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WO2010034736A1 - Détergents liquides - Google Patents

Détergents liquides Download PDF

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Publication number
WO2010034736A1
WO2010034736A1 PCT/EP2009/062313 EP2009062313W WO2010034736A1 WO 2010034736 A1 WO2010034736 A1 WO 2010034736A1 EP 2009062313 W EP2009062313 W EP 2009062313W WO 2010034736 A1 WO2010034736 A1 WO 2010034736A1
Authority
WO
WIPO (PCT)
Prior art keywords
premix
castor oil
hydrogenated castor
liquid
temperature
Prior art date
Application number
PCT/EP2009/062313
Other languages
English (en)
Inventor
Richard Michael Craven
Colin Lee Doyle
Andrew David Green
Ian James Hussey
Aidan Joseph Lavery
Jojo Philip
Jayne Rice
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to EP20090783318 priority Critical patent/EP2326705A1/fr
Priority to CN2009801468533A priority patent/CN102224233A/zh
Publication of WO2010034736A1 publication Critical patent/WO2010034736A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D3/20—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to a method for the production of liquid detergent compositions for laundry, comprising hydrogenated castor oil.
  • the invention relates also to liquid detergent compositions obtainable by this method.
  • Liquid detergents are increasingly used by the consumer for cleaning laundry, as they are convenient in their use.
  • the liquid detergents are increasingly marketed as concentrated liquid detergents that generally contain surfactant at a total concentration of 30-60% by weight, more than 40% active specifically, as compared to a maximum level of 20% by weight for non-concentrated liquid detergents. This has the advantage for the consumer and industry that the amount of liquid that needs to be dosed is small, and consequently much less tonnage of liquids need to be manufactured, packed, transported and stored, while keeping the detergency power the same.
  • HCO hydrogenated castor oil
  • US 3 354 091 discloses a substantially homogeneous, pourable, heavy-duty aqueous liquid detergent composition which consists essentially of 5-30 wt% alkali metal anionic organic sulfonated detergent, 10-30 wt% potassium polyphosphate, a 4-12 wt% hydrotrope, 0.1-1 wt% alkali metal carboxymethyl cellulose normally tending to separate from the solution of detergent and phosphate and 0.01-1 wt% hydrogenated castor oil sufficient 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 are preferably added as a mixture in molten form.
  • lauric isopropanolamide and castor wax are premelted and added as a blend at 71 0 C with stirring.
  • the melting point of the castor wax is given as 84-87 0 C and the melting point of the alkanolamide would have been about 65-66 0 C.
  • Insufficient information is given in this document to know if the castor wax melted or if it dissolved in the melted isopropanolamide.
  • GB 1 ,034,202 discloses an alternative process of preparing a liquid detergent composition which comprises preparing an aqueous concentrate of castor wax and an anionic detergent in water with agitation at a temperature above 88°C and slowly cooling this mixture at a rate not exceeding 2.8°C per minute to form a stable, fine dispersion of the castor wax in the concentrate, and mixing the concentrate with additional water and the same or a different detergent to form a homogeneous, liquid detergent composition, pourable at room temperature, and containing 0.1 to 1 % by weight of the castor wax in fine stable dispersion and 5 to 50% total detergent by weight.
  • GB 1 ,034,202 represents the process that has become the normal one for making HCO external structuring systems. Essentially a concentrated structured liquid is made in the form of an aqueous emulsion, which can be cooled as a concentrate and then cold mixed with the remainder of the formulation that is required to be structured. Any solid material to be suspended can then be added to the liquid so formed.
  • WO 02/40627 A2 discloses liquid detergent compositions comprising a structuring system, wherein the structuring system may comprise hydrogenated castor wax.
  • the structuring systems are specifically thread-like structuring systems and/or non-thread- like structuring systems (i.e., disk-like structuring systems wherein structuring agents aggregate together to form disk-like structures that can interact with other disk-like structures to result in a structuring system).
  • the process for making the thread-like structuring system is described as comprising heating a mixture of water and HCO to above the melting point of the HCO and then cooling the mixture to room temperature while stirring, so that a thread-like structuring system is formed.
  • surfactant and salt are also added to this premix.
  • EP 1 396 536 A1 discloses structuring systems that are suitable for stabilising liquid fabric treatment compositions, comprising:
  • A a non-polymeric, crystalline, hydroxyl-containing structuring agent, which can crystallize to form a thread-like structuring network throughout liquid matrices (e.g. HCO), at concentrations from 0.1-80% by weight, most preferably 2-6% by weight of the structuring system;
  • B a nonionic emulsifier (e.g. ethoxylated C 8 -C 2 O alcohols having 1-11 EO groups);
  • anionic emulsifier e.g. C 11 -C 1 3 alkylbenzene sulfonates
  • the anionic emulsifier is believed to control the particle size of a thread-like structuring material by mixing with the structuring agent, wherein the threads are relatively long and thick.
  • a structuring system constitutes preferably 4-15% by weight of the liquid fabric treatment composition.
  • the system will always include some water (e.g. from the surfactant) in order for the anionic emulsifier to function in the HCO premix. All of the examples use such added water.
  • EP 1 396 536 A1 is a process to prepare such thread-like structuring systems, by mixing the various components, heating to a temperature above the melting temperature of the structuring agent (90 0 C), storing for at least an hour at this temperature under agitation, and cooling to a temperature below the melting temperature of the structuring agent (70 0 C), at a rate between preferably 1.5 and 2.5°C per minute.
  • This process is again based on the crystallisation of an emulsion droplet of melted hydrogenated castor oil.
  • Surfactant acid is neutralised in the pre-mix in the presence of the water and the heat of neutralisation could be used to melt the HCO.
  • Spicer PT. and Hartel R.W. describe a mechanism for the formation of such thread-like structures by crystallisation from an emulsion.
  • EP 1 502 944 A1 discloses a similar structuring system, wherein hydrogenated castor oil is mixed with anionic surfactant in a premix, and this premix is subsequently mixed - A - with other ingredients of aqueous liquid detergents to formulate liquid detergents comprising up to 5% by weight of visibly distinct beads.
  • the premix is made by heating the aqueous premix to above the melting temperature of the hydrogenated castor oil (about 90 0 C) and making an emulsion, this emulsion is then flash cooled to 70 0 C in order to crystallise the hydrogenated castor oil, followed by slowly cooling to room temperature.
  • the thread-like structuring is thus formed within the aqueous matrix.
  • surfactant acid is neutralised in the pre-mix in the presence of the water and the heat of neutralisation could be used to melt the HCO to form the pre-mix oil in water emulsion.
  • the remainder of the surfactant system may then be mixed with 2.5 parts of this aqueous structured concentrate at room temperature and finally neutral density beads may be mixed in to the structured liquid.
  • the detergent compositions most preferably comprise 10 to 35% by weight of surfactants.
  • WO 2006/005068 A1 discloses liquid detergent compositions comprising hydrogenated castor oil, which is used as a structurant that can form thread-like structuring systems throughout the liquid matrix.
  • the liquid detergent compositions preferably comprise surfactants at a concentration from 10 to 45% by weight, while the concentration of hydrogenated castor oil is exemplified at about 0.19-0.28% by weight of the total composition. No details are provided regarding temperature and cooling rates in a method for production of this liquid detergent composition.
  • WO 2007/130562 A2 describes liquid laundry detergent compositions, which may contain an organic external structurant like hydrogenated castor oil. These structurants are believed to function by forming thread-like structuring systems when they are crystallised in situ within the aqueous liquid matrix of the compositions herein or within a pre-mix, which is used to form such an aqueous liquid matrix. Such crystallisation is brought about by heating an aqueous mixture of these materials to a temperature above the melting point of the structurant, followed by cooling of the mixture to room temperature while maintaining the liquid under shear.
  • the thread-like system can comprise a fibrous or entangled thread-like network. Non-fibrous particles, in the form of rosettes, may also be formed. The particles in the network may have an aspect ratio of from about 1.5:1 to about 200:1 , and may have dimensions that range from about 1 micrometre to about 100 micrometres.
  • WO 99/38389 discloses liquid personal cleansing compositions that comprise a lipophilic skin moisturizing agent, a weighting oil, a stabilizer (for example trihydroxystearin), a surfactant and water. This mixture is made by incorporating steps like making separate premixes, mix these, keep at a temperature of about 88°C and cool slowly to a temperature of about 25-40 0 C.
  • the recent prior art using HCO as an external structurant follows a process of making a premix by crystallising the HCO from an aqueous emulsion to form a thread -like structuring concentrate which can then be diluted to form a liquid with some suspending properties.
  • the disadvantages of this are that any surfactants used for the emulsification also find their way into the final product where they may interact unfavourably with the surfactant system chosen for that product.
  • the premix must be cooled before it is admixed with the remaining ingredients, which can cause long waiting times in a continuous process.
  • the thread-like structuring system has extreme shear thinning behaviour, which means it does not reliably keep suspended and dispersed particles of solid material during repeated dispensing of the product by squeezing of the container.
  • a method for the production of a liquid detergent composition wherein hydrogenated castor oil is added to a liquid organic solvent at temperatures of at least 70 0 C, wherein the organic solvent preferably comprises free fatty acid, or nonionic surfactant, or mixtures thereof, to form a premix.
  • This premix is then added to a batch of another premix comprising surfactants and neutralising agent in water at a temperature of at least 55°C to provide micellar solubilisation of the hydrogenated castor oil into the surfactants.
  • solubilised hydrogenated castor oil Upon controlled cooling of this mixture, solubilised hydrogenated castor oil self-assembles into a dendritic structure, thereby creating an effective structurant for a liquid detergent composition with the ability to suspend solid particles, especially encapsulated perfume with a particle size of less than 200 micrometre.
  • the dendritic structure formed from this solubilised molecular dispersion of HCO process is different in appearance and properties from the prior art thread-like structurant formed by the melt emulsion process.
  • the dendritic structure is thought to be a result of crystallising from a solution and directly into the bulk product without any subsequent redispersal of the structuring system into the second part of the liquid formulation.
  • this process forms a different structuring morphology and that the shear thinning and solids suspending properties of the liquid so formed are, for some applications, superior to those formed using the emulsion process route to the different morphology of the thread-like structuring system.
  • An advantage of the present invention is that detergent liquids are obtained that are especially suitable for suspending encapsulated fragrances, which are not visible to the human eye. An appealing liquid detergent composition is thereby created, which has an attractive fragrance for the consumer.
  • a first aspect of the present invention thus provides a method for the production of a phosphate free liquid detergent composition, comprising the following steps: a) preparation of a first premix by adding surfactants and a base to water under agitation at a temperature of at least 55°C, having a pH from 7.5 to 11 ; b) preparation of a second premix by adding hydrogenated castor oil to a liquid non- aqueous organic solvent, preferably selected from nonionic surfactants and free fatty acid and mixtures thereof, at a temperature of at least 70 0 C, under agitation to dissolve the hydrogenated castor oil in the liquid non-aqueous organic solvent; c) addition of the second premix from step b) to the first premix from step a) at a temperature of at least 55°C under mixing, at a weight ratio of b) to a) of from 1 :40 to 1 :10, whereby the hydrogenated castor oil remains in solution; d) cooling of the mix of step c) to a temperature
  • non-aqueous organic solvent for the HCO in step b) has advantages over use of the aqueous emulsion systems in the prior art: they include the formation of a more concentrated premix, which means less heat input is required for the premix due to its lower mass, its lower specific heat and the lower temperature to which it has to be heated.
  • the solvent process also gives a different and superior microstructure for the HCO when it is used to suspend solid material in the liquid, especially encapsulated fragrance.
  • a second aspect of the invention provides a liquid detergent composition comprising suspended encapsulated fragrance with a particle size up to 200 micrometer obtainable by a process according to the first aspect of the invention, wherein the hydrogenated castor oil external structurant is present at a concentration of from 0.15 to 0.5% by weight of the total composition, and has a dendritic structure with a minor dimension up to 40 nanometres and an aspect ratio of about 1000:1 .
  • Primary detergency is herein described as the detergency effect on a stain in the primary or first wash.
  • the fabric is stained and subsequently treated with the laundry detergent composition of the invention.
  • the detergency effect (measured as stain removal) of the laundry composition on the stain is termed as primary detergency.
  • This is a separate process to so-called soil release using a polymer, which is treatment of fabric with a polymer (through a wash or other such treatment), with subsequent staining of the fabric, the soil release polymer having the effect of the easier removal of the stain.
  • Transparent as used herein means that an ingredient, or a mixture, or a phase, or a composition preferably has a transmittance of light of more than 25%, more preferably more than 30%, most preferably more than 40%, optimally more than 50% in the visible part of the spectrum (approx. 410-800 nm).
  • absorbency may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals: 1/10 absorbancy x 100%.
  • % transmittance equals: 1/10 absorbancy x 100%.
  • translucent materials are defined as materials that only allow light to pass through them diffusely so that objects on the other side cannot be clearly distinguished.
  • shear-thinning liquids refers to liquids that are relatively viscous at low shear conditions (e.g. at rest) and less viscous at high shear conditions (e.g. when pouring the liquid from a bottle).
  • Shear-thinning rheological properties can be measured with a viscometer or a sophisticated rheometer and the correct measurement spindle.
  • a method for the production of a phosphate free liquid detergent composition comprising the following steps: a) preparation of a first premix by adding surfactants and a base to water under agitation at a temperature of at least 55°, preferably at a temperature from 55 to 70 0 C, more preferably from 60 to 65°C, and most preferably at about 65°C, having a pH from 7.5 to 11 , preferably from 8 to 10; b) preparation of a second premix by adding hydrogenated castor oil to a liquid nonaqueous organic solvent at a temperature of at least 70 0 C, preferably at a temperature from 70 to 75°C, under agitation to dissolve the hydrogenated castor oil in the liquid non-aqueous organic solvent, wherein the non-aqueous organic solvent preferably comprises free fatty acid, or nonionic surfactant, or mixtures thereof; c) addition of the second premix from step b) to the first premix from step a) at a temperature
  • the concentration of surfactants is from 20 to 65% by weight, more preferably from 25 to 60% by weight, and mostly preferably from 25 to 45% by weight of the total mix in this step.
  • the detergent composition obtainable by the method according to the invention is a concentrated detergent composition.
  • the surfactants preferably comprise synthetic anionic and/or nonionic surfactants. More preferably, the surfactants in step a) comprise the synthetic anionic surfactant linear alkylbenzene sulphonate (LAS).
  • the pH of the premix in step a) is preferably from 9 to 10.
  • the temperature is at least 55°C, in order to produce the correct structuring on addition of the dissolved external structurant from the second premix in step b).
  • the first premix in step a) comprises surfactants and a base in water, and preferably also a hydrotrope.
  • a hydrotrope is a compound that solubilises hydrophobic compounds in aqueous solutions.
  • hydrotropes consist of a hydrophilic part and a hydrophobic part, however the hydrophobic part is too small to cause spontaneous self-aggregation and so they do not form micelles like surfactants.
  • Hydrotropes are used in detergent formulations to allow more concentrated formulations of surfactants. Suitable hydrotropes are, for example, glycerol and propylene glycol.
  • the first premix in step a) is a transparent liquid at the prevailing temperature of step c).
  • the base in the premix in step a) preferably comprises an alkali metal hydroxide or triethanolamine, more preferably the neutralising agent comprises sodium hydroxide, triethanolamine or mixtures thereof.
  • the premix in step a) is a micellar solution of the surfactants in water.
  • a second premix is prepared containing hydrogenated castor oil dissolved in a liquid non-aqueous organic solvent at a temperature of at least 70 0 C, preferably from 70 to 75°C.
  • the solvent comprises free fatty acid, or nonionic surfactant, or a mixture of these. More preferably, the solvent comprises a free fatty acid and most preferably, the free fatty acid comprises linear alkyl saturated Ci 2 -Ci 8 fatty acid. Free water is not added to the solvent in the vessel in this step b).
  • the second premix is made under low shear conditions; more preferably, only gentle mixing is applied. This has as an advantage that only low energy input is required when mixing the second premix.
  • this second premix in step b) is a transparent liquid at the prevailing temperatures in this step b).
  • the concentration of hydrogenated castor oil in the second premix is such that the concentration in the final liquid detergent composition obtainable by the method of the invention is from 0.15 to 0.5% by weight of the composition, preferably from 0.15 to 0.3% by weight, even more preferably from 0.15 to 0.25%, and most preferably from 0.17 to 0.25% by weight of the total composition. Consequently the concentration of hydrogenated castor oil in the second premix in step b) is preferably from 1.5 to 20% by weight of the premix, more preferably from 1.5 to 10%, even more preferably from 1.7 to 5%, and most preferably from 3.4% to 5% by weight of the premix.
  • the second premix comprises only solvent and hydrogenated castor oil, wherein the solvent preferably comprises free fatty acid, or nonionic surfactant, or mixtures thereof, most preferably the solvent is free fatty acid, for the reasons explained below in relation to step c).
  • the solvent preferably comprises free fatty acid, or nonionic surfactant, or mixtures thereof, most preferably the solvent is free fatty acid, for the reasons explained below in relation to step c).
  • step c) the second premix is added to the first premix under agitation, wherein the weight ratio of the second and first premix is from 1 :40 to 1 :10, preferably from 1 :30 to 1 :15, and more preferably at about 1 :20. Most preferred the second premix constitutes less than 6% by weight of the total formulation, most preferred about 5% by weight of the total formulation.
  • the temperature in step c) is at least 55°C, preferably between 55 and 70 0 C, more preferably between 55 and 65°C, most preferred between 60 and 65°C.
  • the base in the first premix acts as neutralising agent for the fatty acid
  • soap is formed by mixing the first and second premix in step c).
  • This formation of soap leads to complete or partial elimination of the solvent for the hydrogenated castor oil and this process is thought to act as a seed for its subsequent crystallisation to the dendritic structure.
  • a similar effect can be obtained by careful selection of nonionic surfactant solution that will have a phase change on addition to anionic surfactant solution, but this type of physical phase change is less preferred than the chemical phase change due to the neutralisation of the free fatty acid solvent.
  • the second premix only forms a small proportion of the total liquid detergent composition, a relatively small volume of liquid needs to be heated to a temperature that is relatively low as compared to the methods of the prior art.
  • This is an advantage of the method of the invention, which leads to energy saving.
  • Another advantage is that the mixing of the first and second premix preferably occurs at low shear, only gently mixing is preferably applied to the mixing process. This also leads to energy saving on mixing as compared to the prior art.
  • step c) the first and second premixes are combined under gentle mixing, and, without wishing to be bound by theory, after addition of the second premix (from step b)) to the first premix (from step a)), the hydrogenated castor oil is believed to be held in solution by micellar solubilisation due to the interaction between the hydrogenated castor oil and the water and surfactants in the formulation.
  • the mix in step c) is also clear at the prevailing temperature in step c), which is at least 55°C, preferably from 55 to 70 0 C, indicating that the second premix suitably completely dissolves in the first premix.
  • the solubilised hydrogenated castor oil is homogeneously mixed before the crystallization process commences.
  • step d) the mix from step c) is cooled to a temperature below 50 0 C, preferably below 40°, more preferred below 35°C, even more preferred below 30 0 C. Subsequently this mix is stored until the hydrogenated castor oil has crystallised from solution.
  • the skilled person is able to determine when the hydrogenated castor oil has crystallised, as the crystallisation of the hydrogenated castor oil can be visually observed by the liquid becoming cloudy. Otherwise by conventional light microscopy it can be observed whether crystals of hydrogenated castor oil have formed.
  • this cooling step d) is carried out while the mix is gently mixed, at low shear conditions. In this case, low shear means that the shear is insufficient to break up the emerging dendritic structure.
  • step d) the mix of step c) is cooled to a temperature below 50 0 C at a cooling rate of maximally 1 °C per minute.
  • step d) the mix of step c) is cooled to a temperature below 40 0 C, more preferably 30 0 C, at a cooling rate of maximally 1 0 C per minute, preferably maximally 0.7°C per minute, even more preferably maximally 0.5°C per minute, mostly preferably maximally 0.4 0 C per minute.
  • the hydrogenated castor oil present in the premix suitably starts to crystallise during the cooling step, at a temperature below 55°C.
  • step d) the mix of step c) is cooled to a temperature below 40°C within 5 minutes, followed by storing this mix at a temperature below 40 0 C for at least 5 minutes.
  • the mix of step c) is cooled to a temperature below 35°C within 5 minutes, more preferably within 3 minutes, followed by storing this mix at a temperature below 35°C for at least 5 minutes.
  • the mix of step c) is cooled to a temperature below 30 0 C within 5 minutes, most preferably within 3 minutes, followed by storing this mix at a temperature below 30°C for at least 5 minutes.
  • the mix of step c) is cooled to a temperature below 40°C within 3 or even 2 minutes, followed by storage at a temperature below 40 0 C for at least 5 minutes. Most preferably, the mix of step c) is cooled to a temperature below 30°C within 3 or even 2 minutes, followed by storage at a temperature below 30 0 C for at least 5 minutes. In another preferred embodiment, the mix is stored for at least 8 minutes, or more preferably, at least 10 minutes at the prevailing temperature after the cooling step has taken place.
  • the hydrogenated castor oil present in the premix suitably starts to crystallise during the storage of the mix after the rapid cooling.
  • An example of such a rapid cooling process is flash cooling in a plate heat exchanger, wherein the mixture is cooled to below 30°C within a period of about 1 minute.
  • the mixture will be kept at the temperature below 40°C for a period of at least 5 minutes.
  • the temperature of the mix is kept constant below 40 0 C, and crystallisation of the hydrogenated castor oil will occur at the temperature at which the premix is kept after the rapid cooling has taken place.
  • this step d) an opacified non-Newtonian liquid is obtained, which preferably has a shear thinning profile to provide a pourable liquid easily dispensed into a washing machine.
  • a dendritic structure is a highly branched structure of solid material having a core with branches extending from that core.
  • the dendritic structure seems to be formed by a series of nucleations on cooling the mix in step d), followed by crystal growth from these nucleation sites leading to the formation of the dendrites.
  • the nucleating site can be described as the core of the dendrimer.
  • the hydrogenated castor oil grows out into a three-dimensional branched structure from this core throughout the formulation, leading to a three- dimensional scaffold.
  • the hydrogenated castor oil in the form of dendrimers, forms a structuring network, where the dimensions of dendrimers are preferably micron-sized (up to about 100 micrometer).
  • the dendrimers form a highly-tangled fibrous network.
  • the branches (or fibres) of a dendrimer typically have a thickness from 20 to 40 nanometre and typically extend up to more than 10 micrometer. These branches of the dendrimers are relatively long and thin and have an aspect ratio of the order of 1000:1.
  • the prior art thread-like structuring system formed by crystallising from an emulsion has an aspect ratio of up to 200:1.
  • the minor dimension of the particles produced by the solvent process according to the present invention is also much smaller than that obtained by the aqueous emulsion process.
  • the preferred minor dimension for the thread-like structurant is from 5 to 15 micrometres. Even at the lower extreme of 1 micrometre mentioned in EP1 502 944 the fibres of the prior art thread-like structures are more than twice as thick as the dendrimers formed by the solvent process.
  • the crystallisation of the hydrogenated castor oil causes the formulation to become translucent due to the size of the dendritic structure interfering with the transmittance of the light through the formulation.
  • the microstructure of the dendrimers and the prior art thread-like structures are easily distinguished by microscopic examination as well as by their rheological and suspending properties.
  • the most striking feature of the prior art is the discrete nature of the fibres of the threads in comparison to the entangled and extensive dendrimer networks of the structuring system according to the present invention.
  • the three-dimensional dendritic scaffold of hydrogenated castor oil supports the incorporation of particles, especially encapsulated fragrances (perfumes), which are not visible to the human eye.
  • encapsulated fragrances are added subsequently to the mix from step d), and the encapsulated fragrances preferably have an average particle size from 0.01 to 200 micrometre. More preferably, the encapsulated fragrance has an average particle size from 1 and 100 micrometre, most preferably from 1 to 50 micrometre.
  • the liquid detergent composition so formed has a good physical stability. The rheological properties of the dendritic structuring system appear to be advantageous for the manufacture and the subsequent transportation, storage and use of the composition.
  • composition shear thins to a sufficient extent that the fragile encapsulates can be mixed in without rupture and yet as soon as the low shear mixing is removed the encapsulates stay dispersed and do not settle of cream to the surface if high shear is subsequently applied during transportation and especially as the product is dispensed from the pack by squeezing and/or pouring.
  • the viscosity profile of the product is superior for perfume encapsulates compared to the thread-like structuring system which has a lower viscosity under high shear which can lead to some movement of the encapsulates over time.
  • the second aspect of the invention provides a liquid detergent composition obtainable by a process according to the first aspect of the invention, wherein the hydrogenated castor oil is present at a concentration of from 0.15 and 0.5% by weight of the total composition, and has a dendritic structure as defined above.
  • the concentration of hydrogenated castor oil is from 0.15 to 0.3% by weight, even more preferably from 0.15 to 0.25%, and most preferably from 0.17 to 0.25% by weight of the total composition.
  • the concentration of hydrogenated castor oil when the concentration of hydrogenated castor oil is too high in the liquid detergent composition obtainable by the method of the invention, this liquid detergent composition will be thick and viscous and not well pourable, leading to dispensing problems and dissolution properties when in use.
  • the concentration of hydrogenated castor oil is too low, the structured liquid cannot stably suspend the encapsulated fragrance particles in the formulation.
  • the concentration of surfactants in the liquid detergent composition according to the invention is from 20 to 65% by weight, more preferred from 25 to 60% by weight, and most preferably from 25 to 45% by weight of the total composition.
  • 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.
  • the composition and method 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 encapsulated fragrance attaches itself to suitable substrates to provide persistent fragrance that is desirably released after the cleaning process is complete.
  • the liquid detergent compositions obtainable by the method according to the present invention are preferably concentrated liquid cleaning compositions.
  • the liquid compositions according to the second aspect of the present invention have a physical form which 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.
  • pourable liquid detergent compositions according to the second aspect of the present invention preferably have a viscosity of not more than 1 ,500 mPa.s, more preferably not more than 1 ,000 mPa.s, still more preferably, not more than 500 mPa.s. Typically, the viscosity is lower than 500 mPa.s at 21 s "1 .
  • liquid detergent compositions obtainable by the method according to the present invention which are 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.
  • compositions according to any aspect of the present invention that are 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.
  • the viscosity at a shear stress of 5 Pa is about 1 Pa. S compared with 0.3 Pa. S and at the higher shear of 10 Pa it is 0.7 Pa. S versus 0.2 Pa. S.
  • the viscosity at low shear stress (0.1 Pa) is similar for the two types of structuring. This means that the tendency for the suspended encapsulates to separate out in transportation is lower for the products according to the invention.
  • the inventive structuring system compared well with the thread-like system in terms of ease of mixing in the encapsulates during manufacture.
  • composition is considered to be physically stable when it remains homogeneous with dispersed and suspended perfume encapsulates over a period of about 3 months at temperatures from 5 to 50 0 C.
  • Castor oil also known as ricinus oil, is a vegetable oil obtained from the bean of the castor plant (Ricinus communis). Castor oil is a colorless to very pale yellow liquid with mild or no odor or taste. It is a triglyceride in which approximately ninety percent of fatty acid chains are ricinoleic acid (12-hydroxy-9-c/s-octadecenoic acid). Oleic and linoleic acids are the other significant components.
  • the controlled hydrogenation of castor oil yields fully hydrogenated castor oil, which is used in the method and products according to the present invention. At room temperature, hydrogenated castor oil is a hard white wax that melts at a temperature of about 86-88 ° C.
  • a hydrogenated castor oil suitable in the present invention is for example Thixcin ® R available from Elementis.
  • the amount of water in the liquid detergent composition according to the invention is from 10 to 80%, more preferred from 20 to 60%, most preferred from 20 to 50% by weight of the total composition.
  • the liquid detergent composition of the invention may comprise from 20 to 65% by weight, more preferred from 25 to 60% by weight, and most preferably from 25 to 45% of a surfactant, preferably selected from anionic, nonionic, cationic, zwitterionic active detergent materials or mixtures thereof.
  • anionic surfactants refer to synthetic anionic surfactants.
  • the surfactants of the surfactant system may be chosen from the surfactants described in 'Surface Active Agents' Vol. 1 , by Schwartz & Perry, lnterscience 1949, Vol. 2 by Schwartz, Perry & Berch, lnterscience 1958, in the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in Tenside-Taschenbuch', H. Stache, 2 nd Edn., Carl Hauser Verlag, 1981.
  • a preferred compound in the liquid detergent composition according to the invention is soap (salt of fatty acid).
  • the organic non-aqueous solvent used in step b) of the method of the invention comprises a fatty acid.
  • the fatty acid comprises linear alkyl saturated C 12 - C 1 8 fatty acids.
  • fatty acids suitable for use of the present invention include pure or hardened fatty acids derived from palmitoleic, safflower, sunflower, soybean, oleic, linoleic, linolenic, ricinoleic, rapeseed oil or mixtures thereof.
  • An example of a preferred fatty acid is a hydrogenated coconut fatty acid, for example Prifac 5908 (supplied by Uniqema, Gouda, Netherlands). Mixtures of saturated and unsaturated fatty acids can also be used herein.
  • 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% by weight of fatty acid is present in the liquid detergent composition according to the invention.
  • Mixtures of synthetic anionic and nonionic surfactants are especially useful in a liquid detergent composition of the invention.
  • Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilising polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which primary, secondary or tertiary aliphatic alcohols (or alkyl- capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylene.
  • alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms
  • dialkylphenols in which primary, secondary or tertiary aliphatic alcohols (or alkyl- capped derivatives thereof), preferably having from 8 to 20 carbon atoms
  • monocarboxylic acids having from 10 to about 24 carbon atoms in the
  • 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.
  • ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 18 carbon atoms condensed with from 3 to 11 moles of ethylene oxide.
  • condensation products of Cg.i8 alcohols with on average 3 to 9 moles of ethylene oxide Preferred for use in the liquid detergent composition of the invention are C 12 -C 1 5 primary, linear alcohols with on average 3 to 9 ethylene oxide groups.
  • a nonionic surfactant that may be used in the present invention is a C 12 -C 1 8 ethoxylated alcohol, comprising 3 to 9 ethylene oxide units per molecule. More preferred are C 12 -C 1 5 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 C 12 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 C 12 -C 1 5 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% by weight of the total surfactant material.
  • the detergent compositions 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% by weight of the total surfactant.
  • Suitable cationic surfactants that may be used are, substituted or unsubstituted, straight-chain or branched quaternary ammonium salts.
  • the cationic surfactant is of the formula:
  • R 1 is C 8 -C 22 -alkyl, C 8 -C 22 -alkenyl, C 8 -C 22 -alkylalkenylamidopropyl or C 8 -C 22 - alkoxyalkenylethyl
  • R 2 is Ci-C 22 -alkyl, C 2 -C 22 -alkenyl or a group of the formula -A-(OA) n - OH
  • R 3 and R 4 are C r C 22 -alkyl, C 2 -C 2r alkenyl or a group of the formula -A-(OA) n -OH
  • A is -C 2 H 4 - and/or -C 3 H 6 - and n is a number from 0 to 20 and X is an anion.
  • a commercially available and preferred example of this type of cationic surfactant is a compound of the formula above, where R 1 is a C 12 / 14 alkyl group, R 2 is a group of the formula -A-(OA) n -OH, wherein A is -C 2 H 4 - and n is nil, and R 3 and R 4 are both -CH 3 (i.e. Ci-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.
  • a wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, etc.
  • Carriers
  • 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.
  • suitable organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinates, carboxymethyloxymalonat.es, ethylene diamine-N,N-disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexa-acetic acid salts, N- alkyl imino diacetates or dipropionates, alpha sulpho- fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonat.es and mixtures thereof.
  • 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 (VoI 3, pg 424) and in Uhlmans Encyclopedia (VoI 3, pg 91 ).
  • One class of anti-oxidants that could be used in the present invention is alkylated phenols having the general formula:
  • R is Ci-C2 2 linear or branched alkyl, preferably methyl or branched C 3 -C 6 alkyl; C 3 -C 6 alkoxy, preferably methoxy; Ri is a C 3 -C 6 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:
  • R7 wherein R 1 and R 2 are each independently alkyl or R 1 and R 2 can be taken together to form a C 5 -C 6 cyclic hydrocarbyl moiety; B is absent or CH 2 ; R 4 is d-C 6 alkyl; R 5 is hydrogen or -C(O)R 3 wherein R 3 is hydrogen or C r Ci 9 alkyl; R 6 is Ci-C 6 alkyl; R 7 is hydrogen or CrC 6 alkyl; X is -CH 2 OH, Or -CH 2 A wherein A is a nitrogen comprising unit, phenyl, or substituted phenyl. Preferred nitrogen comprising A units include amino, pyrrolidine 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.
  • 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 composition 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.
  • At least part of the perfume component comprises encapsulated fragrances like perfume microcapsules.
  • the entirely of the perfume may be provided in this form.
  • the preferred perfume microcapsules utilised in the present invention are core-in-shell microcapsules.
  • the term core-in-shell microcapsules refers to encapsulates whereby a shell which is substantially or totally water-insoluble at 40 0 C surrounds a core which comprises or consists of perfume (including any liquid carrier therefor).
  • a preferred class of core-in-shell perfume microcapsule comprises those disclosed in WO 2006/066654 A1. These comprise a core having from about 5% to about 50% by weight of perfume dispersed in from about 95% to about 50% by weight of a carrier material.
  • This carrier material preferably is a non-polymeric solid fatty alcohol or fatty ester carrier material, or mixtures thereof.
  • the esters or alcohols have a molecular weight of from about 100 to about 500 and a melting point from about 37°C to about 80 0 C, and are substantially water-insoluble.
  • the core comprising the perfume and the carrier material are coated in a substantially water-insoluble coating on their outer surfaces.
  • core-in-shell microcapsules preferably have a d 4 , 3 average particle size of from 0.01 to 200 micrometer, more preferably from 1 to 100 micrometer. Similar microcapsules are disclosed in US 5,154,842 and these are also suitable.
  • the 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.
  • Core-in-shell perfume microcapsules of other kinds are also suitable for use in the present invention.
  • Ways of making such other microencapsulates of perfume include precipitation and deposition of polymers at the interface such as in coacervates, as disclosed in GB-A-751 600, US-A-3 341 466 and EP-A-385 534, as well as other polymerisation routes such as interfacial condensation, as described in US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606.
  • Microcapsules having polyurea walls are disclosed in US-A-6 797 670 and US-A-6 586 107.
  • perfume is added to the compositions after the cooling step d) in the method of the invention. All perfume added in the form of encapsulated perfume must be added in step e) after step d).
  • '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, lipases, 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 are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
  • Suitable examples of proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable protease is obtained from a strain of Bacillis, having maximum activity throughout the pH-range of 8-12, developed and sold as Esperase ® by NovoZymes of Denmark.
  • 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.
  • Suitable lipase enzymes for use in the composition of the invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034.
  • a very suitable lipase enzyme is the lipase derived from Humicola lanuginosa and available from Novozymes under the tradename Lipex ® .
  • enzymes are added to the compositions after the cooling step d) in the 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 detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Ci 8 -C 4 O ketones (e.g., stearone), etc.
  • the preferred category of non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in US-A-4,265,779.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • the compositions herein will generally comprise from 0.1% to about 5% of suds suppressor.
  • suds boosters such as the Ci 0 -Ci 6 alkanolamides can be incorporated into the compositions, typically at 1%- 10% levels.
  • the Ci 0 -Ci 4 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • soluble magnesium salts such as MgCI 2 , MgSO 4 , and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • the liquid detergent compositions herein 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.
  • 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, cournarin, carboxylic acid, methinecyanines, dibenzothiphene-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).
  • Various through-the-wash fabric softeners especially the impalpable smectite clays of US-A-4,062,647 as well as other softener clays known in the art, 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.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • 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. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • 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,N 1 N, 1 -tetraacetylethylene diamine (TAED) and N, N, N 1 , N 1 - tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylgylcoluril (TAGU); triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester.
  • polyacylated alkylene diamines such N,N,N 1 N, 1 -tetraacetylethylene diamine (TAED) and N, N, N 1 , N 1 - tetraacetylmethylene diamine (TAMD)
  • acylated glycolurils such as tetraacetylgylcoluril (TAGU)
  • TAGU tetraacetylgylcoluril
  • 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 % by weight, preferably from about 0.1% to about 0.5% by weight.
  • 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.
  • the Anton Paar ASC is an automated rheometer for measuring liquid viscosities under different shear conditions. It is fitted with a DSR301 measuring head and the concentric cylinder system CC27 with stainless steel cup and measuring bob BCC27/TI (which is placed in the sample cup containing 20-50 ml of the sample detergent) is suitable for measuring shear profiles of liquid detergents, including structured liquids.
  • Samples stored at room temperature are removed from the storage facility and allowed to reach room temperature before being assessed for phase separation & colour change vs the standard 5°C sample, this test is carried out after 4, 8 and 12 weeks storage.
  • Samples stored at 37°C are removed from the storage facility and allowed to reach room temperature before being assessed for phase separation & colour change vs the standard 5°C sample, this test is carried out after 4, 8 and 12 weeks storage.
  • Samples stored at 50 0 C are removed from the storage facility and allowed to reach room temperature before being assessed for phase separation & colour change vs the standard 5°C sample, this test is carried out after 4 weeks storage.
  • Viscosity of samples can be measured using a temperature controlled (25°C) Haake VT500 and MV1 cup and bob (32g sample) for measurements of 106 s "1 and MV2 cup and bob (48g sample) for measurements of 21 s "1 .
  • a temperature controlled (25°C) Haake VT500 and MV1 cup and bob 32g sample
  • 106 s "1 and MV2 cup and bob 48g sample
  • the viscosity of this formulation was 250 mPa.s at 21 s , and the pH was 8.
  • composition 1 (and also composition 2 below) was assessed during storage in time at different temperatures, as indicated in the following table. At each measurement point a visual assessment is made on the stability of the liquid (looking for instabilities like creaming, phase separation), and shear profiles and pH are measured, and compared to standard values (shear profile is compared to a shear thinning profile, and the pH preferably is from 7 to 9).
  • Table 3 Analysis results of liquid detergent composition 1
  • the viscosity of this formulation was 250 mPa.s at 21 s "1 , and the pH was 8 (range 7- 9).
  • liquid detergent compositions according to the invention showed good stability comprising a low concentration of hydrogenated castor oil.
  • the liquid detergent composition 1 was obtained by the method according to the invention in the following way:
  • Premix 1 Under agitation at 150 rpm, using an overhead stirrer, 20Og of deionised water was added to a 3 litre beaker and warmed to 30 0 C. Tinopal 5BM-GX 1.47g was then added to this solution along with glycerol 5Og, propylene glycol 9Og and the neutralising bases sodium hydroxide 57.5g and triethanolamine 31.5g. Then Neodol 25-7, 201 g, linear alkylbenzene sulphonic acid, 128g, and citric acid 2Og were added in quick succession generating considerable heat of neutralisation and bringing the temperature to 65-
  • Prifac 5908, 47g was dissolved in a separate 500ml beaker using agitation at 100 rpm and heating to 70-75 0 C. Then 2g of hydrogenated castor oil, Thixcin R ex Elementis was dissolved in the hot fatty acid. This premix is stirred for a further 5-10 minutes to ensure complete dissolution and mixing of the external structurant. The dissolution is complete when the premix 2 solution is completely transparent.
  • premix 2 70-75 0 C
  • premix 1 65- 70 0 C
  • sequestrant,16g Dequest 2066 was added followed by sodium laurylether sulphate 96g and allowed to mix for a further 10 minutes before cooling to 30°C. Cooling was done by either natural cooling over a period of 2 hours, or alternatively the main batch can be cooled using a plate heat exchanger cooling the main mix from 60-65 0 C to 3O 0 C in less than a minute and keeping it for 10 minutes at this low temperature.
  • dyes 0.07g patent blue V85 and 0.01 g acid yellow 23 were added, as well as enzymes (protease and amylase) 10.5g, and perfume 10g and allowed to mix for a further 10 minutes before pumping out of the vessel and adding encapsulated perfume slurry 15g using a paddle mixer.
  • liquid detergent compositions were made, in which the hydrogenated castor oil had crystallised in the form of dendrimers. This structure can be observed using an optical microscope, and the diameter of the dendrimers was from about 50 to about 100 micrometer.
  • the formulations had become cloudy upon cooling and overall solution was no longer transparent, using the 'X-test'.
  • the required shear thinning profile had been obtained and the encapsulated perfume was suspended homogeneously.
  • the liquid composition with suspended encapsulated perfume was tested in various ways. After each test, the shear profile was measured, to see if there was any breakdown of the structuring system.
  • the formulations were also assessed visually by eye, and by microscopy, to identify if there was phase separation or if the encapsulates were still monodispersed.
  • the compositions exhibited no loss or change of structuring or encapsulate dispersal after being tested for 12 weeks at 5 0 C, 12 weeks at 37 0 C and 4 weeks at 50 0 C.

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Abstract

La présente invention concerne des compositions de détergents liquides exempts de phosphates. L'invention concerne un procédé de production de compositions de détergents liquides, dans lesquelles l'huile de ricin hydrogénée cristallise après refroidissement à partir d'un pré-mélange de solvant organique non aqueux chaud afin de former une structure dendritique. De plus, l'invention concerne une composition de détergent liquide pouvant être obtenue par ce procédé comprenant de l'huile de ricin hydrogénée et un parfum encapsulé.
PCT/EP2009/062313 2008-09-25 2009-09-23 Détergents liquides WO2010034736A1 (fr)

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Application Number Priority Date Filing Date Title
EP20090783318 EP2326705A1 (fr) 2008-09-25 2009-09-23 Détergents liquides
CN2009801468533A CN102224233A (zh) 2008-09-25 2009-09-23 液体洗涤剂

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EP08165086 2008-09-25
EP08165086.3 2008-09-25

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