EP0678119A1 - Composition detergente et son procede de production. - Google Patents

Composition detergente et son procede de production.

Info

Publication number
EP0678119A1
EP0678119A1 EP94903842A EP94903842A EP0678119A1 EP 0678119 A1 EP0678119 A1 EP 0678119A1 EP 94903842 A EP94903842 A EP 94903842A EP 94903842 A EP94903842 A EP 94903842A EP 0678119 A1 EP0678119 A1 EP 0678119A1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent composition
dissolution aid
nonionic
surfactant system
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.)
Granted
Application number
EP94903842A
Other languages
German (de)
English (en)
Other versions
EP0678119B2 (fr
EP0678119B1 (fr
Inventor
Mark Phillip Houghton
Fransiscus Hermannu 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.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10728467&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0678119(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0678119A1 publication Critical patent/EP0678119A1/fr
Application granted granted Critical
Publication of EP0678119B1 publication Critical patent/EP0678119B1/fr
Publication of EP0678119B2 publication Critical patent/EP0678119B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 having a bulk density of at least 600 g/1 comprising a surfactant system, at least one detergency builder and a dissolution aid wherein the dissolution aid is present in an amount of 0.01 to 2% by weight as calculated on the composition and comprises a nonionic material which is an alkoxylated, aliphatic alcohol containing at least 25 alkylene oxide groups.
  • the invention also provides a process for the production of a particulate detergent composition having a bulk density of at least 600 g/1 comprising a surfactant system, at least one detergency builder and a dissolution aid wherein the dissolution aid is present in an amount of from 0,01 to 2% by weight as calculated on the composition and comprises a nonionic material which is an alkoxylated aliphatic alcohol containing at least 25 alkylene oxide groups, which process comprises mixing the dissolution aid with the surfactant system and builder sequentially or simultaneously.
  • the invention further provides the use of an alkoxylated aliphatic alcohol containing at least 25 alkylene oxide groups, as a dissolution aid in a particulate detergent composition having a bulk density of at least 600 g/1.
  • 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. Preferably 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.
  • 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.
  • 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:
  • the preferred sodium aluminosilicates contain 1.5-3.5 Si0 2 units (in the formula above) .
  • Suitable crystalline sodium aluminosilicates ion-exchange detergency builders are described, for example, in
  • 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, hydroxy- ethyliminodiacetates, 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; anti- redeposition 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
  • anti- redeposition 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/1, preferably at least 700 g/1 and most preferably at least 800 g/1 - which may be prepared by processes involving granulation and/or densi ication 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) .
  • 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.
  • 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 .
  • Sokalan (Trade Mark) CP5 Ex BASF
  • Fluorescer sodium carboxymethylcellulose, salts, etc. 4: Tetraacetylethylenediamine, as 83%wt granules.
  • Ethylenediaminetetramethylenephosphonic acid, calcium salt Dequest (Trade Mark) 2047 ex Monsanto (34%wt active) .
  • ethoxylated alcohol containing at least 25 ethylene oxide (EO) groups
  • EO ethylene oxide
  • 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.
  • this detergent powder varying amounts of ethoxylated alcohol containing 80 EO groups were postdosed. The delivery characteristics of the thus obtained powders were tested using the above-described model system and testing process. The results obtained are shown in Table 4
  • Example A To the detergent powder of Example A, varying -minor- amounts of polyethylene glycol having a molecular weight of 4000 (PEG 4000) were postdosed.
  • PEG 4000 polyethylene glycol having a molecular weight of 4000
  • a detergent composition having a bulk density of about 900 g/1 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.
  • 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.

Landscapes

  • 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)
EP94903842A 1993-01-08 1993-12-17 Utilisation d'alcohols aliphatiques ethoxyles comme aides de dissolution Expired - Lifetime EP0678119B2 (fr)

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 (fr) 1993-01-08 1993-12-17 Composition detergente et son procede de production

Publications (3)

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

Family

ID=10728467

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94903842A Expired - Lifetime EP0678119B2 (fr) 1993-01-08 1993-12-17 Utilisation d'alcohols aliphatiques ethoxyles comme aides de dissolution

Country Status (10)

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

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (fr) 2002-11-04 2008-12-24 Unilever Plc Composition de detergent de lessive
EP1690922A1 (fr) * 2005-02-11 2006-08-16 The Procter & Gamble Company Composition détergente solide
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

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH14838A (en) † 1974-03-21 1981-12-16 Procter & Gamble Detergent composition
US4137197A (en) * 1977-11-10 1979-01-30 Lever Brothers Company Powdered detergent compositions containing a calcium salt of an anionic surfactant
EP0026013B1 (fr) † 1979-09-21 1983-09-07 THE PROCTER & GAMBLE COMPANY Compositions de lavage et d'assouplissement et procédés pour leur production
GB8323131D0 (en) † 1983-08-27 1983-09-28 Procter & Gamble Ltd Detergent compositions
GB8712285D0 (en) † 1987-05-23 1987-07-01 Procter & Gamble Laundry products
EP0495345B1 (fr) † 1991-01-16 1994-11-02 The Procter & Gamble Company Agents anti-mousse sous forme de granulés
GB9108639D0 (en) † 1991-04-23 1991-06-12 Procter & Gamble Particulate detergent compositions
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
ES2151483T3 (es) * 1992-03-17 2001-01-01 Procter & Gamble Composiciones diluibles y metodo para la limpieza de superficies duras.
DE69225702T2 (de) * 1992-07-15 1999-01-21 The Procter & Gamble Co., Cincinnati, Ohio Verfahren zur Herstellung von kompakten Reinigungsmitteln

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9416052A1 *

Also Published As

Publication number Publication date
BR9307809A (pt) 1995-11-14
DE69314056D1 (de) 1997-10-23
DE69314056T2 (de) 1998-01-22
CA2153312A1 (fr) 1994-07-21
CA2153312C (fr) 2003-09-16
AU5814294A (en) 1994-08-15
ZA939731B (en) 1995-06-28
DE69314056T3 (de) 2006-02-02
EP0678119B2 (fr) 2005-05-25
JPH08505177A (ja) 1996-06-04
ES2107805T5 (es) 2005-12-01
ES2107805T3 (es) 1997-12-01
GB9300311D0 (en) 1993-03-03
WO1994016052A1 (fr) 1994-07-21
EP0678119B1 (fr) 1997-09-17

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