EP1325104B1 - Feste geformte waschmittelzusammensetzung - Google Patents

Feste geformte waschmittelzusammensetzung Download PDF

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Publication number
EP1325104B1
EP1325104B1 EP01972097A EP01972097A EP1325104B1 EP 1325104 B1 EP1325104 B1 EP 1325104B1 EP 01972097 A EP01972097 A EP 01972097A EP 01972097 A EP01972097 A EP 01972097A EP 1325104 B1 EP1325104 B1 EP 1325104B1
Authority
EP
European Patent Office
Prior art keywords
melt
soap
detergent composition
fatty acid
cast
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
EP01972097A
Other languages
English (en)
French (fr)
Other versions
EP1325104A1 (de
Inventor
Suresh Murigeppa Nadakatti
Vijay Mukund Naik
Shiju Thomas
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1325104A1 publication Critical patent/EP1325104A1/de
Application granted granted Critical
Publication of EP1325104B1 publication Critical patent/EP1325104B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast 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
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/14—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
    • C11D1/38—Cationic 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
    • 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
    • C11D1/88—Ampholytes; Electroneutral 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to providing a suitable type and combination of fatty acid(s) to form soap for obtaining melt-cast solid shaped detergent compositions comprising very high levels of water or liquid benefit agents.
  • Detergent tablets or bars are conventionally manufactured by one of the two methods: (i) shear working /homogenisation of the formulation followed by extrusion and stamping, or (ii) casting.
  • the formulated system is taken to a fluid state by raising the temperature, filled into moulds, and is then cooled.
  • This technology is commonly employed for manufacturing transparent personal wash tablets that contain among other ingredients (such as soap and synthetic surfactants) typically 15-50% of expensive components such as ethanol, polyhydric alcohols, sugars, etc., at the time of casting.
  • fatty acid soap is one or more of neutralised C 6 -C 24 fatty acids.
  • the object of the present invention is thus to provide the required fatty acid combination to form the soap in melt cast detergent bar compositions comprising very high levels of water or liquid benefit agents, such that the detergent composition forms a rigid tablet at temperatures greater than 20°C and retains rigidity at least up to 40°C.
  • the invention relates to a melt-cast solid shaped detergent composition that forms a rigid product at temperatures greater than 20°C and retains rigidity at least up to 40°C comprising:
  • the cooling or heating to detect the solid phase is preferably at a rate of 0.1°C/minute to 10°C/minute, more preferably 1°C/minute.
  • the presence of solid phase is preferably detected using low field NMR technique where the said solid phase exhibits Gaussian decay with relaxation time constant T 2 ⁇ 15 ⁇ sec. During the use of the low field NMR technique to detect the solid phase, it is preferred to equilibrate the sample at the temperature of detection for 30 minutes.
  • the present invention relates to melt-cast solid shaped detergent compositions that essentially comprises selecting the fatty acid soap comprising one or more of salts of C 6 -C 24 fatty acids such that the solution of the soap in water forms a liquid phase with a viscosity ⁇ 50 Pa.s at a shear rate of 1/sec in the temperature range 50-100°C, shows phase separation and presence of a solid phase when cooled up to 20°C and the said solid phase is present at least up to 40°C during heating.
  • the cooling or heating to detect the solid phase is preferably at a rate of 0.1°C/minute to 10°C/minute more preferably 1°C/minute.
  • the presence of solid phase is preferably detected using low field NMR technique where the said solid phase exhibits Gaussian decay with relaxation time constant T 2 ⁇ 15 ⁇ sec.
  • T 2 ⁇ 15 ⁇ sec relaxation time constant
  • the solid shaped articles of the composition according to the invention are rigid enough to be conveniently held in the hand, economical, high foaming, and exhibit good in-use properties.
  • the compositions exhibit yield stress values greater than 75 kPa as measured using the automatic penetrometer..
  • the saturated fatty acid soap is selected from one or more salts of saturated C 6 -C 24 fatty acids.
  • the soap employed may be a sodium, potassium, magnesium, aluminium, calcium or lithium salt of saturated fatty acids. It is especially preferred to have soap obtained as sodium or potassium salt of saturated fatty acid.
  • the saturated fatty acid soap in the composition is preferably 5-50% by weight and more preferably 5-40% by wt.
  • the viscosity of the soap-water system in the temperature range 50-100°C is measured using Carri-Med rheometer (Model CSL 500 from TA instruments) at a shear rate of 1/sec.
  • the viscosity measurements were carried out in the steady state flow mode using cone and plate geometry of 2 cm diameter and 1 deg 58 min dimensions with 55 micron truncation, along with a solvent trap.
  • the melt of the soap-water system at elevated temperature is then cooled to a temperature up to 20°C to determine the temperature at which phase separation occurs and solid phase is formed.
  • the system is then heated to ensure that the said solid phase is present at least up to 40°C during heating.
  • the presence of solid phase is detected using low field NMR with variable temperature accessory where the said solid phase exhibits Gaussian decay with relaxation time constant T 2 ⁇ 15 ⁇ sec., using the procedure described in the following reference: Suresh M. Nadakatti, "Modified Data Handling for Rapid Low Field NMR Characterisation of Lyotropic Liquid Crystal Composites", J. Surfactants and Detergents, Vol. 2, No. 4, pp. 515-521, 1999.
  • compositions according to the invention comprise non-soap detergent actives that are selected from anionic, non-ionic, cationic, amphoteric or zwitterionic surfactants or their mixtures.
  • 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.
  • Some examples of synthetic anionic detergent active compounds are linear alkyl benzene sulphonate, sodium lauryl sulphate, sodium lauryl ether sulphate, alpha olefin sulphonate, alkyl ether sulphate, fatty methyl ester sulphonate, alkyl isothionate, etc.
  • the cations most suitable in above detergent active species are sodium, potassium, ammonium, and various amines e.g. monoethanol amine, diethanolamine and triethanolamine.
  • Suitable non-ionic 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 common non-ionic surfactants are the condensation products 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.
  • Some examples of non-ionic surfactants are alkyl phenol ethylene oxide (EO) condensate, tallow alcohol 10 EO condensate, alkyl demethyl amine oxides, lauryl mono-ethanolamide, sugar esters, etc.
  • amphoteric detergent active Some examples of amphoteric detergent active are coco amidopropyl betaine, cocobetaine, etc.
  • compositions according to the invention It is also possible optionally to include cationic or zwitterionic detergent actives in the compositions according to the invention.
  • the detergent active to be employed in the detergent composition of this invention is preferably anionic and will generally be up to 50% and more preferably from 2 to 30%.
  • Salting-in electrolytes for use in the composition are selected from those listed in the 'Hofmeister' or 'Lyotropic' series.
  • the salting-in electrolytes are generally those wherein the lyotropic number for the anion of the electrolyte is > 10.
  • Some examples of anions with lyotropic number > 10 are NO 2 , ClO 3 - , Br - , NO 3 - , ClO 4 - , I - , CNS - , C 6 H 5 SO 3 - , C 6 H 4 CH 3 SO 3 - and Cr 2 O 7 2- .
  • the preferred examples of salting-in electrolytes for use in compositions according to the present invention are alkali metal salts of the above mentioned anions.
  • the most preferred examples of the salting-in electrolytes for use in compositions according to the present invention are sodium toluene sulphonate, sodium cumene sulphonate and sodium xylene sulphonate.
  • salting-in electrolytes may be selected form those described in (i) Collins, K.D.; Washabaugh, M.W. Quart. Rev. Biophys., 1985, 18, 323; (ii) Schuster. P, Zundel. G and Sandorfy. C, 1976, 'The Hydrogen Bond', Recent developments in theory and experiments, Vol. III, North-Holland Publishing Co. Amsterdam, New York, Oxford.
  • liquid skin benefit materials such as moisturisers, emollients, sunscreens, anti-aging compounds are incorporated in the composition.
  • 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, silicone oil (DC-200 Ex-Dow Corning) may also be included.
  • Sun-screens such as 4-tertiary butyl-4'-methoxy dibenzoylmethane (available under the trade name PARSOL 1789 from Givaudan) and/or 2-ethylhexylmethoxy cinnamate (available under the trade name PARSOL MCX from Givaudan) or other UV-A and UV-B sun-screens.
  • compositions such as hair conditioning agents, fillers, colour, perfume, opacifier, preservatives, one or more water insoluble particulate materials such as talc, kaolin, polysaccharides and other conventional ingredients may be incorporated in the composition.
  • the process of manufacturing of the solid shaped detergent compositions according to the invention comprises following steps:
  • the mould may be suitably selected to produce near net shape tablet or to produce bars/blocks.
  • the bars/blocks may be further shaped into a detergent article.
  • the mould is preferably sealed to obtain a cast-in pack detergent composition.
  • the mould is preferably sealed immediately after filling the mould.
  • the low field NMR used for studies was procured from M/s Resonance Instruments, U.K. (Model MARAN 25).
  • the instrument had the following features: (i) a 600W transmitter that produced 90° pulses of ⁇ 2 ⁇ s and (ii) a 5 MHz digitiser that allowed 2 data points to be collected per ⁇ s.
  • the presence of solid phase in soap-water systems was detected using the procedure described in the following reference: Suresh M. Nadakatti, "Modified Data Handling for Rapid Low Field NMR Characterisation of Lyotropic Liquid Crystal Composites", J. Surfactants and Detergents, Vol. 2, No. 4, pp. 515-521, 1999.
  • the rigidity of the bars processed was determined in terms of yield stress using the procedure described below.
  • the detergent tablets were then kept in ovens maintained at 25°C and 40°C, respectively, for 4 hours and allowed to equilibrate.
  • the yield stress of the tablets at 25°C and 40°C was measured using a automatic penetrometer using the procedure described below.
  • the automatic penetrometer used for yield stress measurements was model PNR 10 from M/s Petrotest Instruments GmbH. Standard Hollow Cone (part # 18-0101, as per ASTM D 217 - IP 50) along with Plunger (part # 18-0042) was used for the measurements.
  • the cone consisted of a conical body of brass with detachable, hardened steel tip. The total mass of the cone was 102.5 g. The total mass of the movable plunger was 47.5 g. Total mass of cone and plunger that fall on the detergent tablet was therefore 150 g. Additional weights of 50 g and 100 g (making the total weight falling on the sample 200 g and 250 g, respectively) were also used.
  • the yield stress values of the sample at 25°C and 40°C were measured using the standard procedure comprising following steps:

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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)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (10)

  1. Schmelzgegossene, feste, geformte Waschmittelzusammensetzung, die Steifigkeit bis mindestens 40°C beibehält, umfassend:
    (a) 2-50 (Xa) Gew.-% gesättigte Fettsäureseife, umfassend ein oder mehrere Salze von C6-C24-Fettsäuren;
    (b) 2-40 Gew.-% einer waschaktiven Nichtseifenspezies;
    (c) 0,5-20 Gew.-% eines Einsalzelektrolyten; und
    (d) 30-80 Gew.-% Wasser,
    wobei die vorliegende Fettsäureseife in Wasser eine Xa-%-ige Lösung mit einer flüssigen Phase bildet, die eine Viskosität von weniger als 50 Pa.s bei einer Scherrate von 1 s-1 im Temperaturbereich 50-100°C aufweist, Phasentrennung und die Gegenwart von einer festen Phase während des Kühlens auf 20°C zeigt und die feste Phase während des Erhitzens mindestens bis 40°C vorliegt.
  2. Schmelzgegossene Waschmittelzusammensetzung nach Anspruch 1, worin die waschaktive Nichtseife ausgewählt ist aus ionischen, nichtionischen, kationischen, amphoteren oder zwitterionischen Tensiden oder Gemischen davon.
  3. Schmelzgegossene Waschmittelzusammensetzung nach Anspruch 1 oder Anspruch 2, worin die Fettsäureseife ein Natrium-, Kalium-, Magnesium-, Aluminium-, Calcium- oder Lithiumsalz von einer gesättigten C6-C24-Fettsäure ist.
  4. Schmelzgegossene Waschmittelzusammensetzung nach einem von Anspruch 1 bis 3, worin der Einsalzelektrolyt eine lyotrope Zahl für das Anion von >10 aufweist.
  5. Schmelzgegossene Waschmittelzusammensetzung nach Anspruch 4, worin der Einsalzelektrolyt ein Alkalimetallsalz von einem Anion, ausgewählt aus NO2 -, ClO3 -, Br--, NO3 -, ClO4 -, I-, CNS-, C6H5SO3 -, C6H4CH3SO3 - oder Cr2O7 2-, ist.
  6. Schmelzgegossene Waschmittelzusammensetzung nach einem der vorangehenden Ansprüche, worin die Zusammensetzung weiterhin ein flüssiges Vorteilsmittel umfasst.
  7. Schmelzgegossene Waschmittelzusammensetzung nach Anspruch 6, worin das flüssige Vorteilsmittel aus Feuchthaltemitteln, Erweichungsmitteln, Sonnenschutzmitteln oder Anti-ageing-Verbindungen ausgewählt ist.
  8. Verfahren zur Herstellung einer schmelzgegossenen, fest geformten Waschmittelzusammensetzung, umfassend die Schritte von:
    (a) Auswählen der Fettsäureseife, umfassend ein oder mehrere von Salzen von C6-C24-Fettsäuren, sodass die Lösung der Seife in Wasser eine flüssige Phase mit einer Viskosität <50 Pa.s bei einer Scherrate von 1/s bei dem Temperaturbereich 50-100°C bildet, Phasentrennung und das Vorliegen von fester Phase zeigt, wenn auf 20°C gekühlt wird und die feste Phase während des Erhitzens bis mindestens 40°C vorliegt;
    (b) Mischen der Fettsäureseife mit 2-40% einer waschaktiven Spezies, 0,5-20% eines Einsalzelektrolyten und 30-80% Wasser;
    (c) Schmelzen der Zusammensetzung von Schritt (b);
    (d) Gießen der Schmelze in eine Form, um die gewünschte Form zu erhalten; und
    (e) Kühlen der Form unter ruhenden Bedingungen, um Verfestigung hervorzurufen.
  9. Verfahren nach Anspruch 8, wobei Schritt (b) weiterhin die Zugabe eines flüssigen Vorteilsmittels umfasst.
  10. Fest geformte Waschmittelzusammensetzung, hergestellt gemäß dem Verfahren von Anspruch 8 oder 9.
EP01972097A 2000-10-13 2001-10-09 Feste geformte waschmittelzusammensetzung Expired - Lifetime EP1325104B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN926MU2000 2000-10-13
INMU092600 2000-10-13
PCT/EP2001/011621 WO2002031099A1 (en) 2000-10-13 2001-10-09 Solid shaped detergent composition

Publications (2)

Publication Number Publication Date
EP1325104A1 EP1325104A1 (de) 2003-07-09
EP1325104B1 true EP1325104B1 (de) 2006-12-13

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EP01972097A Expired - Lifetime EP1325104B1 (de) 2000-10-13 2001-10-09 Feste geformte waschmittelzusammensetzung

Country Status (12)

Country Link
EP (1) EP1325104B1 (de)
JP (1) JP2004511626A (de)
CN (1) CN1225536C (de)
AR (1) AR030881A1 (de)
AT (1) ATE348143T1 (de)
AU (2) AU2001291892B2 (de)
BR (1) BR0114810A (de)
CA (1) CA2425294A1 (de)
DE (1) DE60125206T2 (de)
MX (1) MXPA03003257A (de)
WO (1) WO2002031099A1 (de)
ZA (1) ZA200302694B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1650290A3 (de) * 2004-10-13 2006-05-17 Unilever N.V. Verfahren zur Herstellung von Reinigungsmitteltabletten
CN103013722B (zh) * 2012-12-12 2015-01-21 合肥豪豪日化有限公司 一种高含水量复合洗衣皂及其制备方法
JP2019089927A (ja) * 2017-11-14 2019-06-13 花王株式会社 粘度特性改良剤

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8928902D0 (en) * 1989-12-21 1990-02-28 Unilever Plc Detergent bar
US5340492A (en) * 1990-11-26 1994-08-23 The Procter & Gamble Company Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid
WO1998011864A2 (en) * 1996-09-23 1998-03-26 The Procter & Gamble Company Lathering and cleansing personal cleansing bar compositions which contain elongated lipid particles
US5916856A (en) * 1996-10-16 1999-06-29 Lever Brothers Company Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water
US5929011A (en) * 1996-10-30 1999-07-27 Sunburst Chemicals, Inc. Solid cast chlorinated cleaning composition
GB0003925D0 (en) * 1999-10-25 2000-04-12 Unilever Plc Cast detergent composition

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Publication number Publication date
AR030881A1 (es) 2003-09-03
AU2001291892B2 (en) 2006-03-16
WO2002031099A1 (en) 2002-04-18
CN1479785A (zh) 2004-03-03
CA2425294A1 (en) 2002-04-18
MXPA03003257A (es) 2003-06-06
ZA200302694B (en) 2004-04-07
ATE348143T1 (de) 2007-01-15
DE60125206D1 (de) 2007-01-25
CN1225536C (zh) 2005-11-02
BR0114810A (pt) 2003-09-30
EP1325104A1 (de) 2003-07-09
DE60125206T2 (de) 2007-04-12
JP2004511626A (ja) 2004-04-15
AU9189201A (en) 2002-04-22

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