EP0291261B1 - Flüssiges Waschmittel - Google Patents

Flüssiges Waschmittel Download PDF

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Publication number
EP0291261B1
EP0291261B1 EP88304186A EP88304186A EP0291261B1 EP 0291261 B1 EP0291261 B1 EP 0291261B1 EP 88304186 A EP88304186 A EP 88304186A EP 88304186 A EP88304186 A EP 88304186A EP 0291261 B1 EP0291261 B1 EP 0291261B1
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EP
European Patent Office
Prior art keywords
peptising
clay
electrolyte
swelling
viscosity
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Expired - Lifetime
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EP88304186A
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English (en)
French (fr)
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EP0291261A3 (en
EP0291261A2 (de
Inventor
Robin John Green
Johannes Cornelis Van De Pas
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0291261A3 publication Critical patent/EP0291261A3/en
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the invention relates to a liquid detergent composition, in particular to a liquid detergent composition for washing fabrics and imparting a softness thereto.
  • NPNB's non-peptising/non-building electrolytes
  • the present invention now provides a liquid detergent composition
  • a liquid detergent composition comprising
  • Aqueous liquid detergents in which the aqueous base, detergent active(s) and electrolyte result in a structuring system with solid suspending properties are very well known in the art, although these known compositions do not contain the clay/NPNB combination. Thus, those skilled in the art are readily able to select from a very wide range of surfactant and electrolyte types and amounts to achieve such a system. These systems are known both with and without solids actually being suspended in them.
  • One particular form of such a structuring system comprises a dispersion of lamellar droplets in an aqueous phase which contains dissolved electrolyte.
  • These lamellar dispersions are just one of a number of structuring systems with solid suspending properties which 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.
  • Lamellar droplets consist of an onion-like configuration of concentric bilayers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties. Their presence 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.
  • lamellar dispersions not only used for their solid suspending properties but are also used to endow properties such as consumer preferred flow behaviour and/or turbid appearance.
  • Examples of such structured liquids without suspended solids are given in US patent 4 244 840 whilst examples where solid particles are suspended and disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in the aforementioned US 4 244 840.
  • Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplets are called 'spherulites'.
  • the present invention embraces many aqueous/surfactant/electrolyte systems with solid suspending properties (either without, or preferably with solids additional to the clay suspended therein), the embodiments comprising lamellar dispersions are especially preferred.
  • the present invention requires the claimed compositions at 25°C to have a viscosity of no greater than 2.5 Pas at a shear rate of 21s ⁇ 1. However, most preferred are those which have a viscosity of no greater than 1.75 Pas at the latter temperature and shear rate.
  • the fabric softening clays in general may be classed as low, medium or high swelling.
  • the low swelling types are those having a swellability (determined as herein described) in an 8% sodium tripolyphosphate solution of less than 25%.
  • the medium swelling types are those having a swellability in an 8% sodium tripolyphosphate solution of from 25% to 75%.
  • the high swelling clays are those having a swellability in an 8% sodium tripolyphosphate solution of greater than 75%.
  • the swelling behaviour of the clays is quantified by the following test.
  • a dispersion is prepared at room temperature containing 435g of water, 40g sodium tripolyphosphate and 25g of clay material (the sodium tripolyphosphate is completely dissolved in the water before the addition of the clay).
  • the dispersion is stirred for 5 minutes with a magnetic stirrer and then placed in a 1000 ml measuring cylinder. The dispersion is then left to stand, undisturbed for two weeks. After this time the dispersion is examined. Generally some separation will have occurred. A lower layer of dispersion or gel containing the clay will be visibly distinguishable from a relatively clear upper layer.
  • S percentage swellability
  • the level of fabric softening clay material in the product is at least 1% by weight, but not more than 10% by weight. A most preferred level is from 3% to 7% by weight.
  • the NPNB's are those electrolytes which have the property of preventing peptisation (and hence swelling) of the clay by any peptising electrolyte and/or detergent active which may be present in the formulation. This is useful because it is the swelling which causes a viscosity increase and that is what the present invention seeks to reduce.
  • the peptising phenomenon is one which can be determined by experiment.
  • One suitable methodology for this determination is using a medium- to high-swelling natural sodium bentonite. This is preferred over calcium bentonite, which could result in deviating initial effects being observed on first addition of the electrolyte under test. This effect may be due to ion-exchange and consequent transformation of the calcium clay to the sodium (or other relevant cation) form.
  • the chosen amount of electrolyte is first added with stirring to water, followed by the clay.
  • the amount of clay is determined by prior experiment (as hereinbefore described) as that resulting in a swellability (S) of the sodium bentonite in water is about 75%.
  • the swellability (S) is again tested as a function of electrolyte concentration.
  • a peptising electrolyte will exhibit an increase in swellability up to moderate electrolyte concentrations, whereas a non-peptising electrolyte will show a decrease in swellability, even at relatively low concentrations.
  • Figure 1 shows a plot of the swellability of a high-swelling natural sodium bentonite (Clarsol® W100) in water, as a function of clay concentration. From this, a clay concentration of 1.5% by weight is chosen as corresponding to a swellability of about 75%. The swellability of this amount of clay is plotted as a function of the concentration of a dissolved electrolyte under consideration. A typical result is shown in Figure 2, the clay and its concentration being those derived from Figure 1.
  • the NPNB's are not those electrolytes which are known as calcium ion sequestrant and/or precipitant builders, such as the various alkali metal carbonates, bicarbonates, phosphates, silicates, borates etc. These are already known as ingredients in clay containing liquid detergents.
  • electrolytes can be used and they mitigate the swelling induced viscosity increase when incorporated in amounts which are low relative to the proportions in which builder salts are commonly used.
  • NPNB's also excludes those salts which are usually employed for purposes other than building but which are known to have subsidiary builder properties, or are converted to builders in the wash solution.
  • One example of such a material is sodium perborate bleach.
  • viscosity increase means the viscosity rise substantially immediate upon introduction of the clay in the manufacturing process and it also refers to a clay swelling induced rise in viscosity on standing or during storage. It does not encompass any viscosity increase due to progressive ordering in any active structuring phase which also may be present.
  • the NPNB's do not in general totally negate the viscosity rise due to the clay but they are certainly capable of reducing it to an acceptable level. As a rule, they are incorporated in amounts such as to limit the clay swelling (by the test hereinbefore described) to no more than 45%, preferably 35%, especially 25%. To achieve this, it is necessary for them to be present from about 0.5 to about 10% by weight of the total composition, typically from about 1 to 5%, even from about 1.5 to 2%. In one generally preferred class of embodiments, the amount of NPNB is less than 5% by weight.
  • NPNB's in clay containing compositions is especially useful when the structuring system is used to suspend solid builder particles.
  • most, if not all of the NPNB will be in solution in the aqueous phase, which may contain other dissolved electrolyte material such as builder salts.
  • care must be taken in formulating and manufacturing active structured systems in order to avoid increase of viscosity to an unacceptable level. This problem is exacerbated when clay is present and the NPNB's help to mitigate this effect.
  • the NPNB's are selected from alkali metals, formates, acetates, chlorides and sulphates.
  • the potassium, and especially sodium salts are preferred.
  • the detergent compositions of the present invention necessarily contain one or more detergent active materials.
  • the detergent compounds may be selected from anionic, nonionic, zwitterionic and amphoteric synthetic detergent active materials. Many suitable detergent compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent compounds which can be used are synthetic anionic and nonionic compounds.
  • the former are usually water-soluble alkali metal salts of organic 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 acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18 ) alcohols produced for example from tallow or coconut oil, 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 neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane mono
  • Suitable nonionic detergent compounds which may be used 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-C22) phenols-ethylene oxide condensates, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO, 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 phosphine oxides and dialkyl sulphoxides.
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds.
  • detergent active materials may be used.
  • soap may also be present.
  • the detergent active material is soap
  • this is preferably selected from alkali metal salts of fatty acids having 12 to 18 carbon atoms.
  • fatty acids having 12 to 18 carbon atoms.
  • Typical such fatty acids are oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium salts of these acids can be used.
  • the level of detergent active material in the product is preferably at least 2% by weight, but not more than 45% by weight, most preferably from 6% to 15% by weight.
  • a detergency builder material to reduce the level of free calcium ions in the wash liquor and thereby improve detergency.
  • This material may be selected from precipitating detergency builder materials such as alkali metal carbonates and ortho-phosphates, ion-exchange builder materials such as alkali metal aluminosilicates and sequestering builder materials such as alkali metal tripolyphosphates, citrates and nitrilotriacetates. Particularly preferred is sodium tripolyphosphate for reasons of product structure and building efficiency. At least 5% by weight of the detergency builder material is required to provide a noticeable effect upon detergency.
  • the level of detergency builder material in the product is more than would dissolve at 20°C.
  • a preferred level is from 22 to 35% most preferably from 15 to 35%, based on the weight of the product.
  • the liquid detergent composition of the invention may further contain any of the adjuncts normally used in fabric washing detergent compositions, eg sequestering agents such as ethylenediamine tetraacetate; buffering agents such as alkali silicates; soil suspending and anti-redepositon agents such as sodium carboxymethyl cellulose and polyvinylpyrrolidone; fluorescent agents; perfumes; germicides; and colourants.
  • sequestering agents such as ethylenediamine tetraacetate
  • buffering agents such as alkali silicates
  • soil suspending and anti-redepositon agents such as sodium carboxymethyl cellulose and polyvinylpyrrolidone
  • fluorescent agents such as sodium carboxymethyl cellulose and polyvinylpyrrolidone
  • perfumes germicides
  • colourants eg.g sequestering agents such as ethylenediamine tetraacetate
  • buffering agents such as alkali silicates
  • soil suspending and anti-redepositon agents such as sodium
  • lather depressors such as silicones, and enzymes, particularly proteolytic and amylolytic enzymes
  • peroxygen bleaches such as sodium perborate and potassium dichlorocyanurate, including bleach activators, such as N,N,N',N',- tetraacetyl ethylene diamine, may be useful to formulate a complete heavy duty detergent composition suitable for use in washing machines.
  • agents for improving the thermal stability of the product such as sodium toluene sulphonate, xylene sulphonate or cumene sulphonate, at levels of up to 1% by weight, such as from 0.4% to 0.5%.
  • 'external' structuring agents e.g. of the polymeric type.
  • the products of the present invention may be prepared by a variety of methods. However, we have found that benefits arise from mixing ingredients in a particular order. Thus, it is preferable to add at least a portion of the NPNB and optionally also, any detergency builder which may be present, to water, before adding the clay and the detergent active material. In this way products having uniform rheological properties from batch to batch can be obtained.
  • an example outline of one preferred method comprises adding the necessary quantity of water to a mixing vessel provided with a stirrer. An amount of from one part in four up to the full amount of the total electrolyte (NPNB plus detergency builder) is then added, with stirring. This amount must include at least part, preferably all, of the NPNB.
  • NPNB is water-soluble
  • this amount will dissolve in the water and prevent the clay material from swelling but will not be sufficient to impair the stability of the composition.
  • the clay material is then added and dispersed with stirring.
  • Anionic and nonionic detergents, including soap where this is present, are then added.
  • the remaining part of the electrolyte is then added with stirring until a homogeneous mass is obtained.
  • the mixture is cooled (if necessary) under constant agitation and water is added, if necessary, to compensate evaporation loss. Thereafter perfume may be added when the product is at substantially ambient temperature.
  • compositions according to the present invention comprising the steps of:-
  • step (i) we prefer that substantially all of the non-peptising/non-building electrolyte is incorporated in step (i).
  • the aqueous base incorporated in step (i) will be substantially only water. Furthermore, in some instances, it is advantageous to hold back part of the water (whether or not the aqueous base in step (i) contains other components) so contacting the clay with an even higher eletrolyte concentration, this remaining water then being added after incorporation of the clay.
  • NPNB neuropeptide
  • a product when added to a stable formulation, a product may result which separates on standing. Addition of the clay to such an unstable formulation may result in restabilisation.
  • any step in the process of the present invention entails admixture of more than three components, these may be contacted sequentially or with any two or more simultaneously, in any desired order.
  • Formulations A-E were prepared with the ingredients listed in Table I. In each case the components were added to the water in the order reading from the top of the table to the bottom.
  • compositions were prepared in four series, where the 'clay' was
  • compositions A-E In addition to compositions A-E, a reference formulation, containing no sodium formate (but an equivalent quantity of water) was also prepared for each of the four clay series (a)-(d).
  • compositions where the NPNB is sodium sulphate and sodium chloride in Tables IIA and IIB respectively.
  • the medium and low swelling clays were those used in Example 1 but the high swelling clay was Clarsol® KC1.
  • Table IIB shows very comparable results with sodium chloride, except that with the high swelling clay, a small viscosity reduction was also observed when all the NPNB was added immediately after the clay.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (10)

  1. Flüssige Waschmittelzusammensetzung umfassend
    (i) eine wässerige Grundlage;
    (ii) waschmittelwirksames Material; und
    (iii) Elektrolyt;
       in Verhältnissen, die ausreichen, um ein strukturiertes System mit feststoffsuspendierenden Eigenschaften zu erzeugen und zusätzlich umfassend 1 bis 10 Gew.-% eines textilweichpflegenden Tonmaterials, dadurch gekennzeichnet, daß das Mittel 0,5 bis 10 Gew.-% eines nichtpeptisierenden/nicht als Builder wirkenden Elektrolyts umfaßt, ausgewählt aus Alkalimetallformiaten, -acetaten, -chloriden und -sulfaten, wobei die Zusammensetzung bei 25°C eine Viskosität von nicht mehr als 2,5 Pas bei einer Schergeschwindigkeit von 21 s⁻¹ aufweist und nicht mehr als 2 Vol.-% Phasentrennung nach Lagerung bei 25°C für 21 Tage vom Zeitpunkt der Herstellung an aufweist.
  2. Mittel nach Anspruch 1 mit einer Viskosität bei 25°C von nicht mehr als 1,75 Pas bei einer Schergeschwindigkeit von 21 s⁻¹.
  3. Mittel nach einem vorangehenden Anspruch, wobei das strukturierte System eine lamellare Dispersion umfaßt.
  4. Mittel nach einem vorangehenden Anspruch, wobei der Elektrolyt das Quellen des Tons bis zu einem Maximum von 45 % begrenzt.
  5. Mittel nach Anspruch 4, wobei die Grenze des maximalen Quellen des Tons 35 % beträgt.
  6. Mittel nach Anspruch 5, wobei die Grenze des maximalen Quellen des Tons 25 % beträgt.
  7. Verfahren zur Herstellung eines Mittels nach einem der Ansprüche 1-6, dadurch gekennzeichnet, daß es die Schritte umfaßt:
    (i) Mischen mit einer wässerigen Grundlage, mindestens etwas des nichtpeptisierenden/nicht als Builder wirkenden Elektrolyten und gegebenenfalls eines Buildersalzes, das nicht peptisiert
    (ii) Einmischen des textilweichpflegenden Tonmaterials;
    (iii) Einmischen in das Produkt von (ii), den Rest (falls überhaupt) des nichtpeptisierenden/nicht als Builder wirkenden Elektrolyten und gegebenenfalls etwas oder die Gesamtheit des Restes (falls überhaupt) eines nichtpeptisierenden Buildersalzes;
    (iv) Einmischen des waschmittelaktiven Materials in das Produkt von (iii); und
    (v) Einmischen eines peptisierenden Buildersalzes in das Produkt von Schritt (iv) und des Restes (falls überhaupt) eines nichtpeptisierenden Buildersalzes.
  8. Verfahren nach Anspruch 7, wobei die Gesamtheit des nichtpeptisierenden/nicht als Builder wirkenden Elektrolyten in Schritt (i) eingegeben wird.
  9. Verfahren nach Anspruch 7 oder 8, wobei die wässerige Grundlage nur Wasser umfaßt.
  10. Verfahren nach einem der Ansprüche 7-9, wobei das Wasser als weiterer Schritt unmittelbar vor Schritt (iv) zugegeben wird, so daß das Wasser und die in Schritt (i) eingegebene wässerige Grundlage zusammen die wässerige Grundlage nach Anspruch 1 umfassen.
EP88304186A 1987-05-11 1988-05-09 Flüssiges Waschmittel Expired - Lifetime EP0291261B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8711059 1987-05-11
GB878711059A GB8711059D0 (en) 1987-05-11 1987-05-11 Detergent liquid

Publications (3)

Publication Number Publication Date
EP0291261A2 EP0291261A2 (de) 1988-11-17
EP0291261A3 EP0291261A3 (en) 1990-01-17
EP0291261B1 true EP0291261B1 (de) 1993-10-27

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EP88304186A Expired - Lifetime EP0291261B1 (de) 1987-05-11 1988-05-09 Flüssiges Waschmittel

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EP (1) EP0291261B1 (de)
JP (1) JPH064875B2 (de)
AU (1) AU611434B2 (de)
BR (1) BR8802275A (de)
CA (1) CA1340298C (de)
DE (1) DE3885148T2 (de)
ES (1) ES2059514T3 (de)
GB (1) GB8711059D0 (de)
ZA (1) ZA883351B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8927361D0 (en) * 1989-12-04 1990-01-31 Unilever Plc Liquid detergents
GB0002876D0 (en) * 2000-02-08 2000-03-29 Unilever Plc Fabric conditioning composition
JP4819975B1 (ja) * 2011-02-16 2011-11-24 修 渡 着脱が簡単なおみくじ札

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954632A (en) * 1973-02-16 1976-05-04 The Procter & Gamble Company Softening additive and detergent composition
US4051055A (en) * 1976-12-21 1977-09-27 The Procter & Gamble Company Cleansing compositions
GB1572815A (en) * 1977-05-06 1980-08-06 Procter & Gamble Process for making detergent compositions
DE3163411D1 (en) * 1980-10-16 1984-06-07 Unilever Nv Stable liquid detergent suspensions
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
US4436637A (en) * 1982-12-13 1984-03-13 Colgate-Palmolive Company Fabric softening heavy duty liquid detergent containing a mixture of water insoluble soap and clay
US4582615A (en) * 1984-11-26 1986-04-15 Colgate Palmolive Co. Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
US4609473A (en) * 1984-11-26 1986-09-02 Colgate Palmolive Company Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
SE466963B (sv) * 1984-12-24 1992-05-04 Colgate Palmolive Co Textilmjukgoerande hoegverkande flytande detergent med stabil viskositet
ZA865095B (en) * 1985-07-26 1988-02-24 Colgate Palmolive Co Fabric softening liquid detergent

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ES2059514T3 (es) 1994-11-16
DE3885148T2 (de) 1994-02-24
CA1340298C (en) 1999-01-05
GB8711059D0 (en) 1987-06-17
EP0291261A3 (en) 1990-01-17
JPH064875B2 (ja) 1994-01-19
JPS6411199A (en) 1989-01-13
AU611434B2 (en) 1991-06-13
BR8802275A (pt) 1988-12-06
ZA883351B (en) 1990-01-31
AU1581288A (en) 1988-11-17
EP0291261A2 (de) 1988-11-17
DE3885148D1 (de) 1993-12-02

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