EP0301882B1 - Flüssige Reinigungsmittelzusammensetzungen - Google Patents

Flüssige Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0301882B1
EP0301882B1 EP19880307006 EP88307006A EP0301882B1 EP 0301882 B1 EP0301882 B1 EP 0301882B1 EP 19880307006 EP19880307006 EP 19880307006 EP 88307006 A EP88307006 A EP 88307006A EP 0301882 B1 EP0301882 B1 EP 0301882B1
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EP
European Patent Office
Prior art keywords
polymer
composition according
electrolyte
weight
viscosity
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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EP19880307006
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English (en)
French (fr)
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EP0301882A1 (de
Inventor
Mario Bulfari
Johannes Cornelis Van De Pas
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 date
Priority claimed from GB878718216A external-priority patent/GB8718216D0/en
Priority claimed from GB888813689A external-priority patent/GB8813689D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0301882A1 publication Critical patent/EP0301882A1/de
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Publication of EP0301882B1 publication Critical patent/EP0301882B1/de
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention is concerned with liquid detergent compositions of the kind containing a structure formed from detergent active material, the active structure existing as a separate phase dispersed within predominantly aqueous continuous phase.
  • This aqueous phase usually contains dissolved electrolyte.
  • Such structuring is very well known in the art and may be deliberately brought about to endow properties such as consumer preferred flow properties and/or turbid appearance.
  • Many active-structured liquids are also capable of suspending particulate solids such as detergency builders and abrasive particles.
  • lamellar droplets are called 'spherulites'.
  • the presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
  • lamellar dispersion a dispersion of lamellar droplets (lamellar dispersion). These 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 the droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
  • Electrolyte may be only dissolved in the aqueous continuous phase or may also be present as suspended solid particles. Particles of solid which are insoluble in the aqueous phase may be suspended alternatively or in addition to any solid electrolyte particles.
  • the suspended solid can be substantially the same as the dissolved.
  • This solid is usually present as a detergency builder, i.e. to counteract the effects of calcium ion water hardness in the wash.
  • it may be desirable to suspend substantially insoluble particles of bleach for example diperoxydodecandioic acid (DPDA).
  • DPDA diperoxydodecandioic acid
  • the suspended solid is usually a particulate abrasive, insoluble in the system.
  • the electrolyte is a different, water soluble material, present to contribute to structuring of the active material in the dispersed phase.
  • the abrasive can however comprise partially soluble salts which dissolve on dilution of the product.
  • compositions of the first kind are described, for example, in our patent specification EP-A-38,101; compositions containing suspended DPDA bleach are disclosed in specification EP-A-160342. Examples of those in the second category are described in our specification EP-A-104,452. Those in the third category are described, for example, in US 4,244,840.
  • the present composition provides a liquid detergent composition
  • a liquid detergent composition comprising a structured phase containing detergent active material, dispersed in an aqueous phase containing dissolved electrolyte, and a viscosity reducing polymer, the electrolyte containing aqueous phase being such that the polymer is only partly dissolved therein, said composition yielding 2% or less phase separation upon storage for 21 days at 25°C, and having a viscosity no greater than 1 Pa ⁇ s at a shear rate of 21 s ⁇ 1.
  • curve A This may be illustrated schematically by the curve A in the accompanying Figure 1.
  • the broken line indicates the onset of instability, whereafter there is instability.
  • all polymer samples do not contain molecules of identical configuration and molecular weight, but a spectrum of molecules with varying degrees of polymerisation (and in the case of co-polymers, proportions of different components).
  • the present invention may be due to adjustment of conditions in the liquid until one broad category of the polymers remains soluble at much higher concentrations than another.
  • curve B represents the category which under these particular conditions (different from those for curve A) can remain soluble at higher concentrations, whereas those molecules which become non-dissolved at much lower concentrations are shown as curve C.
  • the invention entails changing a composition of the kind described above, having an early onset of instability with increasing polymer concentration, to bring about the effect described above.
  • the amount of polymer stably incorporated in a composition according to the present invention is greater than that in a reference composition in which at least one parameter thereof is varied from that in the said composition, to permit the maximum amount of polymer to be incorporated by substantially all being dissolved, beyond which amount, dissolving of more polymer would cause the reference composition to have a phase separation of 2% or greater upon storage at 25°C for 21 days.
  • the parameter to be varied in the composition to bring about this effect may be pH, the quantity or nature of electrolyte in the composition or occasionally the quantity or nature of the detergent active material, or other parameters.
  • the viscosity reducing polymers which are susceptible of use in the present invention are selected from a very wide range and in particular include those polymer and co-polymer salts known as detergency builders.
  • the polymer may be used (including building and non-building polymers) polyethylene glycols, polyacrylates, polymaleates, polysugars, polysugarsulphonates and co-polymers of any of these.
  • the polymer comprises a co-polymer which includes an alkali metal salt of a polyacrylic, polymethacrylic or maleic acid or anhydride.
  • compositions with these co-polymers have a pH of above 8.0.
  • the amount of viscosity reducing polymer can vary widely according to the formulation of the rest of the composition. However, typical amounts are from 0.5 to 4.5% by weight, for example from 1 to 3.5% by weight.
  • the incorporation of the second polymer permits formulation with improved stability at the same viscosity (relative to the composition without the second polymer) or lower viscosity with the same stability.
  • the second polymer can also reduce an upwards viscosity drift, even when it also brings about a viscosity reduction.
  • the second polymer when the (first) viscosity reducing polymer has a large insoluble component. That is because although the building capacity of the first polymer will be good (since relatively high quantities can be stably incorporated), the viscosity reduction will not be optimum (since little will be dissolved). Thus, the second polymer can usefully function to reduce the viscosity further, to an ideal level.
  • the second polymer is incorporated at from 0.05 to 20% by weight, most preferably from 0.1 to 2.5% by weight, and especially from 0.2 to 1.5% by weight of the total composition. In many compositions (but not all) levels above these can cause instability. A large number of different polymers may be used as such a second polymer, provided the electrolyte resistance and vapour pressure requirements are met.
  • the former is measured as the amount of sodium nitrilotriacetate (NaNTA) solution necessary to reach the cloud point of 100 ml of a 5% solution of the polymer in water at 25°C, with the system adjusted to neutral pH, i.e. about 7. This is preferably effected using sodium hydroxide.
  • NaNTA sodium nitrilotriacetate
  • the electrolyte resistance is 10 g NaNTA, especially 15 g.
  • the latter indicates a vapour pressure low enough to have sufficient water binding capability, as generally explained in the applicants' specification GB-A-2053249.
  • the measurement is effected with a reference solution at 10% by weight aqueous concentration, especially 18%.
  • Typical classes of polymers which may be used as the second polymer include polyethylene glycols, Dextran, Dextran sulphonates, polyacrylates and polyacrylate/maleic acid co-polymers. Whether a given polymer is only partly, or substantially totally soluble in the total system will depend on the other components, in particular, the amount and type of electrolyte material.
  • the second polymer must have an average molecular weight of at least 1000 but a minimum average molecular weight of 2000 is preferred. Typical average molecular weight ranges resulting in beneficial viscosity control are from 1,200 to 30,000 especially from 5,000 to 30,000.
  • the detergent active material may be any known in the art for forming structured liquids and in general may be selected from one or more of anionic, cationic, nonionic, zwitterionic and amphoteric surfactants. However, one preferred combination comprises:
  • the actives may also include an alkali metal soap of a fatty acid, preferably one containing 12 to 18 carbon atoms.
  • Typical such acids are oleic acid, ricinoleic acid and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palm kernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used, the potassium soaps being preferred.
  • Suitable nonionic surfactants 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, the condensation products of aliphatic (C8-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 phosphine oxides and dialkyl sulphoxides.
  • the anionic surfactants 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 monos
  • compositions of the invention preferably contain a detergency builder material.
  • a detergency builder material may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material. They may be classed as inorganic, organic non-polymeric and organic polymeric.
  • any inorganic builder comprises all or part of the electrolyte (provided water soluble).
  • the liquid contains suspended solids, especially as all or part of the builder (which in that case does not have to be water soluble).
  • the electrolyte will generally form from 1 to 60% by weight of the total composition.
  • the suspended solids comprise water-insoluble amorphous or crystalline aluminosilicates, since these liquids tend to induce high viscosity and are thus in need of viscosity reduction by the polymer.
  • the polymer will itself be a builder and so together with the zeolite forms a very useful phosphorus-free builder system.
  • examples of phosphorus-containing inorganic detergency builders when present, include the water-soluble salts, especially alkaline metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous alumino silicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and silicates.
  • non-polymeric organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • lather boosters e.g 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, lipases (e.g. Lipolase (Trade Mark) ex Novo), and amylases, germicides, colourants and fabric softening clay materials.
  • lather boosters e.g alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors
  • chlorine-releasing bleaching agents such as trichloroisocyanuric acid
  • compositions of the present invention may be prepared using the general techniques known in the art of the processing of liquid detergent products.
  • order of addition of components can be important.
  • one preferred order of addition is to add to the water, the soluble electrolytes, then any insoluble material such as aluminosilicates, followed by the polymer and then the actives, which may be mixed before being added to the electrolyte/water phase.
  • Another preferred order of addition is to add to the water, any insoluble material such as aluminosilicates, the partly soluble polymer and then the detergent active material, followed by the electrolyte. The mixture is then cooled below 30°C, whereafter any minors and additional ingredients can be added.
  • the second polymer (if any) is added to reduce the viscosity to the desired level and it is indeed often possible to 'titrate' the viscosity to the required level by progressive addition of the second polymer.
  • the pH of the composition can be adjusted further, e.g. by the addition of a small quantity of caustic material.
  • Nonionic (1) ethoxylated fatty alcohol (C13 ⁇ 15EO3)
  • Nonionic (2) ethoxylated fatty alcohol (C13 ⁇ 15EO7)
  • Polymer Builder (1) Co-polymer of Acrylate and Maleate sodium salt, maleic acid: acrylic acid approx 3.8: 1, average MW about 70,000.
  • Polymer Builder (2) Co-polymer of Acrylate andMaleate sodium salt, maleic acid: acrylic acid approx 1.6: 1, average MW about 50,000.
  • ′var′ The parameters marked ′var′ were varied and the results of stability and viscosity measurements are shown in Tables 2 and 3 respectively.
  • ′stable′ means not showing more than 2% phase separation at ambient temperature (ca 21-25°C) over three months.
  • ′Unstable′ is to be construed accordingly.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Detergent Compositions (AREA)

Claims (18)

1. Flüssige Detergenszusammensetzung, die eine strukturierte Phase, enthaltend Detergens-aktives Material, dispergiert in einer wässrigen Phase, die gelösten Elektrolyt enthält und ein viskositätsreduzierendes Polymer umfaßt, wobei die den Elektrolyten enthaltende wässrige Phase derart ist, daß das Polymer nur teilweise darin gelöst wird, wobei die Zusammensetzung weniger als 2% Phasentrennung liefert bei einer Lagerung bei 25°C für 21 Tage und eine Viskosität nicht größer als 1 Pas bei einer Schergeschwindigkeit von 21 s⁻¹ aufweist.
2. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das die Viskosität reduzierende Polymer ein Copolymer ist, das ein Alkalimetallsalz einer Polyacryl-, Polymethacryl- oder Maleinsäure oder ― anhydrid einschließt.
3. Zusammensetzung nach Anspruch 6, die einen pH über 8,0 aufweist.
4. Zusammensetzung nach einem der vorhergehenden Ansprüche, die 0,5 bis 4,5 Gew.-% des viskositätsreduzierenden Polymers umfaßt.
5. Zusammensetzung nach Anspruch 4, die 1 bis 3,5 Gew.-% des viskositätsreduzierenden Polymers umfaßt.
6. Zusammensetzung nach einem der vorhergehenden Ansprüche, die weiter ein zweites Polymer umfaßt, das im wesentlichen völlig löslich ist in der wässrigen Phase und eine Elektrolytenresistenz von mehr als 5 Gramm Natriumnitrilotriacetat in 100 ml einer 5 Gew.-% wässrigen Lösung davon aufweist, wobei das zweite Polymer auch einen Dampfdruck in 20% wässriger Lösung aufweist, der gleich oder kleiner ist als der Dampfdruck einer 2 Gew.-% oder größer, wässrigen Bezugspolyethylenglykollösung, die ein durchschnittliches Molekulargewicht von 6000 aufweist, wobei das zweite Polymer ein Molekulargewicht von wenigstens 1000 aufweist.
7. Zusammensetzung nach Anspruch 6, die 0,05 bis 20 Gew.-% des zweiten Polymers umfaßt.
8. Zusammensetzung nach Anspruch 6 oder Anspruch 7, worin das durchschnittliche Molekulargewicht des zweiten Polymers 1200 bis 30000 ist.
9. Zusammensetzung nach einem der Ansprüche 10-12, worin das zweite Polymer ein durchschnittliches Molekulargewicht von wenigstens 2000 aufweist.
10. Zusammensetzung nach einem der Ansprüche 6-9, worin das zweite Polymer ein durchschnittliches Molekulargewicht von 5000 bis 30000 aufweist.
11. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das Detergens-aktive Material
a) ein nicht-ionisches oberflächenaktives Material und/oder ein polyalkoxyliertes anionisches oberflächenaktives Material, und
b) ein nicht-polyalkoxyliertes anionisches oberflächenaktives Material umfaßt.
12. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin der Elektrolyt anwesend ist von 1 bis 60 Gew.-% der Gesamtzusammensetzung.
13. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das viskositätsreduzierende Polymer Buildereigenschaften aufweist.
14. Zusammensetzung nach einem der vorhergehenden Ansprüche, die suspendiertes, festes, teilchenförmiges Material umfaßt.
15. Zusammensetzung nach Anspruch 14, worin das suspendierte, feste, teilchenförmige Material ein wasserunlösliches Aluminosilikatsalz umfaßt.
16. Zusammensetzung nach Anspruch 14 oder Anspruch 15, worin das suspendierte teilchenförmige Material einen Elektrolyt umfaßt, der der gleiche ist, wie der gesamte oder ein Teil des gelösten Elektrolyten.
17. Zusammensetzung nach einem der Ansprüche 14-16, worin das suspendierte teilchenförmige Material eine im wesentlichen wasserunlösliche Bleiche umfaßt.
18. Zusammensetzung nach Anspruch 17, worin die Bleiche DPDA umfaßt.
EP19880307006 1987-07-31 1988-07-29 Flüssige Reinigungsmittelzusammensetzungen Expired - Lifetime EP0301882B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB878718216A GB8718216D0 (en) 1987-07-31 1987-07-31 Liquid detergent compositions
GB8718216 1987-07-31
GB8813689 1988-06-09
GB888813689A GB8813689D0 (en) 1988-06-09 1988-06-09 Liquid detergent compositions

Publications (2)

Publication Number Publication Date
EP0301882A1 EP0301882A1 (de) 1989-02-01
EP0301882B1 true EP0301882B1 (de) 1992-01-15

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EP (1) EP0301882B1 (de)
JP (1) JPH0684520B2 (de)
KR (1) KR920000111B1 (de)
AU (1) AU600587B2 (de)
BR (1) BR8803786A (de)
CA (1) CA1323280C (de)
DE (1) DE3867749D1 (de)
ES (1) ES2029025T3 (de)
NO (1) NO171221C (de)
TR (1) TR23293A (de)

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GB8718217D0 (en) * 1987-07-31 1987-09-09 Unilever Plc Liquid detergent compositions
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GB8823655D0 (en) * 1988-10-07 1988-11-16 Unilever Plc Liquid detergent compositions
EP0385522B1 (de) * 1989-02-27 2001-08-29 Unilever N.V. Flüssiges Reinigungsmittel
GB8924478D0 (en) * 1989-10-31 1989-12-20 Unilever Plc Detergent compositions
JPH05501574A (ja) * 1989-12-01 1993-03-25 ユニリーバー・ナームローゼ・ベンノートシヤープ 液体洗剤
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GB8928067D0 (en) * 1989-12-12 1990-02-14 Unilever Plc Detergent compositions
DE69124090T2 (de) * 1990-03-06 1997-04-30 Unilever Nv Flüssige waschmittel
US5066749A (en) * 1990-09-11 1991-11-19 National Starch And Chemical Investment Holding Corporation Hydrophobically-modified polycarboxylates and process for their preparation
US5308530A (en) * 1990-11-21 1994-05-03 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polycarboxylates and calcium-sensitive enzymes
DE4216405A1 (de) * 1992-05-18 1993-11-25 Henkel Kgaa Pumpfähige alkalische Reinigerkonzentrate
AU6080699A (en) * 1998-09-25 2000-04-17 Bijl, Dirk Johannes Detergent composition
US8440605B2 (en) * 2009-06-08 2013-05-14 The Procter & Gamble Company Process for making a cleaning composition employing direct incorporation of concentrated surfactants
JP6675275B2 (ja) * 2016-06-15 2020-04-01 ライオン株式会社 繊維製品用液体洗浄剤組成物

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JPS63190502A (ja) * 1987-02-02 1988-08-08 Railway Technical Res Inst パンタグラフの上昇検知装置
GB8718217D0 (en) * 1987-07-31 1987-09-09 Unilever Plc Liquid detergent compositions

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CA1323280C (en) 1993-10-19
TR23293A (tr) 1989-09-14
KR890002383A (ko) 1989-04-10
KR920000111B1 (ko) 1992-01-09
NO883388D0 (no) 1988-07-29
AU600587B2 (en) 1990-08-16
AU2007688A (en) 1989-02-02
BR8803786A (pt) 1989-02-21
EP0301882A1 (de) 1989-02-01
NO883388L (no) 1989-02-01
JPH01103700A (ja) 1989-04-20
JPH0684520B2 (ja) 1994-10-26
NO171221B (no) 1992-11-02
NO171221C (no) 1993-02-10
DE3867749D1 (de) 1992-02-27
ES2029025T3 (es) 1992-07-16

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