EP0678119B1 - Waschmittel sowie dessen herstellungsverfahren - Google Patents

Waschmittel sowie dessen herstellungsverfahren Download PDF

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Publication number
EP0678119B1
EP0678119B1 EP94903842A EP94903842A EP0678119B1 EP 0678119 B1 EP0678119 B1 EP 0678119B1 EP 94903842 A EP94903842 A EP 94903842A EP 94903842 A EP94903842 A EP 94903842A EP 0678119 B1 EP0678119 B1 EP 0678119B1
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EP
European Patent Office
Prior art keywords
weight
detergent composition
nonionic
dissolution aid
composition
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
Application number
EP94903842A
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English (en)
French (fr)
Other versions
EP0678119A1 (de
EP0678119B2 (de
Inventor
Mark Phillip Houghton
Fransiscus Hermannus Gortemaker
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
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
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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 a detergent composition suitable for use in fabric washing applications.
  • 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.
  • the invention also relates to a process for producing this composition.
  • 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 a particulate detergent composition as outlined in Claim 1.
  • the invention also provides a process for the production of a particulate detergent composition as outlined in Claim 8.
  • a granular detergent composition according to the invention 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 alkoxylated aliphatic alcohol containing at least 25 alkylene oxide groups.
  • the detergent compositions of the invention are characterised by a dissolution aid comprising a nonionic material which is an alkoxylated aliphatic alcohol containing at least 25 alkylene oxide groups, preferably at least 50 alkylene oxide groups, more preferably at least 80 alkylene oxide groups.
  • a dissolution aid comprising a nonionic material which is an alkoxylated aliphatic alcohol containing at least 25 alkylene oxide groups, preferably at least 50 alkylene oxide groups, more preferably at least 80 alkylene oxide groups.
  • At least 50%, more preferably at least 80% and especially substantially all of the alkylene oxide groups are ethylene oxide.
  • the dissolution aid is suitably present at a level of from 0.01 to 2% by weight, preferably from 0.05 to 0.5% by weight based on the composition.
  • the surfactant system present in the detergent composition of the invention 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 of the invention 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 of the invention. 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 compositions of the invention 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 according to the invention 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 of the invention 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 aluminosilicates 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 compositions of the invention 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.
  • compositions according to the invention 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 are also within the scope of the invention.
  • compositions of the invention preferably do not contain more than 5% by weight of inorganic phosphate builders, and are desirably substantially free of phosphate builders.
  • Fully formulated laundry detergent compositions according to the present invention 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 such as cellulose derivatives and acrylate or acrylate/maleate polymers
  • dyes coloured speckles
  • perfumes foam controllers
  • the particulate detergent compositions of the invention 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.
  • detergent compositions according to the present invention have been found to show improved dissolution properties when employed in a washing process in a washing machine. Additional benefits associated with the invention 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.
  • 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.
  • 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.
  • 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 a* Synperonic A3 ex ICI 7.15 a* Synperonic A7 ex ICI 5.81 Stearic acid 2.04 b* Tallow 80EO 0.20 Sodium carboxymethyl cellulose 0.89 Moisture 4.98 63.88 a About 55% branched.
  • Ethoxylated tallow alcohol having an average degree of ethoxylation of 80.
  • 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 (9)

  1. Eine teilchenförmige Waschmittelzusammensetzung mit einer Schüttdichte von zumindest 600 g/l und enthaltend ein Surfactant-System, einschließend ein oder mehrere anionische und/oder nichtionische Surfactants, zumindest einen Waschkraftbuilder und eine Auflösungshilfe, worin das Surfactant-System in einer Menge im Bereich von 10 bis 50 Gewichtsprozent der Zusammensetzung vorhanden ist, die Auflösungshilfe in einer Menge von 0,05 bis 1 Gewichtsprozent, wie in der Zusammensetzung berechnet, vorhanden ist und ein nichtionisches Material enthält, welches ein alkoxylierter aliphatischer Alkohol ist, enthaltend zumindest 25 Alkylenoxid-Gruppen, und das Gewichtsverhältnis von nichtionischem Surfactant zur Auflösungshilfe größer als 10 : 1 ist.
  2. Eine Zusammensetzung nach Anspruch 1, in welcher zumindest 50 % der Alkylenoxid-Gruppen in dem nichtionischen Material Ethylenoxid-Gruppen sind.
  3. Eine Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, worin der alkoxylierte aliphatische Alkohol zumindest 50 Ethylenoxid-Gruppen enthält.
  4. Eine Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, worin das Surfactant-System zwei nichtionische Surfactants enthält, welche Kondensationsprodukte von Ethylenoxid mit einem aliphatischen C8-15-Alkohol sind mit der Reihe nach einem durchschnittlichen Grad der Ethoxylierung von 2 bis 5 und von 6,5 bis 10.
  5. Eine Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche enthaltend von 0,05 bis 0,5 Gewichtsprozent der Auflösungshilfe, berechnet auf die Zusammensetzung.
  6. Eine Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, worin das Surfactant-System im wesentlichen aus
    (i) von 40 bis 100 Gewichtsprozent des Surfactant-Systems von ethoxyliertem nichtionischen Surfactant, und
    (ii) von 0 bis 60 Gewichtsprozent von linearem Alkylbenzolsulfonat oder primärem C8-18-Alkoholsulfat,
    besteht.
  7. Eine Waschmittelzusammensetzung nach einem der vorstehenden Ansprüche, welche im wesentlichen frei von Phosphaten ist.
  8. Ein Verfahren für die Herstellung einer teilchenförmigen Waschmittelzusammensetzung mit einer Schüttdichte von zumindest 600 g/ℓ, enthaltend ein Surfactant-System, zumindest einen Waschkraftbuilder und eine Auflösungshilfe, worin das Surfactant-System in einer Menge im Bereich von 10 bis 50 Gewichtsprozent, wie in der Zusammensetzung berechnet, vorhanden ist, die Auflösungshilfe in einer Menge im Bereich von 0,05 bis 0,1 Gewichtsprozent, wie in der Zusammensetzung berechnet, vorhanden ist, und ein nichtionisches Material enthält, welches ein alkoxylierter aliphatischer Alkohol ist, enthaltend zumindest 25 Alkylenoxid-Gruppen, welches Verfahren das Mischen der Auflösungshilfe mit dem Surfactant-System und dem Builder, nacheinander oder gleichzeitig, umfaßt und das Gewichtsverhältnis von nichtionischem Surfactant zur Auflösungshilfe größer als 10 : 1 ist.
  9. Ein Verfahren für die Herstellung einer teilchenförmigen Waschmittelzusammensetzung nach Anspruch 8, worin die Auflösungshilfe in einer Menge im Bereich von 0,05 bis 0,5 Gewichtsprozent, wie in der Zusammensetzung berechnet, vorhanden 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
GB9300311 1993-01-08
GB939300311A GB9300311D0 (en) 1993-01-08 1993-01-08 Detergent powders and process for preparing them
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 true EP0678119B1 (de) 1997-09-17
EP0678119B2 EP0678119B2 (de) 2005-05-25

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ID=10728467

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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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CN1170921C (zh) * 1999-06-14 2004-10-13 花王株式会社 基本颗粒物和颗粒状洗涤剂
EP1193310B2 (de) * 1999-06-16 2016-06-29 Kao Corporation Teilchenförmiges waschmitteladditiv
EP1186650A4 (de) * 1999-06-16 2004-07-21 Kao Corp Gebrauchsgegenstand zur verwendung zum waschen in tuchform
GB0030671D0 (en) * 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0030669D0 (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
BR0315968A (pt) 2002-11-04 2005-09-20 Unilever Nv Composição detergente para lavagem de roupa, processo para lavar tecidos têxteis à máquina ou à mão, e, uso de um tensoativo não-iÈnico
EP1690922A1 (de) * 2005-02-11 2006-08-16 The Procter & Gamble Company Feste Waschmittelzusammensetzung
ATE474868T1 (de) 2006-05-31 2010-08-15 Basf Se Amphiphile pfropfpolymere auf basis von polyalkylenoxiden und vinylestern
EP2823029A1 (de) 2012-03-09 2015-01-14 The Procter & Gamble Company Waschmittelzusammensetzungen mit pfropfpolymeren mit breiten polaritätsverteilungen

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EP0561103B1 (de) * 1992-03-17 2000-11-08 The Procter & Gamble Company Verdünnbare Zusammensetzungen und Verfahren zur Reinigung harter Oberflächen
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Also Published As

Publication number Publication date
EP0678119A1 (de) 1995-10-25
DE69314056D1 (de) 1997-10-23
WO1994016052A1 (en) 1994-07-21
CA2153312A1 (en) 1994-07-21
CA2153312C (en) 2003-09-16
EP0678119B2 (de) 2005-05-25
ZA939731B (en) 1995-06-28
DE69314056T3 (de) 2006-02-02
ES2107805T5 (es) 2005-12-01
GB9300311D0 (en) 1993-03-03
ES2107805T3 (es) 1997-12-01
JPH08505177A (ja) 1996-06-04
BR9307809A (pt) 1995-11-14
AU5814294A (en) 1994-08-15
DE69314056T2 (de) 1998-01-22

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