WO1996006151A1 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
WO1996006151A1
WO1996006151A1 PCT/EP1995/002709 EP9502709W WO9606151A1 WO 1996006151 A1 WO1996006151 A1 WO 1996006151A1 EP 9502709 W EP9502709 W EP 9502709W WO 9606151 A1 WO9606151 A1 WO 9606151A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
composition
antioxidant
surfactant
ethoxylated
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.)
Ceased
Application number
PCT/EP1995/002709
Other languages
English (en)
Inventor
Peter William Appel
Ian Mckinlay Clark
Huig Euser
Colin Sydney Fairclough
Franciscus Hermannus Gortemaker
Terry Instone
Christophe Michel Bruno Joyeux
Stephen Thomas Keningley
Peter Cory Knight
Paul Edward Mcdonald
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 NV
Original Assignee
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
Application filed by Unilever NV filed Critical Unilever NV
Priority to PL95318787A priority Critical patent/PL318787A1/xx
Priority to AU29830/95A priority patent/AU2983095A/en
Priority to SK240-97A priority patent/SK24097A3/sk
Priority to BR9508807A priority patent/BR9508807A/pt
Priority to CZ97530A priority patent/CZ53097A3/cs
Priority to EP95925861A priority patent/EP0777715A1/fr
Publication of WO1996006151A1 publication Critical patent/WO1996006151A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic

Definitions

  • the present invention relates to particulate detergent compositions containing high levels of high performance organic surfactants, and especially to compositions containing primary alcohol sulphate or ethoxylated alcohol nonionic surfactants or both.
  • the compositions exhibit improved stability owing to the presence of low levels of antioxidants.
  • EP 283 252B and EP 320 219B disclose particulate detergent compositions in which an antioxidant is incorporated within bleach activator granules, in order to improve bleach activator stability.
  • the benefit is reduced odour and discoloration on storage.
  • the present invention accordingly provides a particulate detergent composition
  • a particulate detergent composition comprising
  • an organic surfactant system comprising anionic and/or nonionic non-soap surfactants, the composition containing more than 5 wt% of C 8 . 20 primary alcohol sulphate and/or at least 8 wt% of an ethoxylated C 8 - 20 alcohol nonionic surfactant and/or more than 15 wt% of total non-soap organic surfactant,
  • composition of the invention contains a high level or non-soap organic surfactant, preferably 15 wt% or above, preferably from 15 to 25 wt%.
  • a high level or non-soap organic surfactant preferably 15 wt% or above, preferably from 15 to 25 wt%.
  • certain compositions containing total surfactant levels below 15 wt% are also within the scope of the invention.
  • the surfactants may be chosen from anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent- active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. Anionic surfactants are well-known to those skilled in the art.
  • alkylbenzene sulphonates particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkylsulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, lactobionamides, and polyhydroxyamides (gluca ide) .
  • compositions containing a surfactant system comprising a C 8 _ 20 primary alcohol sulphate, an ethoxylated C 8 _ 20 alcohol nonionic surfactant, or both.
  • Preferred compositions of the invention contain more than 5 wt% of C 8-20 primary alcohol sulphate, and/or at least 8 wt%, preferably at least 10 wt%, of ethoxylated C 8-20 alcohol nonionic surfactant. If one or both of these conditions is met, the total level of non-soap organic surfactant in the compositions of the invention need not be greater than 15 wt%, but is however preferably at least 10 wt% and is more preferably at least 12 wt%.
  • compositions of the invention comprises compositions containing more than 5 wt%, based on the whole product, of C 8 . 20 primary alcohol sulphate, optionally in combination with an ethoxylated C 8 _ 20 alcohol nonionic surfactant.
  • the preferred compositions may contain at least 8 wt%, more preferably at least 10 wt%, of ethoxylated nonionic surfactant, and advantageously the ratio of primary alcohol sulphate to ethoxylated nonionic sulphate may be less than 1:1.
  • compositions containing lesser proportions of nonionic surfactant for example, those containing additional anionic surfactants, are also within the scope of the invention.
  • compositions of the invention also containing at least 8 wt% and more preferably at least 10 wt% of ethoxylated nonionic surfactant, are those in which the non-soap surfactant system consists wholly or substantially wholly of nonionic surfactants.
  • compositions of the invention may also contain fatty acid soap. However, where the limit of at least 15 wt% total surfactant applies, this does not include any fatty acid soap present.
  • compositions of the invention contain, as detergency builder, an alkali metal aluminosilicate, either alone or in conjunction with one or more supplementary builders.
  • the total amount of detergency builder in the compositions may suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
  • An essential component of the composition of the invention is an alkali metal, preferably sodium, aluminosilicate builder.
  • Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
  • 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). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • 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 zeolites 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 384 070A (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.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • the zeolite is advantageously used in conjunction with a supplementary builder.
  • Supplementary organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates
  • Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • compositions of the invention may also contain lamellar crystalline sodium silicate having the composition
  • M denotes sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • Both natural and synthetic compounds of this formula are of interest, the synthetic material known as Na-SKS-6 being especially preferred.
  • This material is commercially available from Hoechst AG; its preparation is described, and it is defined in terms of its X-ray diffraction pattern, in the aforementioned US 4 664 839.
  • the antioxidant is a material capable of retarding oxidation of the surfactant system of the composition at elevated temperatures, for example, above 100°C.
  • the antioxidant is preferably present in an amount of from 0.01 to 2 wt%, more preferably from 0.05 to 1 wt% and more especially from 0.1 to 0.5 wt%.
  • One class of preferred antioxidants is constituted by the sterically hindered phenols.
  • Suitable antioxidants include the following:
  • BHT butylated hydroxytoluene
  • BHA butylated hydroxyanisole
  • TBHQ tert-butylhydroquinone
  • composition of the invention may also contain a sequestrant for transition metal ions.
  • Preferred sequestrants include aminopolycarboxylates, for example, ethylenediaminetetraacetic acid or its salts; or aminopolyphosphonates, for example, ethylenediamine tetramethylenephosphonic acid (ETDMP) or its salts (Dequest (Trade Mark) 2041 and 2047 ex Monsanto) or higher phosphonates such as diethylenetriamine pentamethylenephosphonic acid (DETPMP) and its salts (Dequest (Trade Mark) 2060 or 2061).
  • ETDMP ethylenediamine tetraacetic acid
  • aminopolyphosphonates for example, ethylenediamine tetramethylenephosphonic acid (ETDMP) or its salts (Dequest (Trade Mark) 2041 and 2047 ex Monsanto) or higher phosphonates such as diethylenetriamine pentamethylenephosphonic acid (DETPMP) and its salts (Dequest (Trade Mark) 2060 or 2061).
  • Such phosphonates are conventionally incorporated into detergent compositions containing peroxy bleach compounds, as bleach stabilisers; but in the context of the present invention sequestrants are advantageously present whether or not a bleach system is also present.
  • compositions of the invention may if desired contain a bleach system.
  • the invention is not concerned with bleach stability and is equally applicable to non-bleaching formulations.
  • Suitable peroxy bleach compounds include organic peroxyacids, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N' ,N'-tetracetyl ethylenediamine (TAED) .
  • a bleach stabiliser (heavy metal sequestrant) may also be present. Suitable sequestrants are discussed above.
  • the bleach system may also include a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever) .
  • compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • fatty acid soap suitably present in an amount of from 1 to 5 wt%.
  • detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; other soil release or antiredeposition polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; detergent enzymes, for example, proteases, lipases, cellulases and amylases; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
  • the invention is of especial value for compact detergent powders in which ingredients are in especially close proximity, for example, compositions having bulk densities of 650 g/1 or more, and especially of 750 g/1 or more.
  • Detergent compositions of high bulk density are generally prepared either by post-tower densification of spray-dried powder, or by wholly non-spray-drying processes such as mixing and granulation. In both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
  • compositions of the invention will include the step of mixing and granulating ingredients in a high-speed mixer/densifier to form a base powder of high bulk density, and optionally postdosing ingredients unsuitable for such processing.
  • the antioxidant may either be included in the high bulk density base powder, or postdosed. It is desirable that the antioxidant should be distributed as homogeneously as possible through the final product.
  • a solution or suspension of the antioxidant in nonionic surfactant or in a nonionic surfactant/fatty acid soap mixture is mixed into the base powder before the postdosing of any solid ingredients.
  • the antioxidant may be postdosed in particulate form, either as such or in the form of granules also containing a carrier material, for example, zeolite or sodium carbonate, and optionally a binder, for example, sodium silicate or acrylate or acrylate/maleate polymer.
  • a carrier material for example, zeolite or sodium carbonate
  • a binder for example, sodium silicate or acrylate or acrylate/maleate polymer.
  • High bulk density bleaching detergent compositions were prepared to the following general formulation:
  • the composition was prepared as follows.
  • a high bulk density base powder was prepared by mixing and granulating surfactants, zeolite, sodium carbonate and sodium carboxymethylcellulose in a continuous high-speed mixer/densifier (L ⁇ dige (Trade Mark) Recycler) . Bleach ingredients, further sodium carbonate, enzyme granules and foam control/fluorescer granules were subsequently postdosed.
  • EDTMP was included in the base in some compositions, and postdosed in others.
  • the BHT was introduced by two different methods:
  • compositions were prepared as follows:
  • a similar formulation was prepared containing sodium perborate instead of sodium percarbonate. It contained postdosed EDTMP, and 0.2% BHT postdosed.
  • High bulk density non-bleaching detergent compositions were prepared to the following general formulation:
  • the method of preparation was as follows: a high bulk density base powder was prepared as described in Examples 1 to 6; sodium citrate, enzyme granules and foam control/fluorescer granules were subsequently postdosed.
  • compositions were prepared as follows:

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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)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

Une composition détergente particulaire contenant plus de 5 % en poids de sulfate d'alcool primaire et/ou au moins 8 % en poids d'un agent tensioactif non ionique d'alcool C8-20 et/ou plus de 15 % en poids d'agent tensioactif sans aucun savon, et un système d'adjuvant contenant de l'aluminosilicate de métaux alcalins, comprend également 0,01 à 5 % en poids d'un antioxydant, de préférence un phénol inhibé de manière stérique, idéalement de l'hydroxytoluène butylé ou de l'hdyroxyanisole butylé. Le système d'agent tensioacitf de cette composition présente une stabilité accrue au stockage en vrac et à la manipulation.
PCT/EP1995/002709 1994-08-24 1995-07-08 Compositions detergentes Ceased WO1996006151A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL95318787A PL318787A1 (en) 1994-08-24 1995-07-08 Washing agent compositions
AU29830/95A AU2983095A (en) 1994-08-24 1995-07-08 Detergent compositions
SK240-97A SK24097A3 (en) 1994-08-24 1995-07-08 Detergent compositions
BR9508807A BR9508807A (pt) 1994-08-24 1995-07-08 Composição detergente em paticulas e processo para a preparação da mesma
CZ97530A CZ53097A3 (en) 1994-08-24 1995-07-08 Loose washing agent and process for preparing thereof
EP95925861A EP0777715A1 (fr) 1994-08-24 1995-07-08 Compositions detergentes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9417140.2 1994-08-24
GB9417140A GB9417140D0 (en) 1994-08-24 1994-08-24 Detergent compositions

Publications (1)

Publication Number Publication Date
WO1996006151A1 true WO1996006151A1 (fr) 1996-02-29

Family

ID=10760361

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/002709 Ceased WO1996006151A1 (fr) 1994-08-24 1995-07-08 Compositions detergentes

Country Status (12)

Country Link
EP (1) EP0777715A1 (fr)
AU (1) AU2983095A (fr)
BR (1) BR9508807A (fr)
CA (1) CA2187311A1 (fr)
CZ (1) CZ53097A3 (fr)
GB (1) GB9417140D0 (fr)
HU (1) HUT77100A (fr)
PL (1) PL318787A1 (fr)
SK (1) SK24097A3 (fr)
TR (1) TR199500943A2 (fr)
WO (1) WO1996006151A1 (fr)
ZA (1) ZA955934B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7084100B2 (en) 2004-04-28 2006-08-01 The Procter & Gamble Company Antioxidant compositions
WO2006128554A1 (fr) * 2005-06-03 2006-12-07 Unilever Plc Incorporation d'antioxydant dans la composition d'un detergent
EP1987120B2 (fr) † 2006-02-24 2013-09-11 Unilever PLC Granules à libération rapide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7411994A (en) * 1973-09-17 1975-03-19 Unilever Nv Enzyme granules with improved storage stability - by incorporating an antioxidant
US4088594A (en) * 1975-12-19 1978-05-09 Shell Oil Company Stabilized detergent compositions
EP0283252A1 (fr) * 1987-03-17 1988-09-21 The Procter & Gamble Company Compositions de blanchiment
EP0320219A1 (fr) * 1987-12-09 1989-06-14 The Procter & Gamble Company Composition de blanchiment
EP0593014A1 (fr) * 1992-10-12 1994-04-20 Kao Corporation Composition détergente non-ionigue pulvérulente

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7411994A (en) * 1973-09-17 1975-03-19 Unilever Nv Enzyme granules with improved storage stability - by incorporating an antioxidant
US4088594A (en) * 1975-12-19 1978-05-09 Shell Oil Company Stabilized detergent compositions
EP0283252A1 (fr) * 1987-03-17 1988-09-21 The Procter & Gamble Company Compositions de blanchiment
EP0320219A1 (fr) * 1987-12-09 1989-06-14 The Procter & Gamble Company Composition de blanchiment
EP0593014A1 (fr) * 1992-10-12 1994-04-20 Kao Corporation Composition détergente non-ionigue pulvérulente

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7084100B2 (en) 2004-04-28 2006-08-01 The Procter & Gamble Company Antioxidant compositions
WO2006128554A1 (fr) * 2005-06-03 2006-12-07 Unilever Plc Incorporation d'antioxydant dans la composition d'un detergent
EP1987120B2 (fr) † 2006-02-24 2013-09-11 Unilever PLC Granules à libération rapide

Also Published As

Publication number Publication date
CZ53097A3 (en) 1997-07-16
ZA955934B (en) 1997-01-17
EP0777715A1 (fr) 1997-06-11
GB9417140D0 (en) 1994-10-12
BR9508807A (pt) 1998-01-06
PL318787A1 (en) 1997-07-07
TR199500943A2 (tr) 1996-06-21
SK24097A3 (en) 1997-08-06
HUT77100A (hu) 1998-03-02
CA2187311A1 (fr) 1996-02-29
AU2983095A (en) 1996-03-14

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