[go: up one dir, main page]

EP2553081B1 - Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln - Google Patents

Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln Download PDF

Info

Publication number
EP2553081B1
EP2553081B1 EP11706854.4A EP11706854A EP2553081B1 EP 2553081 B1 EP2553081 B1 EP 2553081B1 EP 11706854 A EP11706854 A EP 11706854A EP 2553081 B1 EP2553081 B1 EP 2553081B1
Authority
EP
European Patent Office
Prior art keywords
microcapsules
premix
liquid
surfactant
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11706854.4A
Other languages
English (en)
French (fr)
Other versions
EP2553081A1 (de
Inventor
Richard Michael Craven
Colin Lee Doyle
Ian James Hussey
Aidan Joseph Lavery
Jojo Philip
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42648164&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2553081(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP11706854.4A priority Critical patent/EP2553081B1/de
Publication of EP2553081A1 publication Critical patent/EP2553081A1/de
Application granted granted Critical
Publication of EP2553081B1 publication Critical patent/EP2553081B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/50—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 an improved process for the incorporation of microcapsules into a structured aqueous liquid detergent composition comprising at least 30 wt% total surfactant.
  • microcapsules in liquid detergents.
  • Microcapsules having a shell that protects the inner core contents may provide delayed release of their contents and /or provide a stable formulation when their contents would otherwise interact with the bulk liquid.
  • Such microcapsules are well known in the detergent field, and they have been proposed for inclusion in aqueous liquid detergent compositions.
  • the microcapsules are small enough to be usable in large numbers and are generally not visible to the eye when introduced to the liquid. Nevertheless, they may cause the liquid to become hazy.
  • Some microcapsules may be suspendible in an unmodified liquid. Others, with less closely matched specific gravity, may require modification of the liquid via a thickening or structuring system in order to avoid creaming or settling.
  • microcapsules Typical of such microcapsules are perfume encapsulates with melamine formaldehyde shells as described in US-A-5 066 419 .
  • the microcapsules may alternatively contain other liquid fabric treatment additives such as shading dye, lubricants etc.
  • the contents of the microcapsules are not important for the present invention.
  • microcapsules When such microcapsules are added to concentrated surfactant solutions, especially ones comprising an external structurant, such as hydrogenated castor oil, or microfibrous cellulose, the microcapsules have been found to undergo agglomeration into clumps during the incorporation step. These agglomerates remain undispersed in the liquid. This increases visibility of the microcapsules. It also causes uneven dosing of their contents per wash, as liquid is removed from the container. Finally, if the agglomerated microcapsules survive up to the point of deposition onto a fabric then the content of the microcapsules is overdosed at that point and is unevenly distributed across the surface of the fabric. This could cause unwanted effects such as fabric damage or the need to use more microcapsules than would otherwise be necessary. Thus, it is highly desirable to avoid substantial agglomeration of microcapsules in an aqueous liquid detergent.
  • an external structurant such as hydrogenated castor oil, or microfibrous cellulose
  • concentrated is meant a total surfactant content (including soap) of 30 wt% or greater.
  • WO09135765A discloses a process for the manufacture of a structured liquid detergent composition
  • a disperse-phase benefit agent which may be a perfume microcapsule, micro-fibrous cellulose structurant, at least 5 wt% of anionic surfactant and 25 to 55 wt% surfactant, the process comprising the steps of preparation of a micro-fibrous cellulose premix using high shear mixing, (ii) separate preparation of an aqueous surfactant mix, combination of the micro-fibrous cellulose premix and the surfactant mix using high shear mixing, perfume microcapsules may be post dosed to the resulting structured concentrated surfactant structured liquid.
  • the high shear mixing step is achieved using an in-line mixing process, such as by contacting the two process streams directly before an in-line mixer.
  • Microcapsule particle sizes are in the range of 5 to 50 microns, preferably 10 to 30 microns.
  • Example 4 of WO09135765A discloses details of perfume microcapsule addition.
  • 1.5 wt% perfume encapsulates were added to an MFC structured liquid with a surfactant level of 40 to 50 wt%. Addition was performed over 30 sec, using a Heidolph stirrer, mixing continued for 5 min (if required).
  • a Heidolph laboratory mixer is an overhead driven propeller or paddle stirrer. It is not a static in-line mixer. There is not any disclosure made of the quality of the liquid detergent product made this way.
  • microcapsules are stirred into a laundry liquid detergent prepared by combining an aqueous premix of heavy duty liquid (HDL) detergent composition and a structuring premix.
  • the HDL premix is prepared by combining HDL components with water in a suitable vessel under suitable agitation and the structuring agent premix is prepared by combining hydrogenated castor oil and other structuring agent premix ingredients.
  • the microcapsules are then slowly added to the structured liquid while it was maintained under gentle agitation - paragraph 88.
  • HCO hydrogenated castor oil
  • WO2010/034736 we describe the incorporation of perfume microcapsules into a concentrated liquid detergent, structured using hydrogenated castor oil.
  • the microcapsules are added as an encapsulated perfume slurry and mixed in using a paddle mixer.
  • the formulations were 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 °C, 12 weeks at 37 °C and 4 weeks at 50 °C.
  • a process for the incorporation of microcapsules with anionic charge into a structured aqueous concentrated liquid detergent comprising at least 30 wt%, preferably at most 65 wt%, total surfactant of which at least 5 wt% based on the total composition is anionic surfactant, including soap, and an external structurant, the process comprising the combining of two premixes; Premix A which is the structured aqueous concentrated liquid detergent composition without microcapsules and Premix B which comprises an aqueous dispersion of the microcapsules with anionic charge, characterised in that:
  • the maximum viscosity of the Premix B is 50 mPas, more preferably 20 mPas, even more preferably 15 mPas.
  • agglomerated we mean that more than 5 microcapsules are grouped together. This is determined, for example, by taking a photomicrograph of the liquid and counting the number of groups of microcapsules present in the form of groups of 1, 2 3 4 or 5 microcapsules and also counting the number of groups of microcapsules present in the form of agglomerates of more than 5 microcapsules, which we define as being agglomerated microcapsules. If more than 10% of the groups are in the form of such agglomerated microcapsules then the microcapsules are too agglomerated to be within the scope of this invention.
  • Premix B it may be necessary to reduce the viscosity of the raw material slurry concentrate of microcapsules. This can be done, for example, by dilution with water, if necessary.
  • microcapsule slurry can be added to the main liquid by either in line injection or pouring into the vessel whilst mixing.
  • the mixture is then passed through an in-line static mixer that applies enough energy to break the agglomerates whilst avoiding rupture of individual microcapsules and retention of the liquid structure.
  • the resulting structured liquid is highly effective at preventing further agglomeration of the microcapsules over time.
  • the external structurant is preferably hydrogenated castor oil (castor wax, or trihydroxystearin).
  • the external structurant may alternatively be another fibrous agent, such as microfibrous cellulose or any other type of external structurant.
  • microcapsules comprise a solid shell.
  • agglomeration problem seems to be restricted to microcapsules carrying an anionic charge.
  • Microcapsules with a cationic charge may be added into concentrated liquids without formation of agglomerates and therefore without the need for the process of the present invention.
  • the microcapsule has a melamine formaldehyde shell.
  • suitable shell material may be selected from (poly)urea, (poly)urethane, starch/ polysaccharide and aminoplasts.
  • microcapsules may be perfume encapsulates. We have found that inclusion of microcapsules of smaller diameter makes the agglomeration problem worse.
  • Microcapsules in the range 2 to 5 microns cannot be dispersed so effectively using the process according to the invention due to the high surface area of the smaller particles.
  • microcapsules greater than 40 microns generally require no additional processing as the smaller total surface area is sufficient to prevent substantial agglomeration without need for the increased energy input from an in-line static mixer. Nevertheless, the process may be used for larger particles, if desired.
  • microcapsules in the range 5 to 30 microns. Removal of microcapsules ranging from 0.1 to less than 1 micron improves the microcapsule dispersion. This is thought to be due to the reduction of high surface area material.
  • the structure is very effective at preventing any agglomeration, even in the presence of high levels of surfactant.
  • the process may be used to make externally structured concentrated liquid compositions comprising at least 30 wt% surfactant including anionic surfactant (any soap being included in the calculation and being an anionic surfactant) comprising 0.1 to 2.0 wt% microcapsules wherein the ratio microcapsules in groups of 5 or less to agglomerated microencapsulates (in groups of 5 or more) is more than 9:1.
  • anionic surfactant any soap being included in the calculation and being an anionic surfactant
  • hydrogenated castor oil When hydrogenated castor oil is used as the external structurant, it is suitably present at a level of from 0.15 to 0.5 wt% of the total composition. Preferably, it has a dendritic structure wherein the fibres are entangled and the minor dimension of the fibres is at most 40 nm.
  • Premix A may be formed using any of the processes of the prior art, or any other suitable process, when using hydrogenated castor oil as external structurant it is preferable to employ a process such as that described in WO2010/034736 , as also described below.
  • microfibrous cellulose it is preferred to employ an adaptation of the process described in WO09135765A .
  • the preferred external structurant is hydrogenated castor oil.
  • microfibrous cellulose may be used, this material and its properties and use as an external structurant are described in the published literature, for example in WO09135765A (Unilever), and US2008108541 A (C P Kelco).
  • 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 colourless to very pale yellow liquid with mild or no odour or taste. It is a triglyceride in which approximately ninety percent of fatty acid chains are ricinoleic acid (12-hydroxy-9-cis-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 concentration of surfactants is from 20 to 65 wt%, more preferably from 25 to 60 wt%, and mostly preferably from 25 to 45 wt% of the total mix in this step.
  • 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 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°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 C12-C18 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 wt% of the composition, preferably from 0.15 to 0.35 wt%, even more preferably from 0.2 to 0.35 wt%, and most preferably from 0.22 to 0.28 wt% of the total composition.
  • the concentration of hydrogenated castor oil in the second premix in step b) is preferably from 1.5 to 20 wt% of the premix, more preferably from 1.5 to 10 wt%, even more preferably from 1.7 to 5 wt%, and most preferably from 3.4 wt% to 5 wt% 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 wt% of the total formulation, most preferred about 5 wt% of the total formulation.
  • the temperature in step c) is at least 55°C, preferably between 55 and 70°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 first and second premixes are combined under gentle mixing.
  • the mix in step c) is clear at the prevailing temperature in step c), which is at least 55°C, preferably from 55 to 70°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.
  • the mix from step c) is cooled to a temperature below 50°C, preferably below 40°, more preferred below 35°C, even more preferred below 30°C. Subsequently this mix is stored until the hydrogenated castor oil has crystallised from solution.
  • this cooling step d) is carried out while the mix is gently mixed, at low shear conditions.
  • 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°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°C, more preferably 30°C, at a cooling rate of maximally 1°C per minute, preferably maximally 0.7°C per minute, even more preferably maximally 0.5°C per minute, mostly preferably maximally 0.4°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°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°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°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°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. In this holding period the temperature of the mix is kept constant below 40°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.
  • 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.
  • the solubilised hydrogenated castor oil may self-assemble into a dendritic structure.
  • 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 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 invention is particularly suited to the addition of microcapsules to compositions comprising less than 40 wt% water. This low level of water makes dispersal of the microcapsules more difficult when coupled with the high active levels of the compositions of the invention.
  • the invention is, however, also applicable to high surfactant composition with higher water levels.
  • the liquid detergent compositions made using the process of the invention preferably comprise from 30 to 65wt%, more preferred from 30 to 60wt%, and most preferably from 35 to 45% of a surfactant, preferably selected from anionic, nonionic, cationic, zwitterionic active detergent materials or mixtures thereof.
  • anionic surfactants include both soap and synthetic anionic surfactants.
  • the minimum level of anionic surfactant is 5 wt%.
  • 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.
  • a preferred component of the liquid detergent compositions 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 C12-C18 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 wt% 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 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 alky
  • 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 C9-18 alcohols with on average 3 to 9 moles of ethylene oxide are preferred.
  • Preferred for use in the liquid detergent composition of the invention are C12-C15 primary, linear alcohols with on average 3 to 9 ethylene oxide groups.
  • a preferred nonionic surfactant 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 70wt% 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 12wt% 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: R1 R2R3R4N+ X- wherein R1 is C8-C22-alkyl, C8-C22-alkenyl, C8-C22-alkylalkenylamidopropyl or C8-C22-alkoxyalkenylethyl, R2 is C1-C22-alkyl, C2-C22-alkenyl or a group of the formula -A-(OA)n-OH, R3 and R4 are C1-C22-alkyl, C2-C21-alkenyl or a group of the formula -A-(OA)n-OH, A is -C2H4- and/or -C3H6- 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 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. E.g. from 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 A wide variety of optional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, hydrotropes, processing aids, dyes or pigments, carriers, detergency builders, antioxidants, fragrances, detersive enzymes, suds suppressors, chelating agents, clay soil removal/ anti-redeposition agents, brighteners, fabric softeners, dye transfer inhibition agents, bleaches and the like; some of which are describes in more detail below.
  • 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 be present in the liquid detergent composition.
  • suitable organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinates, carboxymethyloxymalonates, 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, polyhydroxysulphonates 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 wt% of an anti-oxidant.
  • the anti-oxidant is present at a concentration in the range of 0.01 to 0.08 wt%.
  • 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 branched 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.
  • the liquid detergent compositions obtainable by the method according to the present invention preferably comprise from 0.001 to 3 wt% of the total composition of a perfume composition, preferably from 0.01 to 2 wt% of the total composition.
  • Said perfume composition preferably comprises at least 0.01 wt% 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 wt% of the perfume component.
  • '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 wt% 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®.
  • Preferably enzymes are added to the compositions after the cooling step d) in the preferred process to form PREMIX A.
  • 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 saturated 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 C18-C40 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 C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • soluble magnesium salts such as MgCl2, MgSO4, 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 wt% of the detergent compositions herein. More preferably, if utilised the chelating agents will comprise from about 0.1% to about 3.0 wt% 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. Suitable 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 can optionally be used typically at levels of from about 0.5% to about 10 wt% 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 wt% 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,N1N,1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylgylcoluril (TAGU); triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester.
  • polyacylated alkylene diamines such N,N,N1N,1-tetraacetylethylene diamine (TAED) and N,N,N1,N1-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 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.
  • Premix B comprises the microcapsules.
  • An essential element of the composition as made by the process according to the invention is at least 0.01 wt% of microcapsules, with an anionic charge.
  • Such microcapsules may deliver a variety of benefit agents by deposition onto substrates such as laundry fabric. To obtain maximum benefit they should be well dispersed through the liquid detergent composition and the vast majority of the microcapsules must not be significantly agglomerated. It is our finding that any microcapsules that become agglomerated during the processing remain so in the container and will thus be dispensed unevenly during use of the composition. This is highly undesirable.
  • the contents of the microcapsules are normally liquid. For example, fragrances, oils, fabric softening additives and fabric care additives are possible contents.
  • the invention is not specific for any particular type of content.
  • Preferred microcapsules are particles termed core-in-shell microcapsules.
  • core-in-shell microcapsules refers to encapsulates whereby a shell which is substantially or totally water-insoluble at 40°C surrounds a core which comprises or consists of a benefit agent (which is either liquid or dispersed in a liquid carrier).
  • Suitable microcapsules are those described in US-A-5 066 419 which have a friable coating, 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 wt% of the particles.
  • Core-in-shell microcapsules of other kinds are also suitable for use in the present invention.
  • Ways of making such other microcapsules of benefit agents such as 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 .
  • White oil is a highly refined, colourless hydrocarbon oil of low volatility and a wide range of viscosities; used for lubrication of food and textile machinery and as medicinal and mineral oils.
  • Melamine shelled microcapsules containing white oil are slightly anionic (negatively charged). Surface charge on the microcapsules has been found to affect their dispersal. A low charge seems to result in there being too little electrostatic repulsion/ stabilisation to keep them apart in low water (concentrated) formulations. This gets even worse for highly concentrated anionic compositions. The problem seems to be worse for weakly anionic particles of certain size.
  • Perfume encapsulates are a preferred type of microcapsule suitable for use in the present invention.
  • the preferred perfume microcapsules utilised in the present invention are core-in-shell microcapsules.
  • core-in-shell microcapsules refers to encapsulates whereby a shell which is substantially or totally water-insoluble at 40°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 wt% of perfume dispersed in from about 95% to about 50wt% 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°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. 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 wt% 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 microcapsules 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 .
  • microcapsules may attach to suitable substrates, e.g. to provide persistent fragrance that is desirably released after the cleaning process is complete.
  • the process provides structured liquid detergent compositions, wherein the microcapsules are present without a significant proportion of them being in wasteful and size enlarged agglomerated form.
  • the composition is concentrated and has greater than or equal to 30 wt% of surfactant and an external structuring system, preferably hydrogenated castor oil, is present at a concentration of from 0.15 and 0.5 wt% of the total composition.
  • the concentration of surfactants in the liquid detergent composition according to the invention is from 30 to 65 wt%, more preferred from 32 to 60 wt%, and most preferably from 35 to 50 wt% 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 liquid detergent compositions obtainable by the method according to the present invention are preferably concentrated liquid cleaning compositions.
  • the liquid compositions have a physical form, which 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 made according to the invention are shear-thinning liquids.
  • Pourable liquid detergent compositions 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 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.
  • 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 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°C.
  • composition as listed in Table 1 was prepared by a process as described in WO 2010 034736 A , the relevant content of which is repeated above. This process is based on a conventional neutralisation process for manufacture of a LAS/SLES/NI and soap based active heavy-duty liquid detergent. The enzymes and perfume are added after the neutralisation.
  • the liquid detergent composition was obtained by the following method:
  • Prifac 5908, 47g was dissolved in a separate 500ml beaker using agitation at 100 rpm and heating to 70-75°C. Then 2g of hydrogenated castor oil, Thixcin ® 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.
  • the two premixes are now combined by adding Premix 2 (70-75°C) to Premix 1 (65-70°C), increasing the agitation to 200rpm and allowing the two premixes to mix thoroughly for 10 minutes. Then the sequestrant,16g was added followed by sodium laurylether sulphate (sLES) 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 was cooled using a plate heat exchanger cooling the main mix from 60-65°C to 30°C in less than a minute and keeping it for 10 minutes at this low temperature.
  • sLES sodium laurylether sulphate
  • the microcapsules used had a melamine formaldehyde shell, were anionic with an average particle size of 15.8 microns. They are available in a slurry with a solids content of 46.8 wt% and a slurry viscosity of 425 mPas. On dilution with an equivalent volume of water the resulting PREMIX B has a viscosity at 25°C of 10 mPas.
  • the mixture was then pumped through an in line static mixer.
  • the typical mixing energy supplied by such a mixer is about 100 times that of a paddle mixer.
  • microcapsules When mixed in to a liquid in the conventional way using such a paddle mixer these microcapsules produce a dispersion ratio of 70:30 (non-agglomerated:agglomerated as defined above) compared to 96:4 using the process according to the present invention.
  • microcapsule level on the final dispersed mix is 0.46%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (6)

  1. Verfahren zum Einführen von Mikrokapseln mit einer anionischen Ladung in ein strukturiertes, wässriges, konzentriertes Flüssigwaschmittel, das mindestens 30 Gew.-%, vorzugsweise höchstens 65 Gew.-% gesamtes Tensid, wovon mindestens 5 Gew.-%, und zwar auf die gesamte Zusammensetzung bezogen, anionisches Tensid sind, wozu Seife gehört, und ein externes strukturbildendes Mittel aufweist,
    wobei das Verfahren das Mischen von zwei Vormischungen aufweist, der Vormischung A, die die strukturierte, wässrige, konzentrierte flüssige Waschmittelzusammensetzung ohne Mikrokapseln ist, und der Vormischung B, die eine wässrige Dispersion der Mikrokapseln mit einer anionischen Ladung aufweist,
    dadurch gekennzeichnet, dass:
    die Vormischung B eine Dickstoffsuspension von Mikrokapseln mit einer maximalen Viskosität bei 25 °C von 100 mPas ist und mindestens 90 Gew.-% der Mikrokapseln eine Teilchengröße im Bereich von 5 bis 30 µm aufweisen, und
    die Vormischung B der Vormischung A zugesetzt wird und das entstandene zusammengeführte Gemisch durch einen statischen Leitungsmischer mit einer zugeführten Energie von 20 bis 500 J/kg geleitet wird, um unmittelbar nach dem Mischer eine strukturierte Flüssigkeit zu bilden, die weniger als 10 %, und zwar auf die Gesamtzahl der Gruppen der Mikrokapseln bezogen, agglomerierte Gruppen von Mikrokapseln aufweist, wobei eine agglomerierte Gruppe von Mikrokapseln als Gruppe mit mehr als 5 miteinander gruppierten Mikrokapseln definiert wird.
  2. Verfahren nach Anspruch 1,
    wobei die Viskosität der Vormischung B durch Verdünnen mit Wasser verringert wird.
  3. Verfahren nach einem der vorstehenden Ansprüche,
    wobei das externe strukturbildende Mittel hydriertes Rizinusöl (Rizinuswachs) ist.
  4. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Mikrokapseln eine Hülle aus Melaminformaldehyd aufweisen.
  5. Verfahren nach einem der Ansprüche 1 bis 3,
    wobei die Mikrokapseln eine Hülle aufweisen, die ein Material aufweist, das aus (Poly)harnstoff, (Poly)urethan, Stärke/Polysaccharid und Aminoplasten ausgewählt ist.
  6. Verfahren nach einem der vorstehenden Ansprüche,
    wobei die Mikrokapseln verkapselte Duftstoffe sind.
EP11706854.4A 2010-03-31 2011-03-09 Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln Active EP2553081B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11706854.4A EP2553081B1 (de) 2010-03-31 2011-03-09 Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10158692 2010-03-31
EP11706854.4A EP2553081B1 (de) 2010-03-31 2011-03-09 Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln
PCT/EP2011/053561 WO2011120772A1 (en) 2010-03-31 2011-03-09 Microcapsule incorporation in structured liquid detergents

Publications (2)

Publication Number Publication Date
EP2553081A1 EP2553081A1 (de) 2013-02-06
EP2553081B1 true EP2553081B1 (de) 2014-01-08

Family

ID=42648164

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11706854.4A Active EP2553081B1 (de) 2010-03-31 2011-03-09 Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln

Country Status (6)

Country Link
EP (1) EP2553081B1 (de)
CN (1) CN102858942B (de)
AU (1) AU2011234744B2 (de)
BR (1) BR112012024804B1 (de)
ES (1) ES2457495T3 (de)
WO (1) WO2011120772A1 (de)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012126786A1 (en) 2011-03-22 2012-09-27 Henkel Ag & Co. Kgaa Liquid laundry detergent comprising capsules
US8853142B2 (en) 2012-02-27 2014-10-07 The Procter & Gamble Company Methods for producing liquid detergent products
CN103489495B (zh) * 2012-06-14 2016-10-05 中国辐射防护研究院 一种用于控制放射性气溶胶的固定剂及制备方法
EP2689835B1 (de) 2012-07-26 2019-05-08 Papierfabrik August Koehler SE Duftölverkapselung
EP2711414B1 (de) * 2012-09-19 2019-05-15 Symrise AG Stabilisierug von Kapselsystemen in Wasch- und Reinigungsmitteln
BR112016008826B1 (pt) * 2013-10-22 2022-05-10 Unilever Ip Holdings B.V Processo para fabricar uma formulação líquida detergente aquosa externamente estruturada, pré-mistura homogeneizada estruturante de pó de argila dilatável em água e polpa de fibra cítrica e formulação líquida detergente aquosa externamente estruturada
EP3129456A1 (de) * 2014-04-10 2017-02-15 Unilever PLC Verfahren zur herstellung einer extern strukturierten, isotropen, wässrigen reinigungsflüssigkeit
WO2016023145A1 (en) * 2014-08-11 2016-02-18 The Procter & Gamble Company Laundry detergent
DE102016219862A1 (de) 2016-10-12 2018-04-12 Henkel Ag & Co. Kgaa Waschmittelzusammensetzung mit Fließgrenze
EP3461879A1 (de) 2017-09-29 2019-04-03 The Procter & Gamble Company Verbesserte strukturierung
DE102018222190A1 (de) * 2018-12-18 2020-06-18 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Partikel- und Tensid-haltigen Flüssigkeit
CN110819473B (zh) * 2019-11-13 2021-09-10 广州立白企业集团有限公司 一种浓缩液体洗涤剂组合物
WO2021115600A1 (de) 2019-12-12 2021-06-17 Henkel Ag & Co. Kgaa Wasch- und reinigungsmittel umfassend umweltverträgliche mikrokapseln
WO2021115601A1 (de) 2019-12-12 2021-06-17 Papierfabrik August Koehler Se Bioabbaubare mikrokapselsysteme
EP3865561B1 (de) * 2020-02-11 2024-02-14 The Procter & Gamble Company Verfahren zur herstellung eines enzymhaltigen, flüssigen verbraucherprodukts
BR112023002386A2 (pt) 2020-08-12 2023-03-21 Unilever Ip Holdings B V Processo para produzir uma composição detergente líquida concentrada para lavagem de roupas, composição detergente concentrada para lavagem de roupas e composição detergente para lavagem de roupas
EP4101528A1 (de) 2021-06-11 2022-12-14 Henkel AG & Co. KGaA Mittel enthaltend farbneutrale abbaubare mikrokapseln
DE102021205957A1 (de) 2021-06-11 2022-12-15 Koehler Innovation & Technology Gmbh Farbneutrale abbaubare Mikrokapseln
US20240287420A1 (en) 2021-06-11 2024-08-29 Henkel Ag & Co. Kgaa Compositions containing colour-neutral degradable microcapsules
EP4101529A1 (de) 2021-06-11 2022-12-14 Henkel AG & Co. KGaA Mittel enthaltend farbneutrale abbaubare mikrokapseln mit parfümzusammensetzung
US20230183620A1 (en) 2021-12-15 2023-06-15 Henkel Ag & Co. Kgaa Agent containing emulsifier and microcapsules
EP4198113A1 (de) 2021-12-15 2023-06-21 Henkel AG & Co. KGaA Mittel enthaltend emulgator und mikrokapseln
DE102021214457A1 (de) 2021-12-15 2023-06-15 Koehler Innovation & Technology Gmbh Mikrokapseldispersionen mit Emulgator
EP4198115A1 (de) 2021-12-15 2023-06-21 Henkel AG & Co. KGaA Mittel enthaltend emulgator und mikrokapseln mit parfümzusammensetzung
CN119463980B (zh) * 2024-10-28 2025-07-29 纳爱斯浙江科技有限公司 一种含微胶囊的悬浮剂组合物及其制备方法和应用

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE530008A (de) 1953-06-30
NL114069C (de) 1955-10-27
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
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
EP0006268B2 (de) 1978-06-20 1988-08-24 THE PROCTER & GAMBLE COMPANY Zusammensetzungen zum Waschen und Weichmachen und Verfahren zu deren Herstellung
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.
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
GB8527772D0 (en) 1985-11-11 1985-12-18 Unilever Plc Non-aqueous built liquid detergent composition
US4946624A (en) 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
US5066419A (en) 1990-02-20 1991-11-19 The Procter & Gamble Company Coated perfume particles
US5154842A (en) 1990-02-20 1992-10-13 The Procter & Gamble Company Coated perfume particles
DE19646110A1 (de) 1996-11-08 1998-05-14 Bayer Ag Mikrokapseln unter Verwendung von Iminooxadiazindion-Polyisocyanaten
ATE213001T1 (de) 1996-12-23 2002-02-15 Ciba Spec Chem Water Treat Ltd Teilchen mit oberflächeneigenschaften und verfahren zu ihrer herstellung
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
WO2000060045A1 (en) 1999-04-01 2000-10-12 The Procter & Gamble Company Transition metal bleaching agents
AU5403500A (en) 1999-06-23 2001-01-31 Breel, Greta J. Bleaching detergent compositions
GB9930697D0 (en) 1999-12-24 2000-02-16 Unilever Plc Method of treating a textile
DE10000223A1 (de) 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
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
US20050271735A1 (en) 2002-05-31 2005-12-08 Stover Harald D H Method of encapsulating hydrophobic organic molecules in polyurea capsules
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
DE60312150T2 (de) 2003-08-01 2007-11-08 The Procter & Gamble Company, Cincinnati Wässriges Flüssigwaschmittel enthaltend sichtbare Teilchen
EP1502645A1 (de) * 2003-08-01 2005-02-02 The Procter & Gamble Company Mikrokapseln
ES2324359T3 (es) 2004-12-23 2009-08-05 Unilever N.V. Composiciones detergentes liquidas y uso de las mismas.
US8772359B2 (en) 2006-11-08 2014-07-08 Cp Kelco U.S., Inc. Surfactant thickened systems comprising microfibrous cellulose and methods of making same
GB0808293D0 (en) 2008-05-08 2008-06-11 Unilever Plc Laundry detergent composition
CN102224233A (zh) 2008-09-25 2011-10-19 荷兰联合利华有限公司 液体洗涤剂

Also Published As

Publication number Publication date
WO2011120772A1 (en) 2011-10-06
BR112012024804A2 (pt) 2017-08-08
AU2011234744B2 (en) 2014-02-13
EP2553081A1 (de) 2013-02-06
ES2457495T3 (es) 2014-04-28
CN102858942B (zh) 2014-07-09
AU2011234744A1 (en) 2012-10-04
CN102858942A (zh) 2013-01-02
BR112012024804B1 (pt) 2020-12-15

Similar Documents

Publication Publication Date Title
EP2553081B1 (de) Mikrokapsel-aufnahme in strukturierten flüssigwaschmitteln
WO2010034736A1 (en) Liquid detergents
EP2553072B1 (de) Strukturierung von Waschmittelflüssigkeiten mit hydriertem Castoröl
CA2769440C (en) Compact fluid laundry detergent composition
EP2495300A1 (de) Strukturierung von Waschmittelflüssigkeiten mit hydriertem Castoröl
CA2893949C (en) Improved structuring with threads of non-polymeric, crystalline, hydroxyl-containing structuring agents
CA2380328C (en) Detergent compositions comprising hydrotropes
JP2021530604A (ja) 洗剤組成物
CA2216855A1 (en) Thickened, highly aqueous, cost effective liquid detergent compositions
MXPA02000063A (es) Composiciones detergentes liquidas acuosas que comprenden un sistema efervescente.
WO2009146276A1 (en) Fabric softening laundry detergents with good stability
JPH09505838A (ja) Ｎ‐アルコキシまたはｎ‐アリールオキシポリヒドロキシ脂肪酸アミド界面活性剤を有する固形組成物
US6949496B1 (en) Detergent compositions comprising hydrotropes
WO2001096519A1 (en) Liquid detergent composition
JP2000505132A (ja) 特定のアルキルベンゼンスルホネート界面活性剤を含有する非水性洗剤組成物
CZ72298A3 (cs) Přípravky obsahující hydrofilní částice oxidu křemičitého
ZA200208736B (en) Concentrated liquid detergent composition.
AU715749B2 (en) Aqueous structured liquid detergent composition comprising aminocarboxylate sequestrant
WO1999064556A1 (en) Non-aqueous, liquid detergent compositions containing gasified particulate matter
WO2001011002A1 (en) Nonaqueous liquid detergent with wash-water soluble low-density filler particles
US6770615B1 (en) Non-aqueous liquid detergents with water-soluble low-density particles
JPH08509012A (ja) 安定な酵素含有洗剤組成物中の第二級（２，３）アルキルサルフェート界面活性剤
JPH01318099A (ja) 液体洗剤組成物
JPH11513069A (ja) 特定のアルキルベンゼンスルホネート界面活性剤を含有する非水性洗剤組成物
EP1754774B1 (de) Hydrotrope enthaltende Waschmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120831

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130906

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 648764

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011004602

Country of ref document: DE

Effective date: 20140220

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2457495

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20140428

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 648764

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140108

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140108

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140508

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140508

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011004602

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140309

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20140930

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011004602

Country of ref document: DE

Effective date: 20140930

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140309

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140331

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140409

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110309

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20140930

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602011004602

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20170328

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140108

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: UNILEVER IP HOLDINGS B.V.; NL

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: UNILEVER NV

Effective date: 20210607

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602011004602

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER NV, ROTTERDAM, NL

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: UNILEVER IP HOLDINGS B.V.

Effective date: 20211117

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230428

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250319

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20250319

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250325

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20250321

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20250303

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20250428

Year of fee payment: 15