EP4634357A1 - Compositions détergentes pour lave-vaisselle automatique contenant des cucurbituriles et leur utilisation pour réduire les mauvaises odeurs - Google Patents

Compositions détergentes pour lave-vaisselle automatique contenant des cucurbituriles et leur utilisation pour réduire les mauvaises odeurs

Info

Publication number
EP4634357A1
EP4634357A1 EP23821984.4A EP23821984A EP4634357A1 EP 4634357 A1 EP4634357 A1 EP 4634357A1 EP 23821984 A EP23821984 A EP 23821984A EP 4634357 A1 EP4634357 A1 EP 4634357A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
dishwashing
machine
acid
malodour
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23821984.4A
Other languages
German (de)
English (en)
Inventor
Hannah Benson
Natascha SCHELERO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP4634357A1 publication Critical patent/EP4634357A1/fr
Pending legal-status Critical Current

Links

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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0068—Deodorant 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
    • 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
    • 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

  • the invention relates to detergent compositions for machine dishwashing comprising one or more specific cucurbiturils and one or more nonionic surfactants, a method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition for machine dishwashing according to the invention, a method for counteracting malodour in a dishwashing machine comprising the application of a detergent composition for machine dishwashing according to the invention in a dishwashing cycle, the use of a detergent composition for machine dishwashing according to the invention to reduce malodour in the dishwashing machine, to reduce the transfer of malodour to plastic items in the dishwashing machine or as dishwasher care product as well as the use of one or more specific cucurbiturils for longterm release during the washing cycle in a dishwashing machine.
  • Malodours are often complex mixtures of different molecules having diverse chemistries and smells.
  • the smell of malodour may be pungent and even minute amounts of such molecules can create uncomfortable impressions to consumers. Therefore, many strategies have been proposed to counteract malodours.
  • Preventive methods involve killing the bacteria that are responsible for the generation of malodours or inhibiting their growth, either by applying biocides, biostatic agents or controlling the microclimatic conditions in the locus where bacteria proliferate. These methods are used for example in the axilla or other part of the human or pet body.
  • Eliminative methods involve using chemically reactive molecules that bind to the malodour and neutralize it; oxidation (burning) and ionization belong to eliminative methods.
  • Malodour suppression methods can involve the use of absorbents and adsorbents. These materials are often environmentally friendly and in most cases have no noticeable odour. Malodour molecules are trapped in the pores of these materials and, therefore, their vapour pressure is depressed. However, these materials are generally not selective to malodour and may also bind desirable fragrance molecules. On the other hand water vapours, such as those present in moist conditions, for example above 50% relative humidity, may displace the malodour which is then released back into the air.
  • Guest molecules are a special class of absorbents, characterized in that each molecule has a well-defined cavity instead of a distribution of pores.
  • Host-guest complexes have been used in the field of perfumery and for malodour counteracting for some time.
  • US 5,942,217 describes the use of an aqueous solution of cyclodextrin, more generally referred to as cyclic oligosaccharides, for neutralizing malodour. Absorption of the malodour molecule in the cyclodextrin cavity results in efficient mitigation of malodour.
  • the malodour binding process occurs during drying, and low molecular weight polyols can be added to the composition to enhance the formation of cyclodextrin inclusion complexes, especially in the case where the malodour molecule is too small to form a stable inclusion complex.
  • cyclodextrins Another disadvantage of cyclodextrins is the tendency of these carbohydrate- derived materials to become sticky at low water levels or with decreasing water activity. This can lead to, for example, an undesirable “tacky” feeling on the skin. Finally, as is usually the case with aqueous carbohydrate solutions, aqueous cyclodextrin solutions must be preserved against micro-organism invasion using significant amounts of preservatives.
  • WO 2014/077642 describes a composition comprising cucurbit[7]uril for use in odour removal and provides some evidence that odour is complexed with the cucrbituril.
  • WO 2018/115822 relates to cucurbiturils, to a process of manufacturing said cucurbiturils and the use of said cucurbiturils in particular in consumer and industrial products, and in industrial processes.
  • WO 2017/141029 relates to the use of compositions comprising cucurbiturils in counteracting malodour.
  • GB 2556619 relates to stable suspension compositions comprising cucurbiturils for use in counteracting malodour.
  • WO 2014/077641 discloses a composition for removing an odour molecule and releasing a fragrant molecule, the composition including a complex of cucurbituril and a fragrant molecule.
  • It was an object of the present invention is to provide a detergent composition for machine dishwashing, which shows a beneficial performance in terms of reducing malodour in the dishwashing machine as well as reducing the transfer of malodour to plastic items within the dishwashing machine.
  • a subject matter of the invention is a detergent composition for machine dishwashing comprising components Z1 ) and Z2):
  • the dashed lines in formula (A) each represent a single bond.
  • the cucurbiturils of formula (A) have cyclic structures, which are typical for cucurbiturils.
  • the detergent composition may advantageously be used in machinated dishwashing, in particular for the reduction of malodour in the dishwashing machine or for the reduction of malodour transfer to plastic items.
  • a further advantage of the invention is that the use of the detergent composition according to the invention has no negative impact on rinse performance, dry capacity or cleaning performance of the detergent.
  • the cucurbiturils used in component Z1) of the detergent compositions according to the invention may be prepared according to methods known to the person skilled in the art, e.g. as described in WO 2018/115822 A1 .
  • the one or more nonionic surfactants of component Z2) of the detergent composition according to the invention are selected from the group consisting of fatty alcohol alkoxylates, modified fatty alcohol alkoxylates, ethoxylated glycerol esters, preferably ethoxylated triglycerides, and N- acylglucamines.
  • component Z2) of the detergent composition according to the invention comprises one or more nonionic surfactants selected from the group consisting of one or more fatty alcohol alkoxylates of the formula (XIV)
  • R a is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,
  • A is selected from the group consisting of -C2H4- and -C3H6-, x is a number from 1 to 150.
  • alkyl- and alkenyl-groups of R a of formula (XIV) are, e.g. the alkyl and alkenyl groups of the following alcohols R a -OH: 1 -octanol (caprylic alcohol), 2 -ethylhexanol, 1 -nonanol (pelargonic alcohol), 1 -decanol (capric alcohol), 1 -undecanol, 1 -dodecanol (lauryl alcohol), 1 -tridecanol, isotridecanol, 1 -tetradecanol (myristyl alcohol), 1 -pentadecanol, 1 -hexadecanol (cetyl alcohol), cis-9-hexadecene-1 -ol (palmitoleyl alcohol), 1 -heptadecanol, 1 -octadecanol (stearyl alcohol), cetearyl alcohol, 16-methyl
  • Ra in formula (XIV) preferably represents a linear or branched saturated alkyl group having 8 to 22 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 22 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 18 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 18 carbon atoms, and particularly preferably a linear or branched saturated alkyl group having 12 to 15 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
  • the groups R a in formula (XIV) are alkyl groups.
  • x in formula (XIV) is a number from 1 to 50, more preferably from 1 to 20, and even more preferably from 5 to 20.
  • variable "x" in the one or more compounds of formula (XIV) represents molar averages, i.e. the detergent composition according to the invention may contain several compounds of formula (XIV) with different degrees of alkoxylation.
  • the group -(-AO-)x- contains one or more -C2H4-O- groups and one or more -C3H6-O- groups.
  • the molar amount of the -C3H6-O- groups, based on the total amount of -C2H4-O- and -C3H6-O- groups, is preferably less than 50%, more preferably 45% or less than 45%, even more preferably 40% or less than 40% and particularly preferably 33% or less than 33%.
  • the molar amount of -C3H6-O- groups is preferably 20 to less than 50%, more preferably 33 to 45%, and even more preferably 33 to 40%.
  • the molar amount of the -C3H6-O- groups is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.
  • compounds of the formula (XIV) contain a molar average of 8 -C2H4-O- groups and 4 -C3H6-O- groups and Ra represents a linear or branched saturated alkyl group having 12 to 15 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 12 to 15 carbon atoms.
  • component Z2) of the detergent composition according to the invention comprises one or more nonionic surfactants selected from the group consisting of one or more modified fatty alcohol alkoxylates of the formula (XI)
  • Ra is a linear or branched saturated alkyl group having 8 to 30 carbon atoms, or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms,
  • A is selected from the group consisting of -C2H4- and -C3H6-, x is a number from 1 to 150,
  • Y is a group -CH2-CH(OH)-Rb or is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, preferably -CH2-CH(OH)-Rb, Rb is a linear or branched saturated alkyl group having 1 to 30 carbon atoms, and where the group -(AO)x- comprises one or more -C2H4-O- groups and may additionally comprise one or more -C3H6-O- groups, and, when the group -(AO)x- simultaneously comprises -C2H4-O- and -C3H6-O- groups, the -C2H4-O- and -CsHe-O- groups may be distributed over the -(AO)x- group in any desired way, preferably in random, gradient-like or block-like manner and more preferably in block-like manner, and the molar amount of the -C2H4-O- groups in the group -(AO)x- is preferably greater than the molar
  • alkyl- and alkenyl-groups R a of formula (XI) are, e.g. the alkyl and alkenyl groups of the following alcohols R a -OH: 1 -octanol (caprylic alcohol), 2 -ethylhexanol, 1 -nonanol (pelargonic alcohol), 1 -decanol (capric alcohol), 1 -undecanol, 1 -dodecanol (lauryl alcohol), 1 -tridecanol, isotridecanol, 1 -tetradecanol (myristyl alcohol), 1 -pentadecanol, 1 -hexadecanol (cetyl alcohol), cis-9-hexadecene-1 -ol (palmitoleyl alcohol), 1 -heptadecanol, 1 -octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylh
  • R a in formula (XI) preferably represents a linear or branched saturated alkyl group having 8 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 30 carbon atoms, more preferably a linear or branched saturated alkyl group having 8 to 20 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, and particularly preferably a linear or branched saturated alkyl group having 8 to 15 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 15 carbon atoms.
  • the groups Ra in formula (XI) are alkyl groups.
  • x in formula (XI) is a number from 1 to 150, more preferably from 5 to 100, even more preferably 5 to 50, and particularly preferably from 15 to 25.
  • alkyl groups Y and Rb of the compounds of the formula (XI) the examples given above for the alkyl group Ra of the compound of formula (XI) may be mentioned. Further examples are the alkyl groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl (2-pentyl), 3-pentyl, 2-methylbutyl, iso-pentyl (3-methylbutyl), 3-methylbut-2-yl, 2-methylbut-2- yl, neo-pentyl (2,2-dimethylpropyl), 1 -hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl,
  • Y in the formula (XI) represents a linear or branched alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms.
  • Rb in formula (XI) preferably represents a linear or branched alkyl group having 8 to 22 carbon atoms.
  • the group -(-AO-)x- consists of one or more -C2H4-O- groups and contains no -C3H6-O- groups.
  • the group -(-AO-)x- contains one or more -C2H4-O- groups and one or more -C3H6-O- groups.
  • the molar amount of the -C3H6-O- groups, based on the total amount of -C2H4-O- and -C3H6-O- groups, is preferably less than 50%, more preferably 45% or less than 45%, even more preferably 40% or less than 40% and particularly preferably 33% or less than 33%.
  • Y in formula (XI) represents an alkyl group having 1 to 4 carbon atoms.
  • the molar amount of the -C3H6-O- groups is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.
  • Y in formula (XI) represents the group -CH2-CH(OH)-Rb, in which Rb is a linear or branched alkyl group having 8 to 22 carbon atoms.
  • the molar amount of the -C3H6-O- groups is preferably 20% or less than 20% and particularly preferably 10% or less than 10%.
  • variable "x" in the one or more compounds of formula (XI) represents molar averages, i.e. the detergent composition according to the invention may contain several compounds of formula (XI) with different degrees of alkoxylation.
  • R a is a linear or branched saturated alkyl group having 8 to 20 carbon atoms, preferably 8 to 15 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 8 to 20 carbon atoms, preferably 8 to 15 carbon atoms,
  • A is -C2H4-, x is a number from 5 to 100, preferably from 15 to 25, and
  • Y is a group -CH2-CH(OH)-Rb, and Rb is a linear or branched alkyl group having 8 to 22 carbon atoms.
  • Ra is a linear or branched saturated alkyl group having 9 to 13 carbon atoms, preferably 11 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 9 to 13 carbon atoms, preferably 11 carbon atoms,
  • A is -C2H4-, x is a number from 15 to 25, preferably from 20 to 25, and
  • Y is a group -CH2-CH(OH)-Rb, and Rb is a linear or branched alkyl group having 8 to 12 and preferably 10 carbon atoms.
  • component Z2) of the detergent composition according to the invention comprises one or more nonionic surfactants selected from the group consisting of one or more ethoxylated glycerol esters of the formula (I) wherein
  • R 1 , R 2 and R 3 are equal or different and are independently selected from saturated or unsaturated, linear or branched C7-C24 aliphatic groups; and m, n and o are equal or different and are each independently an integer number from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, with the proviso that the number-average of the sum of m + n + o is greater than 2, preferably greater than 5, more preferably from 20 to 70, even more preferably from 30 to 60;
  • the one or more ethoxylated glycerol esters of the formula (I) preferably are a product mixture, more preferably a product mixture from the preparation of one or more ethoxylated glycerol esters of the formula (I) and even more preferably a product mixture from the preparation of one or more ethoxylated glycerol esters of the formula (I) by ethoxylating one or more triglycerides and preferably one or more triglycerides of the formula (II) wherein R 1 , R 2 and R 3 in formula (II) are equal or different and are independently selected from saturated or unsaturated, linear or branched C7-C24 aliphatic groups, in particular in the presence of a calcium-based catalyst as described below.
  • the one or more triglycerides of the formula (II) are not particularly limited and may be natural triglycerides or synthetic triglycerides.
  • the one or more triglycerides of the formula (II) may be used in a mixture with by-products occurring in nature together with the triglycerides or generated during their preparation, such as by-products containing free hydroxyl groups, e.g. mono- or diglycerides, or in a purified or enriched form, whereby purification or enrichment can e.g. be achieved by employing column chromatography techniques.
  • the one or more triglycerides of formula (II) are selected from the group of vegetable oils and animal fats known in the art including, but not limited to, abyssinian oil, almond oil, apricot kernel oil, avocado oil, babassu oil, beef tallow, borage oil, canola oil, castor oil, cocoa butter, coconut oil, corn oil, cottonseed oil, crisco shortening, emu oil, grapeseed oil, groundnut oil, hazelnut oil, illipe butter, jojoba oil, kukui nut oil, lard, macadamia nut oil, mango butter, neem oil, olive oil, palm oil, palm kernel oil, peach kernel oil, peanut oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, shea butter, soybean oil, sunflower oil, walnut oil, and wheat germ oil.
  • vegetable oils and animal fats known in the art including, but not limited to, abyss
  • the one or more ethoxylated glycerol esters of the formula (I) are prepared from triglycerides of the formula (II) selected from the group consisting of coconut oil and rapeseed oil, preferably from coconut oil.
  • component Z2) of the detergent composition according to the invention comprises one or more nonionic surfactants prepared from 1 to 200 mol ethylene oxide, preferably from 1 to 80 mol ethylene oxide, more preferably from 20 to 70 mol ethylene oxide and even more preferably from 30 to 60 mol ethylene oxide; and 1 mol of one or more triglycerides of the formula (II)
  • R 1 , R 2 and R 3 in formula (II) are equal or different and are independently selected from saturated or unsaturated, linear or branched C7-C24 aliphatic groups.
  • component Z2) of the detergent composition according to the invention comprises one or more nonionic surfactants selected from the group consisting of N-acylglucamines, which are also known as N-1-deoxysorbityl fatty acid amides or glucamides, of the formula (VI), wherein
  • Rb is a linear or branched saturated alkyl group having 11 to 21 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 11 to 21 carbon atoms and
  • Rc is hydrogen or a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
  • Rc is a methyl group.
  • Rb is preferably a linear or branched saturated alkyl group having 11 to 17 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and 11 to 17 carbon atoms.
  • Rb is a linear or branched saturated alkyl group having 15 to 17 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 15 to 17 carbon atoms.
  • 50 wt.-% or more, more preferably 60 to 99 wt.-% and even more preferably 70 to 98 wt.-% of the groups Rb in the one or more N-acylglucamines of the formula (VI) are linear or branched saturated alkyl groups with 17 carbon atoms.
  • 0.1 to 50 wt.-%, more preferably 0.5 to 40 wt.-% and even more preferably 1 .0 to 30 wt.-% of the groups Rb in the one or more N-acylglucamines of the formula (VI) are linear or branched saturated alkyl groups with 15 carbon atoms.
  • 50 wt.-% or more of the Rb groups in the one or more N-acylglucamines of the formula (VI) are linear or branched unsaturated alkenyl groups having one or more double bonds.
  • 50 wt.-% or more, more preferably 80 wt.-% or more and even more preferably 90 wt.-% or more of the groups Rb in the one or more N-acylglucamines of the formula (VI) are linear or branched alkenyl groups having one or more double bonds and 17 carbon atoms.
  • Rb is a linear group.
  • RbCO in the one or more N-acylglucamines of formula (VI) RbCO derives from lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid. In a more preferred embodiment of the invention, in the one or more N-acylglucamines of the formula (VI) RbCO derives from stearic acid, oleic acid, linoleic acid or linolenic acid.
  • RbCO derives from oleic acid, linoleic acid or linolenic acid
  • RbCO derives from oleic acid.
  • the detergent composition according to the invention can contain said nonionic surfactants of component Z2), preferably the aforementioned fatty alcohol alkoxylates, modified fatty alcohol alkoxylates, ethoxylated glycerol esters, preferably ethoxylated triglycerides, and/or N-acylglucamines, both individually and in the form of mixtures.
  • component Z2 of the detergent composition according to the invention may consist of fatty alcohol alkoxylates, may consist of modified fatty alcohol alkoxylates, may consist of ethoxylated glycerol esters, preferably ethoxylated triglycerides, or may consist of N- acylglucamines or (ii) may comprise a first nonionic surfactant selected from the group consisting of the aforementioned fatty alcohol alkoxylates, modified fatty alcohol alkoxylates, ethoxylated glycerol esters, preferably ethoxylated triglycerides, and N-acylglucamines and may comprise one or more further nonionic surfactants, preferably selected from the group consisting of the aforementioned fatty alcohol alkoxylates, modified fatty alcohol alkoxylates, ethoxylated glycerol esters, preferably ethoxylated triglycerides, or N- acyl
  • the detergent composition according to the invention is low foaming.
  • Foam is an important property when choosing a surfactant for a cleaning formulation or processing application.
  • generating high foam levels is usually a desirable feature. This is because the presence of high and stable foam indicates that the surfactant is activated and performing its cleaning functions.
  • foaming can interfere with certain mechanical cleaning actions and inhibit overall performance. In these cases, formulators need to use low foam surfactants to deliver the desired cleaning performance while also controlling foam levels.
  • Two of the most common and reliable foam tests are the Ross Miles Foam Test and the High Shear Foam Test.
  • the Ross-Miles Foam Test evaluates surfactant initial foam generation (flash foam) and foam stability at low agitation in water. This test may include readings of an initial foam level, and then foam level after 2 minutes. It can also be conducted at different surfactant concentrations (i.e. 0.1 wt.-% and 1 wt.-%) and pH levels.
  • the detergent composition according to the invention preferably comprises from 0.1 to 2.0 wt.-%, more preferably from 0.1 to 1 .0 wt.-% and even more preferably from 0.2 to 0.75 wt.-% of the one or more cucurbitunis of component Z1 ) and preferably from 0.1 to 15 wt.-%, more preferably from 0.5 to 10 wt.-% and even more preferably from 0.5 to 5 wt.-% of the one or more nonionic surfactants of component Z2), in each case based on the total weight of the detergent composition.
  • the detergent composition according to the invention comprises, preferably consists of, further to the components Z1) and Z2), one or more components selected from:
  • one or more further additives preferably selected from the group consisting of chelating agents, glass corrosion inhibitors, water, organic solvents, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.
  • the one or more enzymes of component Z3) are selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases.
  • the enzymes are typically of natural origin. Improved variants that are based on natural molecules are obtainable for the use in detergent compositions for machine dishwashing and are accordingly preferred.
  • subtilisins those of the subtilisin type are preferred.
  • subtilisins BPN and Carlsberg, as well as their advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY and subtilases.
  • amylases applicable according to the invention are a-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as their derivatives improved for use in detergent compositions for machine dishwashing. Furthermore, o-Amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin-glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are preferred.
  • lipases or cutinases may be used in the detergent composition of the invention, in particular due to their triglyceride-cleaving activities, but also for in situ preparing peroxy acids from appropriate precursors.
  • Exemplary lipases are those originating from Humicola lanuginosa (Thermomyces lanuginosus) or their advanced forms, especially those with the amino acid exchange D96L.
  • Exemplary cutinases are those originally isolable from Fusarium solani pisi and Humicola insolens.
  • the detergent composition of the invention may also comprise oxidoreductases, for example oxidases, oxygenases, katalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose Oder mangan-peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases).
  • oxidoreductases for example oxidases, oxygenases, katalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose Oder mangan-peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases).
  • additional, preferably organic, more preferably aromatic compounds that interact with the enzymes are added in order to increase the activity of the corresponding oxidoreductases (enhancers) or in order to facilitate the electron transport between the oxidizing enzymes and the contaminations if their redox potentials have a large difference (medi
  • the enzymes may be used in any form known in the art, for example as granulated, extruded or lyophilized solid preparations or, particularly in liquid or gel formulations, as solutions of the enzymes, preferably highly concentrated, with a low water content and/or mixed with stabilizers.
  • the enzymes may be in an encapsulated form, both in solid and in liquid compositions.
  • an enzyme solution may be spray-dried or extruded together with a preferably natural polymer or in the form of capsules, e.g. such, where the enzymes are enclosed in a solidified gel or such of the core-shell type, where an enzyme-containing core is coated with a water-, air- and/or chemical-impermeable protective coating.
  • further active agents such as stabilizers, emulsifiers, pigments, Whiteners or dyes may be included.
  • Such capsules are prepared by known methods, e.g. shaking granulation or rolling granulation or in fluidized bed processes.
  • such granulates are coated with polymeric film-forming agents and therefore low on dust and storage stable.
  • the detergent composition according to the invention comprises the one or more enzymes Z3) preferably in amounts of from 1x10 6 to 5 wt.-%, more preferably from 1x10 5 to 3 wt.-%, even more preferably from 1x1 O' 4 to 2 wt.-%, based on the total weight of the detergent composition.
  • the protein concentration can be determined by known methods such as the BCA-method or the biuret method.
  • the builders Z4) as well as other ingredients which may be used in detergent compositions according to the invention are disclosed, e.g. in US 2010/0160204 and EP-A 1757676.
  • the builders Z4) may be selected, e.g., from the group consisting of carbonates, bicarbonates, organic builders, preferably methylglycinediacetic acid (MGDA), silicates, phosphates, phosphonates and alkali metal hydroxides.
  • MGDA methylglycinediacetic acid
  • silicates phosphates, phosphonates and alkali metal hydroxides.
  • Organic builders include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins.
  • Useful organic builders are, among others, polycarboxylic acids usable in the form of the free acid and / or their sodium salts, wherein polycarboxylic acids are understood as those carboxylic acids which carry more than one acid moiety.
  • these may be citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and nitrilotriacetic acid (NTA) and mixtures thereof.
  • the free acids typically also have the property of an acidifying agent and thus also serve to set a lower and milder pH for the detergent composition according to the invention.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, tartaric acid and any mixtures thereof are suitable.
  • Common aminocarboxylic acids that are preferred in the context of the present invention are, for example, ethylenediaminetetraacetic acid (EDTA), methylglycine-diacetic acid (MGDA) and glutamic diacetic acid (GLDA) or mixtures thereof.
  • EDTA ethylenediaminetetraacetic acid
  • MGDA methylglycine-diacetic acid
  • GLDA glutamic diacetic acid
  • Further preferred builders are polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to using polyaspartic acids, their salts or their derivatives.
  • Particularly advantageous for the cleaning and rinse aiding properties of the detergent composition according to the invention is the use of citric acid and/or citrates.
  • the detergent compositions according to the invention contain MGDA as one of their builders.
  • Detergent compositions according to the invention preferably contain from 0.5 to 25 wt.-%, more preferably from 2 to 25 wt.-% of MGDA, based on the total weight of the detergent composition.
  • polymeric carboxylates are also suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g/mol.
  • Suitable polymeric carboxylates are in particular polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses of from 2,000 to 10,000 g/mol and more preferably from 3,000 to 5,000 g/mol are even more preferred in this group.
  • copolymeric carboxylates are also suitable.
  • Suitable comonomers are mono- ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • Particularly suitable are copolymeric carboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90 wt.-% of acrylic acid and 10 to 50 wt.-% of maleic acid have proven to be particularly suitable.
  • Their molecular weight relative to free acids is preferably from 2,000 to 70,000 g/mol, more preferably from 20,000 to 50,000 g/mol and in particular from 30,000 to 40,000 g/mol. It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated Ca-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobic modified monomer, as listed below.
  • Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butane, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1-docosene, 1 -tetracosene and 1 -hexacosene, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having a numberaverage of 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups and nonionic monomers with hydroxyl function or alkylene oxide groups and optionally other ionogenic or nonionogenic monomers.
  • Examples of the above listed hydrophilic monomers are allyl alcohol, isoprenol, methoxypolyethylene glycol(meth)acrylate, methoxypolypropylene glycol (meth )acry late, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co- ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth )acry late.
  • Polyalkylene glycols may contain 3 to 50, in particular 5
  • Particularly preferred monomers containing sulfonic acid groups are
  • 3-methacrylamido-2-hydroxypropanesulfonic acid allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1- sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropylmethacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.
  • Particularly preferred phosphonate group-containing monomers are vinylphosphonic acid and its salts.
  • amphoteric polymers can also be used as builders.
  • the amount of these (co)polymeric carboxylates in the detergent composition according to the invention is preferably 0.5 to 20 wt.-% by weight and in particular 3 to 10 wt.-%, based on the total weight of the detergent composition.
  • Oxidisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate are further preferred organic builders, often referred to as co-builders.
  • ethylenediamine-N.N'-disuccinate (EDDS) is preferred, especially used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context.
  • the detergent composition according to the invention may preferably contain builders of crystalline sodium sheet silicates of the general formula NaMSixO2x+i ⁇ yH2O, wherein M is sodium or hydrogen, x is a number from 1 .9 to 22, preferably from 1 .9 to 4, more preferably 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the detergent composition according to the invention preferably contains the crystalline sodium sheet silicates of formula NaMSixO2x+r yFW in an amount of 0.1 to 20 wt.-%, more preferably from 0.2 to 15 wt.-%, even more preferably from 0.4 to 10 wt.-%, based on the total weight of the detergent composition.
  • amorphous sodium silicates having a modulus Na2O:SiO2 of from 1 :2 to 1 :3.3, preferably from 1 :2 to 1 :2.8 and in particular from 1 :2 to 1 :2.6, which preferably show delayed dissolution.
  • the dissolution delay compared to conventional amorphous sodium silicates can be caused in different ways, for example by surface treatment, compounding, compaction, condensing or over- drying.
  • amorphous means that the silicates do not produce sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most cause one or more maxima of the scattered X-ray radiation, which have a width of multiple degrees of the diffraction angle.
  • X-ray-amorphous silicates can be used, the silicate particles of which show blurred or even sharp diffraction maxima in Electron diffraction experiments.
  • X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses.
  • condensed/compacted amorphous silicates compounded amorphous silicates and overdried X-ray-amorphous silicates.
  • these silicates preferably alkali metal silicates, particularly preferably crystalline or amorphous alkalidisilicates, are present in the detergent composition according to the invention in amounts of from 3 to 60 wt.-%, preferably from 8 to 50 wt.-% and more preferably from 20 to 40 wt.-%, based on the total weight of the detergent composition.
  • Phosphates have proven to be effective builders in terms of cleaning performance.
  • alkali metal phosphates have the greatest importance in the washing and cleaning industry, in particular pentasodium triphosphate or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal salts (especially sodium and potassium salts) of the various phosphoric acids such as metaphosphoric acids (HPO3)m, orthophosphoric acid H3PO4 and higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali metal carriers, prevent lime deposits on machine parts and contribute to the cleaning performance of the detergent composition.
  • phosphates are the pentasodium triphosphate NasPsOio (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate K5P3O10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • preferred agents comprise phosphate(s), preferably alkali metal phosphate(s), more preferably pentasodium or pentapotassiumtriphosphat (sodium or potassium tripolyphosphate), in amounts of from 2 to 50 wt.-%, preferably from 2 to 30 wt.-%, more preferably from 3 to 25 wt.-% and particularly preferably from 3 to 15 wt.-%, based on the total weight of the detergent composition.
  • the detergent composition according to the invention may contain one or more phosphonates, which are often referred to as co-builders.
  • the amount of phosphonates in the detergent composition according to the invention is preferably 0.5 to 20 wt.-% and more preferably 1 .0 to 10 wt.-%, based on the total weight of the detergent composition.
  • the chelating phosphonates include a number of different compounds such as 1-hydroxyethane-1 ,1-diphosphonic acid (HEDP) or diethylenetriamine penta(methylenephosphonic acid) (DTPMP). Particularly preferred are hydroxyalkane and aminoalkane phosphonates.
  • HEDP 1-hydroxyethane-1 ,1 -diphosphonate
  • DTPMP diethylenetriamine penta(methylenephosphonic acid)
  • hydroxyalkane and aminoalkane phosphonates are particularly preferred.
  • 1-hydroxyethane-1 ,1 -diphosphonate (HEDP) is of particular importance, preferably as a co-builder. It is preferably used as a sodium salt, of which the disodium salt reacts neutral and the tetrasodium salt reacts alkaline (pH 9).
  • EDTMP ethylenediamine tetramethylene phosphonate
  • DTPMP diethylenetriamine pentamethylenephosphonate
  • HEDP ethylenediamine tetramethylene phosphonate
  • Detergent compositions according to the invention can contain, as further builders, alkali metal hydroxides. These alkali carriers are preferably only used in small amounts, typically in amounts of 10 wt.-% or less, preferably 6 wt.-% or less, more preferably 5 wt.-% or less, even more preferably 0.1 to 5 wt.-% and in particular 0.5 to 5 wt.-%, based on the total weight of the detergent composition.
  • the detergent composition according to the invention comprises one or more builders from the group of organic builders.
  • the detergent composition contains one or more builders from the group consisting of citrate, methylglycinediacetic acid (MGDA) and ethylenediamine-N,N'-disuccinate (EDDS).
  • MGDA methylglycinediacetic acid
  • EDDS ethylenediamine-N,N'-disuccinate
  • the detergent compositions according to the invention contain MGDA, specifically its trisodium salt.
  • the detergent composition according to the invention can contain said builders both individually and in the form of mixtures of two, three, four or more builders. In a preferred embodiment of the invention, the detergent composition according to the invention does not contain any phosphate builders.
  • the detergent composition according to the invention contains the one or more builders of component Z4), preferably in amounts of from 2 to 75 wt.-%, more preferably in amounts of from 10 to 75 wt.-% and especially preferably in amounts of from 40 to 75 wt.-%, based on the total weight of the detergent composition.
  • the bleaching agent Z5) of the detergent composition according to the invention if present, preferably contains one or more substances selected from the group consisting of bleaches, bleach activators and bleach catalysts.
  • the detergent composition according to the invention may contain an oxygen bleach.
  • oxygen bleaches which yield H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further applicable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H2O2-yielding peroxy acid salts or peroxy acids, such as peroxy benzoates, peroxy phthalates, diperoxy azelaic acid, phthaloiminoperoxy acid or diperoxy dodecanedioic acid.
  • Organic bleaches can also be used. Typical organic bleaches are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxy acids, such as alkyl peroxy acids and aryl peroxy acids.
  • the detergent composition according to the invention preferably comprises one or more bleaches selected from the group consisting of oxygen bleaches, peroxy pyrophosphates, citrate perhydrates, and H2O2-delivering peroxy acid salts or peroxy acids and organic bleaches.
  • the detergent composition according to the invention contains 1 .0 to 20 wt.-%, preferably 4.0 to 18 wt.-% and more preferably 8 to 15 wt.-% of an oxygen bleach, preferably sodium percarbonate, based on the total weight of the detergent composition.
  • the inventive detergent composition according to the invention may additionally contain one or more bleach activators.
  • the one or more bleach activators are selected from the group consisting of which, under the conditions of perhydrolysis, result in aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and/or N-acyl groups with the above-stated number of carbon atoms and/or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • Bleach activators in particular TAED, are preferably used in amounts of up to 10 wt.-%, more preferably in amounts of from 0.1 to 8 wt.-% even more preferably in amounts of from 2 to 8 wt.-% and particularly preferably in amounts from 2 to 6 wt.-%, based on the total weight of the detergent composition according to the invention.
  • bleach catalysts can also be used.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salen complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or V which preferably contain one or more macrocyclic ligands with donor functions N, NR, PR, O and/or S.
  • ligands having nitrogen donor functions are particularly preferred.
  • bleach catalyst(s) which contain as macromolecular ligands 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (Me-TACN), 1 ,4,7-triazacyclononane (TACN), 1 ,5,9-tri methy 1-1 ,5,9-triazacyclododecane (Me-TACD), 2-methyl-1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (Me/Me-TACN) and/or 2-methyl-1 ,4,7-triazacyclononane (Me/TACN).
  • macromolecular ligands 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (Me-TACN), 1 ,4,7-triazacyclononane (TACN), 1 ,5,9-tri methy 1-1 ,5,9-triazacyclododecane (Me-TACD), 2-methyl-1 ,4,7-trimethyl-1 ,4,
  • Suitable manganese complexes are, for example, [Mn lll 2(p-O)i(p-OAc)2(TACN)2](CIO4)2, [Mn lll Mn lv (p-O)2(M-OAc)i(TACN) 2 ](BPh4)2, [Mn lv 4(p-O)6(TACN)4](CIO4)4, [Mn'"2(
  • J-O)3(Me/Me- TACN)2](PF6)2(OAC OC(O)CH 3 ).
  • the detergent composition according to the invention comprises one or more bleach catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of the complexes of manganese with 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane (Me-TACN) and 1 ,2, 4, 7-tetramethyl-1 ,4,7- triazacyclononane (Me4-TACN), since the cleaning result can be significantly improved by these bleach catalysts.
  • one or more bleach catalysts from the group of bleach-enhancing transition metal salts and transition metal complexes preferably from the group of the complexes of manganese with 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane (Me-TACN) and 1 ,2, 4, 7-tetramethyl-1 ,4,7- triazacyclononane (Me4-TACN), since the cleaning result can be significantly improved by these bleach catalysts.
  • the bleaching agent Z5) comprises one or more bleaches and one or more substances from the group of bleach activators and bleach catalysts. More preferably, the bleaching agent comprises one or more bleaches, one or more bleach activators, and one or more bleach catalysts.
  • the detergent composition according to the invention contains the bleaching agent of component Z5) preferably in amounts of 1 to 40 wt.-%, more preferably in amounts of 0.5 to 30 wt.-% and even more preferably in amounts of 3 to 25 wt.-%, based on the total weight of the detergent composition.
  • the one or more surfactants of component Z6) of the detergent composition according to the invention are preferably selected from the group consisting of zwitterionic surfactants, anionic surfactants, cationic surfactants and mixtures thereof.
  • Suitable cationic surfactants of component Z6) are, e.g., surfactants of formulae (VII), (VIII) and/or (IX), wherein each R 10 group is independently selected from linear or branched, preferably linear, saturated alkyl groups having 1 to 6 carbon atoms, linear or branched, preferably linear, unsaturated alkenyl groups having one or more double bonds and 2 to 6 carbon atoms, and linear or branched, preferably linear, hydroxyalkyl groups having 1 to 6 carbon atoms; each R 11 group is independently selected from linear or branched saturated alkyl groups having 8 to 28 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and 8 to 28 carbon atoms;
  • R 12 is the same as R 10 or (CH2)n-T-R 11 ;
  • R 13 is the same as R 10 , R 11 or (CH2)n-T-R 11 ;
  • T is selected from -CH2-, -O-CO- or -CO-O-; q is an integer from 0 to 5;
  • X is an inorganic or organic anion having the charge b-; b is a number from 1 to 4; and c is a number having a value of 1/b.
  • cationic surfactants suitable as component Z6) of the detergent composition according to the invention are compounds of formula (X), wherein
  • R 14 is a linear or branched, preferably linear, saturated alkyl group having from 1 to 6 carbon atoms;
  • R 15 , R 16 and R 17 are equal or different and are independently selected from the group consisting of hydrogen, linear or branched saturated alkyl groups having from 1 to 18 carbon atoms, linear or branched unsaturated alkenyl groups having one or more double bonds and from 2 to 18 carbon atoms, and -CO-R 18 ;
  • R 18 is a linear or branched saturated alkyl group having 7 to 19 carbon atoms or a linear or branched unsaturated alkenyl group having one or more double bonds and 7 to 19 carbon atoms; r, s and t are equal or different and are independently a number from 0 to 50; X is an inorganic or organic anion having the charge b-; b is a number from 1 to 4; and c is a number having a value of 1/b; with the proviso that at least one group of R 15 , R 16 and R 17 is -CO-R 18 which forms an ester moiety with the oxygen atom of an ethoxy group; the sum of r + s + t is a number from 1 to 70; and if one or more of r, s and/or t is 0, the corresponding group R 15 , R 16 and/or R 17 is a linear or branched saturated alkyl group having 1 to 18 carbon atoms or a linear or branched uns
  • Preferable zwitterionic surfactants applicable as component Z6) are selected from the group consisting of Cs to Cis, preferably C12 to C18 amine oxides and sulfo- and hydroxyl betaines, such as N-alkyl-N,N-dimethylamino-1 -propanesulfonate, wherein the alkyl group may be Cg to Cis, preferably C10 to C14.
  • Preferable anionic surfactants applicable as component Z6) are selected from alkyl ethoxysulfates having a degree of ethoxylation of more than 3, more preferably 4 to 10 and even more preferably 6 to 8 and an alkyl chain length in the range of Cs to C16 and preferably C11 to C15.
  • branched alkyl carboxylates have been found to be useful for the purposes of the present invention when the branching occurs in the middle and the average total chain length is 10 to 18, preferably 12 to 16 with a side chain length of 2 to 4 carbon atoms.
  • An example of this is 2-butyloctanoic acid.
  • the anionic surfactant is usually of a type having good solubility in the presence of calcium.
  • alkyl (polyethoxy) sulfates AES
  • alkylbenzene sulfonates short-chain Ce-C-io-alkyl sulfates and sulfonates are among such anionic surfactants. It has been revealed that straight-chain fatty acids are ineffective because of their sensitivity to calcium.
  • the detergent composition according to the invention comprises cationic and/or zwitterionic surfactants of component Z6) in amounts smaller than 6 wt.-%, preferably smaller than 4 wt.-%, more preferably smaller than 2 wt.-%, even more preferably smaller than 1 wt.-%, in each case based on the total weight of the detergent composition.
  • the detergent composition according to the invention contains the one or more surfactants of component Z6) preferably in amounts of from 0 to 15 wt.-%, more preferably in amounts of from 0.1 to 15 wt.-%, even more preferably in amounts of from 0.5 to 10 wt.-%, and particularly preferably in amounts of from 0.5 to 5 wt.-%, in each case based on the total weight of the detergent composition.
  • Suitable polymers of component Z7) include washing or cleaning-active polymers, for example rinse aid polymers and/or polymers which act as softeners.
  • the detergent composition according to the invention may include, as polymers of component Z7), nonionic, cationic, anionic and/or amphoteric polymers.
  • Cationic polymers in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylates and methacrylates, vinylpyrrolidone- methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols, or polymers having the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27.
  • cationic polymers are used in component Z7), they are particularly preferably copolymers comprising polyalkylene oxide groups and quaternary nitrogen atoms. More preferably the cationic polymers of component Z7) are copolymers comprising 0.1 to 99.9 mol-%, preferably 20.0 to 80.0 mol-%, more preferably 22.0 to 77.6 mol-% of one or more cationic structural units (D); and
  • R 19 and R 21 are equal or different and are independently selected from hydrogen and/or a methyl group
  • R 20 , R 22 , R 23 and R 24 are equal or different and are independently selected from the group consisting of hydrogen, an aliphatic hydrocarbon residue having 1 to 20, preferably 1 to 4 carbon atoms, a cycloaliphatic hydrocarbon residue having 5 to 20, preferably 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and/or polyethylene glycol (PEG), and preferably are equal or different and independently selected from the group consisting of hydrogen and/or methyl, and particularly preferably are methyl; is the same or different and is selected from oxygen, NH and/or NR 22 ,
  • V is the same or different and is selected from -(CH2)x-, x is the same or different and is a number from 1 to 6;
  • X and Xi are equal or different and are independently selected from a halogen atom, Ci to C4-alkylsulfate and/or Ci to C4 alkylsulfonate; and the one or more macromonomeric structural units (E) are represented by the following general formula (XIII): wherein
  • R 25 is the same or different and is H and/or methyl
  • Amphoteric polymers in the context of the present invention have, alongside positively charged groups, also negatively charged groups or monomeric units in the polymer chain. These negatively charged groups or monomeric units may be derived, e.g. from carboxylic acids, sulfonic acids ot phosphonic acids.
  • Preferable amphoteric polymers applicable in component Z7) of the detergent composition according to the invention are selected from the group consisting of alkylacrylamide/acrylic acid-copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkyl aminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkylmethacrylate copolymers, and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non-ionic mono
  • amphoteric polymers are selected from the group consisting of acrylamidoalkyl-trialkylammonium chloride/acrylic acid copolymers and their alkaline metal or ammonium salts, acrylamidoalkyl-trialkylammonium chloride/methacrylic acid copolymers and their alkaline metal or ammonium salts, and methacroylethylmetaine/methacrylate copolymers.
  • the detergent composition according to the invention contains cationic and/or amphoteric polymers in component Z7), these polymers are preferably present in amounts of from 0.01 to 10 wt.-%, based on the total weight of the detergent composition.
  • alkoxylated polyalkyleneimines Another group of preferably applicable polymers applicable in component Z7) of the detergent composition according to the invention are alkoxylated polyalkyleneimines.
  • Alkoxylated polyalkyleneimines have a polyalkyleneimine backbone and alkoxy chains.
  • the polyalkyleneimine is polyethyleneimine. More preferably, the alkoxylated polyalkyleneimine is not quaternized.
  • the detergent composition according to the invention comprises alkoxylated polyalkyleneimines in component Z7)
  • the composition preferably comprises from 1 to 10 wt.-%, more preferably from 1 to 8 wt.-% of alkoxylated polyalkyleneimines, based on the total weight of the detergent composition.
  • the alkoxylated polyalkyleneimine used in component Z7) comprises 0.5 to 40 wt.-%, more preferably 1 to 30 wt.-%, even more preferably 2 to 20 wt.-% of the polyalkyleneimine backbone and 60 to 99 wt.-%, more preferably 60 to 95 wt.-%, even more preferably from 60 to
  • the alkoxy chains have an average of from about 1 to about 50, more preferably from about 2 to about 40, even more preferably from about 3 to about 30, particularly preferably from about 3 to about 20, and especially preferably from about 4 to about 15 alkoxy units, which are preferably ethoxy units.
  • the alkoxy chains have an average of from about 0 to 30, more preferably from about 1 to about 12, even more preferably from about 1 to about 10 and particularly preferably from about 1 to about 8 propoxy units.
  • alkoxylated polyethyleneimines wherein the alkoxy chains comprise a combination of ethoxy and propoxy chains, in particular polyethyleneimines comprising chains of from 4 to 20 ethoxy units and from 0 to 6 propoxy units.
  • the alkoxylated polyalkyleneimine is obtained from alkoxylation wherein the starting polyalkyleneimine has a weight-average molecular weight of from about 100 to about 60,000, preferably from about 200 to about 40,000, more preferably from about 300 to about 10,000 g/mol.
  • a polyethyleneimine with a weight average molecular weight of 600 g/mol ethoxylated with 20 EO groups per NH group is used as the alkoxylated polyalkyleneimine.
  • Suitable polyalkyleneimines applicable in component Z7) of the detergent composition according to the invention include compounds having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H2x-N + -(CH3)- bis((C2H 5 0)(C2H4o)n), wherein n is a number from 20 to 30, and x is a number from 3 to 8, or sulfated or sulfonated variants thereof.
  • the one or more further additives Z8) are preferably selected from the group consisting of chelating agents, glass corrosion inhibitors, water, organic solvents, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors are, among others, magnesium, cobalt and zinc salts and magnesium, cobalt and zinc complexes.
  • Proteins and/or enzymes such as those in component Z3), may be particularly sensitive to damage such as inactivation, denaturation or degradation during storage (e.g. by physical influences, oxidation or proteolytic cleavage).
  • damage such as inactivation, denaturation or degradation during storage (e.g. by physical influences, oxidation or proteolytic cleavage).
  • inhibition of the proteolysis is particularly preferred, in particular if the detergent compositions according to the invention also contain proteases. Therefore, the detergent composition according to the invention may contain enzyme stabilizers. The provision of such agents in the detergent composition constitutes a particularly preferred embodiment of the invention.
  • such detergent compositions according to the invention contain 0.1 to 12 wt.-%, more preferably 0.2 to 10 wt.-%, even more preferably 0.5 to 8 wt.-%, based on the total weight of the detergent composition, of such enzyme stabilizers.
  • a preferred embodiment of the present invention is therefore a detergent composition according to the invention which contains at least one organic solvent.
  • Preferred liquid detergent compositions according to the invention contain organic solvent in amounts of from 0.2 to 15 wt.-%, more preferably in amounts of from 0.5 to 12 wt.-% and even more preferably in amounts of from 1 .0 to 10 wt.-%, based on the total weight of the detergent composition.
  • organic solvents are for example monoalcohols, diols, triols, polyols, ethers, esters and/or amides. Particular preference is given to organic solvents which are water-soluble.
  • “Water-soluble” solvents in the sense of the present application are solvents which are completely miscible with water at room temperature (i.e., without miscibility gaps).
  • the organic solvents from the group of organic amines and/or alkanolamines are effective in terms of cleaning performance and in particular with regard to the cleaning performance of bleachable soiling, especially on tea stains.
  • thickeners can be added to this composition.
  • the thickeners commonly used in detergent compositions for machine dishwashing can be used.
  • liquid detergent compositions according to the invention contain one or more thickeners in amounts preferably from 0.1 to 8 wt.-%, more preferably from 0.2 to 6 wt.-% and even more preferably from 0.4 to 4 wt.-%, based on the total weight of the liquid detergent composition.
  • Foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators may be selected from the corresponding substances commonly used in detergent compositions for machine dishwashing.
  • the detergent composition according to the invention comprises, preferably consists of:
  • component Z7) 0 to 10 wt.-% of component Z7), and Z8) 0 to 70 wt.-% of component Z8), in each case based on the total weight of the detergent composition.
  • the detergent composition according to the invention contains no phosphate-based builders, and more preferably the detergent compositions according to the invention contains no phosphates, i.e. they are phosphate-free.
  • the detergent composition according to the invention can be prepared in solid or liquid form and as a combination of solid and liquid forms.
  • detergent compositions according to the invention which are solid at 20 °C. Powder, granules, extrudates or compactates, in particular tablets in single-phase or multiphase form are particularly suitable as solid forms. Tablets are formulated for single-dose applications.
  • the solid detergent compositions according to the invention preferably contain 20 wt.-% or less than 20 wt.-% of water, more preferably 0.1 to 20 wt.-% of water and even more preferably 0.5 to 5 wt.-% of water, based on the total weight of the detergent composition.
  • the detergent composition according to the invention is anhydrous.
  • the solid detergent composition according to the invention is in the form of a tablet.
  • detergent compositions according to the invention which are wrapped or enclosed in a water-soluble foil, preferably in a water- soluble foil based on polyvinyl alcohol or a water-soluble polyvinyl alcohol containing foil.
  • water-soluble foil means that the foil comprises a water-soluble polymer, copolymer or mixtures thereof in a weight fraction of at least 90 wt.-%, based on the total weight of the foil.
  • Water-soluble polymers in the context of the present invention are polymers which are soluble in water at 25 °C to an amount of more than 2.5 wt.-%, based on the amount of water.
  • Preferable materials of the water-soluble foil are at least partially composed of a substance selected from the group consisting of polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, gelatine, polyvinyl alcohols substituted with sulfate, carbonate and/or citrate, polyalkylene oxides such as polyethylene oxides, acrylamides, cellulose esters, cellulose ethers, cellulose acetate, polycarboxylic acids and their salts, polyaminoacids or peptides, copolymers of acrylamides and (meth)acrylic acid, polysaccharides such as starch or guar derivatives, and compounds with the INCI names polyquaternium 2, polyquaternium 17, polyquaternium 18 and polyquaternium 27.
  • the material of the water-soluble foil comprises polyvinyl alcohol.
  • the material of the water- soluble foil comprises mixtures of different substances, such as copolymers. Such mixtures enable the adjustment of the mechanical properties of the foil and the container formed thereof and may affect the degree of water solubility.
  • the water-soluble foil contains at least one polyvinyl alcohol and/or at least one polyvinyl alcohol copolymer.
  • the detergent composition according to the invention is liquid at 20 °C.
  • the liquid formulation preferably based on water and/or organic solvents, can be provided in a thickened form, as a gel.
  • Capsules (caps) are particularly suited for liquid formulations in single-phase or multiphase form.
  • the liquid detergent composition according to the invention contains up to 60 wt.-% of water, more preferably from 10 to 60 wt.-% of water, even more preferably from 25 to 60 wt.-% of water, based on the total weight of the liquid detergent composition.
  • the detergent composition according to the invention is present in the form of a powder, a gel, a pod or a cap or is provided as a liquid rinse aid.
  • the detergent compositions according to the invention may advantageously be used in a dishwashing machine. Therefore, a further subject matter of the invention is a method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition for machine dishwashing according to the invention.
  • the pH value of the aqueous alkaline composition is preferably 8 or above and more preferably 9 or above. In a particularly preferred embodiment, the pH value of the aqueous alkaline composition is from 8 to 13 and preferably from 9 to 12.
  • the detergent compositions according to the invention may advantageously be used for counteracting malodour in a dishwashing machine. Therefore, a further subject matter of the invention is a method for counteracting malodour in a dishwashing machine, comprising the application of a detergent composition according to the invention in a dishwashing cycle.
  • malodour refers to unpleasant odours which are frequently encountered in everyday life and have a variety of origins.
  • Typical malodours include odours that emanate from uncontrolled industrial activity, from human and pet body such as perspiration and excretion, from kitchen and food processing, from tobacco smoke, and from mould.
  • Some of the most disturbing malodour for the human being are sweat; faecal; urine; wet pet; cooking odours, especially garlic, cabbage, fish and onion; and the like.
  • Malodours may also emanate from the fatty acid and fatty acid derivatives present in consumer products, for example in soaps, detergents, shampoos, and conditioners.
  • malodours are those produced by depilatory creams (sulphur compounds). All of these malodours are particularly pungent.
  • the cucurbiturils as described for component Z2) of the detergent compositions according to the invention may be used to counteract a broad range of malodour molecules.
  • malodour counteraction or “malodour counteracting” is considered as equivalent to “malodour suppression”, “malodour mitigation” or “malodour neutralization”.
  • the result is a significant decrease of the intensity of the malodour perception by any person exposed to the source of the malodour.
  • the intensity of odours is generally measured by using the Labelled Magnitude Scale (LMS), a definition of which can be found in Green BG, Shaffer GS and Gilmore MM 1993, Derivation and evaluation of a semantic scale of oral sensation magnitude with apparent ratio properties, Chemical Senses. 18(6):683-702.
  • LMS Labelled Magnitude Scale
  • the scale encompasses the following strength attributes: Barely Detectable, Weak, Moderate, Strong, Very Strong and Strongest Imaginable.
  • a “significant decrease” means that the intensity attribute of the malodour, after application of the cucurbiturils, is Weak or Barely Detectable.
  • a linear scale may be used, extending for example from 0 (no intensity perceived) and 10 (highest intensity perceived).
  • Odour intensity scores are preferably obtained by a panel of several people.
  • the malodour to be counteracted is a complex malodour, comprising more than one malodour component.
  • the complex malodour comprises malodour components having a diversity of chemical functions.
  • the malodour may be selected from, but not limited to:
  • Nitrogen- and sulphur-containing molecules such as Allyl amine; Methyl amine; Ethyl amine; Cyclobutyl amine (cyclobutanamine, urine), Cyclopentyl amine (cyclopentanamine); Cyclohexyl amine (cyclohexanamine); Cycloheptyl amine (cyclobutanamine); Isopropylamine; Butylamine; Dibutylamine (N-Butyl-1-butanamin); Dimethyl ethanolamine (2-(Dimethylamino)ethanol); Methyl ethanolamine (2-(Methylamino)ethanol); Diethyl ethanolamine (2-(Diethylamino)ethanol); Diethylamine (N-methylethanamine, fishy); Dipropyl amine (N-Propyl-1-propanamine); Diiso-propylamine (N-lsopropyl-2-propanamine); Dimethyl acetamide (N,N-Dimethylace
  • Oxygen-containing five-member ring molecules such as Sotolone; nor- Sotolone.
  • Saturated and unsaturated alkyl and hydroxyalkyl carboxylic acids such as Acetic acid, Propionic acid, Butyric acid, iso-Valeric acid, n-Valeric acid, 2-Methyl-butyric acid, 3-Methyl-2-hexenoic acid, and 3-Methyl-3-hydroxy hexanoic acid.
  • the detergent compositions used in the invention may also include one or more additives known to those skilled in the art.
  • the detergent compositions used in the present invention further comprise one or more molecules, mixtures of molecules or polymers useful in counteracting malodour, in addition to cucurbituril.
  • Suitable molecules, mixtures of molecules or polymers useful in counteracting malodour are known to the skilled person and include other host molecules.
  • other members of the cavitand family which includes cyclodextrin, calixarene and crown ether, could be used in combination with cucurbituril.
  • Further suitable classes of molecules or compounds include charcoal and zinc ricinolate.
  • the cucurbituril-based detergent compositions for use in the present invention can be provided in a multitude of forms and formats.
  • the mixture of cucurbiturils may be provided in powder form, in solution or as a dispersion in a liquid, in a super-critical liquid or as a compressed gas, adsorbed on a substrate, for example on a fabric, a non-woven pad, an adsorbent, and the like, or in spray form.
  • an advantage of the invention is that the detergent composition according to the invention can be used to reduce malodour in the dishwashing machine and/or to reduce the transfer of malodour to plastic items in the dishwashing machine.
  • a further subject matter of the invention is the use of a detergent composition according to the invention to reduce malodour in a dishwashing machine and/or to reduce the transfer of malodour to plastic items in the dishwashing machine.
  • the detergent compositions according to the invention may advantageously be used as dishwasher care product. Therefore, a further subject matter of the invention is the use of a detergent composition according to the invention as dishwasher care product.
  • dishwasher care product and “dishwasher care product” are used interchangeably.
  • Such dishwasher care product may be used to clean and/or care a dishwashing machine. For instance, it may reduce or remove malodours, grease and/or limescale.
  • a dishwasher care product may optionally comprise further ingredients in addition to those mentioned in the context of the detergent composition.
  • Longterm release may be understood in the broadest sense as released over a longer time.
  • the one or more cucurbiturils and optionally one or more other ingredients may be gradually dissolved by contact with water. Longterm release of the one or more cucurbiturils and optionally one or more other ingredients may preferably continue for at least 5, more preferably for at least 10, even more preferably for at least 20 dishwashing cycles. Longterm release may be achieved in that the one or more cucurbiturils are embedded in a delayed release formulation, which may optionally be solid such as, e.g., may be a tablet or a deodorant, or may be a solid gel.
  • delayed release formulation may be placed in a cassette or dispenser, and/or may be mounted in a dishwashing machine.
  • Such delayed release formulation may optionally contain one or more water-soluble polymers such as, e.g., polyethyleneglycol (PEG) and/or one or more fragrances. It may optionally not contain a detergent/surfactant.
  • PEG polyethyleneglycol
  • the one or more cucurbiturils are embedded in a delayed release formulation, which allows gradually dissolvance thereof by contact with water, and which comprises polyethyleneglycol (PEG) and one or more fragrances and does not contain a detergent/surfactant.
  • a further subject matter of the invention is the use one or more cucurbiturils as described for component Z1 ) of the detergent composition according to the invention for longterm release during the washing cycle in a dishwashing machine, preferably in up to 60 dishwashing cycles.
  • the one or cucurbiturils are present in a detergent composition according to the invention.
  • the use of the detergent composition according to the invention has no negative impact on rinse performance, dry capacity or cleaning performance of the detergent.
  • the preferred embodiments specified above for the detergent compositions of the invention and for the one or more cucurbiturils of component Z1 ) of the detergent compositions of the invention are also applicable in a corresponding manner to the method of cleaning dishes in a dishwashing machine, in which contaminated dishes are treated in the dishwashing machine with an aqueous alkaline composition comprising a detergent composition for machine dishwashing according to the invention, to the method of the invention for counteracting malodour in a dishwashing machine comprising the application of a detergent composition according to the invention in a dishwashing cycle, to the inventive use of a detergent composition for machine dishwashing according to the invention to reduce malodour in the dishwashing machine, to reduce the transfer of malodour to plastic items in the dishwashing machine or as dishwasher care product as well as the inventive use of the one or more cucurbiturils of component Z1 ) of the detergent compositions according to the invention or of the detergent compositions according to the invention for longterm release during the washing cycle in a dishwashing machine.
  • Genapol EP 2584 Nonionic surfactant (fatty alcohol alkoxylate) HEDP: 1-hydroxyethane-1 ,1-diphosphonic acid MGDA-Na 3 : methylglycinediacetic acid, trisodium salt PE: polyethylene PP: polypropylene
  • TAED tetraacetylethylenediamine
  • the dishwashing machine (Miele GSL 2) was equipped with soiled porcelain plates, a stainless steel pan and clean plastic items.
  • malodour soiling were used: mustard, bumt-in minced meat, dripping and garlic.
  • the soiled and clean items were stored in the dishwashing machine with closed door overnight. On the next morning the intensity of the malodor was determined by three trained sniffers according to the following scale:
  • a total amount of 18.0 g of the Composition is prepared and used in a cycle (also: run) of the dishwashing machine. Results
  • Table B Malodour intensity of dishwashing machine and items after treatment with
  • Formulations 2-4 according to the invention *
  • the experimentally used curcurbit[n]uril mixture is specified as essentially consisting of 45-65 wt.-% of CB[6], 20-40 wt.-% of CB[7], 10-25 wt.-% of CB[8], and ⁇ 10 wt.-% of water.
  • This material is a white to off-white particulate/powder that has a CB[n] purity (corrected for water content) of >85 wt.-%.
  • the results demonstrate that the malodour directly after end of the program and 24 hours after end of the program can be reduced significantly with Formulations 2-4 according to the invention. Furthermore, the results show that malodour transfer to plastic items in the dishwashing machine can be reduced by using Formulations 2-4 according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des compositions détergentes pour le lavage de vaisselle en machine, comprenant Z1) un ou plusieurs cucurbituriles choisis dans le groupe constitué par CB[5], CB[6], CB[7] et CB[8] représentés par la formule (A) dans laquelle n = 5 à 8 et Z2) un ou plusieurs tensioactifs non ioniques. Les compositions détergentes peuvent avantageusement être utilisées dans le lavage de vaisselle en machine, en particulier pour la réduction de mauvaises odeurs dans la machine de lave-vaiselle ou pour la réduction du transfert de mauvaises odeurs vers des articles en plastique.
EP23821984.4A 2022-12-12 2023-12-08 Compositions détergentes pour lave-vaisselle automatique contenant des cucurbituriles et leur utilisation pour réduire les mauvaises odeurs Pending EP4634357A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22212689 2022-12-12
PCT/EP2023/084991 WO2024126313A1 (fr) 2022-12-12 2023-12-08 Compositions détergentes pour lave-vaisselle automatique contenant des cucurbituriles et leur utilisation pour réduire les mauvaises odeurs

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EP4634357A1 true EP4634357A1 (fr) 2025-10-22

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Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942217A (en) 1997-06-09 1999-08-24 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5912218A (en) 1996-09-11 1999-06-15 The Procter & Gamble Company Low foaming automatic dishwashing compositions
US6869466B2 (en) 1999-05-07 2005-03-22 Unisearch Limited Cucurbiturils and method for binding gases and volatiles using cucurbiturils
GB2377451A (en) * 2001-07-11 2003-01-15 Reckitt Benckiser Nv Delayed release cleaning composition for automatic dishwashers
DE102007042860A1 (de) 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2014077641A1 (fr) 2012-11-16 2014-05-22 Postech Academy-Industry Foundation Composition pour l'élimination d'odeur et l'émission de parfum comprenant des complexes de cucurbituril et un parfum
WO2014077642A1 (fr) 2012-11-16 2014-05-22 Postech Academy-Industry Foundation Composition pour l'élimination d'odeur comprenant du cucurbituril
DE102014007288A1 (de) * 2014-05-20 2015-11-26 Friedrich-Alexander-Universität Erlangen-Nürnberg Die Primärwaschkraft verbessernde Wirkstoffe
US11484615B2 (en) 2016-02-15 2022-11-01 Aqdot Limited Cucurbituril compositions and their use
GB2573656A (en) * 2016-02-15 2019-11-13 Aqdot Ltd Use of compositions comprising a mixture of two or more cucurbiturils in a moist environment
GB2556619B (en) 2016-08-24 2019-01-02 Aqdot Ltd Suspension compositions
AU2017381271B2 (en) 2016-12-22 2021-08-12 Aqdot Limited Process for the preparation of cucurbituril derivatives

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