WO2019075684A1 - CLEANING COMPOSITIONS CONTAINING FATTY ACID MIXTURE - Google Patents
CLEANING COMPOSITIONS CONTAINING FATTY ACID MIXTURE Download PDFInfo
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- WO2019075684A1 WO2019075684A1 PCT/CN2017/106819 CN2017106819W WO2019075684A1 WO 2019075684 A1 WO2019075684 A1 WO 2019075684A1 CN 2017106819 W CN2017106819 W CN 2017106819W WO 2019075684 A1 WO2019075684 A1 WO 2019075684A1
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- Prior art keywords
- weight
- composition
- cleaning composition
- laundry detergent
- suds
- Prior art date
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- 229920002451 polyvinyl alcohol 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
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000001509 sodium citrate 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
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the present invention concerns cleaning compositions, preferably granular laundry detergent compositions.
- Sudsing profile of a detergent composition which includes but is not limited to: the speed and volume of suds generated upon dissolving the detergent composition in a washing solution, look and feel of the suds so generated, retention of suds during the wash cycle, and easiness in rinsing the suds off during the rinse cycle, is particularly important for consumers who still hand wash their garments and fabrics, because their laundering experience is directly impacted thereby.
- Linear alkylbenzene sulphonate is one of the most commonly used anionic surfactants in laundry detergents. Although sufficient cleaning can be achieved by using detergent compositions with relatively lower levels of LAS, e.g., 20 wt%or less, the volume of suds generated by such detergent compositions is significantly reduced, which will inevitably be perceived by the consumers as insufficient cleaning and in turn correlated with inferior quality of the laundry detergents used. In order to avoid such negative consumer perception, one or more co-surfactants can be added into the detergent compositions to boost suds volume during the wash cycle.
- LAS Linear alkylbenzene sulphonate
- MCAS Mid-cut alkyl sulphate
- WO2009010911 discloses the use of MCAS for boosting suds in a LAS-based surfactant system and forming a detergent composition with a reduced total surfactant level, but without apparently deteriorating the sudsing profile of the detergent composition.
- WO2009149276 discloses a detergent composition containing a specific surfactant system formed of LAS and MCAS with relatively low levels of inorganic builders, such as aluminosilicates and phosphates, while such detergent composition exhibits improved sudsing property while maintaining the cleaning properties of the composition.
- the present invention employs a specific mixture or blend of fatty acids or salts thereof in combination with a specific surfactant system to improve and optimize the sudsing profile of a cleaning composition, preferably a granular laundry detergent composition, during wash.
- a specific surfactant system to improve and optimize the sudsing profile of a cleaning composition, preferably a granular laundry detergent composition, during wash.
- the specific mixture or blend of fatty acids or salts thereof may also advantageously reduce undissolvable residues on fabrics after wash.
- the present invention relates to a cleaning composition
- a cleaning composition comprising:
- LAS and AS are present in such cleaning composition at a LAS-to-AS weight ratio of from 3: 1 to 50: 1.
- the cleaning composition further comprises from 0%to 1%by weight of a linear or branched alkylalkoxy sulphate having a weight average degree of alkoxylation ranging from 0.1 to 10.
- the LAS surfactant is preferably present at an amount ranging from 8%to 30%, more preferably from 10%to 25%, by weight of such composition.
- the AS surfactant is preferably present at an amount ranging from 0.2%to 3%, more preferably from 0.3%to 2%, by weight of such composition.
- the cleaning composition of the present invention may further comprise from 0.3%to 3%, by weight of the composition, of an amphiphilic graft copolymer comprising a polyalkylene oxide backbone grafted with one or more side chains selected from the group consisting of polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, and combinations thereof, while the weight ratio of the polyalkylene oxide backbone over said one or more side chains ranges from 1: 0.2 to 1: 10; and while preferably the graph copolymer has a polyethylene oxide backbone grafted with polyvinyl acetate side chains.
- an amphiphilic graft copolymer comprising a polyalkylene oxide backbone grafted with one or more side chains selected from the group consisting of polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, and combinations thereof, while the weight ratio of the polyalkylene oxide backbone over said one or more side chains ranges from 1: 0.2 to 1:
- the cleaning composition is a granular laundry detergent composition that comprises: (1) from 5%to 50%, preferably from 10%to 40%, more preferably from 15%to 30%, by weight of such granular laundry detergent composition, of a water-soluble alkali metal carbonate and/or bicarbonate, which is preferably sodium carbonate and/or sodium bicarbonate; and/or (2) from 10%to 80%, preferably from 20%to 70%, more preferably from 30%to 60%, by weight of such granular laundry detergent composition, of a water-soluble alkali metal sulphate, which is preferably sodium sulphate.
- the above-mentioned granular laundry detergent composition is preferably characterized by a moisture content of less than 3%by weight of said composition. More preferably, the granular laundry detergent composition is substantially free of any phosphate builder and comprises from 0%to 15%, preferably from 0%to 10%, more preferably from 0%to 5%, by weight of the granular laundry detergent composition, of a zeolite builder.
- the present invention relates to the use of a cleaning composition as mentioned hereinabove for hand-washing fabrics.
- cleaning composition includes, unless otherwise indicated, granular or powder-form all-purpose or “heavy-duty” washing agents, especially cleaning detergents, for fabrics, as well as cleaning auxiliaries such as bleach, rinse aids, additives, or pre-treat types; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents; mouthwashes, denture cleaners, car or carpet shampoos, bathroom cleaners; hair shampoos and hair-rinses; shower gels and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives or pre-treat types.
- the cleaning composition is a solid laundry detergent composition, and more preferably a free-flowing particulate laundry detergent composition (i.e., a granular laundry detergent product) .
- the terms “essentially free of, ” “substantially free of” or “substantially free from” means that the indicated material is present in the amount of from 0 wt%to about 0.5 wt%, or preferably from 0 wt%to about 0.1 wt%, or more preferably from 0 wt%to about 0.01 wt%, and most preferably it is not present at analytically detectable levels.
- substantially pure or “essentially pure” means that the indicated material is present in the amount of from about 99.5 wt%to about 100 wt%, preferably from about 99.9 wt%to about 100 wt%, and more preferably from 99.99 wt%to about 100 wt%, and most preferably all other materials are present only as impurities below analytically detectable levels.
- water-soluble refers to a solubility of more than about 30 grams per liter (g/L) of deionized water measured at 20°C and under the atmospheric pressure.
- sucher indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid.
- suds indicates a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of a liquid.
- suds can be used interchangeably within the meaning of the present invention.
- suds profile refers to the properties of a detergent composition relating to suds character during the wash and rinse cycles.
- the suds profile of a detergent composition includes, but is not limited to, the speed of suds generation upon dissolution in the laundering liquor, the volume and retention of suds in the wash cycle, and the volume and disappearance of suds in the rinse cycle.
- the suds profile includes the wash suds volume and rinse suds volume. It may further include additional suds-related parameters, such as suds stability measured during the washing cycle and the like.
- co-surfactant refers to one or more surfactants in a cleaning composition which is mainly used to improve the sudsing profile of the cleaning composition.
- Co-surfactants can be categorized into suds-boosting co-surfactants (i.e., those that increase suds volume during both the wash and rinse cycles) , suds-suppressing co-surfactants (i.e., those that decrease suds volume during both the wash and rinse cycles) , and suds-optimizing co-surfactants (i.e., those that “boost” suds or increase suds volume during the wash cycle but “suppress” suds or decrease suds volume during the rinse cycle) .
- the cleaning composition of the invention comprises a surfactant system constituted of anionic surfactants, and optionally one or more non-ionic surfactants, zwitterionic surfactants, and/or cationic surfactants.
- a surfactant system constituted of anionic surfactants, and optionally one or more non-ionic surfactants, zwitterionic surfactants, and/or cationic surfactants.
- the fatty acids or salts described hereinabove are not considered a part of the surfactant system for the purpose of the present invention.
- the cleaning composition may comprise a surfactant system in the amount ranging anywhere from about 5%to about 90%by total weight of the composition.
- the composition may comprise such a surfactant system at levels ranging from about 6%to about 70%, typically from about 8%to about 60%, or from about 10%to about 50%, or from about 12%to about 40%by weight.
- the cleaning composition is in a concentrated form, especially a concentrated powder or granular form, while the total surfactant level is from about 10%to about 40%, preferably from about 15%to about 40%, by total weight of the composition.
- the surfactant system of the present invention includes at least a first anionic surfactant that is a C 10 -C 20 linear alkylbenzene sulphonate (LAS) .
- LAS anionic surfactants are well known in the art and can be readily obtained by sulphonating commercially available linear alkylbenzenes.
- Exemplary C 10 -C 20 linear alkylbenzene sulphonates that can be used in the present invention include alkali metal, alkaline earth metal or ammonium salts of C 10 -C 20 linear alkylbenzene sulphonic acids, and preferably the sodium, potassium, magnesium and/or ammonium salts of C 11 -C 18 or C 11 -C 14 linear alkylbenzene sulphonic acids.
- sodium or potassium salts of C 12 linear alkylbenzene sulphonic acids More preferred are the sodium or potassium salts of C 12 linear alkylbenzene sulphonic acids, and most preferred is the sodium salt of C 12 linear alkylbenzene sulphonic acid, i.e., sodium dodecylbenzene sulphonate.
- the amount of LAS used in the cleaning composition may range from about 5%to about 40%, preferably from about 8%to about 30%, and more preferably from about 10%to about 25%, by total weight of the composition.
- the cleaning composition contains from about 10%to about 25%by weight of a sodium, potassium, or magnesium salt of C 12 linear alkylbenzene sulphonic acid.
- the surfactant system of the present invention further includes at least a second anionic surfactant, which is an anionic alkyl sulphate (AS) surfactant having a branched or linear unalkoxylated alkyl group containing from about 6 to about 18 carbon atoms.
- AS anionic alkyl sulphate
- the AS has the generic formula of R-O-SO 3 - M + , while R is branched or linear unalkoxylated C 6 -C 18 alkyl group, and M is a cation of alkali metal, alkaline earth metal or ammonium.
- the R group of the AS surfactant contains from about 6 to about 16 carbon atoms, and more preferably from about 6 to about 14 carbon atoms.
- R can be substituted or unsubstituted, and is preferably unsubstituted. R is substantially free of any alkoxylation.
- M is preferably a cationic of sodium, potassium, or magnesium, and more preferably M is a sodium cation.
- AS surfactant acts as a co-surfactant for the LAS to boost suds volume during the wash.
- the surfactant system of the present invention contains a mixture of C 6 -C 18 AS surfactants, in which C 6 -C 14 AS surfactants are present in an amount ranging from about 85%to about 100%by total weight of the mixture.
- This mixture can be referred to as a “C 6 -C 14 -rich AS mixture. ” More preferably, such C 6 -C 14 -rich AS mixture contains from about 90 wt%to about 100 wt%, or from 92 wt%to about 98 wt%, or from about 94 wt%to about 96 wt%, or 100 wt% (i.e., pure) , of C 6 -C 14 AS.
- the surfactant system in the cleaning composition contains a mixture of C 6 -C 18 AS surfactants with from about 30 wt%to about 100 wt%or from about 50 wt%to about 99 wt%, preferably from about 60 wt%to about 95 wt%, more preferably from about 65 wt%to about 90 wt%, and most preferably from about 70 wt%to about 80 wt%of C 12 AS.
- such mixture of C 6 -C 18 AS surfactants may contain from about 10 wt%to about 100 wt%, preferably from 15 wt%to about 50 wt%, and more preferably from 20 wt%to about 30 wt%of C 14 AS. This mixture can be referred to as a “C 12 -C 14 -rich AS mixture. ”
- the surfactant system of the cleaning composition contains a mixture of AS surfactants that consists essentially of C 12 and/or C 14 AS surfactants.
- AS surfactants may consist essentially of from about 70 wt%to about 80 wt%of C 12 AS and from 20 wt%to about 30 wt%of C 14 AS, with little or no other AS surfactants therein.
- Such mixture may also consist of substantially pure C 12 AS, or alternatively, substantially pure C 14 AS.
- a commercially available AS mixture particularly suitable for practice of the present invention is V95 G from Cognis (Monheim, Germany) .
- the surfactant system of the present invention may contain a mixture of C 6 -C 18 AS surfactants comprising more than about 50 wt%, preferably more than about 60 wt%, more preferably more than 70 wt%or 80 wt%, and most preferably more than 90 wt%or even at 100 wt%(i.e., substantially pure) , of linear AS surfactants having an even number of carbon atoms, including, for example, C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , and C 18 AS surfactants.
- the mixture of C 6 -C 18 AS surfactants as described can be readily obtained by sulphonation of alcohol (s) with the corresponding numbers of carbon atoms.
- the required carbon chain length distribution can be obtained by using alcohols with the corresponding chain length distribution prepared either synthetically or extracted/purified from natural raw materials or formed by mixing corresponding pure starting materials.
- the mixture of C 6 -C 18 AS surfactants may be derived from naturally occurring triglycerides, such as those contained in palm kernel oil or coconut oil, by chemically processing such triglycerides to form a mixture of long chain alcohols and then sulphonating such alcohols to form AS surfactants.
- the mixture of alcohols derived from the naturally occurring triglycerides typically contain more than about 20 wt%of C 16 -C 18 alcohols.
- a mixture containing a lower proportion of C 16 -C 18 alcohols may be separated from the original mixture before the sulphonation step, in order to form the desired mixture of C 6 -C 18 AS surfactants as described hereinabove.
- the desired mixture of C 6 -C 18 AS surfactants can be readily obtained by separating and purifying the already formed AS mixtures. Suitable separation and purification methods include, but are not limited to: distillation, centrifugation, recrystallization and chromatographic separation.
- the AS surfactants used in the cleaning composition of the present invention may range from about 0.1%to about 5%, preferably from about 0.2%to about 3%, more preferably from about 0.3%to 2%, by total weight of the composition.
- the cleaning composition contains from about 0.3%to about 2%of an AS mixture consisting essentially of from about 70 wt%to about 80 wt%of C 12 AS and from 20 wt%to about 30 wt%of C 14 AS.
- the AS is the most effective if it is provided in the cleaning composition at an amount to render a weight ratio of LAS to AS within the range of from about 3:1 to about 50: 1, preferably from about 3.5: 1 to about 45: 1, more preferably from about 4: 1 to about 40: 1, and most preferably from about 5: 1 to about 30: 1.
- the cleaning composition of the present invention with such a LAS-to-AS weight ratio exhibits a right balance between the amounts of wash and rinse suds generated. It also helps to maintain good sudsing profile across different regions with diverse dosing habit.
- the cleaning composition of the present invention employs alkyl sulphate or AS instead of alkylalkoxy sulphate as a co-surfactant to boost the suds of LAS.
- the AS co-surfactant has a significant better rinse suds profile (i.e., reduced rinse suds volume) and is therefore particularly useful for imparting the easy rinse benefit to the cleaning composition so formed. Consequently, the cleaning composition of the present invention is substantially free of alkylalkoxy sulphate, especially alkylethoxy sulphate (AES) .
- the cleaning composition of the present invention contains alkylalkoxy sulphate, or more specifically AES, in an amount ranging from 0 wt%to about 1 wt%, preferably from 0 wt%to about 0.8 wt%, or more preferably from 0 wt%to about 0.5 wt%, and most preferably at a level that is not analytically detectable.
- Alkylalkoxy sulphate as used herein refers to any linear or branched alkylalkoxy sulphate having a weight average degree of alkoxylation ranging from about 0.1 to about 10.
- the surfactant system employed by the cleaning composition of the present invention may comprise one or more additional surfactant (s) selected from other anionic surfactants (other than LAS, AS, and AES described hereinabove) , nonionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof.
- additional surfactant selected from other anionic surfactants (other than LAS, AS, and AES described hereinabove) , nonionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof.
- the cleaning compositions of the invention may comprise additional anionic surfactants which comprise one or more moieties selected from the group consisting of carbonate, phosphate, phosphonate, sulphate, sulfonate, carboxylate and mixtures thereof and which do not fall within the above descriptions for the LAS, AS, and AES surfactants.
- the cleaning compositions of the present invention may comprise one or more non-ionic surfactants in amounts of from about 0.1%to about 20%, preferably from about 0.2%to about 4%, more preferably from about 0.4%to about 3%by total weight of the composition.
- Suitable non-ionic surfactants can be selected from the group consisting of: alkyl polyglucoside and/or an alkyl alkoxylated alcohol; C 10 -C 18 alkyl ethoxylates, such as, non-ionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as from BASF; C 14 -C 22 mid-chain branched alcohols; C 14 -C 22 mid-chain branched alkyl alkoxylates, BAEx, wherein
- the cleaning compositions of the present invention may comprise a cationic surfactant.
- the composition typically comprises from about 0.05 wt%to about 5 wt%, or from about 0.1 wt%to about 2 wt%of such cationic surfactant.
- Suitable cationic surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, and alkyl ternary sulfonium compounds.
- the cationic surfactant can be selected from the group consisting of: alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium surfactants; polyamine cationic surfactants; cationic ester surfactants; amino surfactants, specifically amido propyldimethyl amine; and mixtures thereof.
- AQA alkoxylate quaternary ammonium
- Highly preferred cationic surfactants are mono-C 8-10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C 10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C 10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
- Cationic surfactants such as Praepagen HY (tradename Clariant) may be useful and may also be useful as a suds booster.
- the cleaning composition of the present invention employs a specific mixture or blend of fatty acids or salts thereof to help improving the sudsing profile of the cleaning composition during wash and reducing undissolvable residues on fabrics after wash.
- the fatty acid mixture contains from 15%to 30%, by weight of such mixture, of fatty acids or salts derived from palm kernel oil (PKO) and/or coconut oil (CNO) , and from 70%to 85%, by weight of such mixture, of fatty acids or salts derived from palm oil (PO) . If the PKO/CNO-derived fatty acids or salts in the mixture is present in an amount lower than 15%by weight of such mixture, the sudsing profile of the cleaning composition during wash is less than optimal, and more undissolvable residues are observed on the treated fabrics after wash.
- PKO palm kernel oil
- CNO coconut oil
- PO palm oil
- the particles formed by such fatty acid mixture may be too soft and may affect the overall flowability of the resulting granular composition formed thereby.
- Suitable salts of fatty acids include monovalent or divalent alkali metal salts like sodium, potassium, lithium and/or magnesium salts as well as the ammonium and/or alkylammonium salts of fatty acids, preferably the sodium salt.
- the total amount of such fatty acids or salts ranges from about 0.5%to about 1.2%, preferably from about 0.8%to about 1.1%, by total weight of the cleaning composition.
- the cleaning composition of the present invention contains from about 0.8%to about 1.1%, by weight of such composition, of a mixture or blend of fatty acids or salts that contains from about 20%to about 30%, by weight of such mixture or blend, of PKO/CNO-derived fatty acids or salts and from about 70%to about 80%, by weight of such mixture or blend, of PO-derived fatty acids or salts.
- the cleaning composition of the present invention when it is in a powder or granular form, may also contain a water-soluble alkali metal carbonate or bicarbonate.
- Suitable alkali metal carbonate or bicarbonate that can be used for practice of the present invention include, but are not limited to, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate (which are all referred to as “carbonates” or “carbonate” hereinafter) .
- Sodium carbonate is particularly preferred. Potassium carbonate, sodium bicarbonate, and potassium bicarbonate can also be used.
- Such water-soluble alkali metal carbonate can be present in the cleaning composition at a level ranging from about 5 wt%to about 50 wt%.
- Carbonates have been used in relatively high concentrations (e.g., 25 wt%or more) in cleaning compositions containing a surfactant system formed of LAS and AS anionic surfactants as described hereinabove, in order to provide generate sufficient suds during the wash cycle.
- the high carbonate concentration in the cleaning composition inevitably increase the pH of the wash liquor, rendering it harsher and more damaging to the skin surface of hand-wash consumers.
- the specific mixture or blend of fatty acids or salts thereof is employed to boost or maintain wash suds, which enables reduction of the carbonate level in the cleaning composition without compromising the overall sudsing profile of such composition, thereby providing a milder formulation more suitable for hand-wash consumers.
- the cleaning composition preferably contains a relatively low level of the water-soluble alkali metal carbonate or bicarbonate, such as, for example, from about 10 wt%to about 40 wt%, and preferably from about 15 wt%to about 30 wt%.
- the cleaning composition of the present invention includes from about 15 wt%to about 30 wt%of sodium carbonate or sodium bicarbonate.
- amphiphilic graft copolymers employed by the present invention are characterized by a polyalkylene oxide (also referred to as poyalkylene glycol) backbone grafted with one or more side chains.
- polyalkylene oxide also referred to as poyalkylene glycol
- the polyalkylene oxide backbone of the amphiphilic graft copolymers of the present invention may comprise repeated units of C 2 -C 10 , preferably C 2 -C 6 , and more preferably C 2 -C 4 , alkylene oxides.
- the polyalkylene oxide backbone may be a polyethylene oxide (PEO) backbone, a polypropylene oxide (PPO) backbone, a polybutylene oxide (PBO) backbone, or a polymeric backbone that is a linear block copolymer of PEO, PPO, and/or PBO, while the PEO backbone is preferred.
- Such a polyalkylene oxide backbone preferably has a number average molecular weight of from about 2, 000 to about 100, 000 Daltons, more preferably from about 4, 000 to about 50, 000 Daltons, and most preferably from about 5, 000 to about 10, 000 Daltons.
- the one or more side chains of the amphiphilic graft copolymers of the present invention are formed by polymerizations of vinyl esters of C 2 -C 10 , preferably C 2 -C 6 , and more preferably C 2 -C 4 , carboxylic acids.
- the one or more side chains may be selected from the group consisting of polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, and combinations thereof, while polyvinyl acetate is preferred.
- the polyvinyl ester side chains may be partially saponified, for example, to an extent of up to 15%.
- amphiphilic graft copolymer is preferably characterized by an average of no more than 1 graft site (i.e., the site on the polymeric backbone where a polyvinyl ester side chain is grafted thereto) per 50 alkyleneoxide units on the backbone.
- amphiphilic graft copolymers of the present invention may have an overall mean molar masses (M w ) of from about 3000 to about 100, 000 Daltons, preferably from about 10, 000 to about 50,000 Daltons, and more preferably from about 20, 000 to about 40, 000 Daltons.
- amphiphilic graft copolymers of the present invention have a polyethylene oxide backbone grafted with one or more side chains of polyvinyl acetate. More preferably, the weight ratio of the polyethylene oxide backbone over the polyvinyl acetate side chains ranges from about 1: 0.2 to about 1: 10, or from about 1: 0.5 to about 1: 6, and most preferably from about 1: 1 to about 1: 5.
- One example of such preferred amphiphilic graft copolymers is the Sokalan TM HP22 polymer, which is commercially available from BASF Corporation. This polymer has a polyethylene oxide backbone grafted with polyvinyl acetate side chains.
- the polyethylene oxide backbone of this polymer has a number average molecular weight of about 6,000 Daltons (equivalent to about 136 ethylene oxide units) , and the weight ratio of the polyethylene oxide backbone over the polyvinyl acetate side chains is about 1: 3.
- the number average molecular weight of this polymer itself is about 24, 000 Daltons.
- the amphiphilic graft copolymers of the present invention have the following properties: (i) the surface tension of a 39 ppm by weight polymer solution in distilled water is from about 40 mN/m to about 65 mN/m as measured at 25°C by a tensiometer; and (ii) the viscosity of a 500 ppm by weight polymer solution in distilled water is from about 0.0009 to about 0.003 Pa ⁇ Sas measured at 25°C by a rheometer.
- the surface tension of the polymer solution can be measured by any known tensiometer under the specified conditions.
- Non-limiting tensiometers useful herein include Kruss K12 tensiomerter available from Kruss, Thermo DSCA322 tensiometer from Thermo Cahn, or Sigma 700 tensiometer from KSV Instrument Ltd. Similarly, the viscosity of the polymer solution can be measured by any known rheometer under the specified conditions. The most commonly used rheometer is a rheometer with rotational method, which is also called a stress/strain rheometer.
- Non-limiting rheometers useful herein include Hakke Mars rheometer from Thermo, Physica 2000 rheometer from Anton Paar.
- amphiphilic graft copolymer (s) may be present in the cleaning composition of the present invention in an amount ranging from about 0.3 wt%to about 3 wt%or from about 0.35 wt%to about 2 wt%by total weight of the composition. They are found to provide excellent hydrophobic soil suspension even in the presence of cationic coacervating polymers.
- the cleaning composition of the present invention may comprise one or more additional adjunct components.
- additional adjunct components include, but are not limited to, builders, carriers, structurants, flocculating aid, chelating agents, dye transfer inhibitors, enzymes, enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, hydrotropes, processing aids, and/or pigments.
- the cleaning composition of the present invention is a granular laundry detergent composition comprising one or more builders (not including the carbonate as described hereinabove) in the amount ranging from about 1 wt%to about 40 wt%, typically from 2 wt%to 25 wt%, or even from about 5 wt%to about 20 wt%, or from 8 wt to 15 wt%by total weight of such composition.
- Builders as used herein refers to any ingredients or components that are capable of enhancing or improving the cleaning efficiency of surfactants, e.g., by removing or reducing “free” calcium/magnesium ions in the wash solution to “soften” or reducing hardness of the washing liquor.
- such granular laundry detergent composition has relatively low levels of phosphate builder, zeolite builder, and silicate builder.
- it may contain at most 15 wt%by weight of phosphate builder, zeolite builder, and silicate builder in total.
- such granular laundry detergent composition is substantially free of phosphate builder. More preferably, it comprises from 0 wt%to about 5 wt%of zeolite builder and/or from 0 wt%to about 10 wt%of silicate builder, while the total amounts of such zeolite and silicate builders add up to no more than 10 wt%by total weight of the composition.
- the granular laundry detergent composition contains from 0 wt%to about 2 wt%of zeolite builder and from 0 wt%to about 2 wt%of silicate builder, while the total amounts of such builders add up to no more than 5 wt%by total weight of the composition.
- the granular laundry detergent composition contains from 0 wt%to about 1 wt%of zeolite builder and from 0 wt%to about 1 wt%of silicate builder, while the total amounts of these builders add up to no more than 2 wt%by total weight of the composition.
- the composition may further comprise any other supplemental builder (s) , chelant (s) , or, in general, any material which will remove calcium ions from solution by, for example, sequestration, complexation, precipitation or ion exchange.
- the composition may comprise materials having at a temperature of 25°C and at a 0.1M ionic strength a calcium binding capacity of at least 50 mg/g and a calcium binding constant log K Ca 2+ of at least 3.50.
- the granular laundry detergent composition of the present invention may contain one or more solid carriers selected from the group consisting of sodium chloride, potassium chloride, sodium sulphate, and potassium sulphate.
- such granular laundry detergent composition includes from about 10 wt%to about 80 wt%of sodium chloride and/or from about 10 wt%to about 80 wt%of sodium sulphate. More preferably, such granular laundry detergent composition comprises from about 10 wt%to about 80 wt%, preferably from about 20 wt%to about about 70 wt%, more preferably from about 30 wt%to about 60 wt%of sodium sulphate.
- the cleaning composition of the present invention may further comprise one or more suitable detergent ingredients such as transition metal catalysts; imine bleach boosters; enzymes such as amylases, carbohydrases, cellulases, laccases, lipases, bleaching enzymes such as oxidases and peroxidases, proteases, pectate lyases and mannanases; source of peroxygen such as percarbonate salts and/or perborate salts, preferred is sodium percarbonate, the source of peroxygen is preferably at least partially coated, preferably completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or mixtures, including mixed salts, thereof; bleach activator such as tetraacetyl ethylene diamine, oxybenzene sulphonate bleach activators such as nonanoyl oxybenzene sulphonate, caprolactam bleach activators, imide bleach activators such as N-nonanoyl
- the detergent composition is typically a laundry detergent composition or a dish washing detergent composition.
- the composition is a laundry detergent composition.
- the laundry detergent composition may be in the form of a liquid, gel, paste, dispersion, typically a colloidal dispersion or any combination thereof.
- Liquid compositions typically have a viscosity of from 500 mPa. sto 3, 000 mPa. s, when measured at a shear rate of 20 s -1 at ambient conditions (20°C and 1 atmosphere) , and typically have a density of from 800 g/l to 1300 g/l. If the composition is in the form of a dispersion, then it will typically have a volume average particle size of from 1 micrometer to 5, 000 micrometers, typically from 1 micrometer to 50 micrometers. Typically, a Coulter Multisizer is used to measure the volume average particle size of a dispersion.
- the laundry detergent composition is in a liquid form containing cleaning actives solubilised or dispersed in a solvent.
- suitable solvents include water and other solvents such as lipophilic fluids.
- suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.
- the laundry detergent composition can also be, and is preferably, in a solid or a particulate form, typically in a free-flowing particulate form.
- the composition in solid form can be in the form of an agglomerate, granule, flake, extrudate, bar, tablet or any combination thereof.
- the solid composition can be made by methods such as dry-mixing, agglomerating, compaction, spray drying, pan-granulation, spheronization or any combination thereof.
- the solid composition typically has a bulk density of from 300 g/l to 1, 500 g/l, typically from 500 g/l to 1, 000 g/l.
- the laundry detergent composition may be in unit dose form, including not only tablets, but also unit dose pouches wherein the composition is at least partially enclosed, typically completely enclosed, by a film such as a polyvinyl alcohol film.
- the laundry detergent composition may also be in the form of an insoluble substrate, for example a non-woven sheet, impregnated with detergent actives.
- the laundry detergent composition may be capable of cleaning and/or softening fabric during a laundering process.
- the composition is formulated for use in an automatic washing machine or for hand-washing use, and preferably for hand-wash.
- compositions are typically used for cleaning and/or treating a situs inter alia a surface or fabric.
- surface may include such surfaces such as dishes, glasses, and other cooking surfaces, hard surfaces, hair or skin.
- Such method includes the steps of contacting an embodiment of the laundry detergent or cleaning composition, in neat form or diluted in a wash liquor, with at least a portion of a surface or fabric, then optionally rinsing such surface or fabric.
- the surface or fabric may be subjected to a washing step prior to the aforementioned rinsing step.
- washing includes but is not limited to, scrubbing, wiping, and mechanical agitation.
- composition solution pH is chosen to be the most complimentary to a target surface to be cleaned spanning broad range of pH, from about 5 to about 11.
- For personal care such as skin and hair cleaning pH of such composition preferably has a pH from about 5 to about 8 for laundry cleaning compositions pH of from about 8 to about 10.
- the compositions are preferably employed at concentrations of from about 200 ppm to about 10, 000 ppm in solution.
- the water temperatures preferably range from about 5°C to about 100°C.
- the laundry detergent of the present invention is ideally suited for use in laundry applications.
- the present invention includes a method for laundering a fabric.
- the method may comprise the steps of contacting a fabric to be laundered with a laundry detergent comprising the carboxyl group-containing polymer.
- the fabric may comprise most any fabric capable of being laundered in normal consumer use conditions.
- the solution preferably has a pH of from about 8 to about 10.5.
- the laundry detergent may be employed at concentrations of from about 500 ppm to about 15, 000 ppm in solution, and optionally, more dilute wash conditions can be used.
- the water temperatures typically range from about 5°C to about 90°C.
- the water to fabric ratio is typically from about 1: 1 to about 30: 1.
- the method of laundering fabric may be carried out in a top-loading or front-loading automatic washing machine, or can be used in a hand-wash laundry application.
- the wash liquor formed and concentration of laundry detergent composition in the wash liquor is that of the main wash cycle. Any input of water during any optional rinsing step (s) is not included when determining the volume of the wash liquor.
- the wash liquor may comprise 40 litres or less of water, or 30 litres or less, or 20 litres or less, or 10 litres or less, or 8 litres or less, or even 6 litres or less of water.
- the wash liquor may comprise from above 0 to 15 litres, or from 2 litres, and to 12 litres, or even to 8 litres of water.
- the wash liquor may comprise 150 litres or less of water, 100 litres or less of water, 60 litres or less of water, or 50 litres or less of water, especially for hand washing conditions, and can depend on the number of rinses.
- from 0.01 Kg to 2 Kg of fabric per litre of wash liquor is dosed into the wash liquor.
- from 0.01 Kg, or from 0.05 Kg, or from 0.07 Kg, or from 0.10 Kg, or from 0.15 Kg, or from 0.20 Kg, or from 0.25 Kg fabric per litre of wash liquor is dosed into the wash liquor.
- 50 g or less, or 45 g or less, or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or 20 g or less, or even 15 g or less, or even 10 g or less of the composition is contacted to water to form the wash liquor.
- compositions of the present invention comprising the cationic polymer.
- assays must be used in order that the invention described and claimed herein may be fully understood.
- the wash suds height of a test cleaning composition herein is measured by employing a suds cylinder tester (SCT) .
- SCT suds cylinder tester
- the SCT has a set of 8 cylinders. Each cylinder is typically 60 cm long and 9 cm in diameter and may be together rotated at a rate of 20-22 revolutions per minute (rpm) .
- This method is used to assay the performance of laundry detergent to obtain a reading on ability to generate suds as well as its suds stability.
- the rinse suds height of the test cleaning composition is measured from a 1/4 dilute solution in the cylinder by using a SITA Foam Tester R-2000 manufactured by SITA Lab Solutions (Stuttgart, Germany) .
- Step (4) Lock in an upright position. Wait 1 min and check the suds height very quickly ( ⁇ 10 sec) left to right. Record the total suds height (i.e., height of the suds plus wash liquor) and the height of the wash liquor alone. The height of suds generated by each test detergent composition is calculated by deducting the height of the wash liquor alone out of the total suds height. This marks the after 50 revolutions data, and represents the Wash Suds.
- the suds volume is read at about 1s-15s.
- Steps (1) - (9) are repeated at least twice (i.e., 3 replications) to obtain the average suds volume and ensure repeatibility of the results.
- Average suds height of different categories described above are calculated by average the height data of each replicate.
- This test method is used herein to determine the solubility of a cleaning composition by measuring the weight percentage (Wt%) of undissolved residue left by such cleaning composition on a 250-micron sieve after such cleaning composition is dissolved in water for about 10 minutes.
- the first, comparative granular laundry detergent composition employs a fatty acid blend containing about 10 wt%of PKO-derived fatty acid salt (sodium) and about 90 wt%of PO-derived fatty acid salt (sodium) .
- the second, inventive granular laundry detergent composition employs a fatty acid blend containing about 20 wt%of PKO- derived fatty acid salt (sodium) and about 80 wt%of PO-derived fatty acid salt (sodium) .
- Table I The compositional breakdown of these two formulations are shown in Table I:
- the sudsing profile of the inventive composition hereinabove that contain a blend of fatty acids containing about 20 wt%of PKO-derived fatty acid salt (sodium) and about 80 wt%of PO-derived fatty acid salt (sodium) is measured by the Sudsing Profile Test as mentioned hereinabove, and is compared with that of the comparative composition containing about 10 wt%of PKO-derived fatty acid salt (sodium) and about 90 wt%of PO-derived fatty acid salt (sodium) .
- the 80/20 PO/PKO soap blend can generate a higher wash suds height and a comparative rinse suds volume after the first rinse, in comparison with the 90/10 PO/PKO soap blend that is used at a much greater amount (2.96%) in the comparative granular laundry detergent composition.
- the 80/20 PO/PKO soap blend can provide a satisfactory sudsing profile while used at a much lower concentration, in comparison with the 90/10 PO/PKO soap blend.
- Sample Soap Blend Type Soap Content (wt%) Residue (Wt%) A 90/10 PO/PKO fatty acid blend (Na salt) 2.7 1.57 B 80/20 PO/PKO fatty acid blend (Na salt) 2.7 0.92 C 90/10 PO/PKO fatty acid blend (Na salt) 0.8 0.48 C 80/20 PO/PKO fatty acid blend (Na salt) 1.4 0.46
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP17928967.3A EP3697884A1 (de) | 2017-10-19 | 2017-10-19 | Reinigungszusammensetzungen mit fettsäuremischung |
CN201780095793.1A CN111201310B (zh) | 2017-10-19 | 2017-10-19 | 包含脂肪酸共混物的清洁组合物 |
PCT/CN2017/106819 WO2019075684A1 (en) | 2017-10-19 | 2017-10-19 | CLEANING COMPOSITIONS CONTAINING FATTY ACID MIXTURE |
ZA2020/02173A ZA202002173B (en) | 2017-10-19 | 2020-05-04 | Cleaning compositions containing fatty acid blend |
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PCT/CN2017/106819 WO2019075684A1 (en) | 2017-10-19 | 2017-10-19 | CLEANING COMPOSITIONS CONTAINING FATTY ACID MIXTURE |
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PCT/CN2017/106819 WO2019075684A1 (en) | 2017-10-19 | 2017-10-19 | CLEANING COMPOSITIONS CONTAINING FATTY ACID MIXTURE |
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EP (1) | EP3697884A1 (de) |
CN (1) | CN111201310B (de) |
WO (1) | WO2019075684A1 (de) |
ZA (1) | ZA202002173B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2024020989A1 (en) * | 2022-07-29 | 2024-02-01 | The Procter & Gamble Company | Packaged laundry detergent product |
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JPS59221392A (ja) * | 1983-05-31 | 1984-12-12 | ライオン株式会社 | 無リン洗剤組成物 |
CN1075507A (zh) * | 1991-12-03 | 1993-08-25 | 普罗格特-甘布尔公司 | 漂洗活性的控泡颗粒 |
WO1995014766A1 (en) * | 1993-11-24 | 1995-06-01 | Unilever Plc | Detergent compositions and process for preparing them |
US5443751A (en) * | 1993-03-05 | 1995-08-22 | Church & Dwight Co. Inc. | Powder detergent composition for cold water washing of fabrics |
US6060443A (en) * | 1996-04-16 | 2000-05-09 | The Procter & Gamble Company | Mid-chain branched alkyl sulfate surfactants |
WO2001011005A1 (en) * | 1999-08-10 | 2001-02-15 | The Procter & Gamble Company | Granular detergent compositions having surfactant particle with reduced electrolyte concentrations |
WO2015163175A1 (ja) * | 2014-04-23 | 2015-10-29 | 花王株式会社 | 衣料用粉末洗剤組成物 |
CN106574217A (zh) * | 2014-08-29 | 2017-04-19 | 荷兰联合利华有限公司 | 液体洗涤剂组合物 |
CN106661501A (zh) * | 2014-08-01 | 2017-05-10 | 宝洁公司 | 包含高脂肪酸的清洁组合物 |
-
2017
- 2017-10-19 EP EP17928967.3A patent/EP3697884A1/de not_active Withdrawn
- 2017-10-19 WO PCT/CN2017/106819 patent/WO2019075684A1/en unknown
- 2017-10-19 CN CN201780095793.1A patent/CN111201310B/zh active Active
-
2020
- 2020-05-04 ZA ZA2020/02173A patent/ZA202002173B/en unknown
Patent Citations (9)
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JPS59221392A (ja) * | 1983-05-31 | 1984-12-12 | ライオン株式会社 | 無リン洗剤組成物 |
CN1075507A (zh) * | 1991-12-03 | 1993-08-25 | 普罗格特-甘布尔公司 | 漂洗活性的控泡颗粒 |
US5443751A (en) * | 1993-03-05 | 1995-08-22 | Church & Dwight Co. Inc. | Powder detergent composition for cold water washing of fabrics |
WO1995014766A1 (en) * | 1993-11-24 | 1995-06-01 | Unilever Plc | Detergent compositions and process for preparing them |
US6060443A (en) * | 1996-04-16 | 2000-05-09 | The Procter & Gamble Company | Mid-chain branched alkyl sulfate surfactants |
WO2001011005A1 (en) * | 1999-08-10 | 2001-02-15 | The Procter & Gamble Company | Granular detergent compositions having surfactant particle with reduced electrolyte concentrations |
WO2015163175A1 (ja) * | 2014-04-23 | 2015-10-29 | 花王株式会社 | 衣料用粉末洗剤組成物 |
CN106661501A (zh) * | 2014-08-01 | 2017-05-10 | 宝洁公司 | 包含高脂肪酸的清洁组合物 |
CN106574217A (zh) * | 2014-08-29 | 2017-04-19 | 荷兰联合利华有限公司 | 液体洗涤剂组合物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024020989A1 (en) * | 2022-07-29 | 2024-02-01 | The Procter & Gamble Company | Packaged laundry detergent product |
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CN111201310A (zh) | 2020-05-26 |
ZA202002173B (en) | 2022-10-26 |
EP3697884A1 (de) | 2020-08-26 |
CN111201310B (zh) | 2021-08-06 |
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