EP4041853A1 - Detergent composition - Google Patents
Detergent compositionInfo
- Publication number
- EP4041853A1 EP4041853A1 EP20788776.1A EP20788776A EP4041853A1 EP 4041853 A1 EP4041853 A1 EP 4041853A1 EP 20788776 A EP20788776 A EP 20788776A EP 4041853 A1 EP4041853 A1 EP 4041853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- laundry detergent
- composition according
- datem
- acid
- 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.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the present invention concerns a laundry detergent composition. More particularly a laundry detergent composition comprising a surfactant which is a diacetyltartaric acid ester of monoglyceride and diglyceride.
- Diacetyltartaric acid esters of monoglyceride and diglyceride are emulsifiers used in food processing, for example to strengthen the gluten network in dough thereby increase the volume of the baked bread. They are produced from animal and plant-based ingredients.
- the invention relates in a first aspect to a laundry detergent composition
- a laundry detergent composition comprising: a) from 5 to 50 wt.%, preferably from 5 to 40 wt.%, more preferably from 6 to 30 wt.% of diacetyltartaric acid esters of monoglyceride and diglyceride (DATEM); b) from 0.0001 to 5 wt.% of further laundry ingredients selected from perfumes, protease enzymes, amylase enzymes, cellulase enzymes and preservatives; and, c) from 0.5 to 40 wt.%, more preferably from 1 to 30 wt.% of an anionic surfactant; wherein the preservative, if present, prevents bacterial, mold or fungal growth.
- DATEM diacetyltartaric acid esters of monoglyceride and diglyceride
- the present invention provides a domestic method of treating a textile, the method comprising the steps of> a) treating a textile with an aqueous solution of 0.15 to 20 g/L, more preferably 1 to 10g/L of the detergent composition according to the first aspect of the invention; b) optionally rinsing and drying the textile.
- the laundry detergent composition is a liquid, gel or a powder, more preferably the detergent is a liquid detergent, most preferably an aqueous liquid laundry detergent.
- the fatty acid chain component of the diacetyltartaric acid esters of monoglyceride and diglyceride is a linear or branched, preferably linear, saturated or monounsaturated chain, and contains from 12 to 20 carbon atoms, more preferably from 14 to 18 carbon atoms, most preferably from 16 to 18 carbon atoms.
- the fatty acid chain component is preferably selected from palmitic, cis and trans palmitoleic, stearic, oleic and elaidic, most preferably oleic and elaidic.
- the diacetyltartaric acid esters of monoglyceride and diglyceride is a diacetyltartaric acid ester of monoglyceride and more preferably contains from 1 to 2 mole average of diacetyltartaric acid per mole of diacetyltartaric acid esters of monoglyceride.
- the laundry detergent composition comprises an nonionic surfactant selected from saturated and mono-unsaturated aliphatic alcohol ethoxylates, fatty acid methyl esters ethoxylates, and saturated and mono-unsaturated fatty acid sugar esters; preferably the non-ionic surfactant is saturated and mono-unsaturated aliphatic alcohol ethoxylates, preferably selected from Ci2to C20 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably C16 to Cis with an average of from 6 to 20 ethoxylates.
- the laundry detergent composition comprises an anionic surfactant selected from: rhamnolipids, C12 to Cis alkyl ether carboxylate and water-soluble alkali metal salts of organic sulphates, ether sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms.
- anionic surfactant selected from: rhamnolipids, C12 to Cis alkyl ether carboxylate and water-soluble alkali metal salts of organic sulphates, ether sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms.
- Preferred examples of such surfactants are methyl ester sulfonates, linear alkyl benzene sulfonate, dodecyl sulfate and laureth sulfate.
- the laundry detergent preferably comprises from 0.1 to 8 wt.% more preferably from 0.2 to 6 wt.%, most preferably from 0.5 to 5 wt.% of an alkoxylated polyamine.
- the alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine, more preferably the alkoxylation is ethoxylation or propoxylation or a mixture of both.
- the laundry detergent composition preferably comprises from 0.1 to 8 wt.%, more preferably from 0.2 to 6 wt.%, most preferably from 0.5 to 5 wt.% of a soil release polymer, preferably a polyester soil release polymer.
- the laundry detergent composition comprises one or more enzymes further enzymes selected from the group: lipases, peroxidases/oxidases, pectate lyases, and/or mannanases.
- the laundry detergent composition when a liquid detergent has a viscosity greater than or equal to 1 cP (centipoise), preferably from 1 to 6000 cP, more preferably from 200 to 1000 cP, said viscosity measured at a shear rate of 21 s-1 and at a temperature of 25°C on any commercial stress rheometer, available for example from Anton Paar or Malvern.
- This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
- the pH of the formulation when dissolved at 2g/L in demineralised water at 20°C is from pH 3 to 10, preferably from 4 to 8, more preferably 6.5 to 7.5.
- indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
- the formulation may be in any form for example a liquid, solid, powder, liquid unit dose.
- Hard water is termed herein where water hardness as classified by degrees of French Hardness is 20°fH (degrees French Hardness or greater).
- Diacetyltartaric acid esters of monoglyceride and diglyceride (DATEM) Diacetyltartaric acid esters of monoglyceride and diglyceride (DATEM) are discussed in in Hasenhuettl, G.L and Hartel, R.W. (Eds) Food Emulsifiers and Their Application 2008 (Springer), and in Whitehurst, R.J. (Ed) Emulsifiers in Food Technology 2008 (Wiley-VCH) and in the 2nd edition of this book edited by V. Norn 2015 (Wiley-Blackwell). DATEM are also discussed in WO/2014/184079.
- DATEM preferably of the form:
- Ri, R 2 , and R 3 are selected from the remainder of Ri, R 2 , and R 3 being OX, where X is H or CH 3 CO.
- the DATEM contains one fatty acid chain groups.
- Weights of the DATEM are for the protonated form.
- the fatty acid chains are of the formula R 4 COO- where R 4 is a linear saturated or unsaturated C 7 to C 21 alkyl chain.
- the fatty acid chain component of the DATEM is linear and contains 12 to 20 carbon atoms, more preferably from 14 to 18 carbon atoms, most preferably from 16 to 18 carbon atoms.
- the fatty acid chain is saturated or mono-unsaturated.
- the fatty acid chain component is preferably selected from palmitic, cis and trans palmitoleic, stearic, oleic and elaidic. Most preferably oleic and elaidic.
- Natural fatty acids may be derived from the triglycerides of naturally occurring fats or oils such as rapeseed oil, castor oil, maize oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, sunflower oil, non-edible vegetable oils, tall oil and any mixture thereof and any derivative thereof.
- the oil from trees is called tall oil. Used food cooking oils may be uitiised.
- the fatty acid chain component may be in either the 1 -position or the 2- position of the glycerol.
- Non edible vegetable oils are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L (castor), Simmondsia chinensis (Jojoba), Eruca sativa.
- the triglyceride is hydrogenated to removed polyunsaturated alkyl chains such as linoleic and linoleneic acid.
- Preferred plant sources of oils are palm, rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees, most preferably from rapeseed oil or a derivative thereof.
- the DATEM preparation may be obtained by the reaction of an esterification reaction between the diacetyltartaric acid and glycerides selected from mono-, di-glyceride and triglycerides, preferably mono-glycerides or more preferably by the reaction of diacetyltartaric acid anhydride with a distilled monoglyceride.
- the tartaric acid is preferably obtained from lees (precipitates of dead and residual yeast and other particles that precipitate, or are carried by the action of "fining", to the bottom of a vat of wine after fermentation and aging).
- the acetic anhydride used to make the diacetyltartaric acid anhydride preferably comes from natural fermented acetic acid, or by oxidation of methanol where the methanol is obtained from CO produced by burning of biomass.
- the DATEM can contain 100% of it carbons from natural (non-petrochemical) sources.
- the DATEM preparation preferably contains at least 40% (wt/wt) of a di acetyl tartaric acid ester of a mono-glycerides, preferably at least 70% (wt/wt), more preferably at least 85% (wt/wt), even more preferably at least 90% (wt/wt), and most preferably at least 95% (wt/wt).
- the ratio of (wt.% of diacetyltartaric acid ester of monoglyceride)/(wt.% of diacetyltartaric acid ester of diglyceride) is greater than 1 , more preferably greater than 2, most preferably greater than 4.
- the DATEM preparation comprising carboxylic acid esters of mono- and di-glycerides may furthermore comprise impurities such as triglycerides, diglycerides, monoglycerides and tartaric acids, diacetyltartaric acid esterified to glycerol, glycerol and free fatty acids.
- impurities such as triglycerides, diglycerides, monoglycerides and tartaric acids, diacetyltartaric acid esterified to glycerol, glycerol and free fatty acids.
- the level of these impurities is less than 30 wt.% of the DATEM preparation.
- the sum of the level of triglyceride, diglyceride and monoglycerides is less than 10 wt.%, more preferably less than 5 wt.%, most preferably less than 1 wt.% of the DATEM preparation.
- the DATEM preparation may contain polyglycerol esters, where the polyglycerol moiety is predominantly di-, tri- and tetraglycerol and contains not more than 10% of polyglycerols equal to or higher than heptaglycerol.
- the reaction mixture Prior to and/or during the reaction to form the DATEM, the reaction mixture may advantageously be covered with an inert gas such as nitrogen or place under a vacuum.
- an inert gas such as nitrogen or place under a vacuum.
- the water being released during the reaction may continuously be removed from the reaction mixture by evaporating and condensing the water vapour or by placing under a vacuum.
- the composition preferably comprises a perfume, preferably at a level of 0.05 to 2 wt.%.
- a perfume preferably at a level of 0.05 to 2 wt.%.
- CTFA Cosmetic, Toiletry and Fragrance Association
- OPD Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
- the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; pentanoic acid, 2- methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1 , 1 -dimethylethyl)-, 1 -acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2- phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylen
- Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour Chemicals by S. Arctander 1969, Montclair, N.J. (USA).
- compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
- top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).
- Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
- the Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
- Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
- perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (ie. those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0.
- these materials have been called the "delayed blooming" perfume ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethy
- compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
- perfumes with which the present invention can be applied are the so-called ‘aromatherapy 1 materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium,
- a protease enzyme is preferably present at a level of 0.0001 to 0.01 wt.%.
- Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
- suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred.
- subtilases refers to a sub-group of serine protease according to Siezen et al. , Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.
- Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
- the subtilases may be divided into 6 sub divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
- subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD138 described in (WO 93/18140).
- Bacillus lentus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus lichen
- proteases may be those described in WO 92/175177, WO 01/016285, WO 02/026024 and WO 02/016547.
- trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.
- protease is a subtilase (EC 3.4.21.62).
- subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and W009/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140).
- the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis,
- subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
- Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
- An amylase enzyme is preferably present at a level of 0.0001 to 0.01 wt.%.
- Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha- amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060.
- amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
- a cellulase enzyme is preferably present at a level of 0.0001 to 0.01 wt.%.
- Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
- CelluzymeTM Commercially available cellulases include CelluzymeTM, CarezymeTM, Celluclean TM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation). CellucleanTM is preferred.
- Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 Preservatives
- a polyol such as propylene glycol or glycerol
- a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
- a preservative is preferably present in the formulation to prevent bacterial, mold or fungal growth.
- the composition comprises from 0.0001 to 1 wt.%, preferably from 0.001 to 0.5 wt.%, more preferably from 0.001 to 0.25 wt.% of a preservative.
- preservatives examples include isothiazolinone preservatives.
- the preferred isothiazolinone preservatives are benzisothiazolinone and/or methylisothiazolinone.
- the formulation may contain further ingredients.
- Further surfactant may be present at a preferable level of from 0.5 to 40 wt.%, more preferably from 1 to 30 wt.%.
- the surfactants are preferably readily biodegradable, according to OECD301.
- the composition may preferably comprise nonionic surfactant.
- the non-ionic surfactant is selected from saturated and mono-unsaturated aliphatic alcohol ethoxylates, fatty acid methyl esters ethoxylates, and saturated and mono-unsaturated fatty acid sugar esters; preferably the non-ionic surfactant is saturated and mono-unsaturated aliphatic alcohol ethoxylates, preferably selected from Ci2to C20 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably C16 to C18 with an average of from 6 to 20 ethoxylates.
- the formulation may comprise anionic detergent compounds which preferably are: rhamnolipids; C12 to C18 alkyl ether carboxylate and water-soluble alkali metal salts of organic sulphates, ether sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
- anionic detergent compounds which preferably are: rhamnolipids; C12 to C18 alkyl ether carboxylate and water-soluble alkali metal salts of organic sulphates, ether sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
- Preferred examples of such surfactants are methyl ester sulfonates, linear alkyl benzene sulfonate, dodecyl sulfate and
- anionic detergent compounds are: sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates and alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
- these are present at lower levels than the DATEM material.
- the weight fraction of further anionic surfactant/DATEM is from 0.10 to 0.7, more preferably 0.15 to 0.45.
- surfactants used are saturated or mono-unsaturated.
- an anti-oxidant may be present in the formulation.
- Soil release polymer It is preferred that a soil release polymer is included.
- the laundry detergent composition preferably comprises from 0.1 to 8 wt.% of a soil release polymer.
- Preferred levels of soil release polymer range from 0.2 to 6 wt.%, more preferably from 0.5 to 5 wt.%, most preferably from 1 to 5 wt.%.
- the soil release polymer is a polyester soil release polymer.
- polyester soil release polymer is a polyethylene and/or polypropylene terephthalate based soil release polymer, most preferably a polypropylene terephthalate based soil release polymer.
- polyester based soil release polymers are described in WO 2014/029479 and WO 2016/005338.
- the polyester based soil release polymer is a polyester according to the following formula (I) wherein R 1 and R 2 independently of one another are X-(OC2H4) n -(OC3H6) m wherein X is C1-4 alkyl and preferably methyl, the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6), and preferably are independently of one another X-(OC2H 4 )n-(OC3H6)m, n is based on a molar average number of from 12 to 120 and preferably of from 40 to 50, m is based on a molar average number of from 1 to 10 and preferably of from 1 to 7, and a is based on a molar average number of from 4 to 9.
- polyester provided as an active blend comprising:
- the detergent composition is in the form of a laundry composition, it is preferred that an alkoxylated polyamine is included.
- the laundry detergent preferably comprises from 0.1 to 8 wt.% of an alkoxylated polyamine.
- Preferred levels of alkoxylated polyamine range from 0.2 to 6 wt.%, more preferably from 0.5 to 5 wt.%. Another preferred level is from 1 to 4 wt.%.
- the alkoxylated polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer.
- the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both.
- the alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine, more preferably the alkoxylation is ethoxylation or propoxylation or a mixture of both.
- a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25.
- a preferred material is alkoxylated polyethylenimine, most preferably ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30 preferably from 15 to 25, where a nitrogen atom is ethoxylated.
- Additional enzymes other than the specified protease, amylase or cellulase may be present in the detergent composition. It is preferred that additional enzymes are present in the preferred laundry detergent composition. If present, then the level of each enzyme in the laundry composition of the invention is from 0.0001 wt.% to 0.1 wt.%.
- Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein.
- Preferred further enzymes include those in the group consisting of: lipases, peroxidases/oxidases, pectate lyases, and/or mannanases. Said preferred additional enzymes include a mixture of two or more of these enzymes.
- the further enzyme is a lipase.
- Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa ( T . lanuginosus) as described in EP 258 068 and EP 305216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P.
- lipase variants such as those described in WO 92/05249,
- Preferred commercially available lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM and Lipoclean TM (Novozymes A/S).
- phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
- phospholipase is an enzyme which has activity towards phospholipids.
- Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
- Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
- phospholipases Ai and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
- lysophospholipase or phospholipase B
- Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
- the composition may use cutinase, classified in EC 3.1.1.74.
- the cutinase used according to the invention may be of any origin.
- Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
- Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
- the aqueous solution used in the method preferably has an enzyme present.
- the enzyme is preferably present in the aqueous solution used in the method at a concentration in the range from 0.01 to 10ppm, preferably 0.05 to 1ppm.
- Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
- stabilizing agents e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/197
- Chelating agents may be present or absent from the detergent compositions.
- the detergent compositions described herein may also contain one or more metal ion chelating agents beyond the citric acid compounds concomitant with the citric acid ester of the monoglyceride.
- Suitable molecules include copper, iron and/or manganese chelating agents and mixtures thereof.
- chelating agents can be selected from the group consisting of phosphonates, amino carboxylates, amino phosphonates, succinates, polyfunctionally-substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, and mixtures thereof.
- Chelating agents can be present in the acid or salt form including alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.
- Aminocarboxylates useful as chelating agents include, but are not limited to ethylenediaminetetracetates (EDTA); N-(hydroxyethyl)ethylenediaminetriacetates (HEDTA); nitrilotriacetates (NTA); ethylenediamine tetraproprionates; triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates (DTPA); methylglycinediacetic acid (MGDA); Glutamic acid diacetic acid (GLDA); ethanoldiglycines; triethylenetetraaminehexaacetic acid (TTHA); N-hydroxyethyliminodiacetic acid (HEIDA); dihydroxyethylglycine (DHEG); ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof.
- EDTA ethylenediaminetetracetates
- HEDTA N-(hydroxyethyl)ethylenediaminetriacetates
- NTA ni
- Phosphorus containing chelants include, but are not limited to diethylene triamine penta (methylene phosphonic acid) (DTPMP CAS 15827-60-8); ethylene diamine tetra(methylene phosphonic acid) (EDTMP CAS 1429-50-1); 2-Phosphonobutane 1,2,4-tricarboxylic acid (Bayhibit® AM); hexamethylene diamine tetra(methylene phosphonic acid) (CAS 56744-47- 9); hydroxy-ethane diphosphonic acid (HEDP CAS 2809-21-4); hydroxyethane dimethylene phosphonic acid; 2-phosphono- 1,2,4-Butanetricarboxylic acid (CAS 37971-36-1); 2-hydroxy- 2-phosphono-Acetic acid (CAS 23783-26-8); Aminotri(methylenephosphonic acid) (ATMP CAS 6419-19-8); P,P'-(1,2-ethanediyl)bis-Phosphonic acid (CAS 6145-31
- a biodegradable chelator that may also be used herein is ethylenediamine disuccinate (“EDDS”).
- EDDS ethylenediamine disuccinate
- the trisodium salt of EDDA may be used, though other forms, such as magnesium salts, may also be useful.
- Polymeric chelants such as Trilon P® from BASF may also be useful.
- Polyfunctionally-substituted aromatic chelating agents may also be used in the cleaning compositions.
- Compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene, also known as Tiron.
- Other sulphonated catechols may also be used.
- the term “tiron” may also include mono- or di sulfonate salts of the acid, such as, for example, the disodium sulfonate salt, which shares the same core molecular structure with the disulfonic acid.
- Suitable chelating agents for use herein are the commercial DEQUEST series, and chelants from Monsanto, Akzo-Nobel, DuPont, Dow, the Trilon® series from BASF and Nalco.
- the chelant may be present in the detergent compositions disclosed herein at from about 0.005% to about 15% by weight, about 0.01% to about 5% by weight, about 0.1% to about 3.0% by weight, or from about 0.2% to about 0.7% by weight, or from about 0.3% to about 0.6% by weight of the detergent compositions disclosed herein.
- the chelating agent is present at a level of from 0.01 to 5 wt.%.
- the composition preferably contains less than 1 wt.% of phosphorous containing materials.
- composition may contain alkoxylated polycarboxyl ic acid esters as described in WO/2019/008036 and WO /2019/007636.
- the composition may comprise a builder.
- Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
- calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
- precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
- Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are well known representatives thereof, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
- zeolites are well known representatives thereof, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
- the composition may also contain 0-65 wt.% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
- a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
- Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
- Zeolite and carbonate are preferred builders, with carbonates being particularly preferred.
- the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt.%.
- Aluminosilicates are materials having the general formula:
- the preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
- the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
- phosphate builders may be used.
- phosphate embraces diphosphate, triphosphate, and phosphonate species.
- Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
- the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate. Most preferably the laundry detergent formulation is not built i.e. contain less than 1 wt.% of builder.
- the detergent composition is an aqueous liquid laundry detergent it is preferred that mono propylene glycol is present at a level from 1 to 30 wt.%, most preferably 2 to 18 wt.%, to provide the formulation with appropriate, pourable viscosity.
- the composition preferably comprises a fluorescent agent (optical brightener).
- Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
- the total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt.%, preferably 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.
- Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
- Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31-5; CAS-No 4193-55-9; CAS-No 16090- 02-1; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41-8.
- fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2- yl)]amino ⁇ stilbene-2-2' disulphonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1 ,3,5-triazin- 2-yl)]amino ⁇ stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
- Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wley-VCH Weinheim 2003).
- Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol 1 cm -1 , preferably greater than 10000 L mol 1 cm 1 .
- Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane.
- Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
- Azine dyes preferably carry a net anionic or cationic charge.
- Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric.
- the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300.
- the white cloth used in this test is bleached non-mercerised woven cotton sheeting.
- Shading dyes are discussed in W02005/003274, W02006/032327(Uni lever), W02006/032397(Unilever), W02006/045275(Unilever), WO 2006/027086(Unilever), W02008/017570(Unilever), WO 2008/141880(Unilever), W02009/132870(Uni lever),
- WO 2009/141173 (Unilever), WO 2010/099997(Unilever), WO 2010/102861 (Unilever), WO 2010/148624(Unilever), W02008/087497 (P&G), WO2011/011799 (P&G), W02012/054820 (P&G), WO2013/142495 (P&G), W02013/151970 (P&G), W02018/085211 (P&G), and WO2019/075149 (P&G).
- shading dyes may be used.
- the shading dye chromophore is most preferably selected from mono-azo, bis-azo and azine.
- Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
- Bis-azo dyes are preferably sulphonated bis-azo dyes.
- Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 66, direct violet 99 and alkoxylated versions thereof.
- Alkoxylated bis-azo dyes are discussed in W02012/054058 and WO/2010/151906.
- An example of an alkoxylated bis-azo dye is :
- Azine dyes are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from: wherein:
- X 3 is selected from: -H; -F; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and, -OC 2 H 5 ;
- X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;
- Y 2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH 2 OH; -0C(0)CH 3 ; and, C(0)0CH 3.
- Anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine may be used as described in WO2011/047987 and WO 2012/119859.
- the shading dye is preferably present in the composition in range from 0.0001 to 0.1 wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is preferably a blue or violet shading dye.
- the composition may comprise one or more further polymers.
- suitable polymers are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
- alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains.
- the alkyl groups are preferably linear or branched, most preferably linear.
- the detergent compositions optionally include one or more laundry adjunct ingredients.
- amalgamate ingredient includes: perfumes, dispersing agents, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odour control agent, pro perfumes, cyclodextrin, perfume, solvents, soil release polymers, preservatives, antimicrobial agents, chlorine scavengers, anti-shrinkage agents, fabric crisping agents, spotting agents, anti-oxidants, anti-corrosion agents, bodying agents, drape and form control agents, smoothness agents, static control agents, wrinkle control agents, sanitization agents, disinfecting agents, germ control agents, mould control agents, mildew control agents, antiviral agents, antimicrobials, drying agents, stain resistance agents, soil release agents, malodour control agents, fabric refreshing agents, chlorine bleach odour control agents, dye fixatives, dye transfer inhibitors, shading dyes, colour maintenance agents, colour restoration, rejuvenation agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear
- indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
- Diacetyltartaric acid ester of monoglyceride were dissolved in 24 degree French hard water to give a 0.3g/L solution.
- the diacetyltartaric acid esters were provided by a commercial DATEM (Panodan® 517 ex DuPont). 800ml of the solution was used to wash four 5x5cm EMPA 117 stain monitor (blood/milk/ink stain on polycotton) in a tergotometer set at 100rpm.
- the wash is equivalent to dosing 6g/L of a laundry treatment composition containing 10 wt.% of surfactant and 0.001 wt.% preservative.
- the wash took 60 minutes at a temperature of 30oC.
- the wash was repeated using water alone.
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19201647 | 2019-10-07 | ||
| PCT/EP2020/078157 WO2021069516A1 (en) | 2019-10-07 | 2020-10-07 | Detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP4041853A1 true EP4041853A1 (en) | 2022-08-17 |
| EP4041853B1 EP4041853B1 (en) | 2023-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20788776.1A Active EP4041853B1 (en) | 2019-10-07 | 2020-10-07 | Detergent composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP4041853B1 (en) |
| CN (1) | CN114502705A (en) |
| AR (1) | AR120142A1 (en) |
| BR (1) | BR112022006544A2 (en) |
| WO (1) | WO2021069516A1 (en) |
| ZA (1) | ZA202202881B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4630526A1 (en) | 2022-12-05 | 2025-10-15 | The Procter & Gamble Company | Fabric and home care composition comprising a polyalkylenecarbonate compound |
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| US20120101018A1 (en) | 2010-10-22 | 2012-04-26 | Gregory Scot Miracle | Bis-azo colorants for use as bluing agents |
| WO2011011799A2 (en) | 2010-11-12 | 2011-01-27 | The Procter & Gamble Company | Thiophene azo dyes and laundry care compositions containing the same |
| CN103429670B (en) | 2011-03-10 | 2016-01-27 | 荷兰联合利华有限公司 | Dye polymer |
| WO2013142495A1 (en) | 2012-03-19 | 2013-09-26 | Milliken & Company | Carboxylate dyes |
| EP2834340B1 (en) | 2012-04-03 | 2016-06-29 | The Procter and Gamble Company | Laundry detergent composition comprising water-soluble phthalocyanine compound |
| DE102012016462A1 (en) | 2012-08-18 | 2014-02-20 | Clariant International Ltd. | Use of polyesters in detergents and cleaners |
| GB201308502D0 (en) | 2013-05-13 | 2013-06-19 | Dupont Nutrition Biosci Aps | Composition |
| EP2966160A1 (en) | 2014-07-09 | 2016-01-13 | Clariant International Ltd. | Storage-stable compositions comprising soil release polymers |
| CN105647690A (en) * | 2016-02-03 | 2016-06-08 | 朱仕龙 | Detergent for fruits and production technology thereof |
| CN107779306A (en) * | 2016-08-31 | 2018-03-09 | 吕红林 | A kind of fruits and vegetables detergent containing cumquat extract |
| WO2018085211A1 (en) | 2016-11-03 | 2018-05-11 | Temple University-Of The Commonwealth System Of Higher Education | Broadband and tunable organic-inorganic hybrid short-wave infrared materials |
| EP3649222B1 (en) | 2017-07-07 | 2024-03-13 | Unilever IP Holdings B.V. | Whitening composition |
| EP3424976A1 (en) | 2017-07-07 | 2019-01-09 | Clariant International Ltd | Alkoxylated polycarboxylic acid esters |
| EP3694969B1 (en) | 2017-10-12 | 2021-08-18 | The Procter & Gamble Company | Laundry care compositions comprising leuco compounds |
| EP3546559A1 (en) | 2018-03-28 | 2019-10-02 | The Procter & Gamble Company | Laundry detergent composition |
| EP3853338B1 (en) * | 2018-09-18 | 2022-08-17 | Unilever Global Ip Limited | Detergent composition |
| CN112805362A (en) * | 2018-09-18 | 2021-05-14 | 联合利华知识产权控股有限公司 | Detergent composition |
| CN112955531A (en) * | 2018-09-18 | 2021-06-11 | 联合利华知识产权控股有限公司 | Detergent composition |
-
2020
- 2020-10-02 AR ARP200102737A patent/AR120142A1/en active IP Right Grant
- 2020-10-07 CN CN202080069080.XA patent/CN114502705A/en active Pending
- 2020-10-07 EP EP20788776.1A patent/EP4041853B1/en active Active
- 2020-10-07 WO PCT/EP2020/078157 patent/WO2021069516A1/en not_active Ceased
- 2020-10-07 BR BR112022006544A patent/BR112022006544A2/en not_active Application Discontinuation
-
2022
- 2022-03-09 ZA ZA2022/02881A patent/ZA202202881B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP4041853B1 (en) | 2023-02-22 |
| AR120142A1 (en) | 2022-02-02 |
| ZA202202881B (en) | 2023-11-29 |
| CN114502705A (en) | 2022-05-13 |
| WO2021069516A1 (en) | 2021-04-15 |
| BR112022006544A2 (en) | 2022-06-28 |
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