EP0526539B1 - Flüssige waschmittelzusammensetzungen - Google Patents

Flüssige waschmittelzusammensetzungen Download PDF

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Publication number
EP0526539B1
EP0526539B1 EP91908596A EP91908596A EP0526539B1 EP 0526539 B1 EP0526539 B1 EP 0526539B1 EP 91908596 A EP91908596 A EP 91908596A EP 91908596 A EP91908596 A EP 91908596A EP 0526539 B1 EP0526539 B1 EP 0526539B1
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EP
European Patent Office
Prior art keywords
alkyl sulphate
pas
liquid detergent
compositions
weight
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.)
Expired - Lifetime
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EP91908596A
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English (en)
French (fr)
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EP0526539A1 (de
Inventor
Cornelis Bernard Donker
David Machin
Frederick Jan Schepers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0526539A1 publication Critical patent/EP0526539A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • the present invention is concerned with aqueous liquid detergent compositions which contain a primary alkyl sulphate material.
  • Primary alkyl sulphates are anionic surfactant materials, which are especially preferred for use in detergent compositions for environmental reasons.
  • a problem in the formulating of liquid detergent compositions comprising a primary alkyl sulphate as detergent active material is sometimes the occurrence of high viscosities and/or instability after storage.
  • liquid detergent compositions comprising a primary alkyl sulphate material and having satisfactory stability and/or viscosity properties can be obtained by ensuring that the primary alkyl sulphate is present in a non-solid phase dispersed in the system.
  • the present invention relates to an aqueous liquid detergent composition
  • a aqueous liquid detergent composition comprising a primary alkyl sulphate material, which is present in a non-solid dispersed phase.
  • compositions of the invention are structured liquid detergent compositions. Structuring is especially preferred for providing physical stability to PAS containing compositions. Structured compositions according to the invention may be externally structured (the structuring is provided by materials other than the main active materials) or internally structured (the structuring is provided by main active materials, e.g. detergent active materials in combination with electrolytes). Preferably compositions of the invention are internally structured, more preferably compositions of the invention comprise an internal structure of lamellar droplets of detergent active material, dispersed in the aqueous phase of the composition.
  • Lamellar droplets are a particular class of surfactant structures which, inter alia , are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications', J. Wiley & Sons, Letchworth 1980.
  • Such lamellar droplet systems are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplets are called 'spherulites'.
  • lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase).
  • compositions of the invention comprise as part or all of the detergent active materials a PAS material, preferably a C8 to C20 PAS, more preferably a C9 to C15 PAS, most preferably a C10 to C14 PAS.
  • Suitable materials can for example be made by sulphating primary alcohols or are for example available under the trade names Lial 125 ex Enichem, Dobanol 25 ex Shell, Empicol LX ex Albright and Wilson and Texapon LS ex Henkel.
  • the level of PAS material is from 0.1 to 40% by weight of the composition, preferably from 3 to 20%, more preferably from 5 to 15%.
  • the PAS is present in a non-solid dispersed phase.
  • no or only minor amounts (less than 10%, more preferably less than 5%) of the PAS are present in the form of solid crystallites, also preferably no or only minor amounts (less than 10%, more preferably less than 5% ) of the PAS are present in solubilised or micellar form.
  • the level of PAS in the form of crystallites can be estimated by light microscopy, the level of PAS in solubilised or micellar from can be estimated by centrifuging the composition at 7350 m/s2 (750G) for 16 hours and then determining the level of PAS in the clear layer.
  • the PAS is predominantly (for more than 80% by weight, preferably more than 90%, more preferably more than 95%) incorporated in a non-solid dispersed phase.
  • non-solid dispersed phases are liquid crystal structures, for example lamellar droplet structures.
  • the PAS is part of a lamellar droplet structure either as the sole surfactant in the droplets, or more preferably in combination with other surfactant materials.
  • a non-solid dispersed phase comprising the PAS materials is present, several parameters may be varied, e.g. one or more of the following conditions is fulfilled for incorporating the PAS into a non-solid phase:
  • compositions of the invention contain available counterions for the PAS other than sodium, this will generally lead to less crystallisation of the PAS and therefore generally to a lower viscosity and/or increased stability.
  • Compositions of the invention contain mixtures of sodium and other counterions selected from the group of potassium and ammonium, more preferably the other counterions are potassium ions.
  • the mole ratio of sodium to other counterions in the total composition is preferably from 10 : 1 to 1 : 10, more preferably from 3 : 1 to 1 : 3, most preferably from 2 : 1 to 1 : 2.
  • unsaturated soaps is believed to be advantageous, because this possibly provides a reduced formation of solid complexes of the soap and the PAS material and therefore results in a reduced viscosity and/or an increased stability.
  • At least two of the three above mentioned conditions are satisfied, especially conditions (a) and (b), most preferably all three conditions are satisfied.
  • compositions of the invention are physically stable.
  • physical stability for liquid systems of the invention can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 5%, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation. Especially preferred are compositions which do not yield any phase separation upon storage for 21 days at 25 °C.
  • compositions of the invention have a pH of between 6 and 14, more preferred from 6.5 to 13, especially preferred from 7 to 12.
  • compositions of the invention have a viscosity after storage for 2 weeks of less than 2,500 mPa.s at 21 s-1, preferably less than 2,000 mPa.s, more preferably less than 1,500 mPa.s, most preferred between 100 and 1,000 mPa.s at 21 s-1.
  • these viscosities are observed after storage for at least two weeks at 25°C, but more preferably also at 15 °C and most preferably also at 5°C and 0°C.
  • compositions of the invention comprise detergent active materials, preferably at a level of from 1 to 70% by weight of the composition, more preferred a level of 5 to 50% by weight, most preferred from 10 to 40% by weight.
  • At least 5% by weight of the detergent active materials are PAS materials, most preferably more than 10%, most preferably more than 20%.
  • PAS constitutes less than 60% by weight of the detergent active materials, more preferred less than 50%, most preferred less than 40%.
  • lamellar droplet structured liquid detergent compositions a blend of surfactants is used, the precise proportions of each component which will result in lamellar droplets will depend on the type(s) and amount(s) of the electrolytes, as is the case with conventional structured liquids.
  • the detergent-active material may, in addition to the PAS material as described above, comprise one or more other surfactants, which may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phospine oxides and dialkyl sulphoxides.
  • glyceryl ethers such as for example disclosed in GB 1,506,419.
  • compositions of the invention may be free of nonionic surfactants, generally the level of nonionic surfactants is more than 1% by weight of the composition, preferably from 2.0 to 25.0% by weight of the composition.
  • compositions of the present invention may also contain synthetic anionic surfactant ingredients other than PAS. These other synthetic anionic surfactants are preferably used in combination with the above mentioned nonionic materials. Suitable synthetic anionic surfactants are usually water-soluble alkali metal salts of organic sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are for example sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-20) with sodium bisulphite and those derived from reacting par
  • non-soap, non-PAS anionic surfactant materials is from 0-35% by weight of the composition, for example from 0.5 to 25%.
  • an alkali metal soap of a mono- or di-carboxylic acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil,coconut oil, palmkernel oil, alk(en)yl succinates e.g. dodecyl succinate or mixtures thereof.
  • the sodium or potassium soaps of these acids are preferably used.
  • the level of soap in compositions of the invention is from 0-40% by weight of the composition, more preferred from 5-25%.
  • the soap material is predominantly unsaturated and has a iodine value of at least 70 more preferably more than 75, most preferably the soap consists for at least 70% by weight of unsaturated soap materials such as oleate.
  • the weight ratio of anionic surfactants (including the PAS material and the soap material) to the above mentioned nonionic surfactant materials is from 10 : 1 to 1 : 10, more preferred from 5 : 1 to 1 : 2, most preferred from 4 : 1 to 1 : 2.
  • salting out resistant active materials such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants such as for example disclosed in EP 70 074.
  • alkyl mono glucosides may be used. Preferred levels of these materials are from 0-20% by weight, more preferably from 1 to 15%.
  • compositions optionally also contain electrolyte, preferably in an amount sufficient to bring about lamellar droplet structuring of the detergent-active material.
  • the compositions contain from 1% to 60%, especially from 2 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be included.
  • relatively low amounts of salting-out electrolytes say from 2-10% by weight. These levels are generally sufficiently high to provide structuring of the composition, and do not provide viscosity problems.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • detergency builder material some or all of which may be electrolyte.
  • some detergent active materials such as for example soaps, also have builder properties.
  • phosphorous-containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. Sometimes it is however preferred to minimise the amount of phosphate builders.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention.
  • the level of non-soap builder material is from 5-40% by weight of the composition, more preferred from 5 to 25% by weight of the composition.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase.
  • use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), anti-redeposition agents, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium
  • a preferred further ingredient -which is especially preferred for incorporation in internally structured compositions according to the invention- is a deflocculating polymer e.g one having a hydrophilic backbone and at least one hydrophobic side chain.
  • a deflocculating polymer e.g one having a hydrophilic backbone and at least one hydrophobic side chain.
  • Such polymers are described in our copending patent applications WO/91/06622 (published 16 May 1991), WO/91/06623 (published 16 May 1991) and GB 2,237,813 (published on 15 May 1991) and in our European patent application EP 346 995. Typical levels of these ingredients are from 0.5 to 4.5 % by weight.
  • Compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
  • a preferred method involves the dispersing of the electrolyte ingredient -if any- together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material - if any-, the detergent active materials (preferably as a non-aqueous premix containing the PAS in acid-form) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
  • the deflocculating polymer -if any- may advantageously be added after the electrolyte ingredients, the builder ingredients or just before cooling.
  • a particularly preferred method of making an aqueous liquid detergent composition which contains a PAS material is to use a premix of PAS with nonionic surfactants, said premix containing little or no water.
  • Preferred premixes contain 10 to 50% by weight more preferrably 15 to 40% most preferably 20 to 35% of PAS, and 50 to 90% more preferably 60 to 80% of nonionic surfactant.
  • the water level is preferably less than 20% by weight, more preferably less than 10% most preferably the premix is substantially free of water.
  • the PAS in the premix may be present in acid form, but generally the PAS will be present in salt form for example in its sodium salt form.
  • the premixes can easily be handled and do not suffer from high viscosities. They can for example be supplied as a feedback raw material from as sulphonation or sulphation plant.
  • the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.05 to 10%, more preferred from 0.1 to 3% by weight.
  • compositions were made by adding the ingredients in the listed order to the water at a temperature of 40 °C.
  • compositions A and B This example illustrates that PAS containing compositions of satisfactory viscosity after storage at 25 °C can be obtained by using a Dobanol 91 or Lial 145 PAS (compositions A and B). Further viscosity benefits can be obtained by using mixed counterions (Compositions C and D) or by using unsaturated soap materials (Composition E), especially advantageous results can be obtained by using mixed counterions in combination with unsaturated soaps (Composition F).
  • compositions A-C This example illustrates that the viscosity after storage is less, when more potassium counterions are present (Compositions A-C). From composition D it follows that higher levels of PAS may cause viscosity problems after storage.
  • compositions were made in the following way: A premix of PAS with nonionic sufactants was made. This premix had a water content of about 6%. Oleic acid was mixed with the premix.
  • Borax and citric acid and KOH were added to water under stirring followed by the addition of the Zeolite, polymer, antifoam, the above active mix and the remaining ingredients. Oleic acid could equally well be added sperately after addition of the blends.
  • This example indicates that satisfactory viscosities of PAS-containing compositions can be obtained by using mixtures of non-ionics with PAS in different ratios, together with Zeolite.
  • compositions were made in the following way: The ingredients were mixed in the listed order, with PAS added as the last active, followed by 20 minutes mixing.

Claims (8)

  1. Wäßrige flüssige Waschmittelzusammensetzung mit einer Viskosität von weniger als 2.5 Pas bei 21 s⁻¹ nach Lagerung während zwei Wochen bei 25°C und enthaltend 0.1 bis 40 Gew.% eines primären Alkylsulfat-Materials, das in einer nichtfesten dispergierten Phase enthalten ist, dadurch gekennzeichnet, daß
    (a) das Molverhältnis von Natrium zu den anderen kationischen Gegenionen, ausgewählt aus Kalium und Ammonium in der Zusammensetzung 10:1 bis 1:10 beträgt; und/oder
    (b) das primäre Alkylsulfat-Material ein verzweigtes Alkylsulfat ist, worin mindestens 20% der PAS-Moleküle verzweigt sind; und/oder
    (c) die Zusammensetzung auch eine Seife mit einerJodzahl von mehr als 70 enthält.
  2. Wäßrige flüssige Waschmittelzusammensetzung nach Anspruch 1, enthaltend 1 bis 70 Gew.% waschmittelaktives Material.
  3. Wäßrige flüssige Waschmittelzusammensetzung nach den Ansprüchen 1-2, enthaltend 10 bis 40 Gew.% waschmittelaktives Material.
  4. Wäßrige flüssige Waschmittelzusammensetzung nach den Ansprüchen 1-3, die intern strukturiert ist.
  5. Wäßrige flüssige Waschmittelzusammensetzung nach den Ansprüchen 1-4, worin das Alkylsulfat-Material in einer lamellaren Tröpfchenphase vorhanden ist.
  6. Zusammensetzung nach den Ansprüchen 1-5, worin das Alkylsulfat-Material 5 bis 60 Gew.% waschmittelaktives Material ausmacht.
  7. Verwendung einer Zusammensetzung nach den Ansprüchen 1-6 zum Waschen von Textilgewebe.
  8. Verfahren zur Herstellung einer wäßrigen flüssigen Waschmittelzusammensetzung enthaltend ein primäres Alkylsulfat-Material in einer nicht-festen, dispergierten Phase, wodurch Zusammensetzungen nach den Ansprüchen 1-6 erhalten werden können, wobei besagtes verfahren das Mischen des primären Alkylsulfat-Materials in Wasser bei erhöhter Temperatur, Abkühlen der Mischung, gegebenenfalls gefolgt von der Zugabe der restlichen temperaturempfindlichen Bestandteile umfaßt, wobei das primäre Alkylsulfat-Material zu den Zusammensetzungen als Vormischung hinzugefügt wird umfassend 10-50% primäres Alkylsulfat-Material, 50-90% nichtionisches oberflächenaktives Material und 0-20% Wasser.
EP91908596A 1990-04-25 1991-04-22 Flüssige waschmittelzusammensetzungen Expired - Lifetime EP0526539B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP90304440 1990-04-25
EP90304440 1990-04-25
EP90312402 1990-11-14
EP90312402 1990-11-14

Publications (2)

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EP0526539A1 EP0526539A1 (de) 1993-02-10
EP0526539B1 true EP0526539B1 (de) 1994-01-12

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EP (1) EP0526539B1 (de)
JP (1) JPH0776356B2 (de)
KR (1) KR950013220B1 (de)
CN (1) CN1031890C (de)
AU (1) AU651825B2 (de)
BR (1) BR9106381A (de)
CA (1) CA2080688C (de)
DE (1) DE69101007T2 (de)
ES (1) ES2062787T3 (de)
MY (1) MY105315A (de)
WO (1) WO1991016409A1 (de)

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EP0874041A1 (de) * 1997-04-22 1998-10-28 The Procter & Gamble Company Waschmittelzusammensetzungen
CA2305467A1 (en) * 1997-10-10 1999-04-22 Rinko Katsuda Mid-chain branched surfactants with potassium ions
DE19939991A1 (de) * 1999-08-24 2001-03-01 Henkel Kgaa Tensidzusammensetzung
EP1111031A1 (de) * 1999-12-22 2001-06-27 The Procter & Gamble Company Reinigungsmittel
WO2014190130A1 (en) 2013-05-24 2014-11-27 The Procter & Gamble Company Concentrated surfactant composition
CN105431515A (zh) 2013-05-24 2016-03-23 宝洁公司 低ph洗涤剂组合物
CA2910953C (en) 2013-05-24 2018-06-26 The Procter & Gamble Company Low ph detergent composition comprising nonionic surfactants
EP3004306A1 (de) * 2013-05-24 2016-04-13 The Procter & Gamble Company Kompakte flüssige waschmittelzusammensetzung
EP3623458A1 (de) 2018-09-11 2020-03-18 The Procter & Gamble Company Dosierungsartikel für wasserlösliche einheit

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Publication number Publication date
WO1991016409A1 (en) 1991-10-31
KR930700631A (ko) 1993-03-15
DE69101007D1 (de) 1994-02-24
CA2080688C (en) 1998-11-03
DE69101007T2 (de) 1994-05-05
EP0526539A1 (de) 1993-02-10
CN1031890C (zh) 1996-05-29
CA2080688A1 (en) 1991-10-26
ES2062787T3 (es) 1994-12-16
AU651825B2 (en) 1994-08-04
AU7778191A (en) 1991-11-11
JPH0776356B2 (ja) 1995-08-16
MY105315A (en) 1994-09-30
KR950013220B1 (en) 1995-10-26
BR9106381A (pt) 1993-04-27
CN1056707A (zh) 1991-12-04
JPH05508427A (ja) 1993-11-25

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