcohol combinations, bisfatty acid amides, polyorganosiloxanes and mixtures thereof.
  • Polyorganosiloxanes preferably contained as defoamers are selected from the group consisting of the in the US2004198842 mentioned in aqueous emulsions with highly viscous, high molecular weight organopolysiloxane compounds, the in the EP0579999 aminosiloxanes called defoamers, the in the US6001887 mentioned organopolysiloxane of the general formula I, and
  • defoamers preferably contained according to the invention are those in the US5994415 described alkoxylated partial esters of oligoglycerols with C8 to C22 fatty acids, using 3 to 60 moles of propylene oxide and optionally 1 to 10 moles of styrene oxide and / or 1 to 10 moles of butylene oxide.
  • the granules particularly preferably contain the at least one defoamer in an amount of from 0.001% by weight to 5% by weight, preferably from 0.01% by weight to 2% by weight preferably from 0.05% by weight to 0.5% by weight, the percentages by weight based on the sum of the weights of the biosurfactant, defoamer and carrier.
  • the solid, particulate, inorganic carriers provided in process step A) are preferably selected from the inorganic, solid carriers comprised in the granules according to the invention.
  • the biosurfactants provided in process step B) are preferably selected from sophorolipids, in particular from those which are preferably contained in the granules according to the invention with regard to the acid-to-lactone ratio.
  • the aqueous composition from process step B) preferably has water in an amount from 10% by weight to 90% by weight, preferably from 20% by weight to 70% by weight, particularly preferably from 30% by weight to 60% by weight. -%, on, wherein the weight percentages refer to the total aqueous composition.
  • the aqueous composition from process step B) preferably has the biosurfactant in an amount from 10% by weight to 90% by weight, preferably from 30% by weight to 80% by weight, particularly preferably from 40% by weight to 70% % By weight, the percentages by weight relating to the entire aqueous composition.
  • the aqueous composition additionally contains a defoamer, preferably those which are mentioned above as being preferably present in the granules according to the invention.
  • process step C) the contacting is carried out by spraying the aqueous composition from process step B) onto the carrier from process step A).
  • the contacting by spraying can take place, for example, with the aid of a fluidized bed spray granulator or a ploughshare mixer.
  • a fluidized bed spray granulator is used, the inorganic carrier is fluidized by the flow of a suitable gas, such as air, nitrogen or carbon dioxide, and kept in constant motion. It is preferred according to the invention that when using a fluidized bed spray granulator, process step C) is carried out at a temperature of from 30 ° C. to 100 ° C., preferably from 40 ° C. to 80 ° C. and very particularly preferably from 50 ° C. to 60 ° C. becomes.
  • a fluidized bed spray granulator is used, this is achieved by selecting and regulating the temperature of the inflowing gas such that the fluidized carrier has a temperature of 30 ° C. while the fluidized carrier is in contact with the aqueous composition of the biosurfactant to 100 ° C, preferably from 40 ° C to 80 ° C and very particularly preferably from 50 ° C to 60 ° C.
  • the biosurfactant is brought into contact with the fluidized carrier by spraying on, the spraying on can be carried out in the top spray, bottom spray or tangential spray method, particularly preferably in the top spray method. Coating in the fluidized bed can be carried out in batches or else with constant throughput in continuous fluidized bed systems.
  • the inorganic carrier is coated in process step C) with the aid of the centrifugal and whirling process with an aqueous composition from process step B).
  • the aqueous composition from process step B) is introduced by spraying into a mechanically generated fluidized bed of the inorganic carrier. It is preferred according to the invention that when a ploughshare mixer is used, process step C) is carried out at a temperature of from 15 ° C. to 30 ° C., particularly preferably from 20 ° C. to 25 ° C. Coating when using a ploughshare mixer can be carried out in batches or with constant throughput in continuous systems.
  • process step D) the at least partial removal of the water is preferably achieved by heating. It is preferred according to the invention that process step D) is carried out at a temperature from 50 ° C. to 120 ° C., preferably from 60 ° C. to 100 ° C. and very particularly preferably from 70 ° C. to 80 ° C. In general, drying could also take place at room temperature (20 - 25 ° C).
  • a fluidized bed spray granulator is used, this is achieved by selecting and regulating the temperature of the inflowing gas in process step D) in such a way that it is in the range from 50 ° C. to 120 ° C., preferably from 60 ° C. to 100 ° C and very particularly preferably from 70 ° C to 80 ° C.
  • Another object of the present invention is a granulate obtainable by the process according to the invention.
  • Another object of the present invention is a formulation comprising a granulate according to the invention or a granulate obtainable by the process according to the invention, which is characterized in that the formulation is from 0.1% by weight to 60% by weight, preferably from 1% by weight. % to 50% by weight, particularly preferably from 2% by weight to 40% by weight, of the aforementioned granules, the percentages by weight based on the overall formulation
  • a formulation preferred according to the invention is characterized in that the formulation is a cleaning agent for hard surfaces, in particular a dishwashing agent and very particularly preferably a dishwashing agent for the automatic cleaning of dishes.
  • Dishwashing detergents for the automatic cleaning of dishes are nowadays often in the form of tablets. These are powder detergents which have been brought into a certain shape by pressure. The use of tablets enables the dosage of active substances in the cleaning agent to be suitable for one cleaning cycle.
  • a detergent for dishwashers can be in the form of a powder.
  • the formulations according to the invention are preferably a solid dishwashing detergent.
  • a "solid dishwashing agent” is to be understood as meaning a dishwashing agent which is in a solid state at 25 ° C. and a pressure of 1 bar.
  • the solid dishwashing detergent is in the form of a shaped body, in particular a compact, especially a tablet.
  • the formulation contains at least one further constituent, preferably at least two further constituents, selected from the group consisting of builders, surfactants, polymers, corrosion inhibitors, in particular glass corrosion inhibitors, disintegration aids, enzymes, bleaching agents, bleaching catalysts, bleach activators, fragrances and perfume carriers ,
  • the formulations according to the invention preferably contain at least one further surfactant in addition to the granules according to the invention.
  • This surfactant is selected from the group of anionic, nonionic, cationic and amphoteric surfactants, particularly preferably from the group of nonionic surfactants.
  • the formulations according to the invention can also contain mixtures of several surfactants selected from the same group. All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to Corresponds to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides such as in DE 10 2014 212 622 Paragraph [0026] - [0027].
  • Low-foaming nonionic surfactants are used as preferred nonionic surfactants.
  • the formulations according to the invention particularly preferably comprise nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18- Alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical mean values which can correspond to an integer or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution ( narrow range ethoxylates, NRE ) .
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • Surfactants to be used preferably come from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. Non-ionic surfactants such as those used in the DE 1020142012622 in paragraphs [0036] - [0059].
  • the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • the weight fraction of the nonionic surfactant in the total weight of the formulation according to the invention is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight , based .
  • Anionic surfactants can also be used as a component of automatic dishwashing detergents. They include in particular alkylbenzenesulfonates, fatty alkyl sulfates, fatty alkyl ether sulfates and alkanesulfonates.
  • the anionic surfactant content of the agents is usually 0 to 10% by weight.
  • Preferred formulations are furthermore characterized in that they contain less than 1.0% by weight and in particular no anionic surfactant, since the addition of anionic surfactants is disadvantageous with regard to the tablets (phase) properties, in particular their hardness, friability and post-curing behavior has proven.
  • anionic surfactants instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants can also be used.
  • amphoteric surfactants are understood to be surface-active compounds which carry at least one quaternary ammonium group and at least one -COO or -SO 3 - group in the molecule.
  • amphoteric surfactants in this context are betaine surfactants such as alkyl- or alkylamidopropylbetaines.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinates, e.g. B. the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, e.g. B.
  • the Kokosacylaminopropyldimethylammoniumglycinat the C12-C18-alkyl-dimethyl-acetobetain, the Kokosamidopropyl-dimethyl-acetobetain, 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines and sulfobetaines each with 8 to 18 carbon atoms in the alkyl or acyl group and the coconut acylaminoethyl hydroxyethyl carboxymethyl glycinate are preferred.
  • a particularly preferred zwitterionic surfactant is the N, N-dimethyl-N- (lauroylamidopropyl) ammonium acetobetaine known under the INCI name Cocamidopropyl Betaine.
  • Further suitable amphoteric surfactants are the group of amphoacetates and amphodiacetates, in particular, for example, coconut or laurylamphoacetates or diacetates, the group of amphopropionates and amphodipropionates and the group of amino acid-based surfactants such as acylglutamates, in particular disodium cocoyl glutamates and sodium cocoylglycamate, cocoylglycine Glycinates, and acyl sarcosinates, especially ammonium lauroyl sarcosinate and sodium cocoyl sarcosinate.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight .-% based on the total average.
  • Automatic dishwashing agents according to the invention which contain only nonionic surfactants are very particularly preferred, in particular in combination with a sophorolipid as the biosurfactant contained on the carrier.
  • the formulations according to the invention can contain at least one enzyme or at least one enzyme preparation or enzyme composition which consists of one or more enzymes.
  • Suitable enzymes include, but are not limited to, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin-cleaving enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred.
  • Formulations according to the invention can contain enzymes and / or enzyme preparation (s), preferably in total amounts from 0.01 to 20% by weight, more preferably from 0.1 to 15.0% by weight, even more preferably from 0, 2 to 10% by weight and very particularly preferably from 0.4 to 8.0% by weight, based on the overall formulation.
  • enzymes and / or enzyme preparation preferably in total amounts from 0.01 to 20% by weight, more preferably from 0.1 to 15.0% by weight, even more preferably from 0, 2 to 10% by weight and very particularly preferably from 0.4 to 8.0% by weight, based on the overall formulation.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.
  • Organic builders which may be present in the formulations according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being those Carboxylic acids are understood that carry more than one acid function.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Particularly preferred formulations according to the invention contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably contained in a proportion of 2 to 50% by weight, in particular 5 to 40% by weight, particularly 10 to 40% by weight, based on the total weight of the dishwashing detergent of 100% by weight.
  • Citrates are preferably used in combination with carbonates and / or hydrogen carbonates.
  • Preferred formulations are therefore characterized by a builder combination of citrate and carbonate and / or hydrogen carbonate. It is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons.
  • alkali metal phosphates Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent or cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
  • phosphates are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are preferably used.
  • phosphates are used as washing or cleaning-active substances in the formulations, in particular in automatic dishwashing detergents
  • preferred detergents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate ( Sodium or potassium tripolyphosphate), in amounts of 5 to 80% by weight, preferably 15 to 75% by weight and in particular 20 to 70% by weight, in each case based on the weight of the cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent.
  • the cleaning agents described herein are essentially free of phosphates, in particular the aforementioned phosphates.
  • Phosphate-free means that the composition in question is essentially free of phosphates, ie in particular phosphates in amounts less than 0.1% by weight, preferably less than 0.01% by weight, based on the total composition contains. If phosphates are contained, they are preferably used in amounts that do not correspond to more than 0.3 g / job.
  • g per job (g / job) or g / application means the amount of active substance used in relation to the total weight of the agent used for a complete cleaning cycle (that is, for machine dishwashing detergents, the total amount of detergent used in a complete dishwasher washing program This information is the amount of the active ingredient in g based on the total weight of the pre-proportioned cleaning agent, and the expression "phosphates", as used in this connection, does not include the phosphonates described below.
  • the formulations according to the invention can contain at least one Contain phosphorus-free builders, the further phosphorus-free builders preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiace tat (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA and GLDA, the weight fraction of the builders, based on the total weight of the cleaning agent, preferably 5 to 80% by weight, preferably 10 to 75% by weight. -% and in particular 15 to 70 wt .-%.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiace tat
  • IDS iminodisuccinate
  • EDDS ethylenediamine disucc
  • The% by weight of the (hydrogen) carbonate and citrate is preferably as stated above.
  • the percentage by weight of the further phosphorus-free builder, in particular the MGDA and / or GLDA, is preferably 2 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 20% by weight.
  • Polymeric polycarboxylates are also suitable as builders, which may also be present in the formulations according to the invention. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol.
  • the short-chain polyacrylates with molecular weights of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, can in turn 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.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • the (homo) polymeric polycarboxylate content is preferably 0 to 20% by weight and in particular 0.5 to 10% by weight.
  • Formulations according to the invention can also contain crystalline layered silicates of the general formula NaMSi x 0 2x + 1 ⁇ yH2O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred Values for x are 2, 3 or 4, and y stands for a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.
  • the silicate content based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 3% by weight.
  • Particularly preferred automatic dishwashing agents according to the invention are free of silicate.
  • the formulations according to the invention can contain alkali metal hydroxides. These alkali carriers are preferably used in the formulations only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight and in particular between 0.5 and 5% by weight, in each case based on the total weight of the formulation.
  • Alternative formulations are free from alkali metal hydroxides.
  • Formulations according to the invention can furthermore contain phosphonate (s) as builders.
  • Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylenetriaminepen-ta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1,1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and Nitrilotri (methylenephosphonic acid) (NTMP), 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) being used with particular preference.
  • Phosphonate (s) are preferably used in formulations according to the invention in amounts of 0 to 20% by weight, in particular 0.5 to 10% by weight and
  • the group of polymers includes, in particular, the wash- or cleaning-active polymers, for example the rinse aid polymers and / or as softening polymers.
  • cationic, anionic and amphoteric polymers can also be used in machine dishwashing detergents.
  • “Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by means of (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers indicated under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can e.g. B. are carboxylic acids, sulfonic acids or phosphonic acids.
  • Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany) )), modified polycarboxylate sodium salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)), and polyether (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether)), preferably water-soluble linear polyether having terminal polyether as Tegopren® 5840, 5843 Tegopren®,
  • Tegoprene types 5843 and 5863 are, however, less preferred when used on hard surfaces made of glass, in particular glass dishes, since these can pull silicone surfactants onto glass.
  • the additives mentioned are dispensed with.
  • Preferred embodiments of the formulations according to the invention furthermore comprise a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleaching catalyst.
  • Formulations according to the invention contain an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate as the preferred exposure agent.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Sodium percarbonate is particularly preferred for its good bleaching performance.
  • a particularly preferred oxygen bleach is sodium percarbonate. Chlorine or bromine-releasing substances can also be used as bleaching agents.
  • Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICH) and / or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • the bleaching catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe-Cu and Ru-amine complexes can also be used as bleaching catalysts.
  • Complexes of manganese are used with particular preference in oxidation state II, III, IV or V, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • Ligands which have nitrogen donor functions are preferably used.
  • bleaching catalyst (s) in the formulations according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) contain.
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • the formulations according to the invention can contain further customary auxiliaries and additives.
  • additives include, for example, additives, dyes, preservatives (e.g. the technical 2-bromo-2-nitropropane-1,3-diol, also known as bronopol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide® BT or as Boots Bronopol BT from Boots, these can be contained in amounts of usually not more than 1% by weight.
  • the formulations according to the invention can furthermore contain glass corrosion inhibitors which prevent the occurrence of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of the magnesium and zinc salts and the magnesium and zinc complexes.
  • Formulations according to the invention can be preferred Embodiment contain at least one zinc salt as a further component.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt content in the formulations is preferably between 0 and 5% by weight, preferably between 0.1 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc in oxidized Form (calculated as Zn 2+ ) between 0 and 1 wt .-%, preferably between 0.01 b and is 0.5 wt .-% and in particular between 0.02 and 0.2 wt .-%, each based on the total weight of the agent containing glass corrosion inhibitor.
  • the automatic dishwashing agents according to the invention are preferably in the form of a shaped body, in particular a compact, in particular a tablet. However, they can also be in combination with other supply forms, in particular in combination with solid supply forms such as powders, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.
  • the shaped body can also be, for example, a granulate which is contained in a bag or a casting mold.
  • disintegration aids so-called tablet disintegrants, can be incorporated into these formulations in order to shorten the disintegration times.
  • Tablet disintegrants or disintegration accelerators are understood to mean auxiliary substances which ensure the rapid disintegration of tablets in water or other media and the rapid release of the active substances.
  • Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, in each case based on the total weight of the formulation containing disintegration aids.
  • Formulations according to the invention can be packaged as single-phase or multiphase products.
  • Machine dishwashing detergents with one, two, three or four phases are particularly preferred.
  • Machine dishwashing detergents, characterized in that they are in the form of a prefabricated metering unit with two or more phases, are particularly preferred.
  • Particularly preferred are two-phase or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough.
  • Formulations according to the invention are preferably prefabricated into metering units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle.
  • Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned dosing units and their spatial shape are selected with particular preference so that the pre-assembled units can be dosed via the dosing chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the formulations according to the invention in particular the prefabricated metering units, have a water-soluble coating.
  • the water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the sheath can be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different. Films are particularly preferred which, for example, can be glued and / or sealed to form packaging such as hoses or pillows after they have been filled with an agent. It is preferred that the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and is in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible.
  • At least one layer of the water-soluble covering comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer material containing polyvinyl alcohol suitable for producing the water-soluble covering can additionally be 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 can be added.
  • a preferred additional polymer is polylactic acid.
  • preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol 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 name 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.
  • Another object of the present invention is the use of a formulation according to the invention for use in an automatic dishwashing process.
  • Another object of the present invention is the use of a formulation according to the invention for cleaning hard surfaces, in particular for removing starchy soiling.
  • formulations according to the invention which are preferably emphasized above are preferably used.
  • a sophorolipid obtained by fermentation from rapeseed oil and sugar is used as the sophorolipid.
  • the free fatty acid content is less than 1% by weight, based on the amount of sophorolipid contained.
  • the sophorolipid used has a ratio of sophorolipidic acid to sophorolipid lactone of 60:40.
  • the loading of the carriers with sophorolipid was calculated as follows: mass of the sophorolipid used divided by mass of the dried granules.
  • Example 1 Sodium percarbonate as a carrier
  • Example 2 precipitated silica as a carrier
  • Sipernat® 22 (Evonik Ressource Efficiency GmbH) were placed in a 5 L ploughshare mixer from Lödige, and 1.7 kg dissolved in 3 kg of water were sprayed on at a mixer head speed of 700 scale units. The powder was then sieved, whereby portions with a grain size> 0.4 mm were separated off. The loading with sophorolipid active substance was 43%.
  • Example 3 Sodium carbonate as carrier.
  • the cleaning performance of machine dishwashing detergents was determined according to the current IKW method (S ⁇ FW, 132 (3/2006) 55 ff.) Using the modified soiling with improved differentiation described in the aforementioned literature reference. The tests were carried out at a water hardness of 9 ⁇ 1 ° dH in a household-relevant Miele GSL2 dishwashers carried out using the "R45 ° C / 8min / KI55 ° C" program in the presence of ballast dirt and with the water softener deactivated. The maximum temperature during the cleaning phase was 45 ° C. Each test run was carried out in the presence of 50 g of ballast dirt. The ballast dirt was produced according to the IKW method. The dosing took place at the beginning of the main wash cycle.
  • Table 1 Tested soiling: soiling carrier dirt class tea Porcelain cups bleach sensitive milk glass mug alkali sensitive minced meat Dessert plate, porcelain protease sensitive egg yolk Stainless steel sheets protease sensitive Creme brulee Dessert plate, porcelain protease sensitive Strength glass dish Amylase5, pasta Plate, porcelain Amylaseext
  • the cleaning performance results are the mean of four repetitions for each formulation. 20 g of machine dishwashing detergent are used for each cleaning job. The cleaning performance was determined either gravimetrically or visually and on a performance index scale from 0 (no cleaning) to 100 (complete Cleaning).
  • formulation A contains neither sophorolipid nor Sipernat® 22.
  • Formulation B contains Sipernat® 22 as the formulation not according to the invention and neither supported nor free sophorolipid
  • Formulation C not according to the invention contains 0.3% active content of unsupported sophorolipid.
  • the formulation D not according to the invention contains 4.3% active content of unsupported sophorolipid.
  • the active fraction of sophorolipid is 0.3% by weight in formulation E according to the invention and 4.3% by weight in formulation F according to the invention.
  • a commercially available automatic dishwashing powder from the Finish Classic Powder brand from Reckitt Benckiser was used as a further reference substance not according to the invention.
  • the qualitative composition of Finish Classic powder according to the Detergent Ordinance is sodium carbonate, sodium percarbonate, sodium citrate, TAED, sodium polyacrylate, subtilisin (protease), tetrasodium etidronate, fatty alcohol ethoxylate, amylase, perfume in descending order.
  • the commercial product thus contains the starch-breaking enzyme amylase.
  • Table 3 Cleaning performance compared to the starchy soils starch and pasta (scale from 0 (no cleaning) to 100 (complete cleaning)) recipe Decontamination index pasta Strength Finish Classic Powder (reference - not according to the invention) 42 64 A (not according to the invention) 23 35 B (not according to the invention) 23 35 C (not according to the invention) 22 31 D (not according to the invention) 25 35 E (according to the invention) 30 55 F (according to the invention) 23 74
  • Example 4 precipitated silica as a carrier with defoamer
  • Example 5 Sodium carbonate as a carrier with defoamer
  • Example 6 Sodium carbonate as carrier with defoamer 2

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CN108884413B (zh) 2022-04-01
WO2017157659A1 (de) 2017-09-21
US11254896B2 (en) 2022-02-22
KR20180122666A (ko) 2018-11-13
CA3017990C (en) 2023-08-01
MX2018011099A (es) 2018-11-22
JP2019508564A (ja) 2019-03-28
ZA201806796B (en) 2019-07-31
EP3430112A1 (de) 2019-01-23
BR112018068893A2 (pt) 2019-01-22
BR112018068893B1 (pt) 2022-12-13
CA3017990A1 (en) 2017-09-21
AU2017234866A1 (en) 2018-08-30
US20190031977A1 (en) 2019-01-31
RU2018132032A (ru) 2020-03-10
CN108884413A (zh) 2018-11-23

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