EP0678119B2 - Verwendung ethoxylierter aliphatischer alkohole als lösungsvermittler - Google Patents

Verwendung ethoxylierter aliphatischer alkohole als lösungsvermittler Download PDF

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Publication number
EP0678119B2
EP0678119B2 EP94903842A EP94903842A EP0678119B2 EP 0678119 B2 EP0678119 B2 EP 0678119B2 EP 94903842 A EP94903842 A EP 94903842A EP 94903842 A EP94903842 A EP 94903842A EP 0678119 B2 EP0678119 B2 EP 0678119B2
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EP
European Patent Office
Prior art keywords
weight
composition
dissolution aid
detergent composition
use according
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Expired - Lifetime
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EP94903842A
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English (en)
French (fr)
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EP0678119A1 (de
EP0678119B1 (de
Inventor
Mark Phillip Houghton
Fransiscus Hermannus Gortemaker
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to the use of an ethoxylated aliphatic alcohol containing at least 25 ethylene oxide groups to improve dissolution and/or dispersion in the wash liquor of a particulate detergent composition.
  • the invention is of especial applicability to particulate detergent compositions, containing no, or low levels of, phosphate builder and to compositions of high bulk density.
  • Detergent powders typically comprise anionic and/or nonionic surfactants.
  • Nonionic surfactants are particularly effective in removing hydrophobic soils such as hydrocarbon oils, complex fats and other long-chain unsaturated and saturated glycerides.
  • the nonionic surfactant may form a viscous phase which may impede dissolution.
  • Nonionic surfactants having a low degree of ethoxylation, generally employed because of their oily soil detergency, are especially problematic in this respect.
  • the present invention provides the use set out in Claim 1.
  • the granular detergent composition has a bulk density from 600 to 1100 kg/m 3 , preferably from 700 to 1100 kg/m 3 .
  • Various postdosed ingredients such as sodium carbonate, bleach material and foam depressing agent, may be added to the composition as desired.
  • the composition may be prepared by spray-drying optionally followed by mixing or by dry-mixing/agglomeration. For obtaining high bulk densities, the composition is preferably prepared by dry-mixing/agglomeration.
  • the composition contains surfactant system, builder material and a dissolution aid. It is preferred that the dissolution aid is present in the composition of the invention as a separate granular component. Preferably the dissolution aid is substantially pure ethoxylated aliphatic alcohol containing at least 25 ethylene oxide groups.
  • the dissolution aid contains at least 50 ethylene oxide groups, more preferably at least 80 ethylene oxide groups.
  • the dissolution aid is suitably present at a level of from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight based on the composition.
  • the surfactant system present in the detergent composition suitably contains alkoxylated nonionic surfactants having an average degree of alkoxylation of at most 11.
  • Suitable nonionic surfactants include condensation products of ethylene oxide with an aliphatic alcohol having from 8 to 15 carbon atoms and an average degree of ethoxylation from 2 to 10.
  • a preferred surfactant system comprises a mixture of two C 8-15 nonionic surfactants having an average degree of ethoxylation respectively of 2 to 5, preferably 2.5 to 4 and 6.5 to 10, preferably 6.5 to 8 which, suitably, are present in a weight ratio of 1 to 25:5.
  • the proportion of nonionic surfactant having a branched aliphatic alcohol is in the range from 10 to 60% by weight for example about 55% by weight based on the total amount of nonionic surfactant in the composition.
  • Nonionic detergent-active compounds and the dissolution aid together are suitably present in the compositions in a total amount of from 2 to 50% by weight, preferably from 5 to 30% by weight.
  • detergent-active materials may be present in the compositions. These additional detergent-active materials may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric surfactants, or any combination of these surfactants.
  • Anionic detergent-active compounds may be present in an amount of from 0 to 40% by weight, preferably from 0 to 20% by weight. It is preferred that the ratio of nonionic surfactant and dissolution aid to anionic surfactant is within the range of 1:2 to 9:1.
  • Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -C 15 primary alkyl sulphates, olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinate; and fatty acid ester sulphonates.
  • alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15
  • primary and secondary alkyl sulphates particularly sodium C 12 -C 15 primary alkyl sulphates, olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinate; and fatty acid ester sulphonates.
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
  • the total amount of surfactant in the composition is suitably from 5 to 50% by weight.
  • high-performance compositions containing relatively high levels of surfactant preferably from 10 to 50% by weight and more preferably from 15 to 50% by weight.
  • compositions include surfactant systems consisting especially of nonionic surfactant as described above in combination with linear alkylbenzene sulphonate (LAS) or primary alcohol sulphate (PAS) or both.
  • LAS linear alkylbenzene sulphonate
  • PAS primary alcohol sulphate
  • Surfactant systems of especial interest consist essentially of
  • the detergent powders contain one or more detergency builders, suitably in an amount from 5 to 80% by weight, preferably from 20 to 60% by weight.
  • the invention is especially applicable to compositions containing alkali metal aluminosilicates as builders.
  • Alkali metal (preferably sodium) aluminosilicates may generally be incorporated in an amount from 5 to 60% by weight (anhydrous basis) of the composition, preferably from 25 to 55% by weight, and suitably, in a heavy duty detergent composition, from 25 to 46% by weight.
  • the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O. Al 2 O 3 . 0.8-6 SiO 2
  • These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above).
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1,429,143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolite A and X, and mixtures thereof.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder incorporated in the composition is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP-A-384,070 (Unilever).
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1,437,950 (Unilever).
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di-and trisuccinates, carboxymethyloxysuccinates, hydroxyethyliminodiacetates, alkyl- and alkenyl-malonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • Builders, both inorganic and organic are preferably present in alkali metal salt, especially sodium salt, form.
  • Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15% by weight, especially from 1 to 10% by weight; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20% by weight, more preferably from 5 to 15% by weight.
  • the composition may contain alkali metal, preferably sodium, carbonate, to increase detergency and to ease processing.
  • alkali metal preferably sodium, carbonate
  • Sodium carbonate may generally be present in amounts ranging from 1 to 60%by weight, preferably from 2 to 40% by weight, and most preferably from 2 to 13% by weight.
  • compositions free of alkali metal carbonate may also be used.
  • compositions preferably do not contain more than 5% by weight of inorganic phosphate builders, and are desirably substantially free of phosphate builders.
  • Suitable fully formulated laundry detergent compositions may additionally contain any suitable ingredients normally employed in detergent compositions, for example, inorganic salts such as sodium silicate or sodium sulphate; organic salts such as sodium citrate; antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers; fluorescers; bleaches, bleach precursors and bleach stabilizers; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
  • inorganic salts such as sodium silicate or sodium sulphate
  • organic salts such as sodium citrate
  • antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers
  • fluorescers bleaches, bleach precursors and bleach stabilizers
  • proteolytic and lipolytic enzymes dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
  • the particulate detergent compositions may in principle be prepared by any of the available tower (spray-drying), non-tower (granulation) or combination processes.
  • compositions of high bulk density - at least 600 g/l, preferably at least 700 g/l and most preferably at least 800 g/l - which may be prepared by processes involving granulation and/or densification in a high-speed mixer/granulator.
  • One suitable method comprises spray-drying a slurry of compatible heat-insensitive ingredients, including the zeolite MAP, any other builders, and at least part of the detergent-active compounds; densifying the resulting base powder in a mixer/granulator; and then spraying on or post-dosing those ingredients unsuitable for processing via the slurry (for example bleaches and enzymes).
  • compatible heat-insensitive ingredients including the zeolite MAP, any other builders, and at least part of the detergent-active compounds
  • the spray-drying step can be omitted altogether, a high bulk density base powder being prepared directly from its constituent raw materials, by mixing and granulating in a high speed mixer/granulator, and then post-dosing bleach and other ingredients as in the spray-drying/post-tower densification route.
  • the high-speed mixer/granulator also known as a high-speed mixer/densifier, may be a batch machine such as the Fukae (Trade Mark)FS, or a continuous machine such as the Lodige (Trade Mark) Recycler CB30. Processes using high-speed mixer/granulators are disclosed, for example, in EP-A-340,013, EP-A-367,339, EP-A-390,251 and EP-A-420,317 (Unilever).
  • the dissolution aid may be included in the base powder but is preferably admixed with the finished base powder.
  • Nonionic surfactants having a lower degree of alkoxylation, particularly those containing on average less than 11 ethylene oxide groups, may be included in the base powder, post added, or both.
  • dissolution aid in detergent composition has been found to improve dissolution properties in a washing process in a washing machine. Additional benefits associated with use of the dissolution aid were found to be reduced redeposition characteristics during the washing cycle and improved bleeding behaviour upon storage.
  • a particulate detergent composition having a bulk density of 830 kg/m 3 was prepared by spray-drying an aqueous slurry to form a base powder (including nonionic surfactants as specified), densifying the base powder in a continuous Lodige high-speed mixer/granulator, spraying-on further nonionic surfactants as specified, and then admixing the remaining ingredients.
  • ethoxylated alcohol containing at least 25 ethylene oxide (EO) groups were postdosed, as specified in Table 2.
  • Suitable commercially available nonionic materials containing at least 25 EO groups include the LUTENSOL AT [Trade Mark] series ex BASF and the BRIJ [Trade Mark] series ex ICI.
  • the type of the postdosed nonionic materials is indicated in this Table by number of EO-groups present therein.
  • Example Postdosed high EO nonionic material amount (parts) type A 0.000 -- 1 0.50 25 EO 2 0.125 25 EO 3 0.50 50 EO 4 0.125 50 EO 5 (Comp.) 1.00 80 EO 6 0.50 80 EO 7 0.25 80 EO 8 0.125 80 EO 9 0.0625 80 EO
  • a 30 cm metal rod was inserted to act as a handle, and this handle was attached in an agitator arm positioned above 1 litre water present in a container and having a temperature of 20 C.
  • the cylindrical vessel held at 45 degrees could be rotated through a circle with a 10 cm radius during 2 seconds. Subsequently the vessel could be allowed to rest during 2 seconds before the next rotation-rest cycle started.
  • Example Postdosed high EO nonionic material Residue amount (parts) type (wt%) A 0.000 -- 34 1 0.50 25 EO 22 2 0.125 25 EO 20 3 0.50 50 EO 24 4 0.125 50 EO 18 5 (Comp.) 1.00 80 EO 25 6 0.50 80 EO 22 7 0.25 80 EO 16 8 0.125 80 EO 14 9 0.0625 80 EO 21
  • a particulate detergent composition was prepared in a very similar way and having almost the same formulation as in the above-mentioned Example A, the only difference being that in the present Examples the sprayed-on nonionic surfactant material fully consists of Synperionic A3 (containing 3 EO groups) ex ICI.
  • Example Postdosed PEG 4000 Residue amount (parts) (wt%) A 0.000 34 B 0.50 33 C 0.25 35
  • a detergent composition having a bulk density of about 900 g/l was prepared by a mixing/granulation process to produce a base powder to which further components were post-dosed into the base powder as listed below.
  • Base Powder Sodium primary alkyl sulphate (PAS) 5.81 Zeolite MAP 36.04 Sodium carbonate 0.96 * Synperonic A3 ex ICI 7.15 * Synperonic A7 ex ICI 5.81 Stearic acid 2.04 * Tallow 80EO 0.20 Sodium carboxymethyl cellulose 0.89 Moisture 4.98 63.88
  • the nonionic materials (*) were mixed and then sprayed onto an adjunct comprising PAS, carbonate and part of the zeolite, and sodium carboxymethyl cellulose and stearic acid in a Lodige CB30 "Recycler” mixer.
  • the stearic acid was neutralised by addition of base.
  • the mixture was then layered with the remaining zeolite and passed to a Lodige KM300 "Ploughshare” mixer and then a fluid bed as described in EP-A-367 339 (Unilever) to produce the base powder.
  • a comparative composition E was prepared by the same process and to the same composition as Example 12 save that the Tallow 80EO in the base was replaced by 0.20 parts SYNPERONIC A3.
  • compositions containing a dissolution aid have significantly superior delivery characteristics when compared to a similar composition which does not contain a dissolution aid.
  • the detergencies of the powders of Examples A,D (comparative) and 7 (according to the invention) were compared by means of a washing machine test.
  • the machine used was a Siemens Siwamat (Trade Mark) Plus 3700 front-loading automatic washer.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (6)

  1. Verwendung eines ethoxylierten aliphatischen Alkohols mit wenigstens 25 Ethylenoxidgruppen als Auflösungshilfe zur Verbesserung der Auflösung und/oder Dispersion einer partikulären Reinigungsmittelzusammensetzung in der Waschflüssigkeit, wobei die partikuläre Reinigungsmittelzusammensetzung eine Schüttdichte von wenigstens 600 g/l hat und ein Tensidsystem mit einem oder mehreren nichtionischen Tensid(en), einem oder mehreren anionischen Tensid(en) und wenigstens einem Aufbaustoff umfasst, wobei das Tensidsystem in einer Menge zwischen 10 und 50 Gew.-% der Zusammensetzung vorliegt, wobei die Auflösungshilfe in einer Menge zwischen 0,05 und 1 Gew.-%, berechnet auf die Zusammensetzung, vorliegt und das Gewichtsverhältnis zwischen nichtionischem Tensid und Auflösungshilfe größer als 10:1 ist, vorausgesetzt, die partikuläre Reinigungsmittelzusammensetzung umfasst kein Alkylglycosid der allgemeinen Formel R-O-(G)x, wobei R eine gerade Primärkette oder ein verzweigter, aliphatischer 2-Methyl-Rest mit 8 bis 22 Kohlenstoffatomen ist, G eine Glykosekette mit 5 bis 6 Kohlenstoffatomen ist und der Oligomerisierungsgrad x zwischen 1 und 10 liegt.
  2. Verwendung nach Anspruch 1, wobei die Auflösungshilfe wenigstens 50 Ethylenoxidgruppen enthält.
  3. Verwendung nach einem der vorherigen Ansprüche, wobei das Tensidsystem zwei nichtionische Tenside umfasst, die Kondensationsprodukte von Ethylenoxid mit einem aliphatischen C8-C15 Alkohol sind, mit jeweils einem durchschnittlichen Ethoxylierungsgrad von 2 bis 5 und von 6,5 bis 10.
  4. Verwendung nach einem der vorherigen Ansprüche, wobei die Reinigungsmittelzusammensetzung zwischen 0,05 und 0,5 Gew.-% der Auflösungshilfe, berechnet auf die Zusammensetzung, umfasst.
  5. Verwendung nach einem der vorherigen Ansprüche, wobei das Tensidsystem im Wesentlichen Folgendes umfasst:
    (i) 40 bis 100 Gew.-% des Tensidsystems an ethoxyliertem, nichtionischem Tensid, und
    (ii) 0 bis 60 Gew.-% an linearem Alkylbenzolsulfonat oder C8-C18 Primäralkoholsulfat.
  6. Verwendung nach einem der vorherigen Ansprüche, wobei die Reinigungsmittelzusammensetzung im Wesentlichen frei von Phosphaten ist.
EP94903842A 1993-01-08 1993-12-17 Verwendung ethoxylierter aliphatischer alkohole als lösungsvermittler Expired - Lifetime EP0678119B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB939300311A GB9300311D0 (en) 1993-01-08 1993-01-08 Detergent powders and process for preparing them
GB9300311 1993-01-08
PCT/EP1993/003624 WO1994016052A1 (en) 1993-01-08 1993-12-17 Detergent composition and process for producing it

Publications (3)

Publication Number Publication Date
EP0678119A1 EP0678119A1 (de) 1995-10-25
EP0678119B1 EP0678119B1 (de) 1997-09-17
EP0678119B2 true EP0678119B2 (de) 2005-05-25

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Application Number Title Priority Date Filing Date
EP94903842A Expired - Lifetime EP0678119B2 (de) 1993-01-08 1993-12-17 Verwendung ethoxylierter aliphatischer alkohole als lösungsvermittler

Country Status (10)

Country Link
EP (1) EP0678119B2 (de)
JP (1) JPH08505177A (de)
AU (1) AU5814294A (de)
BR (1) BR9307809A (de)
CA (1) CA2153312C (de)
DE (1) DE69314056T3 (de)
ES (1) ES2107805T5 (de)
GB (1) GB9300311D0 (de)
WO (1) WO1994016052A1 (de)
ZA (1) ZA939731B (de)

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DE19526483A1 (de) * 1995-07-20 1997-01-23 Henkel Kgaa Tensidabmischungen mit verbesserter Löslichkeit von Aniontensiden auf Basis langkettiger Alkylsulfatsalze auch bei niederen Flottentemperaturen
WO2000077158A1 (fr) * 1999-06-14 2000-12-21 Kao Corporation Base granulaire et detergent particulaire
JP3249815B2 (ja) * 1999-06-16 2002-01-21 花王株式会社 洗剤添加用粒子群
US6818606B1 (en) 1999-06-16 2004-11-16 Kao Corporation Article for use in washing in sheet form
GB0030669D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0030671D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0124308D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
GB0124307D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
EP1558717B1 (de) 2002-11-04 2008-12-24 Unilever Plc Waschmittel
EP1690922A1 (de) * 2005-02-11 2006-08-16 The Procter & Gamble Company Feste Waschmittelzusammensetzung
BRPI0712159B1 (pt) 2006-05-31 2018-04-24 Basf Se Polímero de enxerto anfifílico, e, processo para preparar polímeros de enxerto
US8859484B2 (en) 2012-03-09 2014-10-14 The Procter & Gamble Company Detergent compositions comprising graft polymers having broad polarity distributions

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US4294711A (en) † 1979-09-21 1981-10-13 The Procter & Gamble Company Washing and softening compositions and methods for their manufacture
EP0142910A1 (de) † 1983-08-27 1985-05-29 The Procter & Gamble Company Schaum unterdrückende Zusammensetzungen und ihre Verwendung in Detergenszusammensetzungen
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ES2151483T3 (es) * 1992-03-17 2001-01-01 Procter & Gamble Composiciones diluibles y metodo para la limpieza de superficies duras.
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US4294711A (en) † 1979-09-21 1981-10-13 The Procter & Gamble Company Washing and softening compositions and methods for their manufacture
EP0142910A1 (de) † 1983-08-27 1985-05-29 The Procter & Gamble Company Schaum unterdrückende Zusammensetzungen und ihre Verwendung in Detergenszusammensetzungen
US4876023A (en) † 1987-05-23 1989-10-24 The Procter & Gamble Company Laundry products
EP0495345A1 (de) † 1991-01-16 1992-07-22 THE PROCTER & GAMBLE COMPANY Schaumkontrollmittel in granulierter Form
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BR9307809A (pt) 1995-11-14
DE69314056D1 (de) 1997-10-23
DE69314056T2 (de) 1998-01-22
CA2153312A1 (en) 1994-07-21
CA2153312C (en) 2003-09-16
AU5814294A (en) 1994-08-15
ZA939731B (en) 1995-06-28
DE69314056T3 (de) 2006-02-02
JPH08505177A (ja) 1996-06-04
ES2107805T5 (es) 2005-12-01
ES2107805T3 (es) 1997-12-01
GB9300311D0 (en) 1993-03-03
EP0678119A1 (de) 1995-10-25
WO1994016052A1 (en) 1994-07-21
EP0678119B1 (de) 1997-09-17

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