WO2003010272A1 - Composition en barre de savon/detergent et son procede de fabrication - Google Patents

Composition en barre de savon/detergent et son procede de fabrication Download PDF

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Publication number
WO2003010272A1
WO2003010272A1 PCT/EP2002/008061 EP0208061W WO03010272A1 WO 2003010272 A1 WO2003010272 A1 WO 2003010272A1 EP 0208061 W EP0208061 W EP 0208061W WO 03010272 A1 WO03010272 A1 WO 03010272A1
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WO
WIPO (PCT)
Prior art keywords
weight
soap
bar
water
sodium
Prior art date
Application number
PCT/EP2002/008061
Other languages
English (en)
Inventor
Robert William Anderson
Ashley Raynor Bassett
Geoffrey Irlam
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Limited
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 Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Priority to BRPI0211662-6A priority Critical patent/BR0211662B1/pt
Publication of WO2003010272A1 publication Critical patent/WO2003010272A1/fr

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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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/18—Water-insoluble 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts
    • C11D9/14—Phosphates; Polyphosphates

Definitions

  • the invention relates to a synergistic composition of soap/detergent bars, and in particular soap/detergent bars for personal washing. It also relates to a process for the preparation of such soap/detergent bars for personal and/or fabric washing.
  • the invention particularly relates to a low total fatty matter (TF as defined below) soap/detergent bar comprising high levels of water and other liquid benefit agents, and a process for its manufacture.
  • Conventional detergent bars based on soap for personal washing usually contain over about 70% by weight TFM, the remainder being water (about 10-20%) and other ingredients such as colour, perfume, preservatives, etc.
  • Structurants and fillers are also present in such compositions in small amounts, which replace some of the soap in the bar while retaining the desired hardness of the bar.
  • Known fillers include starch, kaolin and talc.
  • Hard non-milled soap bars containing moisture of less than 35% are also available. These bars have a TFM of about 30-65%. The reduction in TFM has usually been achieved by the use of insoluble particulate materials and/or soluble silicates. Milled bars generally have a water content about 8-15%, and the hard non-milled bars have a water content of about 20-35%.
  • IN 176384 discloses a detergent composition with low TFM content having high ratio of water to TFM without affecting hardness, cleaning and lathering properties of the bar by the incorporation of up to 20% colloidal aluminium hydroxide (A-gel) .
  • A-gel/TFM combination enables the preparation of bars with higher water content while using TFM at a lower level.
  • the demonstration of the invention is restricted to the use of 7.5% by weight A-gel in combination with 40% TFM with an additional structurant such as 5% by weight of alkaline silicate.
  • IN 177828 discloses a process wherein, by providing a balanced combination of aluminium hydroxide and TFM, it is possible to prepare a low TFM bar having high water content but with satisfactory hardness.
  • the patent teaches the generation of colloidal aluminium hydroxide in-situ by a reaction of fatty acid/fat with an aluminium containing alkaline material such as sodium aluminate to form bars which are obtained by plodding.
  • our co-pending application 81l/Bom/98 discloses that use of A-gel from 9 to 16% by weight of the composition synergistically improves the processability, sensory and physical properties of low TFM bars .
  • our co-pending application WO 00/36075 discloses a process of preparing a low TFM bar that gives superior bar properties, utilising a reaction of fatty acid with an aluminium containing alkaline material such as sodium aluminate solution, that specifically has a solid content of 20 to 55% by weight, wherein the alumina (Al 2 0 3 ) and sodium oxide (Na 2 0) are in a ratio of 0.5 to 1.55 by weight . These bars have improved hardness and smoother feel. This reaction can take place in a broader temperature range of 40 to 95°C.
  • Our application WO 01/42419 discloses a process of preparing a low TFM bar that gives superior bar properties comprising in situ reaction of phosphoric acid with an aluminium containing material such as sodium aluminate to generate aluminium hydroxide and a mix of orthophosphates .
  • the sodium aluminate solution has a solid content of 20 to 55% by weight, and the alumina (A1 2 0 3 ) to sodium oxide (Na 2 0) is in a ratio of 0.5 to 1.55 by weight.
  • Bars produced using this process have a lower density relative to bars filled with conventional materials such as calcite, kaolin and talc, and improved physical properties, without interfering with the sensory properties. By this process it is possible to formulate bars that are suitable for both soft and hard water situations.
  • alumina gel and tetra sodium pyrophosphate decahydrate produced by the reaction of sodium aluminate and di sodium di hydrogen pyrophosphate, or sodium acid pyrophosphate (SAPP) as it is known commercially.
  • the reaction is preferably carried out in the presence of a freshly formed soap, to ensure good dispersion of the pyrophosphate formed in the soap mix and hence minimise particle size, either with or without the glycerol removed. If the soap is formed by the reaction of sodium aluminate with an oil blend or with fatty acids the reaction to form TSPP is preferably carried out after the saponification stage is essentially complete.
  • the first aspect of the present invention comprises a low total fatty matter toilet soap bar composition
  • a low total fatty matter toilet soap bar composition comprising 40-78% by weight total fatty matter, 0.4-13% by weight colloidal alumina gel (as A1203) , 0-23% by weight TSPP, expressed as the anhydrous salt, 0-15% by weight glycerol, and 7 to 30% by weight water including water of hydration.
  • the extra aluminate to neutralise the SAPP may be added during the saponification stage, the excess aluminate being neutralised with SAPP after completion of the saponification reaction.
  • the ratio of TSPP to alumina gel in the final formulation may be varied within certain limits. To maximise the alumina ratio sodium aluminate is neutralised with the oil/fatty acid. To increase the proportion of TSPP requires the addition of SAPP that is neutralised with the required amount of alkali.
  • the weight ratio of Al 2 0 3 to Na20 from the soap in the soap base noodles after adjusting their water content is in the range 0.05:1 to 1.75:1 by weight.
  • the total content of free plus hydrated water is in the range 7-30% by weight.
  • the amount of TSSP in the composition, expressed as anhydrous salt is from 1% to 20% by weight.
  • glycerol produced during saponification is left in place it will generally give a level of 0-10% by weight in the final formulation.
  • Extra glycerol may be added to provide a specified level of glycerol if the amount produced by the saponification reaction is insufficient.
  • the glycerol content of the final bar may be raised to a maximum of 15% by weight.
  • Other additives conventionally present in soap bars may also be added.
  • the process of the invention can be carried out in any batch mixer conventionally used in soap/detergent manufacture and is preferably carried out in a high shear mixer.
  • the preferred mixers include a ploughshare mixer, mixers with kneading members of Sigma type, multi-wiping overlap, single curve or double arm.
  • the double arm kneading mixers can be of overlapping or the tangential design.
  • the invention can be carried out in a conventional paddle mixer, a helical screw agitator vessel or multi-head dosing pump/high shear mixer and spray drier combinations as in conventional processing.
  • a process for preparing a low total fatty matter detergent bar comprises the steps of: a. Making soap by reacting a mixture of one or more fats and/or fatty acids with alkaline aluminium-containing material and/or sodium hydroxide at a temperature of 60-150°C;
  • total fatty matter referred to above and subsequently, usually abbreviated to TFM, is used to denote the percentage by weight of fatty acid and triglyceride residues present in the composition without taking into account the accompanying cations.
  • an accompanying sodium cation will generally amount to about 8% by weight.
  • Other cations may be employed as desired, for example zinc, potassium, magnesium, alkyl ammonium and aluminium.
  • soap denotes salts of carboxylic fatty acids.
  • the soap may be derived from any of the triglycerides conventionally used in soap manufacture. Consequently the carboxylate anions in the soap may contain from 8 to 22 carbon atoms .
  • the soap may be obtained by saponifying a fat and/or a fatty acid.
  • the fats or oils generally used in soap manufacture may be such as tallow, tallow stearines, palm oil, palm stearines, soya bean oil, fish oil, caster oil, rice bran oil, sunflower oil, coconut oil, babassu oil, palm kernel oil, and others.
  • the fatty acids are derived from oils/fats selected from coconut, rice bran, groundnut, tallow, palm, palm kernel, cotton seed, soybean, castor etc.
  • the fatty acid soaps can also be synthetically prepared (e.g. by the oxidation of petroleum or by the hydrogenation of carbon monoxide by the Fischer-Tropsch process) .
  • Resin acids such as those present in tall oil, may be used. Naphthenic acids are also suitable.
  • Tallow fatty acids can be derived from various animal sources and generally comprise about 1-8% myristic acid, about 21-32% palmitic acid, about 14-31% stearic acid, about 0-4% palmitoleic acid, about 36-50% oleic acid and about 0-5% linoleic acid.
  • a typical distribution is 2.5% myristic acid, 29% palmitic acid, 23% stearic acid, 2% palmitoleic acid, 41.5% oleic acid, and 3% linoleic acid (all percentages by weight) .
  • Other similar mixtures, such as those from palm oil and those derived from various animal tallow and lard are also included.
  • coconut oil refers to fatty acid mixtures having an approximate carbon chain length distribution of 8% C 8 , 7%
  • benefit agents such as non-soap surfactants, skin benefit materials such as moisturisers, emollients, sunscreens, or anti-ageing compounds can be incorporated at any step prior to step of milling.
  • skin benefit materials such as moisturisers, emollients, sunscreens, or anti-ageing compounds
  • benefit agents can be introduced as macro domains during plodding.
  • a typical suitable fatty acid blend consists of 5 to 30% by weight coconut fatty acids and 70 to 95% by weight fatty acids ex-hardened rice bran oil.
  • Fatty acids derived from other suitable oils/fats such as groundnut, soybean, tallow, palm, palm kernel, etc. may also be used in other desired proportions .
  • the non-soap surfactants may be anionic, nonionic, cationic, amphoteric or zwitterionic, or a mixture thereof.
  • moisturisers and humectants include polyols, glycerol, cetyl alcohol, carbopol 934, ethoxylated castor oil, paraffin oils, lanolin and its derivatives.
  • Silicone compounds such as silicone surfactants like DC3225C (Dow Corning) and/or silicone emollients, or silicone oil (DC-200 Ex-Dow Corning) may also be included.
  • Suitable sun-screens include 4- tertiary butyl-4 ' -methoxy dibenzoylmethane (available under the trade name PARSOL 1789 from Givaudan) and/or 2 -ethyl hexyl methoxy cinnamate (available under the trade name PARSOL MCX from Givaudan) or other TJV-A and UV-B sun-screens.
  • additives such as one or more water insoluble particulate materials such as talc, kaolin, polysaccharides such as starch or modified starches and celluloses may be incorporated .
  • minor additives such as perfume, colour, preservatives, fillers and other conventional additives at 1 to 10 % by weight can be incorporated.
  • composition according to the invention will preferably comprise detergent actives which are generally chosen from both anionic and nonionic detergent actives.
  • Suitable anionic detergent active compounds are water soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphuric acid ester radicals and mixtures thereof.
  • Suitable anionic detergents are sodium and potassium alcohol sulphates, especially those obtained by sulphating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulphonates such as those in which the alkyl group contains from 9 to 15 carbon atoms; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphates; sodium and potassium salts of sulphuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide; sodium and potassium salts of alkyl phenol ethylene oxide ether sulphate with from 1 to 8 units of ethylene oxide molecule and in which the alkyl radicals contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with sodium hydroxide where, for example,
  • the preferred water-soluble synthetic anionic detergent active compounds are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulphonates and mixtures with olefin sulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of structure
  • compositions according to the invention It is also possible to include cationic, amphoteric, or zwitterionic detergent actives in the compositions according to the invention.
  • Suitable cationic detergent actives that can be incorporated are alkyl substituted quaternary ammonium halide salts e.g. bis (hydrogenated tallow) dimethylammonium chlorides, cetyltrimethyl ammonium bromide, benzalkonium chlorides and dodecylmethyl-polyoxyethylene ammonium chloride and amine and imidazoline salts for e.g. primary, secondary and tertiary amine hydrochlorides and imidazoline hydrochlorides .
  • alkyl substituted quaternary ammonium halide salts e.g. bis (hydrogenated tallow) dimethylammonium chlorides, cetyltrimethyl ammonium bromide, benzalkonium chlorides and dodecylmethyl-polyoxyethylene ammonium chloride and amine and imidazoline salts for e.g. primary, secondary and tertiary amine hydrochlorides and imidazoline hydrochlorides .
  • Suitable amphoteric detergent-active compounds that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilising group, for instance sodium 3- dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyltaurate .
  • Suitable zwitterionic detergent-active compounds that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water- solubilising group, for instance 3- (N-N-dimethyl-N- hexadecylammonium) propane-1-sulphonate betaine, 3- (dodecylmethyl sulphonium) propane-1-sulphonate betaine and 3- (cetylmethylphosphonium) ethane sulphonate betaine.
  • Example 1 The invention will now be further described by way of illustration only, with reference to the following non- limiting examples which amongst other things show comparative results of the composition prepared by the present invention and beyond the invention.
  • Example 1 The invention will now be further described by way of illustration only, with reference to the following non- limiting examples which amongst other things show comparative results of the composition prepared by the present invention and beyond the invention.
  • Example 1 The invention will now be further described by way of illustration only, with reference to the following non- limiting examples which amongst other things show comparative results of the composition prepared by the present invention and beyond the invention.
  • Example 1 Example 1
  • 100 kg of a soap base was prepared in a ploughshare mixer by first adding 4.73 kg of 90% active alpha olefin sulphate (AOS) , 0.85 kg sodium chloride and 38.81 kg of sodium aluminate solution containing 20.5% by weight Na 2 0 and 24.4% by weight Al 2 0 3 .
  • AOS active alpha olefin sulphate
  • DFAs molten distilled fatty acids
  • the DFA' s were allowed to saponify and then 0.12 kg of a 35% by weight solution of sodium EDTA and 0.35 kg of a 60% by weight solution of EHDP (etidronic acid) preservative were added and dispersed in the mix.
  • EHDP etidronic acid
  • the following soap bases were prepared by mixing ca . 100 kgs of a neat soap with the glycerol extracted at approximately 30% water and 0.5% salt with an appropriate quantity of SAPP slurried in a 2% brine solution at 80 to 90 degrees centigrade. To this mixture was added sufficient sodium aluminate solution containing 20% by weight Na20 and 20% by weight Al 2 0 3 at 70 to 90°C to completely neutralise the SAPP. The reaction between the aluminate solution and the SAPP took place in situ and the alumina gel and TSPP formed were fully dispersed in throughout the soap.
  • Dilute brine solution was added to the mixture to enable the soap/alumina gel/TSPP mixture to be pumped via heat exchangers to a vacuum dryer where the mixture was dried and cooled to about 40°C for subsequent finishing into soap bars.
  • a range of soap bases were made in this way to the following nominal compositions prior to finishing.
  • soap base 40.33 kg of soap base was prepared in a ploughshare mixer by adding 20 kg of an 80 parts tallow/20 parts coconut oil blend pre-heated to 90 degrees centigrade to the mixer. To this oil blend was added 14.8 kg of sodium aluminate solution, containing 20% by weight Na 2 0 and 20% by weight A1 2 0 3 , that had been pre-heated to 90 degrees centigrade. The mixture was allowed to react under agitation until the saponification of the triglyceride was essentially complete. To the neat soap blend was added 2.1 kg of SAPP slurried in 3.4 kg water at 85 degrees centigrade. Mixing was continued for a further 30 minutes to ensure complete neutralisation of the SAPP with the excess sodium aluminate after saponification. Finally, 20g of a 40% by weight solution of NaEDTA and llg of a 60% by weight solution of EHDP were added and mixing continued for a further 5 minutes to ensure complete dispersion of the ingredients. A soap base of the following composition resulted.

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

Abstract

L'invention concerne un savon ou un détergent en barre, spécialement indiqué pour l'hygiène personnelle ou pour le lavage de tissus. La barre présente des niveaux relativement faibles de matières grasses au total, ce qui permet d'avoir des niveaux relativement élevés d'eau et/ou d'autres additifs liquides. Par ailleurs, l'invention fait preuve de bonnes propriétés physiques grâce à l'addition d'un hydroxyde d'aluminium et de tetra sodium pyrophosphate décahydrate dans la barre. Font également l'objet de cette invention des procédés de fabrication associés.
PCT/EP2002/008061 2001-07-26 2002-07-19 Composition en barre de savon/detergent et son procede de fabrication WO2003010272A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BRPI0211662-6A BR0211662B1 (pt) 2001-07-26 2002-07-19 Composição de barra de sabonete e processo de preparação de barra detergente

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0118283A GB0118283D0 (en) 2001-07-26 2001-07-26 Soap/detergent bar composition and manufacturing process
GB0118283.1 2001-07-26

Publications (1)

Publication Number Publication Date
WO2003010272A1 true WO2003010272A1 (fr) 2003-02-06

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Application Number Title Priority Date Filing Date
PCT/EP2002/008061 WO2003010272A1 (fr) 2001-07-26 2002-07-19 Composition en barre de savon/detergent et son procede de fabrication

Country Status (7)

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CN (1) CN100350033C (fr)
AR (1) AR034910A1 (fr)
BR (1) BR0211662B1 (fr)
GB (1) GB0118283D0 (fr)
MX (1) MXPA04000809A (fr)
WO (1) WO2003010272A1 (fr)
ZA (1) ZA200400412B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072031A2 (fr) * 2007-12-04 2009-06-11 The Procter & Gamble Company Composition détergente
WO2011073139A1 (fr) 2009-12-16 2011-06-23 Unilever Plc Procédé permettant d'améliorer la rétention d'un parfum lors de l'entreposage ou l'éclosion d'un parfum à l'aide de savonnettes extrudées à basse teneur en matières grasses totales ayant un système structurant de type polyol issu de l'amidon
US7981852B2 (en) 2009-12-16 2011-07-19 Conopco, Inc. Method of enhancing perfume retention during storage using low total fatty matter extruded bars having starch polyol structuring system
US7989410B2 (en) 2009-12-16 2011-08-02 Conopco, Inc. Method of enhancing perfume bloom in extruded diluted bars having low total fatty matter and using starch polyol structuring system
WO2017202577A1 (fr) * 2016-05-27 2017-11-30 Unilever N.V. Composition de nettoyage solide formée et son procédé de fabrication
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent

Citations (6)

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Publication number Priority date Publication date Assignee Title
CH226570A (de) * 1942-03-10 1943-04-15 Wander Ag Dr A Seifenersatz.
US3340196A (en) * 1965-10-23 1967-09-05 Colgate Palmolive Co Detergent bar
EP0194126A2 (fr) * 1985-03-05 1986-09-10 The Procter & Gamble Company Compositions détergentes
WO2000036075A1 (fr) * 1998-12-14 2000-06-22 Unilever Plc Procede de preparation d'une composition de pain de detergent a faible teneur en matiere grasse totale
WO2001042414A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Procede de preparation d'une composition de tablette de detergent
WO2002046346A1 (fr) * 2000-12-05 2002-06-13 Unilever Plc Composition amelioree de detergent en pain

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH226570A (de) * 1942-03-10 1943-04-15 Wander Ag Dr A Seifenersatz.
US3340196A (en) * 1965-10-23 1967-09-05 Colgate Palmolive Co Detergent bar
EP0194126A2 (fr) * 1985-03-05 1986-09-10 The Procter & Gamble Company Compositions détergentes
WO2000036075A1 (fr) * 1998-12-14 2000-06-22 Unilever Plc Procede de preparation d'une composition de pain de detergent a faible teneur en matiere grasse totale
WO2001042414A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Procede de preparation d'une composition de tablette de detergent
WO2002046346A1 (fr) * 2000-12-05 2002-06-13 Unilever Plc Composition amelioree de detergent en pain

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072031A2 (fr) * 2007-12-04 2009-06-11 The Procter & Gamble Company Composition détergente
EP2071017A1 (fr) * 2007-12-04 2009-06-17 The Procter and Gamble Company Composition de détergent
WO2009072031A3 (fr) * 2007-12-04 2009-07-30 Procter & Gamble Composition détergente
US7854770B2 (en) 2007-12-04 2010-12-21 The Procter & Gamble Company Detergent composition comprising a surfactant system and a pyrophosphate
WO2011073139A1 (fr) 2009-12-16 2011-06-23 Unilever Plc Procédé permettant d'améliorer la rétention d'un parfum lors de l'entreposage ou l'éclosion d'un parfum à l'aide de savonnettes extrudées à basse teneur en matières grasses totales ayant un système structurant de type polyol issu de l'amidon
US7981852B2 (en) 2009-12-16 2011-07-19 Conopco, Inc. Method of enhancing perfume retention during storage using low total fatty matter extruded bars having starch polyol structuring system
US7989410B2 (en) 2009-12-16 2011-08-02 Conopco, Inc. Method of enhancing perfume bloom in extruded diluted bars having low total fatty matter and using starch polyol structuring system
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent
WO2017202577A1 (fr) * 2016-05-27 2017-11-30 Unilever N.V. Composition de nettoyage solide formée et son procédé de fabrication

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CN1738895A (zh) 2006-02-22
GB0118283D0 (en) 2001-09-19
AR034910A1 (es) 2004-03-24
MXPA04000809A (es) 2004-05-21
BR0211662A (pt) 2004-07-13
BR0211662B1 (pt) 2014-09-02
ZA200400412B (en) 2005-01-20
CN100350033C (zh) 2007-11-21

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