EP3363889A1 - Use of liquid laundry detergent composition to minimize adverse effects upon accidental exposure to contents of water-soluble unit dose articles - Google Patents
Use of liquid laundry detergent composition to minimize adverse effects upon accidental exposure to contents of water-soluble unit dose articles Download PDFInfo
- Publication number
- EP3363889A1 EP3363889A1 EP18157949.1A EP18157949A EP3363889A1 EP 3363889 A1 EP3363889 A1 EP 3363889A1 EP 18157949 A EP18157949 A EP 18157949A EP 3363889 A1 EP3363889 A1 EP 3363889A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- acid
- laundry detergent
- liquid laundry
- water
- 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.)
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- 150000002689 maleic acids Chemical class 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004081 narcotic agent Substances 0.000 description 1
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 description 1
- 229940052490 naringin Drugs 0.000 description 1
- 229930019673 naringin Natural products 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 229960001811 quinine hydrochloride Drugs 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940013883 sucrose octaacetate Drugs 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/043—Liquid or thixotropic (gel) compositions
Definitions
- the present invention relates to the use of a liquid laundry detergent composition to minimize the adverse effects of rare accidental exposure of the detergent composition comprised with a liquid laundry detergent composition.
- Laundry water-soluble unit dose articles are liked by consumers as they are efficient and convenient to use. They offer simple unit dosing of laundry detergent composition to be used in the laundry wash operation removing the need for inconvenient and messy dosing.
- a liquid laundry detergent composition according to the present invention comprised within a water-soluble unit dose article provided a desired reduction in adverse effects from rare accidental exposures to the contents of the water-soluble unit dose article whilst providing laundry cleaning, especially greasy food stain cleaning, and freshness benefits and still maintaining a good whiteness profile.
- a first aspect of the present invention is the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article, wherein the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- a second aspect of the present invention is the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article, wherein the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- the present invention is to the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize potential adverse effects associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article.
- water-soluble unit dose articles contain a single dose of a laundry detergent composition enveloped in a water-soluble film.
- the consumer places the entire article into the drum of a washing machine or other wash receptacle together with fabrics to be washed.
- the water-soluble film dissolves releasing the laundry detergent composition contained within into the water and into contact with the fabrics.
- the concept is that the laundry detergent composition remains contained within the unit dose article until the unit dose article is contacted with water during use.
- Nearcosis is herein defined as a reversible state of stupor, unconsciousness, or arrested activity, driven by a temporary depression of the central nervous system induced by narcotics or other chemical or physical agents.
- Emesis is herein defined as an act or instance of spontaneous vomiting as a consequence of accidental ingestion of a chemical substance, such as a detergent composition.
- the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- the liquid laundry detergent composition according to the present invention suitable for use in a water-soluble unit dose article has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter and between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7
- the liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant and between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- liquid laundry detergent composition is described in more detail below.
- the potential adverse effects associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article is for example when the water-soluble unit dose article is accidentally prematurely ruptured and the skin, eye or mixture thereof of the user are contacted with the liquid laundry detergent composition, or (part of) the liquid laundry detergent composition is accidently swallowed.
- the water-soluble unit dose article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film.
- the unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment.
- the water-soluble unit dose article is constructed such that the liquid laundry detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
- the compartment should be understood as meaning a closed internal space within the unit dose article, which holds the liquid laundry detergent composition.
- a first water-soluble film may be shaped to comprise an open compartment into which the liquid laundry detergent composition is added.
- a second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.
- the water-soluble film is described in more detail below.
- the unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments.
- the compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise three films, top, middle and bottom.
- the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other.
- the compartments may even be orientated in a 'tyre and rim' arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment.
- one compartment may be completely enclosed within another compartment.
- the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment.
- the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment.
- the superposed compartments preferably are orientated side-by-side.
- the liquid laundry detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be comprised in just one compartment, or may be comprised in two compartments, or even in three compartments.
- Each compartment may comprise the same or different compositions.
- the different compositions could all be in the same form, or they may be in different forms.
- the water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.
- the water-soluble unit dose article comprises at least two compartments and the liquid laundry detergent composition is comprised in at least one compartment, preferably wherein the water-soluble unit dose article comprises at least two compartments of different sizes and the liquid laundry detergent composition is comprised in at least the larger compartment.
- the film of the present invention is soluble or dispersible in water.
- the water-soluble film preferably has a thickness of from 20 to 150 micron, preferably 35 to 125 micron, even more preferably 50 to 110 micron, most preferably about 76 micron.
- the film has a water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
- Preferred film materials are preferably polymeric materials.
- the film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
- Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
- More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
- the level of polymer in the pouch material for example a PVA polymer, is at least 60%.
- the polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
- polymers and/or copolymers can also be used as the pouch material, especially mixtures of polyvinylalcohol polymers and/or copolymers, especially mixtures of polyvinylalcohol homopolymers and/or anionic polyvinylalcohol copolymers preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers.
- the water soluble film comprises a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
- Preferred films exhibit good dissolution in cold water, meaning unheated distilled water.
- Preferably such films exhibit good dissolution at temperatures of 24°C, even more preferably at 10°C.
- good dissolution it is meant that the film exhibits water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
- Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310.
- the film may be opaque, transparent or translucent.
- the film may comprise a printed area.
- the area of print may be achieved using standard techniques, such as flexographic printing or inkjet printing.
- the film may comprise an aversive agent, for example a bittering agent.
- Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof.
- Any suitable level of aversive agent may be used in the film. Suitable levels include, but are not limited to, 1 to 5000ppm, or even 100 to 2500ppm, or even 250 to 2000rpm.
- the water-soluble unit dose article comprises a water-soluble film, preferably wherein the water-soluble film comprises polyvinyl alcohol, preferably wherein the water-soluble film comprises polyvinyl alcohol polymer or copolymer, preferably a blend of polyvinylalcohol polymers and/or polyvinylalcohol copolymers, more preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, most preferably a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
- liquid laundry detergent composition refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to, liquids, gels, pastes, dispersions and the like.
- the liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.
- the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- Ionic Strength is a measure of ion concentration in a finished liquid detergent formulation.
- IS is ionic strength
- weight % of species in a finished liquid detergent composition is weight percent of species from which an ion can be formed in the composition
- MW s is molecular weight of a species from which an ion y can be formed
- n y is number of ions
- q y is the charge of the ion in the composition under the pH of the finished liquid detergent composition
- liquid density is the density of the finished liquid detergent formulation. Only dissolved species in the finished liquid detergent formulation are considered in the
- the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- the liquid laundry detergent composition according to the present invention suitable for use in a water-soluble unit dose article has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter and between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of the fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and
- the liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- chelation means the binding or complexation of a bi- or multidentate ligand.
- ligands which are often organic compounds, are called chelants, chelators, chelating agents, and/or sequestering agent.
- Chelating agents form multiple bonds with a single metal ion.
- Chelants are chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale.
- the ligand forms a chelate complex with the substrate. The term is reserved for complexes in which the metal ion is bound to two or more atoms of the chelant.
- the chelant is preferably selected from the group consisting of amino carboxylates, amino phosphonates, polycarboxylates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, preferably selected from the group consisting of glutamic-N,N- diacetic acid (GLDA), methyl-glycine-diacetic acid (MGDA), Diethylenetriamine penta methylphosphonic acid (DTPMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), ethylenediaminetetra-acetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates (NTA), ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N- mono
- the liquid laundry detergent composition comprises between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant.
- the liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of the chelant and between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- Suitable alcohol ethoxylate nonionic surfactants include the condensation products of aliphatic alcohols with ethylene oxide.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, substituted or unsubstituted.
- the starting alcohol can be naturally derived, e.g. starting from natural oils, or synthetically derived, e.g. alcohols obtained from for example oxo-, modified oxo- or Fischer-Tropsch processes.
- oxo-process derived alcohols include the Lial and Isalchem alcohols ex Sasol company and Lutensol alcohols ex BASF company.
- modified-oxo process derived alcohols include the Neodol alcohols ex Shell company.
- Fischer-Tropsch derived alcohols include Safol alcohols ex Sasol company.
- the alkoxylate chain of alcohol ethoxylates is made up solely of ethoxylate groups.
- the fatty alcohol ethoxylate has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15.
- the fatty alcohol ethoxylate has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- Suitable for use herein are the ethoxylated alcohol of the formula R(OC 2 H 4 )n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 22 carbon atoms and the average value of n is from about 5 to about 22.
- particularly useful materials are condensation products of C 9 -C 16 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol.
- particularly useful materials are condensation products of C 12 -C 16 alcohols with from about 6 to about 9 moles of ethylene oxide per mole of alcohol.
- nonionic surfactants may include: C12-C18 alkyl ethoxylates based on modified oxo alcohols, such as, NEODOL® nonionic surfactants from Shell; C12-C15 alkyl ethoxylates based on Fischer Tropsch Oxo alcohols, such as, SAFOL® nonionic surfactants from Sasol; C12-C18 alkyl ethoxylates based on natural or Ziegler alcohols, such as, Surfonic® nonionic surfactants from Huntsman; C14-C22 mid-chain branched alcohols ethoxylates, BAEx, wherein x is from 1 to 30.
- modified oxo alcohols such as, NEODOL® nonionic surfactants from Shell
- C12-C15 alkyl ethoxylates based on Fischer Tropsch Oxo alcohols such as, SAFOL® nonionic surfactants from Sasol
- the liquid laundry detergent composition may comprise up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 35%, most preferably between 15% and 30% or even between 15% and 25% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant.
- the non-soap anionic surfactant may comprises a sulphate or a sulphonate anionic surfactant or a mixture thereof, preferably linear alkylbenzene sulphonate, alkyl sulphate, alkoxylated alkyl sulphate or a mixture thereof, more preferably a mixture of linear alkylbenzene sulphonate and alkoxylated alkyl sulphate.
- the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate more preferably the ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more preferably from 1.3:1 to 5:1, most preferably from 1.4:1 to 3:1.
- the alkoxylated alkyl sulphate is an ethoxylated alkyl sulphate with an average degree of ethoxylation of between 0.5 and 7, preferably between 1 and 5, more preferably between 2 and 4, most preferably about 3.
- the non-soap surfactant comprises a mixture of one or more alkoxylated alkyl sulphates, preferably ethoxylated alkyl sulphates, and optionally an alkyl sulphate, the mixture having an average degree of ethoxylation of between 0.5 and 7, preferably between 1 and 5, more preferably between 2 and 4, most preferably about 3.
- the alkyl sulphate and/or alkoxylated alkyl sulphate preferably have an alkyl chain comprising on average between 8 and 18 carbon atoms, preferably between 10 and 16 carbons atoms, most preferably between 12 and 14 carbon atoms.
- the alkoxylated alkyl sulphate is an ethoxylated alkyl chain comprising on average between 12 and 14 carbon atoms in its alkyl chain and has an average degree of ethoxylation of about 3.
- the alkyl chain of the alkoxylated alkyl sulphate surfactant may be linear or branched or a mixture thereof.
- the linear alkylbenzene sulphonate may be a C 10 -C 16 linear alkylbenzene sulphonate or a C 11 -C 14 linear alkylbenzene sulphonate or a mixture thereof.
- Exemplary linear alkylbenzene sulphonates are C 10 -C 16 alkyl benzene sulfonic acids, or C 11 -C 14 alkyl benzene sulfonic acids.
- 'linear' we herein mean the alkyl group is linear.
- Alkyl benzene sulfonates are well known in the art.
- the weight ratio of non-soap anionic surfactant to fatty alcohol ethoxylate non-ionic surfactant is between 5:1 and 23:1 preferably between 7:1 and 23:1, more preferably between 8:1 and 23:1, most preferably between 9:1 and 20:1.
- the liquid laundry detergent composition comprises between 15% and 40%, preferably between 20% and 35%, more preferably between 25% and 30% by weight of the liquid laundry detergent composition of non-soap surfactant.
- the liquid laundry detergent composition may comprise less than 10%, preferably less than 8%, more preferably less than 5%, most preferably between 1% and 5% by weight of the liquid laundry detergent composition of fatty acid, neutralised fatty acid soap or a mixture thereof.
- the neutralised fatty acid soap may be alkali metal neutralised, amine neutralised or a mixture thereof.
- the alkali metal may be selected from sodium, potassium, magnesium or a mixture thereof, preferably sodium.
- the amine is preferably an alkanolamine, preferably selected from monethanolamine, diethanolamine, triethanolamine or a mixture thereof, more preferably monoethanolamine.
- the fatty acid, neutralised fatty acid soap or mixture thereof may be selected from palm kernel fatty acid, coconut fatty acid, rapeseed fatty acid, neutralized palm kernel fatty acid, neutralized coconut fatty acid, neutralized rapeseed fatty acid, or mixture thereof, preferably neutralized palm kernel fatty acid.
- the liquid laundry detergent composition may comprise between 0.1% and 10%, preferably between 0.5% and 8%, more preferably between 1% and 7%, even more preferably between 2% and 6%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of a soil release polymer, wherein the soil release polymer is preferably selected from polyester terephthalates, polyethylene glycol containing soil release polymers and a mixture thereof.
- An example of a preferred polyethyleneglycol containing soil release polymer comprises a polyethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, comprising 40% by weight of the polymer system of a polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains.
- Polyester terephtalate soil release polymers are commercially available from Clariant under the Texcare SRN and SRA tradenames.
- One particularly preferred polyester terephtalate soil release polymer is Texcare SRA300.
- the liquid laundry detergent composition may comprise a polyethyleneimine, preferably an alkoxylated polyethyleneimine, more preferably an ethoxylated polyethyleneimine and wherein preferably the liquid laundry detergent composition comprises greater than 0.5%, preferably between 1% and 10%, more preferably between 2% and 7%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of the polyethyleneimine, preferably ethoxylated polyethyleneimine.
- An example of an ethoxylated polyethyleneimine includes an ethoxylated polyethyleneimine with a polyethyleneimine backbone with a molecular weight of about 600, and comprising on average about 20 ethoxy units per ethoxylation chain.
- the ratio of polyethyleneimine to soil release polymer is higher than 1:1, preferably between 1.1:1 and 5:1, more preferably between 1.2:1 and 3:1, most preferably between 1.3:1 and 2:1.
- the liquid laundry detergent composition may comprise a polysaccharide polymer, a modified polysaccharide polymer, a polysaccharide derived polymer, or a mixture thereof, preferably a cellulosic polymer, a modified cellulosic polymer or a mixture thereof, most preferably a cationically modified cellulosic polymer or a mixture thereof.
- the polysaccharide polymer is a cationically modified hydroethylcellulose ("Polyquaternium 10).
- the water-soluble unit dose article comprises up to 60% preferably up to 50%, more preferably up to 40% by weight of the liquid laundry detergent composition of a non-aqueous solvent, preferably selected from propylene glycol, dipropylene glycol, glycerol, sorbitol, ethanol or a mixture thereof.
- a non-aqueous solvent preferably selected from propylene glycol, dipropylene glycol, glycerol, sorbitol, ethanol or a mixture thereof.
- the liquid laundry detergent composition has a pH from 6 to 10 preferably from 7 to 9, more preferably from 7 to 8.
- the liquid laundry detergent composition comprises a pH adjusting agent selected from alkanolamines, preferably monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, most preferably monoethanolamine.
- the liquid laundry detergent composition comprises an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments, amphoteric surfactants, cyclic diamines, zwitterionic polyamines, anti-oxidants, preservatives and mixtures thereof.
- an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments, amphoteric surfactants, cyclic di
- the water-soluble unit dose article comprises 15% or less by weight of the unit dose article of water, preferably the unit dose article comprises between 0.1% and 15%, more preferably between 1% and 12.5% by weight of the unit dose article of water.
- a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added.
- a second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment.
- the first and second films are then sealed together along a seal region using known sealing means such as solvent, heat or a mixture thereof.
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Abstract
The use of a liquid laundry detergent composition to minimize the adverse effects of rare accidental exposure of the detergent composition contained within a water-soluble unit dose article.
Description
- The present invention relates to the use of a liquid laundry detergent composition to minimize the adverse effects of rare accidental exposure of the detergent composition comprised with a liquid laundry detergent composition.
- Laundry water-soluble unit dose articles are liked by consumers as they are efficient and convenient to use. They offer simple unit dosing of laundry detergent composition to be used in the laundry wash operation removing the need for inconvenient and messy dosing.
- All laundry detergent compositions have to meet stringent regulatory requirements and industry standards in order to be placed on the market. However, detergent products, due to their primary function of cleaning, all have intrinsic hazards and are labeled as such. On rare occasions accidental misuse or accidental rupture may occur resulting in the potential for consumers to be exposed to their contents. Given the nature of the cleaning compositions contained within the unit dose article, in a minority of instances adverse effects may be associated with these exposures including, but not limited to, emesis, narcosis or a mixture thereof. While such unit dose products already meet existing safety standards and regulatory expectation, there is a desire within the industry to further reduce the severity or potential of adverse effects associated with these rare accidental exposures, whilst still providing cleaning performance and other benefits.
- It is known from the prior art, e.g.
WO2016155993 , that addition of soil release polymers can reduce the irritation of liquid laundry compositions. However, this approach requires addition of materials and due to the compacted nature of water-soluble unit dose articles, there is limited space for the addition of further ingredients or increasing the overall levels of ingredients. - Therefore, there is a need to provide alternative means to minimize the adverse effects of rare accidental exposure of the detergent composition, including reducing the emesis and narcosis profiles whilst still providing laundry cleaning benefits, especially greasy food stain cleaning, whiteness and freshness benefits. It is especially preferred to find ways to reduce the adverse effect from rare accidental exposure to the contents without the addition of further ingredients.
- It was surprisingly found that a liquid laundry detergent composition according to the present invention comprised within a water-soluble unit dose article provided a desired reduction in adverse effects from rare accidental exposures to the contents of the water-soluble unit dose article whilst providing laundry cleaning, especially greasy food stain cleaning, and freshness benefits and still maintaining a good whiteness profile.
- A first aspect of the present invention is the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article, wherein the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- A second aspect of the present invention is the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article,
wherein the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant. - The present invention is to the use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize potential adverse effects associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article.
- The water-soluble unit dose article is described in more detail below. Without wishing to be bound by theory, water-soluble unit dose articles contain a single dose of a laundry detergent composition enveloped in a water-soluble film. The consumer places the entire article into the drum of a washing machine or other wash receptacle together with fabrics to be washed. Upon application of water, the water-soluble film dissolves releasing the laundry detergent composition contained within into the water and into contact with the fabrics. The concept is that the laundry detergent composition remains contained within the unit dose article until the unit dose article is contacted with water during use.
- By 'accidental exposure' we herein mean unintentional exposure, for example from premature rupture of the unit dose article. Such accidental premature rupture is rare, but given the nature of the cleaning compositions contained within the unit dose article, in a minority of instances adverse effects may be associated with these exposures including, but not limited to, emesis, narcosis, or a mixture thereof.
- "Narcosis" is herein defined as a reversible state of stupor, unconsciousness, or arrested activity, driven by a temporary depression of the
central nervous system induced by narcotics or other chemical or physical agents. - "Emesis" is herein defined as an act or instance of spontaneous vomiting as a consequence of accidental ingestion of a chemical substance, such as a detergent composition.
- In one aspect the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- In another aspect of the present invention, the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- In another aspect, the liquid laundry detergent composition according to the present invention suitable for use in a water-soluble unit dose article, has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter and between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- The liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant and between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- The liquid laundry detergent composition is described in more detail below.
- Without wishing to be bound by theory it is the specific use of the present liquid laundry detergent composition in a water-soluble unit dose article that minimises the adverse effects of accidental exposure to said laundry detergent composition.
- The potential adverse effects associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article is for example when the water-soluble unit dose article is accidentally prematurely ruptured and the skin, eye or mixture thereof of the user are contacted with the liquid laundry detergent composition, or (part of) the liquid laundry detergent composition is accidently swallowed.
- The water-soluble unit dose article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film. The unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment. The water-soluble unit dose article is constructed such that the liquid laundry detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
- The compartment should be understood as meaning a closed internal space within the unit dose article, which holds the liquid laundry detergent composition. During manufacture, a first water-soluble film may be shaped to comprise an open compartment into which the liquid laundry detergent composition is added. A second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.
- The water-soluble film is described in more detail below.
- The unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments. The compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise three films, top, middle and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other. The compartments may even be orientated in a 'tyre and rim' arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively one compartment may be completely enclosed within another compartment.
- Wherein the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. Wherein the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment. The superposed compartments preferably are orientated side-by-side.
- In a multi-compartment orientation, the liquid laundry detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be comprised in just one compartment, or may be comprised in two compartments, or even in three compartments.
- Each compartment may comprise the same or different compositions. The different compositions could all be in the same form, or they may be in different forms.
- The water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.
- Preferably, the water-soluble unit dose article comprises at least two compartments and the liquid laundry detergent composition is comprised in at least one compartment, preferably wherein the water-soluble unit dose article comprises at least two compartments of different sizes and the liquid laundry detergent composition is comprised in at least the larger compartment.
- The film of the present invention is soluble or dispersible in water. The water-soluble film preferably has a thickness of from 20 to 150 micron, preferably 35 to 125 micron, even more preferably 50 to 110 micron, most preferably about 76 micron.
- Preferably, the film has a water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
- 5 grams ± 0.1 gram of film material is added in a pre-weighed 3L beaker and 2L ± 5ml of distilled water is added. This is stirred vigorously on a magnetic stirrer, Labline model No. 1250 or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for 30 minutes at 30°C. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersability can be calculated.
- Preferred film materials are preferably polymeric materials. The film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
- Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
- Mixtures of polymers and/or copolymers can also be used as the pouch material, especially mixtures of polyvinylalcohol polymers and/or copolymers, especially mixtures of polyvinylalcohol homopolymers and/or anionic polyvinylalcohol copolymers preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers. Most preferably the water soluble film comprises a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
- Preferred films exhibit good dissolution in cold water, meaning unheated distilled water. Preferably such films exhibit good dissolution at temperatures of 24°C, even more preferably at 10°C. By good dissolution it is meant that the film exhibits water-solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
- Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310.
- The film may be opaque, transparent or translucent. The film may comprise a printed area.
- The area of print may be achieved using standard techniques, such as flexographic printing or inkjet printing.
- The film may comprise an aversive agent, for example a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable level of aversive agent may be used in the film. Suitable levels include, but are not limited to, 1 to 5000ppm, or even 100 to 2500ppm, or even 250 to 2000rpm.
- Preferably, the water-soluble unit dose article comprises a water-soluble film, preferably wherein the water-soluble film comprises polyvinyl alcohol, preferably wherein the water-soluble film comprises polyvinyl alcohol polymer or copolymer, preferably a blend of polyvinylalcohol polymers and/or polyvinylalcohol copolymers, more preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, most preferably a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
- The term 'liquid laundry detergent composition' refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to, liquids, gels, pastes, dispersions and the like. The liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.
- In one aspect the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter.
- Those skilled in the art will know how to calculate the ionic strength. Without wishing to be bound by theory, Ionic Strength, IS, is a measure of ion concentration in a finished liquid detergent formulation. In this application ionic strength is calculated and the calculation is based in the Debye-Huckel theory of strong electrolytes:
where IS is ionic strength, weight % of species in a finished liquid detergent composition is weight percent of species from which an ion can be formed in the composition, MWs is molecular weight of a species from which an ion y can be formed, ny is number of ions, and qy is the charge of the ion in the composition under the pH of the finished liquid detergent composition, and liquid density is the density of the finished liquid detergent formulation. Only dissolved species in the finished liquid detergent formulation are considered in the calculation, e.g. suspended or dispersed actives are excluded. - For example ionic strength of a mixture of 1% sodium chloride and 1% sodium citrate at pH 9 can be calculated as follow (MWsodium chloride = 58, MWsodium citrate = 260) :
In another aspect of the present invention, the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant. - In another aspect, the liquid laundry detergent composition according to the present invention suitable for use in a water-soluble unit dose article, has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter and between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of the fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8. The fatty alcohol ethoxylate non-ionic surfactant is described in more detail below.
- The liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant.
- As commonly understood in the detergent field, chelation herein means the binding or complexation of a bi- or multidentate ligand. These ligands, which are often organic compounds, are called chelants, chelators, chelating agents, and/or sequestering agent. Chelating agents form multiple bonds with a single metal ion. Chelants, are chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale. The ligand forms a chelate complex with the substrate. The term is reserved for complexes in which the metal ion is bound to two or more atoms of the chelant.
- The chelant is preferably selected from the group consisting of amino carboxylates, amino phosphonates, polycarboxylates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, preferably selected from the group consisting of glutamic-N,N- diacetic acid (GLDA), methyl-glycine-diacetic acid (MGDA), Diethylenetriamine penta methylphosphonic acid (DTPMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), ethylenediaminetetra-acetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates (NTA), ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP), iminodisuccinic acid (IDS), Imino diacetic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), alanine-N,N-diacetic acid (ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid- N ,N - diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA), ethylenediamine disuccinate ("EDDS"), Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid, Hydroxyethylene diaminetriacetic acid, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, fumaric acid, citric acid, or a mixture thereof, most preferably the chelant is selected from the group consisting of glutamic-N,N- diacetic acid (GLDA), methyl-glycine-diacetic acid (MGDA) and derivatives thereof, and/or Diethylenetriamine penta methylphosphonic acid (DTPMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), and derivatives thereof, and mixtures thereof.
- Preferably, the liquid laundry detergent composition comprises between 0% and 15%, preferably between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant.
- The liquid laundry detergent composition may comprise less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of the chelant and between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of a fatty alcohol ethoxylate non-ionic surfactant, wherein the fatty alcohol ethoxylate preferably has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15 and wherein the fatty alcohol ethoxylate preferably has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- Suitable alcohol ethoxylate nonionic surfactants include the condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, substituted or unsubstituted. The starting alcohol can be naturally derived, e.g. starting from natural oils, or synthetically derived, e.g. alcohols obtained from for example oxo-, modified oxo- or Fischer-Tropsch processes. Examples of oxo-process derived alcohols include the Lial and Isalchem alcohols ex Sasol company and Lutensol alcohols ex BASF company. Examples of modified-oxo process derived alcohols include the Neodol alcohols ex Shell company. Fischer-Tropsch derived alcohols include Safol alcohols ex Sasol company. The alkoxylate chain of alcohol ethoxylates is made up solely of ethoxylate groups.
- Preferably, the fatty alcohol ethoxylate has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15.
- Preferably, the fatty alcohol ethoxylate has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- Suitable for use herein are the ethoxylated alcohol of the formula R(OC2H4)n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 22 carbon atoms and the average value of n is from about 5 to about 22. In one aspect, particularly useful materials are condensation products of C9-C16 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol. In another aspect, particularly useful materials are condensation products of C12-C16 alcohols with from about 6 to about 9 moles of ethylene oxide per mole of alcohol.
- Other non-limiting examples of nonionic surfactants may include: C12-C18 alkyl ethoxylates based on modified oxo alcohols, such as, NEODOL® nonionic surfactants from Shell; C12-C15 alkyl ethoxylates based on Fischer Tropsch Oxo alcohols, such as, SAFOL® nonionic surfactants from Sasol; C12-C18 alkyl ethoxylates based on natural or Ziegler alcohols, such as, Surfonic® nonionic surfactants from Huntsman; C14-C22 mid-chain branched alcohols ethoxylates, BAEx, wherein x is from 1 to 30.
- The liquid laundry detergent composition may comprise up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 35%, most preferably between 15% and 30% or even between 15% and 25% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant.
- The non-soap anionic surfactant may comprises a sulphate or a sulphonate anionic surfactant or a mixture thereof, preferably linear alkylbenzene sulphonate, alkyl sulphate, alkoxylated alkyl sulphate or a mixture thereof, more preferably a mixture of linear alkylbenzene sulphonate and alkoxylated alkyl sulphate. Preferably, the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate more preferably the ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more preferably from 1.3:1 to 5:1, most preferably from 1.4:1 to 3:1.
- Preferably, the alkoxylated alkyl sulphate is an ethoxylated alkyl sulphate with an average degree of ethoxylation of between 0.5 and 7, preferably between 1 and 5, more preferably between 2 and 4, most preferably about 3. Alternatively, the non-soap surfactant comprises a mixture of one or more alkoxylated alkyl sulphates, preferably ethoxylated alkyl sulphates, and optionally an alkyl sulphate, the mixture having an average degree of ethoxylation of between 0.5 and 7, preferably between 1 and 5, more preferably between 2 and 4, most preferably about 3. The alkyl sulphate and/or alkoxylated alkyl sulphate preferably have an alkyl chain comprising on average between 8 and 18 carbon atoms, preferably between 10 and 16 carbons atoms, most preferably between 12 and 14 carbon atoms. Most preferably the alkoxylated alkyl sulphate is an ethoxylated alkyl chain comprising on average between 12 and 14 carbon atoms in its alkyl chain and has an average degree of ethoxylation of about 3. The alkyl chain of the alkoxylated alkyl sulphate surfactant may be linear or branched or a mixture thereof.
- The linear alkylbenzene sulphonate may be a C10-C16 linear alkylbenzene sulphonate or a C11-C14 linear alkylbenzene sulphonate or a mixture thereof.
- Exemplary linear alkylbenzene sulphonates are C10-C16 alkyl benzene sulfonic acids, or C11-C14 alkyl benzene sulfonic acids. By 'linear', we herein mean the alkyl group is linear. Alkyl benzene sulfonates are well known in the art.
- Preferably, the weight ratio of non-soap anionic surfactant to fatty alcohol ethoxylate non-ionic surfactant is between 5:1 and 23:1 preferably between 7:1 and 23:1, more preferably between 8:1 and 23:1, most preferably between 9:1 and 20:1.
- Preferably the liquid laundry detergent composition comprises between 15% and 40%, preferably between 20% and 35%, more preferably between 25% and 30% by weight of the liquid laundry detergent composition of non-soap surfactant.
- The liquid laundry detergent composition may comprise less than 10%, preferably less than 8%, more preferably less than 5%, most preferably between 1% and 5% by weight of the liquid laundry detergent composition of fatty acid, neutralised fatty acid soap or a mixture thereof.
- The neutralised fatty acid soap may be alkali metal neutralised, amine neutralised or a mixture thereof. The alkali metal may be selected from sodium, potassium, magnesium or a mixture thereof, preferably sodium. The amine is preferably an alkanolamine, preferably selected from monethanolamine, diethanolamine, triethanolamine or a mixture thereof, more preferably monoethanolamine.
- The fatty acid, neutralised fatty acid soap or mixture thereof may be selected from palm kernel fatty acid, coconut fatty acid, rapeseed fatty acid, neutralized palm kernel fatty acid, neutralized coconut fatty acid, neutralized rapeseed fatty acid, or mixture thereof, preferably neutralized palm kernel fatty acid.
- The liquid laundry detergent composition may comprise between 0.1% and 10%, preferably between 0.5% and 8%, more preferably between 1% and 7%, even more preferably between 2% and 6%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of a soil release polymer, wherein the soil release polymer is preferably selected from polyester terephthalates, polyethylene glycol containing soil release polymers and a mixture thereof. An example of a preferred polyethyleneglycol containing soil release polymer comprises a polyethylene glycol graft polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, comprising 40% by weight of the polymer system of a polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains. Polyester terephtalate soil release polymers are commercially available from Clariant under the Texcare SRN and SRA tradenames. One particularly preferred polyester terephtalate soil release polymer is Texcare SRA300.
- The liquid laundry detergent composition may comprise a polyethyleneimine, preferably an alkoxylated polyethyleneimine, more preferably an ethoxylated polyethyleneimine and wherein preferably the liquid laundry detergent composition comprises greater than 0.5%, preferably between 1% and 10%, more preferably between 2% and 7%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of the polyethyleneimine, preferably ethoxylated polyethyleneimine. An example of an ethoxylated polyethyleneimine includes an ethoxylated polyethyleneimine with a polyethyleneimine backbone with a molecular weight of about 600, and comprising on average about 20 ethoxy units per ethoxylation chain.
- Preferably, the ratio of polyethyleneimine to soil release polymer, more preferably the ratio of ethoxylated polyethyleneimine to soil release polymer is higher than 1:1, preferably between 1.1:1 and 5:1, more preferably between 1.2:1 and 3:1, most preferably between 1.3:1 and 2:1.
- The liquid laundry detergent composition may comprise a polysaccharide polymer, a modified polysaccharide polymer, a polysaccharide derived polymer, or a mixture thereof, preferably a cellulosic polymer, a modified cellulosic polymer or a mixture thereof, most preferably a cationically modified cellulosic polymer or a mixture thereof. Most preferably the polysaccharide polymer is a cationically modified hydroethylcellulose ("Polyquaternium 10).
- Preferably, the water-soluble unit dose article comprises up to 60% preferably up to 50%, more preferably up to 40% by weight of the liquid laundry detergent composition of a non-aqueous solvent, preferably selected from propylene glycol, dipropylene glycol, glycerol, sorbitol, ethanol or a mixture thereof.
- Preferably, the liquid laundry detergent composition has a pH from 6 to 10 preferably from 7 to 9, more preferably from 7 to 8. Preferably, the liquid laundry detergent composition comprises a pH adjusting agent selected from alkanolamines, preferably monoethanolamine, diethanolamine, triethanolamine or a mixture thereof, most preferably monoethanolamine.
- Preferably, the liquid laundry detergent composition comprises an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments, amphoteric surfactants, cyclic diamines, zwitterionic polyamines, anti-oxidants, preservatives and mixtures thereof.
- Preferably, the water-soluble unit dose article comprises 15% or less by weight of the unit dose article of water, preferably the unit dose article comprises between 0.1% and 15%, more preferably between 1% and 12.5% by weight of the unit dose article of water.
- Those skilled in the art will know how to make the unit dose article and laundry detergent composition of the present invention using known techniques in the art.
- During manufacture, a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added. A second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region using known sealing means such as solvent, heat or a mixture thereof.
- The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
Claims (20)
- The use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article,
wherein the liquid laundry detergent composition has an ionic strength of less than 2Mol/Liter, preferably less than 1.5Mol/Liter, even more preferably less than IMol/Liter. - The use of a liquid laundry detergent composition comprised in a water-soluble unit dose article to provide laundry cleaning benefits and to minimize emesis effect, narcosis effect or a mixture thereof associated with accidental exposure to said liquid laundry detergent composition contained within the water-soluble unit dose article,
wherein the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant. - The use according to any preceding claims wherein the liquid laundry detergent composition comprises less than 3%, preferably less than 2.5%, more preferably less than 2%, even more preferably less than 1.5%, most preferably less than 1% by weight of the liquid laundry detergent composition of a chelant, and wherein the chelant is selected from the group consisting of amino carboxylates, amino phosphonates, polycarboxylates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, preferably selected from the group consisting of glutamic-N,N- diacetic acid (GLDA), methyl-glycine-diacetic acid (MGDA), Diethylenetriamine penta methylphosphonic acid (DTPMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), ethylenediaminetetra-acetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates (NTA), ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDS), Imino diacetic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2-sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), alanine-N,N-diacetic acid (ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA) , anthranilic acid- N ,N - diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA), ethylenediamine disuccinate ("EDDS"), Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid, Hydroxyethylene diaminetriacetic acid, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, fumaric acid, citric acid, or a mixture thereof, most preferably the chelant is selected from the group consisting of glutamic-N,N- diacetic acid (GLDA), methyl-glycine-diacetic acid (MGDA) and derivatives thereof, and/or Diethylenetriamine penta methylphosphonic acid (DTPMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP), and derivatives thereof, and mixtures thereof.
- The use according to any preceding claims, wherein the liquid laundry detergent composition comprises a fatty alcohol ethoxylate non-ionic surfactant and wherein the liquid laundry detergent composition comprises between 0% and 9.5%, preferably between 0.01% and 9%, more preferably between 0.1% and 7%, even more preferably between 1% and 5%, most preferably between 1% and 3% by weight of the liquid laundry detergent composition of the fatty alcohol ethoxylate non-ionic surfactant.
- The use according to claim 4 wherein the fatty alcohol ethoxylate has an average alkyl carbon chain length of between 5 and 30, preferably between 8 and 18, more preferably between 10 and 16, most preferably between 12 and 15.
- The use according to claims 4 or 5 wherein the fatty alcohol ethoxylate has an average degree of ethoxylation of between 0.5 and 20, preferably between 1 and 15, more preferably between 5 and 12, even more preferably between 6 and 10, most preferably between 7 and 8.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises up to 50%, preferably between 5% and 50%, more preferably between 7.5% and 45%, even more preferably between 10% and 40%, or even more preferably between 12% and 35%, most preferably between 15% and 30% or even between 15% and 25% by weight of the liquid laundry detergent composition of a non-soap anionic surfactant.
- The use according to claim 7 wherein the non-soap anionic surfactant comprises linear alkylbenzene sulphonate, alkoxylated alkyl sulphate or a mixture thereof, more preferably a mixture thereof wherein the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate preferably the ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from 1:2 to 20:1, preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more preferably from 1.3:1 to 5:1, most preferably from 1.4:1 to 3:1.
- The use according to claims 4 to 8 wherein the weight ratio of non-soap anionic surfactant to fatty alcohol ethoxylate non-ionic surfactant is between 5:1 and 23:1 preferably between 7:1 and 23:1, more preferably between 8:1 and 23:1, most preferably between 9:1 and 20:1.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises less than 10%, preferably less than 8%, more preferably less than 5%, most preferably between 1% and 5% by weight of the liquid laundry detergent composition of fatty acid, neutralised fatty acid soap or a mixture thereof.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises between 0.1% and 10%, preferably between 0.5% and 8%, more preferably between 1% and 7%, even more preferably between 2% and 6%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of a soil release polymer, wherein the soil release polymer is preferably selected from polyester terephthalates, polyethylene glycol containing soil release polymers and a mixture thereof.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises a polyethyleneimine, preferably an ethoxylated polyethyleneimine and wherein preferably the liquid laundry detergent composition comprises greater than 0.5%, preferably between 1% and 10%, more preferably between 2% and 7%, most preferably between 3% and 5% by weight of the liquid laundry detergent composition of the polyethyleneimine, preferably ethoxylated polyethyleneimine.
- The use according to any of claims 11-12 wherein the ratio of polyethyleneimine to soil release polymer, preferably the ratio of ethoxylated polyethyleneimine to soil release polymer is higher than 1:1, preferably between 1.1:1 and 5:1, more preferably between 1.2:1 and 3:1, most preferably between 1.3:1 and 2:1.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises a polysaccharide polymer, a modified polysaccharide polymer, a polysaccharide derived polymer, or a mixture thereof, preferably a cellulosic polymer, a modified cellulosic polymer or a mixture thereof, most preferably a cationically modified cellulosic polymer or a mixture thereof.
- The use according to any preceding claims wherein the water-soluble unit dose article comprises a water-soluble film, preferably wherein the water-soluble film comprises polyvinyl alcohol, preferably wherein the water-soluble film comprises polyvinyl alcohol polymer or copolymer, preferably a blend of polyvinylalcohol polymers and/or polyvinylalcohol copolymers, preferably selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers especially carboxylated anionic polyvinylalcohol copolymers, most preferably a blend of a polyvinylalcohol homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
- The use according to any preceding claims wherein the water-soluble unit dose article comprises up to 60% preferably up to 50%, more preferably up to 40% by weight of the liquid laundry detergent composition of a non-aqueous solvent, preferably selected from propylene glycol, dipropylene glycol, glycerol, sorbitol, ethanol or a mixture thereof.
- The use according to any preceding claims wherein the liquid laundry detergent composition has a pH from 6 to 10 preferably from 7 to 9, more preferably from 7 to 8, preferably wherein the liquid laundry detergent composition comprises a pH adjusting agent selected from alkanolamines, preferably monethanolamine, diethanolamine, triethanolamine or a mixture thereof, most preferably monoethanolamine.
- The use according to any preceding claims wherein the liquid laundry detergent composition comprises an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments, amphoteric surfactants, cyclic diamines, zwitterionic polyamines, anti-oxidants, preservatives and mixtures thereof.
- The use according to any preceding claims wherein accidental exposure is a consequence of the water-soluble unit dose article accidentally prematurely rupturing and at least part of the liquid laundry detergent composition is ingested.
- The use according to any preceding claims wherein the water-soluble unit dose article comprises at least two compartments and the liquid laundry detergent composition is comprised in at least one compartment, preferably wherein the water-soluble unit dose article comprises at least two compartments of different sizes and the liquid laundry detergent composition is comprised in at least the larger compartment.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201762461369P | 2017-02-21 | 2017-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3363889A1 true EP3363889A1 (en) | 2018-08-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18157949.1A Withdrawn EP3363889A1 (en) | 2017-02-21 | 2018-02-21 | Use of liquid laundry detergent composition to minimize adverse effects upon accidental exposure to contents of water-soluble unit dose articles |
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| Country | Link |
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| EP (1) | EP3363889A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210277339A1 (en) * | 2018-11-23 | 2021-09-09 | Henkel Ag & Co. Kgaa | Cleaning Agent Having Clear Rinser For Automatic Dosing Unit |
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| US20160060574A1 (en) * | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Method of treating a fabric |
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| US20160340619A1 (en) * | 2015-05-22 | 2016-11-24 | The Procter & Gamble Company | Surfactant and detergent compositions containing propoxylated glycerine |
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2018
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| US20150065410A1 (en) * | 2012-05-16 | 2015-03-05 | Henkel Ag & Co. Kgaa | Low-water-content, liquid detergent comprising surfactants obtained from renewable raw materials |
| US20160060574A1 (en) * | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Method of treating a fabric |
| WO2016155993A1 (en) | 2015-04-02 | 2016-10-06 | Unilever Plc | Composition |
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| US20210277339A1 (en) * | 2018-11-23 | 2021-09-09 | Henkel Ag & Co. Kgaa | Cleaning Agent Having Clear Rinser For Automatic Dosing Unit |
| US12252668B2 (en) * | 2018-11-23 | 2025-03-18 | Henkel Ag & Co. Kgaa | Cleaning agent having clear rinser for automatic dosing unit |
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