EP2553072B1 - Strukturierung von Waschmittelflüssigkeiten mit hydriertem Castoröl - Google Patents

Strukturierung von Waschmittelflüssigkeiten mit hydriertem Castoröl Download PDF

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Publication number
EP2553072B1
EP2553072B1 EP20110708472 EP11708472A EP2553072B1 EP 2553072 B1 EP2553072 B1 EP 2553072B1 EP 20110708472 EP20110708472 EP 20110708472 EP 11708472 A EP11708472 A EP 11708472A EP 2553072 B1 EP2553072 B1 EP 2553072B1
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EP
European Patent Office
Prior art keywords
surfactant
hco
premix
liquid
water
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EP20110708472
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English (en)
French (fr)
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EP2553072A1 (de
Inventor
Philip Michael Ryan
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to EP20110708472 priority Critical patent/EP2553072B1/de
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • Example 1 of US3354091 Colgate disclose a system where the HCO is mixed with another material to form a premelt or blend.
  • the blend is added at 71 °C to other components of a substantially homogeneous, pourable, heavy-duty aqueous liquid detergent composition comprising 5-30 wt% alkali metal anionic organic sulfonated detergent, 10-30 wt% potassium polyphosphate, 4-12 wt% hydrotrope, 0.1-1 wt% alkali metal carboxymethyl cellulose normally tending to separate from the solution of detergent and phosphate.
  • the HCO (0.01-1 wt%) is added to inhibit the separation of the carboxymethyl cellulose salt.
  • the composition may optionally further comprise a fatty acid alkanolamide to improve detergency and modify foaming power.
  • the solid alkanolamide and the castor wax hydrogenated castor oil
  • the solid alkanolamide and the castor wax are preferably added as a mixture in molten form.
  • lauric isopropanolamide and castor wax are premelted and added as a blend at 71 °C with stirring.
  • the melting point of the castor wax is given as 84-87 °C and the melting point of the alkanolamide would have been about 65-66 °C. Insufficient information is given in this document to know if the castor wax melted or if it dissolved in the melted isopropanolamide.
  • step b) the solvent is conveniently chosen from materials that would be in the eventual liquid.
  • the examples use fatty acid, but nonionic solvents are also contemplated.
  • this process adds the HCO premix to a system that comprises the bulk of the remainder of the formulation so that the structuring system is created in situ. Attempts to adapt this process to reduced surfactant compositions designed to work with high polymer levels as described in WO09153184 have met with problems due to less surfactant (and more water) being used.
  • the amount of nonionic available to dissolve the HCO is reduced and coupled with the reduced exotherm from neutralisation of the anionic surfactant acid. Insufficient structuring develops when the process is applied to such formulations.
  • WO96/25144 represents an early disclosure of this hot melt process.
  • the process comprises four steps. Firstly, the trihydroxystearin (a major component of HCO) is added to distilled water and allowed to mix until fully hydrated. Then the surfactants (anionic, amphoteric, cationic and nonionic) are added and the mixture is heated to 88°C until the trihydroxystearin is fully melted and dissolved. While heating the mixture is subjected to shear via a medium to high agitator speed. Then the trihydroxystearin dispersion is fast cooled utilising a plate and frame heat exchanger to a temperature of about 43°C to 27°C to form trihydroxystearin crystals. Perfume is then added. The mixture is continuously stirred at a medium speed. Polymer and silicones may subsequently be mixed in.
  • the hot melt process may be used to make a concentrated HCO premix.
  • nonionic is used, but it is never used as a solvent for the HCO.
  • EP1396535 discloses at paragraph 87 a preferred premix preparation process comprising the following steps:
  • WO 2005/012474 gives a further disclosure on page 31 for incorporation of a twin external structuring system into a detergent liquid intended to suspend visible beads.
  • the first structurant may be HCO
  • the second structurant is a polymeric structurant such as a polyacrylate or a polymer gum.
  • the aqueous liquid compositions herein can generally be prepared by first forming a pre-mix within which the structurants are dispersed in a portion of the water eventually used to comprise the aqueous liquid matrix of the compositions herein. This pre-mix is formed in such a way that it comprises a structured aqueous liquid. It is thought that this is only made possible by the presence of the second (polymeric) structurant.
  • HCO on its own would only form a structuring system in water if melted and used with surfactant.
  • To this structured pre-mix can be added, while the pre-mix is under agitation, surfactant(s) and any other ingredient, along with water. Any convenient order of addition of these materials, or for that matter, simultaneous addition of these composition components to the pre-mix can be carried out.
  • a premix is formed by combining the crystalline, hydroxyl-stabilizing agent, preferably in an amount of from about 0.1 percent to about 5 percent by weight of the premix, with water which comprises at least 20 percent by weight of the premix, and one or more of the surfactants to be used in the composition, and optionally, any salts which are to be included in the detergent composition.
  • the pre-mix formed is heated to above the melting point of the crystalline, hydroxyl-containing structurant and then cooled to form the structuring system.
  • Example I a solution of neutralised LAS acid is first heated to 90°C then the HCO is added and emulsified before cooling to form the structurant pre-mix. Thus the HCO is melted, as in previous hot melt processes.
  • a process to manufacture a structured aqueous liquid detergent composition comprising 7 to 40 wt% surfactant, of which at least 2 wt% is nonionic surfactant, optionally, and preferably, 4 to 30 wt% water soluble polymer, and 0.1 to 0.4 wt% Hydrogenated Castor oil (HCO) external structurant, the process comprising the step of formation of a structured premix which is then mixed in an amount of 40 to 80 vol% with an unstructured liquid comprising 20 to 60 vol% of the liquid detergent composition, characterised in that:
  • the amount of nonionic is preferably at least 15 times as much as the amount of HCO in the premix. Using only 8 times as much nonionic as HCO in the structured water premix proved insufficient to provide a structure to suspend cues. Thus, viscosity build appears to be related to relative levels of nonionic and HCO present in the premix when nonionic is used as the main solvent for the HCO.
  • step c) use of demineralised water at 65°C provides a good structured water premix.
  • the demineralised water to which the HCO solution is added may be higher than 65°C provided the HCO/NI premix is added in at 70 to 85°C under conditions of high shear (250rpm or higher, e.g. using an L4R Silverson, mixer).
  • Use of lower temperatures than 65°C for the demineralised water significantly reduce the degree of external structuring both for the structured water premix and for the final fully formulated liquid detergent compositions. If the temperature of the water to which solvated HCO is added is too high (above the melting point of HCO) then we see seeding effects. If the water temperature is too low ( ⁇ 55°C) we see creaming and phase separation in the final liquid.
  • the preferred water temperature is 60-70°C preferably about 65°C.
  • the premix formed in step c) is maintained above 55°C for a holding period of at least 30 minutes before it is cooled.
  • quench cooling has been found to yield good structure, as has slow cooling. Rapid (crash) cooling appears to lead to significant loss of structure.
  • the preferred cooling rate, especially after a holding period, is between 1.5 and 2.5 °C per minute, to allow the correct crystallisation to develop for best structuring effect for suspending duty.
  • the structuring system provides the advantage that in liquids where such polymer solution addition would provide thinning of the liquid and loss of structuring the compositions of the invention retain acceptable structuring properties.
  • the water soluble polymers preferably comprise ethoxylated polyethylene imine or other anti redeposition polymers and/or soil release polymers as described below.
  • the main utility of the HCO structuring system is for suspending duty.
  • the components to be suspended may range from invisible microcapsules, such as perfume encapsulates, to visible visual cues such as cues made from film material or large capsule type visual cues with a diameter of at least 2mm.
  • the amount of HCO in the liquids preferably ranges from 0.2 to 0.4 wt% to achieve this suspending duty.
  • the level of HCO in the final composition is less than 0.35, most preferably less than 0.3 wt%.
  • the viscosity of the structured water premix formed in step c is preferably at most 200 cp.
  • the structured water premix will have been formed from part of the ingredients that would already have been included in the liquid detergent. How these are mixed with the remaining ingredients of the liquid detergent is relatively flexible.
  • Water may be structured by adding a solution of HCO in nonionic surfactant to warm water.
  • the advantage of adding the HCO as a solution rather than a hot melt form is that it can be liquefied and therefore formed into a colloidal dispersion at a temperature below 90°C, preferably below 87°C, even below 85°C. This is significant.
  • HCO is a complex mix of components and their lowest melting point is 85°C. By operating below that melting point, the HCO is not melted and emulsified into an aqueous medium.
  • the cooled colloidal dispersion formed by the process according to the present invention is stable and can subsequently used as a premix to provide excellent structuring.
  • the structured fabric cleaning compositions containing cleaning polymers may also contain optional functional/non functional/visual cues and/or stable fragrance encapsulates for which significant rheology modification/structuring afforded by this invention is intended to prevent their sedimentation or creaming (under different storage conditions) to provide consumers uniform fragrance delivery in every dose per wash.
  • cleaning polymers such as anti redeposition polymers, soil release polymers and dye transfer inhibition polymers.
  • soil release polymers Particularly EPEI and polyester soil release polymers. Addition of these polymers does cause a low shear viscosity reduction (0.001 to 0.1 Pas)-due to polymer surfactant interactions between cleaning polymers/surfactant and structurant - but the process according to the invention provides unexpectedly high levels of structuring despite this.
  • the structured liquid may also provide a stable network through which dispersed encapsulates may be prevented from re-aggregating.
  • the structured water premix has an opaque appearance and is storage stable at ambient to 37°C.
  • the premix route solves the problem of manufacturing liquids with low to moderate 50 to 10 000 Pas low shear viscosities and having a critical stress consistent with suspending duty.
  • the low level of surfactants and use of polymers in such liquids requires the presence of a rheology modifier such as HCO.
  • the hot water to which the HCO solution is added may comprise other ingredients predissolved in the water.
  • Anionic surfactant, and soap are preferred pre-additives to the water ,
  • the structured water may be added to other components to manufacture a full structured liquid detergent at various points in the process flow for the manufacture of a full liquid. It is preferably added before any polymers. Usually it is added after any neutralisation reactions have been completed. The temperature of addition does not seem to be critical which leads to good process flexibility. We have added with success using structured water at temperatures from 20 to 40°C.
  • the liquid cleaning composition may be formulated as a concentrated cleaning liquid for direct application to a substrate, or for application to a substrate following dilution, such as dilution before or during use of the liquid composition by the consumer or in washing apparatus.
  • compositions made according to the present invention may be used for cleaning any suitable substrate
  • the preferred substrate is a laundry fabric. Cleaning may be carried out by simply leaving the substrate in contact for a sufficient period of time with a liquid medium constituted by or prepared from the liquid cleaning composition. Preferably, however, the cleaning medium on or containing the substrate is agitated.
  • the liquid detergent compositions obtained by the method according to the present invention are preferably concentrated liquid cleaning compositions.
  • the liquid compositions have a physical form that preferably ranges from a pourable liquid, a pourable gel to a non-pourable gel. These forms are conveniently characterised by the product viscosity. In these definitions, and unless indicated explicitly to the contrary, throughout this specification, all stated viscosities are those measured at a shear rate of 21 s-1 and at a temperature of 25°C. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
  • the liquid detergent compositions according to the invention are shear-thinning liquids. For suspending duty the fully formulated structured liquids may also be characterised as having a critical stress. Typical yield stresses for liquids according to the invention lie in the range 0.1 to 0.8 Pa.
  • Pourable gels preferably have a viscosity of at least 1,500 mPa.s but no more than 6,000 mPa.s, more preferably no more than 4,000 mPa.s, still more preferably no more than 3,000 mPa.s and especially no more than 2,000 mPa.s.
  • Non-pourable gels preferably have a viscosity of at least 6,000 mPa.s but no more than 12,000 mPa.s, more preferably no more than 10,000 mPa.s, still more preferably no more than 8,000 mPa.s and especially not more than 7,000 mPa.s.
  • composition is considered to be physically stable when it remains homogeneous over a period of about 3 months at temperatures from 5 to 50°C.
  • the surfactants of the surfactant system may be chosen from the surfactants described in 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in 'Tenside Taschenbuch', H. Stache, 2nd Edn., Carl Hanser Verlag, 1981 .
  • fatty acid will be present in the (final) liquid detergent composition primarily in the form of a soap.
  • Suitable cations include sodium, potassium, ammonium, monoethanol ammonium diethanol ammonium, triethanol ammonium, tetraalkyl ammonium, e.g. tetra methyl ammonium up to tetradecyl ammonium cations.
  • the amount of fatty acid will vary depending on the particular characteristics desired in the final liquid detergent composition. Preferably 0 to 30%, more preferably 1 to 20% most preferably 2 to 10 wt% of fatty acid is present in the liquid detergent compositions made according to the invention.
  • Mixtures of synthetic anionic and nonionic surfactants are especially useful in a liquid detergent compositions made using the invention.
  • fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
  • the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
  • the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups. Amongst the latter class, particularly preferred are those described in EP 225 654 A .
  • a nonionic surfactant that may be used in the present invention is a C12-C18 ethoxylated alcohol, comprising 3 to 9 ethylene oxide units per molecule. More preferred are C12-C15 primary, linear ethoxylated alcohols with on average 5 to 9 ethylene oxide groups, more preferably on average 7 ethylene oxide groups.
  • Suitable synthetic anionic surfactants for the detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals, including alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkoyl sarcosinates, alkyl ether carboxylates, alpha-olefin sulphonates and acyl methyl taurates, especially their sodium, magnesium ammonium and mono, di- and triethanolamine salts.
  • the alkyl and acyl groups generally contain from 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be unsaturated.
  • the alkyl ether sulphates and alkyl ether carboxylates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule.
  • Suitable synthetic anionics include sodium lauryl sulphate, sodium lauryl ether sulphate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium cocoyl isethionate, sodium lauroyl isethionate, and sodium N-lauryl sarcosinate.
  • the synthetic anionic surfactants comprise the synthetic anionic surfactant linear alkylbenzene sulphonate (LAS).
  • Another synthetic anionic surfactant suitable in the present invention is sodium alcohol ethoxy-ether sulphate (SAES), preferably comprising high levels of sodium C12 alcohol ethoxy-ether sulphate.
  • Preferred surfactant systems are mixtures of synthetic anionic with nonionic detergent active materials and additionally cationic or amphoteric surfactant.
  • a surfactant system that is a mixture of alcohol ethoxy-ether sulphate (AES) and a C12-C15 primary ethoxylated alcohol 3-9 EO ethoxylate and a quaternary ammonium cationic surfactant.
  • Preferred surfactant systems are mixtures of synthetic anionic with nonionic detergent active materials and soap, additionally with cationic or amphoteric surfactant.
  • Synthetic anionic surfactants can be present for example in amounts in the range from about 5% to about 70 wt% of the total surfactant material.
  • the detergent composition also comprises a cationic surfactant or an amphoteric surfactant, wherein the cationic or amphoteric surfactant is present in a concentration of 1 to 20%, preferably 2 to 15% more preferably 3 to 12 wt% of the total surfactant.
  • a commercially available and preferred example of this type of cationic surfactant is a compound of the formula above, where R1 is a C12/14 alkyl group, R2 is a group of the formula -A-(OA)n-OH, wherein A is -C2H4- and n is nil, and R3 and R4 are both -CH3 (i.e. C1-alkyl).
  • This type of cationic surfactant is commercially available from e.g. Clariant under the name Praepagen® HY.
  • amphoteric and zwitterionic surfactants are alkyl betaines, alkylamido betaines, amine oxides, aminopropionates, aminoglycinates; amphoteric imidazolinium compounds, alkyldimethylbetaines or alkyldipolyethoxybetaines.
  • compositions herein can further comprise a variety of optional ingredients.
  • additional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, etc.
  • Liquid detergent compositions of the invention may contain various solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Other suitable carrier materials are glycols, such as mono-, di-, tri-propylene glycol, glycerol and polyethylene glycols (PEG) having a molecular weight of from 200 to 5000.
  • the compositions may contain from 1 % to 50%, typically 5% to 30%, preferably from 2% to 10%, by weight of such carriers.
  • One or more detergency builders may suitably be present in the liquid detergent composition of the invention.
  • phosphate builders are not used.
  • the dendritic structuring system may not form in the same way when high levels of dissolved phosphate are present in the solution prior to crystallisation of the hydrogenated castor oil.
  • Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamino-tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.
  • liquid detergent compositions obtainable by the method according to the present invention preferably comprise from 0.005 to 2% by weight of an anti-oxidant.
  • the anti-oxidant is present at a concentration in the range of 0.01 to 0.08% by weight.
  • Anti-oxidants are substances as described in Kirk-Othmer (Vol 3, pg 424 ) and in Uhlmans Encyclopedia (Vol 3, pg 91 ).
  • One class of anti-oxidants that could be used in the present invention is alkylated phenols having the general formula: wherein R is C1-C22 linear or branched alkyl, preferably methyl or blanched C3-C6 alkyl; C3-C6 alkoxy, preferably methoxy; R1 is a C3-C6 branched alkyl, preferably tert-butyl; x is 1 or 2.
  • Hindered phenolic compounds are a preferred type of alkylated phenols according to this formula.
  • a preferred hindered phenolic compound of this type is 2, 6-di-tert-butyl-hydroxy-toluene (BHT).
  • a further class of anti-oxidants which could be suitable for use in the present invention is a benzofuran or benzopyran derivative having the formula: wherein R1 and R2 are each independently alkyl or R1 and R2 can be taken together to form a C5-C6 cyclic hydrocarbyl moiety; B is absent or CH2; R4 is C1-C6 alkyl; R5 is hydrogen or -C(O)R3 wherein R3 is hydrogen or C1-C19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is CH2OH, or CH2A wherein A is a nitrogen comprising unit, phenyl, or substituted phenyl. Preferred nitrogen comprising A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.
  • Anti-oxidants such as tocopherol sorbate, butylated hydroxy benzoic acids and their salts, gallic acid and its alkyl esters, uric acid and its salts and alkyl esters, sorbic acid and its salts, and dihydroxy fumaric acid and its salts may also be used.
  • Preservatives such as Proxel may advantageously be included. They may be added to the water in step c).
  • the liquid detergent compositions obtainable by the method according to the present invention preferably comprise from 0.001 to 3% by weight of the total composition of a perfume composition, preferably from 0.01 to 2% by weight of the total composition.
  • Said perfume composition preferably comprises at least 0.01% by weight based on the liquid compositions of a perfume component selected from terpenes, ketones, aldehydes and mixtures thereof.
  • the perfume composition may fully consist of the perfume component but generally the perfume composition is a complex mixture of perfumes of various differing perfume classifications.
  • the perfume composition preferably comprises at least 0.1 %, more preferably at least 1.0%, still more preferably at least 5% by weight of the perfume component.
  • core-in-shell microcapsules preferably have a d4,3 average particle size of from 1 to 100 micrometer.
  • Microcapsules as described in US-A-5 066 419 have a friable coating which is preferably an aminoplast polymer.
  • the coating is the reaction product of an amine selected from urea and melamine, or mixtures thereof; and an aldehyde selected from formaldehyde, acetaldehyde, glutaraldehyde or mixtures thereof.
  • the coating is from 1 to 30% by weight of the particles.
  • 'Detersive enzyme' means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry application.
  • Suitable enzymes that could be used in the composition of the present invention include proteases, amylases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, such as vegetable, animal bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity, thermostability, and stability to active bleach detergents, builders and the like. In this respect bacterial and fungal enzymes are preferred such as bacterial proteases and fungal cellulases.
  • Enzymes are included in the present detergent compositions for a variety of purposes, including removal of protein-based, saccharide-based, or triglyceride-based stains, for the prevention of refugee dye transfer, and for fabric restoration.
  • Enzymes are normally incorporated into detergent composition at levels sufficient to provide a "cleaning-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, or freshness improving effect on the treated substrate. In practical terms for normal commercial operations, typical amounts are up to about 50 mg by weight, more typically 0.01 mg to 30 mg, of active enzyme per gram of detergent composition. Stated otherwise, the composition of the invention may typically comprise from 0.001 to 3%, preferably from 0.01 to 1 % by weight of a commercial enzyme preparation.
  • proteases include Alcalase® and Savinase® Relase® from Novozymes and Maxatase® from International Bio-Synthetics, Inc., The Netherlands.
  • composition may additionally comprise enzymes as found in WO 01/00768 . It may additionally comprise Mannanase.
  • enzymes are added to the compositions after the cooling step d) in a preferred method of the invention.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430- 447 (John Wiley & Sons, Inc., 1979 ).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See US-A-2,954,347 .
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. Favourable anti-foaming results were obtained with fatty acid mixtures comprising lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. A preferred fatty acid of this type is Prifac 5908 (trademark ex Uniqema).
  • the liquid detergent compositions may also optionally contain one or more iron, copper and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures therein, all as hereinafter defined.
  • these chelating agents will generally comprise from about 0.1 % to about 10% by weight of the detergent compositions herein. More preferably, if utilised the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.
  • Detergent compositions often employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
  • Any suitable dye-transfer inhibition agents may be used in accordance with the present invention.
  • dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone (PVP), and/or vinyl imidazole (PVI) are preferred.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferably pKa ⁇ 6.
  • Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. Suitable PVPVI polymers include Sokalan(TM) HP56, available commercially from BASF, Ludwigshafen, Germany.
  • PVP polyvinylpyrrolidone polymers
  • PVP's are disclosed for example in EP-A-262,897 and EP-A-256,696 .
  • Suitable PVP polymers include Sokalan(TM) HP50, available commercially from BASF.
  • Compositions containing PVP can also contain polyethylene glycol (PEG) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 8, or even to 5 %, more preferably from 0.03 to 6, or even to 2 %, by weight of the composition.
  • the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from place to place. This preservation of whiteness assists in cleaning and counteracts the reduction in surfactants present in the wash liquor.
  • Particularly suitable polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials.
  • Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967 .
  • the preferred polycarboxylate is sodium polyacrylate.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published Dec. 15, 1982 , as well as in EP 193,360, published Sep. 3, 1986 , which also describes such polymers comprising hydroxypropylacrylate. Still other useful polymers maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360 , including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Polyethylene glycol (PEG) can act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 3,000 to about 10,000. Polyaspartate and polyglutamate dispersing agents may also be used.
  • polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the amount of anti redeposition polymer in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 8 %, more preferably from 0.03 to 6 %, by weight of the composition.
  • modified polyethyleneimine polymers as disclosed for example in WO-A-0005334 .
  • modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines.
  • Modified polyamines are further disclosed in US-A-4,548,744 ; US-A-4,597,898 ; US-A- 4,877,896 ; US-A- 4,891 , 160 ; US-A-4,976,879 ; US-A-5,415,807 ; GB-A-1,537,288 ; GB-A-1,498,520 ; DE-A-28 29022 ; and JP-A-06313271 .
  • the modified ethoxylated polyamines are described above and are generally linear or branched poly (>2) amines.
  • the amines may be primary, secondary or tertiary.
  • a single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain.
  • the alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer.
  • the terminal group of the alkylene oxide side chain can be further reacted to give an anionic character to the molecule (for example to give carboxylic acid or sulphonic acid functionality).
  • polyethylene imine is polyethylene imine, preferably modified polyethylene imine.
  • Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939 ; U.S. Pat. No.
  • these comprise a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; wherein the modification of the polyethyleneimine backbone is:
  • the polyethyleneimine polymer is present in the composition provided in step (a), prior to the dilution step (b), preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 3 wt% and/or less than 9.5 wt%, most preferably from 4 to 9 wt% and with a ratio of non-soap surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
  • the composition comprises a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl
  • PVP pyrrolidone
  • PVVI N-vinylimidazole copolymers
  • the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
  • the polymeric soil release agents useful herein especially include those soil release agents having:
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4 -C6 alkylene hydrophobic segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CH2 O--, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink .
  • Soil release agents characterized by poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl ester), e.g., C1 -C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C1 -C6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 .
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27,1987 to Gosselink .
  • Another preferred polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink .
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al , the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink , and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27,1987 to Gosselink .
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31,1989 to Maldonado et al , which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composition, typically greater than or equal to 0.2 wt% even from 3 wt% to 9 wt%, but more preferably they are used at greater than 1 wt%, even greater than 2 wt% and most preferably greater than 3 wt%, even more preferably greater than 5 wt%, say 6 to 8 wt% in the composition.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • Suitable soil release polymers are described in WO 2008095626 (Clariant); WO 2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120 (Rhodia Chimie); US 6242404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741197 (BASF); EP 728795 (BASF); US 5008032 (BASF); WO 2002077063 (BASF); EP 483606 (BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble ); EP 201124 (Proctor & Gamble ); EP 199403 (Proctor & Gamble ); DE 2527793 (Proctor & Gamble ); WO 9919429 (Proctor & Gamble ); WO 985
  • EPEI and soil release polymers of the above types enables increased performance at lower in wash surfactant levels compared to 1.0g/L or higher non soap surfactant wash liquors with betaine but without either EPEI or SRP.
  • SRP performance is enhanced significantly by repeated pre-treatment. There is some evidence of a build-up effect of EPEI performance.
  • the most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (Gerol), polyesters sold under the Texcare brand by Clariant, especially Texcare SRN170, and heavily branched polyesters such as those available from Sasol and described in US 7119056 .
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Liquid detergent compositions typically contain about 0.01 % to about 5% of these agents.
  • One preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • Exemplary ethoxylated amines are further described in US-A-4,597,898 .
  • CMC carboxy methyl cellulose
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the liquid detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention, can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered- ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in " The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982 ).
  • Optical brighteners are preferably added to the water in step c) to dissolve them easily.
  • Various through-the-wash fabric softeners can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in US-A-4,375,416 and US-A-4,291,071 .
  • the composition according to the present invention may contain a bleach or bleach system.
  • This bleach or bleach system may be, for example: (a) a peroxygen bleach species alone and/or in combination with a bleach activator and/or a transition metal catalyst; and (b) a transition metal catalysts in a composition substantially devoid of peroxygen species.
  • Bleaching catalysts for stain removal have been developed over recent years and may be used in the present invention.
  • transition metal bleaching catalysts that may be used are found, for example, in: WO-01/48298 , WO-00/60045 , WO-02/48301 , WO-00/29537 and WO-00/12667 .
  • the catalyst may alternatively be provided as the free ligand that forms a complex in situ.
  • Bleach activators are also well known in the art.
  • the exact mode of action of bleach activators for peroxybleach compounds is not known, but it is believed that peracids are formed by reaction of the activators with the inorganic peroxy compound, which peracids then liberate active-oxygen by decomposition.
  • They are generally compounds which contain N-acyl or O-acyl residues in the molecule and which exert their activating action on the peroxy compounds on contact with these in the washing liquor.
  • activators within these groups are polyacylated alkylene diamines, such N,N,N1,N1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester.
  • polyacylated alkylene diamines such N,N,N1,N1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD)
  • acylated glycolurils such as tetraacetylglycoluril (TAGU)
  • TAGU tetraacetylglycoluril
  • Peroxygen bleaching agents are also well known in the art, for example, peracids (e.g., PAP), perborates, percarbonates, peroxyhydrates, and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available in the form of mono- and tetra-hydrates, and sodium carbonate peroxyhydrate. Other examples of peroxyl species and activators as well as other transition metal catalyst are found in WO 02/077145 .
  • a stabiliser for the bleach or bleach system for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonate or salt thereof.
  • These stabilisers can be used in acid or salt form which is the calcium, magnesium, zinc or aluminium salt form.
  • the stabiliser may be present at a level of up to about 1 wt%, preferably from about 0.1 % to about 0.5 wt%.
  • bleaches and bleach systems are unstable in aqueous liquid detergents and/or interact unfavourably with other components in the composition, e.g. enzymes, they may for example be protected, e.g. by encapsulation or by formulating a structured liquid composition, whereby they are suspended in solid form.
  • Photobleaches including singlet oxygen photobleaches, could, also be used.
  • the structured water premix so formed was stable and could be kept until needed for use in formulation of concentrated heavy-duty aqueous laundry liquids.
  • the premix had a low shear viscosity of 625 Pa.s.
  • Example 1 was repeated except that the amount of nonionic used was reduced to 70g and the amount of water was increased to 800g.
  • the HCO nonionic solution was added to the water at a temperature of 83°C. Cooling to room temperature commenced immediately.
  • the structured water premix formed had a low shear viscosity of 415 Pa.s; and a viscosity at 21s-1 of 0.0957 Pa.s.
  • the HCO nonionic solution was prepared in the same way but instead of adding it to hot water it was added to a solution made up by neutralising 48.5g LAS acid, then 17g Prifac 5908 fatty acid by addition to a solution of caustic in the water. To this fully neutralised LAS soap solution was added 24.2g SLES solids under stirring at 250 rpm. To this solution, the HCO/nonionic solution was then added at 83°C. It was held at a temperature of 65°C for 30 minutes before cooling to room temperature to form a structured water premix with very good structuring.
  • Structured water premix C as prepared in example 3 was used to structure a low active and medium water level liquid comprising a high level of polymers with composition as shown in table 1.
  • the yield stress before polymer addition was 0.6 Pa. After polymers were added it dropped to 0.5 Pa. Some 5mm diameter visual film cues made of a modified polyvinyl alcohol polymer were mixed in at low shear. The liquid was subsequently stored for 12 weeks at 37°C. The liquid passed as storage stable under these conditions and no creaming or sedimentation of the film cues was observed.
  • Example 4 was repeated but using structured water premix A as prepared in Example 1.
  • the yield stress before polymer or visual cues addition was > 0.5 Pa.
  • Table 1 composition of Examples 4 & 5 Raw Material % as 100% Demin WATER 57.20 Opacifier 0.100 MPG 15.00 NaOH 0.74 Neodol 25-7 7.28 LAS acid 4.85 Optical brightener 0.10 Prifac 5908 1.70 Thixcin R (hydrogenated castor oil) 0.25 SLES 3EO 2.42 Dequest 2066 0.50 Colour 0.00078 Enzymes 1.89 Perfume 1.39 Proxel 0.02 EPEI (polymer) 3.10 Betaine 0.86 PET/POET Soil release polymer (polymer) 2.10 Visual cue 0.50 TOTAL 100.0
  • the yield stress of the resulting liquid was 0.8 Pa and it was found to be capable of suspending visible (5mm diameter) film cues made of a modified polyvinyl alcohol polymer added by low shear mixing.
  • the liquid was stored for 12 weeks at 37°C. The liquid was passed as storage stable under these conditions and no creaming or sedimentation of the film cues was observed.
  • a pre-mix of HCO in the Neodol was prepared by heating the mixture to 70 -75°C. The clear HCO solution was then added to the main mixer and mixed in. To this was added SLES 3EO, Dequest 2066, adjusted the pH to 7.5 and the mixture was cooled slowly to 30°C Then we added dyes, microcapsules, perfume, and enzymes to obtain the final product.
  • Example 1 shows the effect of heating the HCO above its melting point compared with the inventive process when it is kept below its melting point at all times.
  • Example B and C Example 1 was repeated except that the HCO was heated to a temperature in excess of 90°C.
  • Example B it was then crash cooled for 15 minutes using ice and low shear mixing.
  • Example C it was cooled over about 3 hours, again using low shear mixing.
  • the Structured water premix made by keeping the HCO below its melting point had the expected structuring and viscosity the crash cooled overheated example B failed to make effective structuring and Example C gave a thick paste. Neither is suitable for use to generate the liquids in accordance with Examples 4 to 6.
  • Example Comments Eta0 / Pa ⁇ s 1 Good structure 625 B thin liquid 125 C paste 150000

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Claims (9)

  1. Verfahren zur Herstellung einer strukturierten, wässrigen, flüssigen Detergenszusammensetzung, die 7 bis 40 Gew.-% oberflächenaktives Mittel, von dem es sich bei mindestens 2 Gew.-% um ein nicht-ionisches oberflächenaktives Mittel handelt, gegebenenfalls und vorzugsweise 4 bis 30 Gew.-% wasserlöslichens Polymeres und 0,1 bis 0,4 Gew.-% hydriertes Rizinusöl (HCO) als externes Strukturierungsmittel umfasst, wobei das Verfahren die Stufe der Bildung eines strukturierten Wasservorgemisches umfasst, das anschließend in einer Menge von 40 bis 80 Vol.-% mit einer unstrukturierten Flüssigkeit, die weiteres oberflächenaktives Mittel umfasst und 20 bis 60 Vol.-% der flüssigen Detergenszusammensetzung ausmacht, vermischt wird, wobei das Verfahren dadurch gekennzeichnet ist, dass das strukturierte Wasservorgemisch gebildet wird durch:
    a) Zugeben von 0,1 bis 0,4 Gew.-% und vorzugsweise von etwa 0,25 Gew.-% HCO (bezogen auf die flüssige Detergenszusammensetzung) zu 2 bis 8 Gew.-% oberflächenaktivem Mittel (bezogen auf die flüssige Detergenszusammensetzung),
    b) Erwärmen dieses Gemisches auf 70 bis 84°C, um eine molekular dispergierte, transparente Lösung eines untergeordneten Anteils an HCO in einem übergeordneten Anteil an oberflächenaktivem Mittel herzustellen, anschließend
    c) Zugeben der Lösung von Stufe b) zu Wasser bei einer Temperatur von mindestens 55°C, vorzugsweise von mindestens 65°C und insbesondere von mindestens 75°C, das gegebenenfalls ferner ein anionisches oberflächenaktives Mittel, jedoch keine Base umfasst, zur Bildung einer warmen, strukturierten Wasservorgemisch-Vorstufe und Abkühlenlassen dieser Vorstufe auf eine Temperatur unter 40°C zur Bildung eines strukturierten Wasservorgemisches,
    d) gegebenenfalls Altern des strukturierten Wasservorgemisches vor dessen Vereinigung mit der unstrukturierten Flüssigkeit, die weiteres oberflächenaktives Mittel umfasst, und
    e) gegebenenfalls weitere Zugabe von zusätzlichen Bestandteilen der Detergensflüssigkeit, die vorzugsweise 4 bis 30 Gew.-% wasserlösliche Polymere umfassen, zur Bildung einer extern strukturierten wässrigen Detergenszusammensetzung, mit der Maßgabe, das zu keinem Zeitpunkt während des Verfahrens die Temperatur des HCO dessen Schmelzpunkt übersteigt.
  2. Verfahren nach Anspruch 1, wobei das zum Lösen des HCO in Stufe b) verwendete oberflächenaktive Mittel aus anionischen oberflächenaktiven Mitteln, nicht-ionischen oberflächenaktiven Mitteln, kationischen oberflächenaktiven Mitteln, Seifen und Gemischen davon ausgewählt ist.
  3. Verfahren nach einem der vorstehenden Ansprüche, wobei die Menge des nicht-ionischen Mittels mindestens das 15-fache der Menge des HCO im Vorgemisch beträgt.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei das in Stufe c) gebildete Vorgemisch oberhalb von 55°C, vorzugsweise bei mindestens 60°C und insbesondere bei mindestens 65°C für eine Haltezeit von mindestens 15 Minuten gehalten wird, bevor es abgekühlt wird.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei die Abkühlgeschwindigkeit 1,5 bis 2,5°C pro Minute beträgt.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei 4 bis 30% Polymere in Stufe e) zugesetzt werden und die Polymeren wasserlösliche Polymere umfassen, die aus ethoxyliertem Polyethylenimin, schmutzfreisetzenden Polymeren und Gemischen davon ausgewählt sind.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei das Volumen des strukturierten Wasservorgemisches größer ist als das Volumen der restlichen Zusammensetzung.
  8. Verfahren nach einem der vorstehenden Ansprüche, wobei Teilchen in der Flüssigkeit suspendiert sind.
  9. Verfahren nach einem der vorstehenden Ansprüche, wobei die suspendierten Teilchen ausgewählt sind aus verkapselten Duftstoffen mit einem Durchmesser von weniger als 100 µm und sichtbaren Signalprodukten mit einem Durchmesser von mehr als 2 mm und Gemischen davon.
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US10945935B2 (en) 2016-06-27 2021-03-16 The Procter And Gamble Company Shampoo composition containing a gel network
MX382464B (es) 2016-10-10 2025-03-13 Procter & Gamble Composiciones para el cuidado personal sustancialmente libres de surfactantes sulfatados y que contienen una red de gel
DE102016219862A1 (de) 2016-10-12 2018-04-12 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Fließgrenze
HUE063260T2 (hu) * 2017-06-08 2024-01-28 Procter & Gamble Eljárások mosószerkészítmények struktúrálására
CN112261931B (zh) 2018-06-05 2023-12-08 宝洁公司 透明清洁组合物
EP3894015A1 (de) 2018-12-14 2021-10-20 The Procter & Gamble Company Shampoozusammensetzung mit blattförmigen mikrokapseln
WO2020229661A1 (en) 2019-05-16 2020-11-19 Unilever Plc Laundry composition
BR112021022370A2 (pt) * 2019-05-16 2022-01-04 Unilever Ip Holdings B V Composição de lavagem de roupas auxiliar, método para lavar tecidos brancos e uso de uma composição de lavagem de roupas auxiliar
US11896689B2 (en) 2019-06-28 2024-02-13 The Procter & Gamble Company Method of making a clear personal care comprising microcapsules
EP4103335A1 (de) 2020-02-14 2022-12-21 The Procter & Gamble Company Flasche zum aufbewahren einer flüssigen zusammensetzung mit einem darin suspendierten ästhetischen design
US12053130B2 (en) 2021-02-12 2024-08-06 The Procter & Gamble Company Container containing a shampoo composition with an aesthetic design formed by bubbles
US11633072B2 (en) 2021-02-12 2023-04-25 The Procter & Gamble Company Multi-phase shampoo composition with an aesthetic design

Family Cites Families (107)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4891A (en) 1846-12-15 wilson
US160A (en) 1837-04-17 Process of mabrtji actubind white lead
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US2208095A (en) 1937-01-05 1940-07-16 Ig Farbenindustrie Ag Process of producing insoluble condensation products containing sulphur and nitrogen
US2553696A (en) 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2806839A (en) 1953-02-24 1957-09-17 Arnold Hoffman & Co Inc Preparation of polyimines from 2-oxazolidone
NL95043C (de) 1953-06-30
NL211637A (de) 1955-10-27
BE615597A (de) 1958-06-19
NL259347A (de) 1959-12-22
US3308067A (en) 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3577515A (en) 1963-12-13 1971-05-04 Pennwalt Corp Encapsulation by interfacial polycondensation
US3341466A (en) 1966-10-31 1967-09-12 Brynko Carl Process for making capsules
CA989557A (en) 1971-10-28 1976-05-25 The Procter And Gamble Company Compositions and process for imparting renewable soil release finish to polyester-containing fabrics
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
GB1498520A (en) 1974-04-22 1978-01-18 Procter & Gamble Detergent compositions having soil release properties
US3959230A (en) 1974-06-25 1976-05-25 The Procter & Gamble Company Polyethylene oxide terephthalate polymers
CA1049367A (en) 1974-06-25 1979-02-27 The Procter And Gamble Company Liquid detergent compositions having soil release properties
DE2613790A1 (de) 1975-04-02 1976-10-14 Procter & Gamble Waschmittel
US4116885A (en) 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
EP0006268B2 (de) 1978-06-20 1988-08-24 THE PROCTER & GAMBLE COMPANY Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung
DE2829022A1 (de) 1978-07-01 1980-01-10 Henkel Kgaa Verfahren zur nachbehandlung gewaschener textilien zwecks verbesserung der auswaschbarkeit von anschmutzungen
EP0008830A1 (de) 1978-09-09 1980-03-19 THE PROCTER & GAMBLE COMPANY Schaumunterdrückende Zusammensetzungen und sie enthaltende Reinigungsmittel
ATE1863T1 (de) 1978-11-20 1982-12-15 The Procter & Gamble Company Reinigungsmittelzusammensetzung mit textilweichmachereigenschaften.
EP0066915B1 (de) 1981-05-30 1987-11-11 THE PROCTER & GAMBLE COMPANY Reinigungsmittelzusammensetzung enthaltend einen wirkungsfördernden Zusatz und ein Kopolymer zum Gewährleisten der Verträglichkeit desselben
US4489574A (en) 1981-11-10 1984-12-25 The Procter & Gamble Company Apparatus for highly efficient laundering of textiles
US4489455A (en) 1982-10-28 1984-12-25 The Procter & Gamble Company Method for highly efficient laundering of textiles
US4597898A (en) 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
SE459972B (sv) 1983-03-29 1989-08-28 Colgate Palmolive Co Smutsavvisande partikelformig tvaettmedelskomposition innehaallande en smutsavvisande polymer, foerfarande foer dess framstaellning och dess anvaendning vid tvaettning av syntetiska organiska polymera fibermaterial
NZ207692A (en) 1983-04-04 1986-04-11 Colgate Palmolive Co Soil-release promoting liquid detergent containing terephthalate polymers
US4548744A (en) 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
GB8504733D0 (en) 1985-02-23 1985-03-27 Procter & Gamble Ltd Detergent compositions
DE3689385T2 (de) 1985-04-15 1994-05-19 Procter & Gamble Stabile flüssige Reinigungsmittel.
GB8511089D0 (en) 1985-05-01 1985-06-12 Procter & Gamble Cleaning compositions
DE3536530A1 (de) 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
GB8527772D0 (en) 1985-11-11 1985-12-18 Unilever Plc Non-aqueous built liquid detergent composition
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
PL148326B1 (en) 1986-07-15 1989-10-31 A softerner for teytile products
GB8618635D0 (en) 1986-07-30 1986-09-10 Unilever Plc Detergent composition
US4954292A (en) 1986-10-01 1990-09-04 Lever Brothers Co. Detergent composition containing PVP and process of using same
US4721580A (en) 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
AU616190B2 (en) 1987-08-10 1991-10-24 Colgate-Palmolive Company, The Nonionic detergent composition of increased soil release promoting properties
US4976879A (en) 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US4877896A (en) 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
DE68925765T2 (de) 1988-08-26 1996-10-02 Procter & Gamble Schmutzabweisende Mittel mit von Allylgruppen abgeleiteten sulphonierten Endgruppen
US4968451A (en) 1988-08-26 1990-11-06 The Procter & Gamble Company Soil release agents having allyl-derived sulfonated end caps
DE3837013A1 (de) 1988-10-31 1990-05-03 Basf Ag Verwendung von partiell veresterten copolymerisaten in fluessigwaschmitteln
US4946624A (en) 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
DE4001415A1 (de) 1990-01-19 1991-07-25 Basf Ag Polyester, die nichtionische tenside einkondensiert enthalten, ihre herstellung und ihre verwendung in waschmitteln
US5066419A (en) 1990-02-20 1991-11-19 The Procter & Gamble Company Coated perfume particles
DE4034334A1 (de) 1990-10-29 1992-04-30 Basf Ag Verwendung von weinsaeure einkondensiert enthaltenden polyestern als waschmittelzusatz, verfahren zur herstellung der polyester und polyester aus weinsaeure und tetracarbonsaeuren
JPH06313271A (ja) 1993-04-27 1994-11-08 Unitika Ltd セルロース繊維の防汚加工方法
JPH08512351A (ja) 1993-07-08 1996-12-24 ザ、プロクター、エンド、ギャンブル、カンパニー 汚れ放出剤を含んでなる洗剤組成物
US5415807A (en) 1993-07-08 1995-05-16 The Procter & Gamble Company Sulfonated poly-ethoxy/propoxy end-capped ester oligomers suitable as soil release agents in detergent compositions
DE4344357A1 (de) 1993-12-24 1995-06-29 Henkel Kgaa Flüssiges Wasch- und Reinigungsmittel
EP0759947B1 (de) 1994-05-20 2000-07-19 Henkel Kommanditgesellschaft auf Aktien Schmutzablösevermögende polyester
DE4440956A1 (de) 1994-11-17 1996-05-23 Henkel Kgaa Schmutzabweisendes Waschmittel mit bestimmter Tensidkombination
JP3269824B2 (ja) 1995-02-15 2002-04-02 ザ、プロクター、エンド、ギャンブル、カンパニー ストレス安定性泡立ち性皮膚クレンジングリキッド組成物及び個人用バス及びボディクレンジングキット
DE19506634A1 (de) 1995-02-25 1996-08-29 Basf Ag Verfahren zur Herstellung von feinteiligen Mischungen aus amphiphilen Polymeren und Polycarboxylaten und ihre Verwendung
ATE255157T1 (de) 1995-05-18 2003-12-15 Textil Color Ag Zusammensetzung zum waschen und reinigen von textilmaterialien
GB2303146A (en) 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
US5728671A (en) 1995-12-21 1998-03-17 The Procter & Gamble Company Soil release polymers with fluorescent whitening properties
DE19616570A1 (de) 1996-04-25 1997-10-30 Basf Ag Vor exothermer Zersetzung durch Oxidation geschützte Waschmittelbestandteile
AU2811097A (en) 1996-05-03 1997-11-26 Procter & Gamble Company, The Cotton soil release polymers
US5922663A (en) 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
AR010265A1 (es) 1996-11-01 2000-06-07 Procter & Gamble Composiciones detergentes para el lavado a mano que comprende una combinacion de surfactantes y polimero de liberacion de suciedad
DE19646110A1 (de) 1996-11-08 1998-05-14 Bayer Ag Mikrokapseln unter Verwendung von Iminooxadiazindion-Polyisocyanaten
ZA9711578B (en) 1996-12-23 1999-06-23 Quest Int Compositions containing perfume
DE19725508A1 (de) 1997-06-17 1998-12-24 Clariant Gmbh Wasch- und Reinigungsmittel
WO1998059030A1 (en) 1997-06-20 1998-12-30 The Procter & Gamble Company Soil release polymers with fluorescent whitening properties
DE69727983T2 (de) 1997-10-10 2005-02-10 The Procter & Gamble Co., Cincinnati Eine waschmittelzusammensetzung
JP4053124B2 (ja) 1997-12-26 2008-02-27 ライオン株式会社 洗剤粒子組成物及びその製造方法
AU2284699A (en) 1998-02-11 1999-08-30 Rhodia Chimie Dirt removing detergent compositions
RO114357B1 (ro) 1998-02-26 1999-03-30 Sc Prod Cresus Sa Compoziție pentru tratarea anti-murdărire a materialelor textile
FR2781233B1 (fr) 1998-07-15 2000-08-18 Rhodia Chimie Sa Composition polyester terephtalique et son utilisation comme agent antisalissure
WO2000005334A1 (en) 1998-07-23 2000-02-03 The Procter & Gamble Company Laundry detergent composition
PH11999002190B1 (en) 1998-09-01 2007-08-06 Unilever Nv Composition and method for bleaching a substrate
DE69926390T2 (de) 1998-11-13 2006-03-30 The Procter & Gamble Company, Cincinnati Bleichmittelzusammensetzungen
AU4061900A (en) 1999-04-01 2000-10-23 Procter & Gamble Company, The Transition metal bleaching agents
AU5403500A (en) 1999-06-23 2001-01-31 Breel, Greta J. Bleaching detergent compositions
WO2001023515A1 (en) 1999-09-29 2001-04-05 Rhodia Inc. Novel polymer based cleaning compositions for use in hard surface cleaning and laundry applications
DE19954831A1 (de) 1999-11-13 2001-05-17 Henkel Kgaa Tensid-haltige Wasch- und Reinigungsmittel
GB9930697D0 (en) 1999-12-24 2000-02-16 Unilever Plc Method of treating a textile
JP2001181692A (ja) 1999-12-27 2001-07-03 Lion Corp 部分洗い用液体洗浄剤組成物
DE10000223A1 (de) 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
DE10043604A1 (de) 2000-09-02 2002-03-28 Rwe Dea Ag Fließfähige, amphiphile und nichtionische Oligoester
DE10051190A1 (de) 2000-10-16 2002-04-25 Bayer Ag Mikrokapseln mit Wänden aus Polyharnstoff
DE10051194A1 (de) 2000-10-16 2002-04-25 Bayer Ag Mikrokapseln mit Wänden aus Polyharnstoff
GB0030673D0 (en) 2000-12-15 2001-01-31 Unilever Plc Ligand and complex for catalytically bleaching a substrate
GB0102826D0 (en) 2001-02-05 2001-03-21 Unilever Plc Composition and method for bleaching a substrate
GB0106560D0 (en) 2001-03-16 2001-05-02 Quest Int Perfume encapsulates
DE10115250A1 (de) 2001-03-28 2002-10-10 Basf Ag Schmutzablösende Polyester
JP2005528200A (ja) 2002-05-31 2005-09-22 マクマスター・ユニバーシテイ ポリウレアカプセル中に疎水性有機分子をカプセル化する方法
EP1396535B1 (de) 2002-09-05 2004-12-15 The Procter & Gamble Company Strukturierte flüssige Weichmacherzusammensetzungen
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
US20040142868A1 (en) 2003-01-21 2004-07-22 Sleeman Mark W. Method of treating liver steatosis in a mammal
EP1502943A1 (de) 2003-08-01 2005-02-02 The Procter & Gamble Company Wässriges flüssiges Reinigungsmittel mit sichtbaren Teilchen
EP1502944B1 (de) 2003-08-01 2007-02-28 The Procter & Gamble Company Wässriges Flüssigwaschmittel enthaltend sichtbare Teilchen
DE102004018051A1 (de) 2004-04-08 2005-11-10 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend Farbfixiermittel und Soil Release Polymere
DE102005027604A1 (de) 2005-06-15 2006-12-28 Clariant Produkte (Deutschland) Gmbh Reinigungsmittel für harte Oberflächen
DE102005027605A1 (de) 2005-06-15 2006-12-28 Clariant Produkte (Deutschland) Gmbh Geschirrspülmittelformulierungen enthaltend Oligoester
DE102007005532A1 (de) 2007-02-03 2008-08-07 Clariant International Limited Wässrige Oligo- und Polyesterzubereitungen
ES2406948T5 (es) 2007-03-20 2019-10-15 Procter & Gamble Composición tratante líquida
EP2300586B1 (de) 2008-06-16 2015-04-08 Unilever PLC Verbesserungen im zusammenhang mit stoffreinigung
WO2010034736A1 (en) 2008-09-25 2010-04-01 Unilever Plc Liquid detergents
EP2216391A1 (de) * 2009-02-02 2010-08-11 The Procter & Gamble Company Flüssige Handspülmittelzusammensetzung

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