EP2841550B1 - Extern strukturierte wässrige isotrope flüssigwaschmittelzusammensetzungen - Google Patents

Extern strukturierte wässrige isotrope flüssigwaschmittelzusammensetzungen Download PDF

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Publication number
EP2841550B1
EP2841550B1 EP13709939.6A EP13709939A EP2841550B1 EP 2841550 B1 EP2841550 B1 EP 2841550B1 EP 13709939 A EP13709939 A EP 13709939A EP 2841550 B1 EP2841550 B1 EP 2841550B1
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EP
European Patent Office
Prior art keywords
clay
liquid
composition
citrus fibre
water
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EP13709939.6A
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English (en)
French (fr)
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EP2841550A1 (de
Inventor
Lee James Brennan
Adam Jan Kowalski
Philip Michael Ryan
Alastair Richard Sanderson
Ami Swapnil WAGLE
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • This invention relates to externally structured aqueous isotropic liquid detergent compositions.
  • Isotropic liquid detergent compositions have no innate ability to suspend solid particles, for example cues and encapsulates.
  • a suspending medium may be achieved by appropriate manipulation of the surfactant and electrolyte levels. However this imposes undesirable constraints on the composition.
  • Use of so-called external structurants can achieve the required suspending duty without imposing such constraints on the composition.
  • Citrus fibres and their uses for structuring of foodstuffs and personal care compositions are described in US2004/0086626 , US2009/269376 , and WO 2010/069732 .
  • the compatibility of an activated citrus fibre structured liquid detergent composition with cleaning and care enzymes is described in WO 2012/052306 .
  • Its use with cationic deposition polymer (Jaguar quaternised guar gum) for anti-dandruff shampoo is disclosed in WO2012/019934 .
  • US 7981855 discloses detergent liquid surfactant compositions comprising up to 15 wt% surfactant, including at least 1% anionic surfactant, up to 2 wt% bacterial cellulose (preferably MFC) and from 0.001 to 5 wt% citrus fibres.
  • Clays have the disadvantage when used as the main thickening agent that they tend to interact with some ingredients of liquid detergent compositions, with the result that the viscosity of the composition changes over time and syneresis can occur.
  • an externally structured aqueous isotropic liquid detergent composition comprising:
  • the mixed clay and activated citrus fibre external structuring system visibly reduces drainage residues: for example, when a transparent PET pack is used.
  • Higher weight ratios of clay to activated citrus fibre give the lowest drainage residues.
  • Preferably the ratio lies in the range 1:1 to 15:1. Drainage residues are further reduced with increased level of activation of citrus fibre.
  • the liquid detergent composition is provided in a transparent container.
  • a transparent container For example, PET with a shrink sleeve.
  • the advantages of the composition are most apparent when a transparent container is used. However, the benefit of not depleting the composition of activated citrus fibre structurant when it is left behind on a container wall is obtained whether the container is transparent or opaque.
  • the water-swellable clay is preferably synthetic, more preferably a synthetic hectorite.
  • a suitable synthetic hectorite is Laponite® EL from Rockwood.
  • Preferably clay is included at greater than 0.1 wt%, more preferably at least 0.2 wt%, and even 0.4 wt%, or higher, based on the total composition.
  • 0.6 wt% Laponite EL with 0.05 wt% activated citrus fibre gives a stable detergent liquid composition having good suspending ability over a wide range of mixed surfactant comprising anionic surfactant.
  • the clay raw material may be dry powder or a sol.
  • the sol generates higher yield stress for the same level of clay used.
  • a lower level of sol may be used to generate the same yield stress, or suspending power, with a given level of activated citrus fibre.
  • Higher levels of clay are preferably combined with lower levels of activated citrus fibre and vice versa .
  • a liquid composition with an external structuring system consisting in part of 0.05 wt% activated citrus fibre may have another part of its external structuring system provided by around 0.4 wt% water-swellable clay
  • a liquid with an external structuring system consisting in part of 0.1 wt% activated citrus fibre may have another part of its external structuring system provided by around 0.2 wt% clay.
  • Higher levels of clay allow use of lower levels of activated citrus fibre and this enables use of raw citrus pulp material of lower quality because stable structuring is less dependent on the contribution from the activated citrus fibres.
  • compositions comprise the optional suspended non-clay particles.
  • These particles may include: encapsulated fragrance and / or other benefit ingredients, e.g. functional or non-functional visual cues / beads, pearliser, micas and other insoluble ingredients (enzymes, polymers, etc). They may be incorporated into the composition either alone or in combination.
  • the externally structured compositions have the ability to suspend a wide range of solid particles. Generally these particles encompass benefit ingredients: including encapsulated ingredients such as fragrance, enzymes, visual beads/cues, mica/pearlescer, silicone, etc.
  • the suspended particles preferably comprise encapsulates and most preferably they comprise perfume encapsulates.
  • the term solid particles encompasses liquids contained in a solid shell.
  • the solid particles may comprise visual cues (film) which may have benefit ingredient embedded or located within or on them.
  • the solid particulate material may comprise abrasive material, for example ground olive stones.
  • a further advantage of an external structuring system comprising the claimed combination of water-swellable clay and activated citrus fibre is that high yield stresses needed to suspend solid particles of very different density from the liquid composition can be achieved with relatively low amounts of activated citrus fibre. This improves the clarity of the externally structured detergent composition compared to one structured to the same high yield stress with only activated citrus fibres. Improved clarity is a particular advantage if visual cues are suspended in the liquid composition. Clearer liquid compositions are also preferred by consumers.
  • compositions provide a uniformly representative dose of any suspended encapsulated fragrance or other suspended particulate benefit ingredient for each liquid dose, over the time of use. Furthermore they have a good appearance and desirable pouring characteristics. I.e. they are not lumpy from continued rheology build on storage as has been found with the known polymer and clay combinations.
  • the mixed surfactant system preferably consists of 10 to 45 wt% surfactant including the anionic surfactant(s) (100% active basis).
  • liquids comprising up to 60 wt% mixed surfactant, even up to 75 wt% may be structured with the clay and activated citrus fibre external structuring system.
  • composition is desirably free from cationic polymers, as these can destabilise an otherwise stable isotropic composition.
  • the detergent compositions are aqueous and water forms the majority of the solvent in the composition. Hydrotropes such as propylene glycol and glycerol/glycerine may be included as co-solvents in a lesser amount than the water. Water is needed in the composition in order to keep the surfactant, any polymers, soluble builders, enzymes etc in solution. The water amount stated includes both free and any bound waster. The amount of water in the composition is preferably at least 20 wt%, more preferably at least 30 wt%.
  • Synthetic surfactants preferably form a major part of the surfactant system.
  • Mixtures of synthetic anionic and nonionic surfactants, or a wholly anionic mixed surfactant system or admixtures of anionic surfactants, nonionic surfactants and amphoteric or zwitterionic surfactants may all be used according to the choice of the formulator for the required cleaning duty and the required dose of the detergent composition.
  • the surfactants forming the mixed surfactant system may be chosen from the surfactants described in 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in 'Tenside Taschenbuch', H. Stache, 2nd Edn., Carl Hanser Verlag, 1981 .
  • the amount of surfactant in the composition may range from 3 to 75 wt%, preferably 10 to 60 wt%, more preferably from 16 to 50 wt%.
  • the skilled worker will appreciate that the optimum surfactant concentration will largely depend on the product type and the intended mode of use.
  • the anionic surfactant may include soap (salt of fatty acid).
  • a preferred soap is made by neutralisation of hydrogenated coconut fatty acid, for example Prifac® 5908 (ex Croda). Mixtures of saturated and unsaturated fatty acids may also be used.
  • Nonionic detergent surfactants are well-known in the art.
  • 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 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 (SLES). It is preferred for the composition to comprise LAS.
  • a preferred mixed surfactant system comprises synthetic anionic with nonionic detergent active materials and optionally amphoteric surfactant, including amine oxide.
  • Another preferred mixed surfactant system comprises two different anionic surfactants, preferably linear alkyl benzene sulphonate and a sulphate, for example LAS and SLES.
  • Synthetic anionic surfactants can be present, for example, in amounts in the range from about 5% to about 70 wt% of the mixed surfactant system.
  • the detergent compositions may further comprise an amphoteric surfactant, wherein the amphoteric surfactant is present in a concentration of 1 to 20 wt%, preferably 2 to 15 wt% more preferably 3 to 12 wt% of the mixed surfactant system.
  • suitable amphoteric and zwitterionic surfactants are alkyl betaines, alkylamido betaines, amine oxides, aminopropionates, aminoglycinates, amphoteric imidazolinium compounds, alkyldimethylbetaines or alkyldipolyethoxybetaines.
  • the albedo of citrus fruits is used to make powdered citrus fibre. It has a 'spongy microstructure'. Citrus fruits (mainly lemons and limes) are dejuiced to leave the insoluble plant cell wall material and some internally contained sugars and pectin. It is dried and sieved and then washed to increase the fibre content. Dried materials are large (100's micron cell fragment, consisting of tightly bound/ bonded fibrils). After milling a powdered citrus fibre material is obtained. The process used leaves much of the natural cell wall intact while the sugars are removed. The resulting highly swelling citrus fibre materials are typically used as food additives and have been used in low fat mayonnaise. The pH of the dispersed powder is acidic.
  • Microscopy shows that powdered citrus fibre is a heterogeneous mixture of particles with various sizes and shapes.
  • the majority of the material consists of aggregated lumps of cell walls and cell wall debris.
  • a number of tubelike structures with an open diameter of about 10 micron, often arranged in clusters, can be identified.
  • These, so called, xylem vessels are water transport channels that are mainly located in the peel of citrus fruits.
  • the xylem vessels consist of stacks of dead cells, joined together to form relatively long tubes, 200 to 300 micron long.
  • the outsides of the tubes are reinforced by lignin, which is often laid down in rings or helices, preventing the tubes from collapse due to the capillary forces acting on the tube walls during water transport.
  • a preferred type of powdered citrus fibre is Herbafoods' Herbacel AQ+ type N citrus fibre.
  • This citrus fibre has a total (soluble and insoluble) fibre content of greater than 80% and soluble fibre content of greater than 20%. It is supplied as a fine dried powder with low colour and has a water binding capacity of about 20 kg water per kg of powder.
  • powdered citrus fibre is activated (hydrated and opened up structurally) via a high shear dispersion at a low concentration in water to form a premix. Because the dispersed activated citrus fibre is biodegradable, it is advantageous to include a preservative into the premix.
  • the shear should not be high enough to lead to defibrillation. If a high-pressure homogeniser is used it should be operated between 200 and 600 bar. The more shear that is applied the less dense the resulting particles. Whilst the morphology is changed by the high shear, process aggregate size appears not to be changed. The fibres break down and then fill the water phase. The shear also rubs loose the outer parts of the cell walls and these are able to form a matrix that structures the water outside of the volume of the original fibre.
  • An activated citrus fibre structuring premix may alternatively be made by milling using a high shear mixer, such as a Silverson.
  • the premix may be passed through several sequential high-shear stages in order to ensure full hydration and dispersal of the citrus fibre to form the activated citrus fibre dispersion.
  • the premix may be left to hydrate further (age) after the high shear dispersal.
  • the activated premix is preferably used fresh.
  • High Pressure Homogenised premixes are preferred over milled premixes, as they are more weight effective to provide sufficient suspending duty to liquids.
  • a suitable operational pressure is about 500 barg.
  • the level of activated citrus fibre in a premix preferably lies in the range 1 to 5 wt%, more preferably 1.5 to 2.5 wt%.
  • the concentration of activated citrus fibre in the pre-mix depends on the ability of the equipment to deal with the higher viscosity due to higher concentrations.
  • the amount of water in the premix is at least 20 times greater than the amount of citrus fibres, more preferably at least 25 times even as much as 50 times. It is advantageous that there is excess water in order to hydrate the activated citrus fibre fully.
  • Preferred premixes have a measured yield stress of at least 70 Pa measured using an Anton Paar serrated cup and bob geometry at 25°C.
  • activated citrus fibre When added to a detergent liquid composition activated citrus fibre boosts the yield stress and the pour viscosity of the composition at 20 s-1 and the composition is a shear thinning liquid. Yield stress and viscosity at 20 s-1 increase generally in line with the level of activated citrus fibre.
  • Activated citrus fibre is compatible with enzymes used in laundry and household care detergent compositions.
  • the premix may either be added to the detergent liquid as a post dosed ingredient, or alternatively the composition can be formed by starting with the premix and then adding the other ingredients to it. Some high shear is required to disperse the premix in the composition fully but the duty is not as demanding as for the premix preparation.
  • the activated citrus fibre should be used at a high enough level to ensure that the external structuring network does not settle under its own weight. If the network settles then any suspended solid particles settle with the network. To avoid air entrapment in the structuring network the amount of activated citrus fibre is preferably reduced to close to the minimum required to suspend the solid particles, for example encapsulated fragrance or ground olive stones for household cleaning compositions.
  • the clay portion of the external structuring system assists in reduction of the level of the activated citrus fibre needed. Activated citrus fibre benefits from air free processing as this improves the stability of the resulting liquid compositions, especially to bottom clear layer separation.
  • Suitable water swellable clays are hydrous aluminium phylosilicates, sometimes with variable amounts of iron, magnesium, alkali metals, alkaline earths, and other cations. Clays form flat hexagonal sheets similar to the micas. Clays are ultrafine-grained (normally considered to be less than 2 micrometres in size on standard particle size classifications).
  • Clays are commonly referred to as 1:1 or 2:1. Clays are fundamentally built of tetrahedral sheets and octahedral sheets.
  • a 1:1 clay consists of one tetrahedral sheet and one octahedral sheet, and examples include kaolinite and serpentine.
  • a 2:1 clay consists of an octahedral sheet sandwiched between two tetrahedral sheets and examples are illite, smectite, and attapulgite.
  • the Smectite group includes dioctahedral smectites such as montmorillonite and nontronite and trioctahedral smectites for example saponite. Also, bentonite, pyrophylite, hectorite, sauconite, talc, beidellite. Other 2:1 clay types include sepiolite or attapulgite, clays with long water channels internal to their structure. Phylosilicates include: Halloysite, Kaolinite, Illite, Montmorillonite, Vermiculite, Talc, Palygorskite, Pyrophylite.
  • Montmorillonite is a smectite phylosilicate (Na,Ca) 0.33 (Al,Mg) 2 (Si 4 O 10 )(OH)2 ⁇ nH 2 O.
  • Montmorillonite is a very soft phylosilicate group of minerals that typically form in microscopic crystals to form a clay.
  • Montmorillonite is a 2:1 clay, meaning that it has 2 tetrahedral sheets sandwiching a central octahedral sheet. The particles are plate-shaped with an average diameter of approximately one micrometre.
  • Montmorillonite is the main constituent of bentonite - a volcanic ash weathering product.
  • Hectorite is a natural smectite clay with high silica content. Natural hectorite is a rare soft, greasy, white clay mineral.
  • Suitable water-swellable clays include: smectites, kaolins, ilites, chlorites and attapulgites. Specific examples of such clays include bentonite, pyrophylite, hectorite, saponite, sauconite, nontronite, talc and beidellite as smectite type clays.
  • the water-swellable clay is preferably a smectite-type clay.
  • Montmorillonite clays even in the presence of stabilising agents are sensitive to ionic strength. They lose their liquid structuring efficiency at high electrolyte levels normally present in many detergent compositions. Clays tend to collapse onto themselves or flocculate under these conditions. If this collapse occurs during storage the liquid will lose its physical stability, suffer syneresis and /or settling of solids.
  • the preferred water-swellable clay is a smectite-type clay, selected from the group consisting of Laponites, aluminium silicate, bentonite and fumed silica.
  • Most preferred commercial synthetic hectorites are the Laponites from Rockwood. Particularly preferred synthetic hectorites are: Laponite S, Laponite RD, Laponite RDS, Laponite XLS and Laponite EL. Most preferred is Laponite EL.
  • Laponite RD, XLG, D, EL, OG, and LV are all lithium magnesium sodium silicates.
  • Other synthetic hectorite type clays include: Veegum Pro and Veegum F from RT Vanderbilt and the Barasymacaloids and Proaloids from Baroid division of National Lead Company.
  • Synthetic smectites are synthesised from a combination of metallic salts such as salts of sodium, magnesium and lithium with silicates, especially sodium silicates, at controlled ratios and temperature. This produces an amorphous precipitate which is then partially crystallised. The resultant product is then filtered washed dried and milled to give a powder containing platelets which have an average platelet size of less than 100 nm. Platelet size refers to the longest lineal dimension of a given platelet. Synthetic clay avoids the use of impurities found in natural clay.
  • Laponite is synthesised by combining salts of sodium magnesium and lithium with sodium silicate at carefully controlled rates and temperatures. This produces an amorphous precipitate which is then partially crystallised by a high temperature treatment. The resulting product is filtered, washed, dried and milled to a fine white powder.
  • the size of the clay is important. Thus the very fine synthetic hectorites are especially preferred because of their small particle size.
  • Particle size is the size of a discreet grain of moistened clay.
  • a suitable particle size is 0.001 to 1 micron, more preferably 0.005 to 0.5 micron and most preferably from 0.01 to 0.1 micron.
  • the clay may be ground or crushed to bring the average size within the desired range.
  • Laponite has an average platelet size maximum dimension less than 100 nm.
  • Laponite has a layer structure, which in dispersion in water, is in the form of disc-shaped crystals each being about 1 nm thickness and about 25 nm diameter.
  • Small platelet size provides good sprayability, rheology and clarity.
  • the clay has a particle size range in the colloidal range. Typically such clays provide a clear solution when they are hydrated, possibly because the clay particles do not scatter light when the clay is hydrated and exfoliates. Other larger clays will provide low shear viscosity build as required but the compositions will lack clarity.
  • the clay is present in the composition in an amount of at least 0.05 wt%. Preferably at least 0.1 wt%, more preferably at least 0.2 wt%.
  • the clay is present in an amount of no more than 0.7 wt%, more preferably no more than 0.6 wt%, most preferably no more than 0.5 wt%.
  • sol grade of synthetic clay decreases batch time which can be advantageous.
  • the water swellable clay is the synthetic clay supplied under the name Laponite EL from Rockwood. It combines a very small grain size with a tolerance to high ionic strength as found in detergent liquids. Laponite EL forms a dispersion in water and has a high surface charge. This is said to give it improved tolerance to electrolyte (including anionic surfactant). Laponite EL is available in both powder and sol forms. Either is suitable for use in the detergent liquid compositions.
  • Laponite has a layer structure which, in dispersion in water, is in the form of disc-shaped crystals. It can be envisaged as a two dimensional "inorganic polymer" where the empirical formula forms a unit cell in the crystal having six octahedral magnesium ions sandwiched between two layers of four tetrahedral silicon atoms. These groups are balanced by twenty oxygen atoms and four hydroxyl groups. The height of the unit cell represents the thickness of the Laponite crystal. The unit cell is repeated many times in two directions, resulting in the disc shaped appearance of the crystal. It has been estimated that a typical Laponite crystal contains up to 2000 of these unit cells. Macromolecules of this particle size are known as colloids.
  • Natural clay mineral thickeners such as bentonite and hectorite have a similar disc shaped crystal structure but are more than one order of magnitude larger in size.
  • the primary particle size of Laponite is much smaller than either natural hectorite or bentonite.
  • the idealised structure would have a neutral charge with six divalent magnesium ions in the octahedral layer, giving a positive charge of twelve. In practice, however, some magnesium ions are substituted by lithium ions (monovalent) and some positions are empty.
  • the clay has a negative charge of 0.7 per unit cell, which becomes neutralized during manufacture as sodium ions are adsorbed onto the surfaces of the crystals.
  • the crystals become arranged into stacks which are held together electrostatically by sharing of sodium ions in the interlayer region between adjacent crystals. At 25oC in tap water and with rapid agitation, this process is substantially complete after 10 minutes. High shear mixing, elevated temperature or chemical dispersants are not required. A dilute dispersion of Laponite in deionised water may remain a low viscosity dispersion of non-interacting crystals for long periods of time.
  • the crystal surface has a negative charge of 50 to 55 mmol. 100 g-1 .
  • the edges of the crystal have small localised positive charges generated by absorption of ions where the crystal structure terminates. This positive charge is typically 4 to 5 mmol, 100 g-1 .
  • the addition of polar compounds in solution e.g.
  • the process may continue to give a "house of cards" structure which, in a simple system of Laponite, water and salt, is seen as a highly thixotropic gel.
  • This gel consists of a single flocculated particle held together by weak electrostatic forces.
  • the composition preferably comprises suspended non-clay particles.
  • These particles are preferably solid; that is to say they are neither liquid nor gas.
  • the solid particles may be microcapsules such as perfume encapsulates, or care additives in encapsulated form.
  • the particles may take the form of insoluble ingredients such as silicones, quaternary ammonium materials, insoluble polymers, insoluble optical brighteners and other known benefit agents as described, for example, in EP1328616 .
  • the amount of suspended particles may be from 0.001 to up to 10 or even 20 wt%.
  • One type of solid particle to be suspended is a visual cue, for example the type of flat film cue described in EP1319706 .
  • the cue may itself contain a segregated component of the detergent composition. Because the cue must be water-soluble, yet insoluble in the composition, it is conveniently made from a modified polyvinyl alcohol that is insoluble in the presence of the mixed surfactant system. In that case, the detergent composition preferably comprises at least 5 wt% anionic surfactant.
  • the suspended non-clay particles can be any type. This includes perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials.
  • perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials.
  • suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials.
  • up to 5 wt% of suspended particles may be suspended stably using the mixed external structuring system; however, amounts up to 20 wt% are possible.
  • Microcapsules preferably comprise a solid shell. Microcapsules carrying an anionic charge should be well dispersed to avoid agglomeration issues.
  • Microcapsules with a cationic charge may also be used.
  • the microcapsule may have a melamine formaldehyde shell.
  • Other suitable shell material may be selected from (poly)urea, (poly)urethane, starch/ polysaccharide, xyloglucan and aminoplasts.
  • the average particle diameter of the microcapsules lies in the range from 1 to 100 micrometer and at least 90 wt% of the microcapsules preferably has a diameter in this range. More preferably, 90 wt% of the microcapsules have a diameter in the range 2 to 50 micrometers, even more preferably 5 to 50 micrometers. Most preferred are microcapsules with diameters less than 30 micrometers.
  • microcapsules in the range 8 to 11 microns it is advantageous to have a very narrow particle size distribution, for instance 90 wt% of microcapsules in the range 8 to 11 microns. Microcapsules in the range 2 to 5 microns cannot be dispersed so effectively due to the high surface area of the smaller particles.
  • the composition comprises at least 0.01 wt% of microcapsules, preferably with an anionic charge.
  • 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. Any microcapsules that become agglomerated during manufacture of the liquid 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.
  • 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 .
  • Perfume encapsulates are a preferred type of microcapsule suitable for use in the present invention.
  • 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 50 wt% 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.
  • microcapsules may attach to suitable substrates, e.g. to provide persistent fragrance that is desirably released after the cleaning process is complete.
  • the detergent compositions have sufficient yield stress, also called critical stress, of at least 0.08 Pa, preferably at least 0.09 Pa, more preferably at least 0.1 Pa, even at least 0.15 Pa measured at 25°C. These increasing levels of yield stress are capable of suspending particles of increasingly different density from the bulk liquid.
  • a yield stress of 0.09 Pa has been found sufficient to suspend most types of perfume encapsulates. Pure clay is unstable and cannot provide effective structuring of an aqueous isotropic detergent liquid composition.
  • the mixed external structuring system also stays dispersed; neither floating (to give bottom clear layer separation) nor sinking (to give top clear layer separation). This self suspension is achieved by ensuring that the structuring system wants to occupy all the volume of the detergent liquid. This is a function of the amounts of clay and activated citrus fibre used. To obtain this from activated citrus fibre alone has been found to generate a yield stress so high that air bubbles are suspended and these then destabilise the structuring network.
  • the detergent liquid may be formulated as a concentrated detergent 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.
  • 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.
  • a liquid medium constituted by or prepared from the liquid cleaning composition.
  • the cleaning medium on or containing the substrate is agitated.
  • the liquid detergent compositions are preferably concentrated liquid cleaning compositions.
  • the liquid compositions are pourable liquids.
  • liquid detergent compositions according to the invention are shear-thinning liquids.
  • structured detergent compositions may be prepared starting with the activated fibre to which the other ingredients are added in their normal order of addition.
  • this has the further advantage that dispersion of the activated fibre by high shear continues during the addition of the later ingredients (including the later added clay) rather than as a post shearing step, thereby reducing the batch time.
  • the best practice is to de-aerate the liquid composition before filling it into containers.
  • the external structuring system allows for more process flexibility and this step is not essential.
  • Activated citrus fibre has been found to be compatible with usual ingredients that may be found in detergent liquids.
  • polymeric thickeners include enzymes, particularly: lipase, cellulase, protease, mannanase, amylase and pectate lyase; cleaning polymers, including ethoxylated polyethylene imines (EPEI) and polyester soil release polymers; chelating agents or sequestrants, including HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid) which is available, for example, as Dequest® 2010 from Thermphos; detergency builders; hydrotropes; neutralising and pH adjusting agents; optical brighteners; antioxidants and other preservatives, including Proxel®; other active ingredients, processing aids, dyes or pigments, carriers, fragrances, suds suppressors or suds boosters, chelating agents, clay soil removal/ anti-redeposition agents, fabric soft
  • compositions may be packaged in any form of container.
  • the bottle may be rigid or deformable.
  • a deformable bottle allows the bottle to be squeezed to aid dispensing.
  • clear bottles may be formed from PET.
  • Polyethylene or clarified polypropylene may be used.
  • the container is clear enough that the liquid, with any visual cues therein, is visible from the outside.
  • the bottle may be provided with one or more labels, or with a shrink wrap sleeve which is desirably at least partially transparent, for example 50% of the area of the sleeve is transparent.
  • the adhesive used for any transparent label should not adversely affect the transparency.
  • the yield stress in Pa is taken to be the value of the stress at a shear rate of 0.1. s-1 . i.e. the equivalent of the y-axis intercept in a Herschel-Buckley plot of shear stress vs. shear rate.
  • a 2 wt% activated citrus fibre premix was prepared using the materials given in Table 1, according to the following method.
  • the demineralised water was stirred using an agitator stirrer with overhead drive operated at 160 rpm.
  • the Proxel GXL preservative was added.
  • Herbacel AQ plus N Citrus Fibre (ex: Herbafoods) was added gradually to ensure no clumping. Stirring was continued for a further 15 minutes to allow the fibres to swell sufficiently prior to the activation stage.
  • the activation stage was carried out by high pressure homogenisation (HPH) at 500 barg.
  • Detergent liquids as specified in the following examples were made using the 2 wt% activated citrus fibre premix described above. Sufficient freshly made premix was added to a mixer to give the required level of activated citrus fibre in the finished composition and it was milled for 10 minutes. The mill was then stopped and Laponite clay was added at the required level while stirring with a dual blade impelled. The mix was then stirred at 300 rpm for a further 15 minutes. The remaining ingredients to make up the liquid were then combined with this mix. The fragrance encapsulates were combined last, when used. Dispersion was carried out using an in-line Silverson (L5T).
  • L5T in-line Silverson
  • Visible residues were assessed by adding a sample of the externally structured liquid composition to a transparent Nunc bottle.
  • the bottle was manipulated to ensure that the sample thoroughly wetted the vertical walls and then left for a few minutes to drain.
  • the resulting on wall drainage residue was assessed visually against a comparative liquid C made using the same detergent base and structured only with activated citrus fibre.
  • An externally structured isotropic laundry liquid was prepared as specified in Table 2.
  • Table 2 Ingredient % Active Water and minors* 58.464 Laponite EL (Liq.) 0.200 ACF 0.100 Perfume encapsulates 0.300 Glycerol 5.000 MPG 2.000 NaOH 1.200 TEA 1.690 NI 13.720 LAS Acid 9.150 Prifac 5908 1.500 SLES 3EO 4.570 Dequest 2066 0.340 Proxel GXL 0.016 Perfume 1.000 Enzymes 0.750 *Minors are fluorescers, opacifier and colorants.
  • Variants of this liquid were also prepared using the powder variant of Laponite EL (100% active) and using Laponite RD. The level of Laponite was carried up to 0.5 wt% successfully. Liquids with and without the perfume encapsulates were prepared. All liquids were storage stable over a range of temperatures from 5 to 50 °C.
  • the drainage residues from the activated citrus fibre and polymer examples according to the invention were visibly less than the 0.25 wt% comparative example.
  • 0.25 wt% was chosen as a realistic comparison as that is the amount of citrus fibres needed to suspend perfume encapsulates stably.
  • To ensure that the result could not be attributed to a lowering of the amount of activated citrus fibre in the liquid we compared a liquid structured with only 0.1 wt% activated citrus fibre with one structured with the same level of citrus fibre and having 0.4 wt% of the clay additionally in the composition. At 0.1 wt% the activated citrus fibre composition is not stable and serves only for this residues comparison work. Again the composition containing the clay gave visibly lower drainage residues.
  • a second set laundry liquid compositions based on the ingredients in Table 3 was prepared and again the clay and activated citrus fibre combination resulted in visibly lower on wall drainage residues across a range of levels of clay from 0.1 to 0.4 wt% and with different levels of activated citrus pulp.
  • the liquids suspended the perfume encapsulates and were storage stable at temperatures of from 5 to 50 °C for at least 12 weeks.
  • the mixed activated citrus fibre and clay co-structuring systems exemplified enable stable suspension of encapsulated fragrance or other benefit ingredients.
  • abrasive particles namely olive stone particulates
  • Control liquid 1 5.1 Pa
  • Control liquid 2 2.1 Pa HSC 1 0.9 Pa HSC 2 0.5 Pa

Claims (10)

  1. Extern strukturierte, wässrige, isotrope Flüssigwaschmittelzusammensetzung, umfassend:
    a) mindestens 10 Gew.-% Wasser,
    b) mindestens 3 Gew.-% gemischtes Tensidsystem, das ein anionisches Tensid umfasst,
    c) aktivierte Citrusfasern als externes Strukturierungsmittel,
    dadurch gekennzeichnet, dass die Flüssigkeit ferner mindestens 0,05 Gew.-% in Wasser quellbaren Ton umfasst und dass die Zusammensetzung eine Viskosität von mindestens 0,3 Pa.s bei 20 s-1 und 25°C aufweist.
  2. Zusammensetzung nach Anspruch 1, wobei die Viskosität der Flüssigkeit bei 20 s-1 und 25°C mindestens 0,4 Pa.s beträgt.
  3. Zusammensetzung nach einem der vorstehenden Ansprüche in einem durchsichtigen Behälter.
  4. Zusammensetzung nach einem der vorstehenden Ansprüche mit einer Fließspannung von mindestens 0,1 Pa, die ferner mindestens 0,01 Gew.-% suspendierte Nichtton-Teilchen umfasst.
  5. Zusammensetzung nach Anspruch 4, wobei die suspendierten Nichtton-Teilchen Mikrokapseln und vorzugsweise verkapselte Duftstoffe umfassen.
  6. Zusammensetzung nach Anspruch 4, wobei die suspendierten Nichtton-Teilchen visuelle Signalstoffe umfassen.
  7. Zusammensetzung nach Anspruch 6, wobei es sich bei den visuellen Signalstoffen um lamellare Teilchen handelt, die aus Schichten eines Polymerfilms gebildet sind.
  8. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 0,2 Gew.-% Ton.
  9. Zusammensetzung nach einem der vorstehenden Ansprüche, ferner umfassend ein farbgebendes Mittel.
  10. Zusammensetzung nach Anspruch 1, umfassend mindestens 0,025 Gew.-% und vorzugsweise mindestens 0,1 Gew.-% aktivierte Citrusfasern.
EP13709939.6A 2012-04-23 2013-03-19 Extern strukturierte wässrige isotrope flüssigwaschmittelzusammensetzungen Active EP2841550B1 (de)

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EP12165195 2012-04-23
PCT/EP2013/055647 WO2013160022A1 (en) 2012-04-23 2013-03-19 Externally structured aqueous isotropic liquid detergent compositions
EP13709939.6A EP2841550B1 (de) 2012-04-23 2013-03-19 Extern strukturierte wässrige isotrope flüssigwaschmittelzusammensetzungen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287366B2 (en) 2017-02-15 2019-05-14 Cp Kelco Aps Methods of producing activated pectin-containing biomass compositions

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112016029326B1 (pt) * 2014-06-20 2022-02-01 Unilever Ip Holdings B.V. Processo para produzir uma composição detergente líquida aquosa externamente estruturada e composição detergente líquida isotrópica aquosa externamente estruturada
WO2016023145A1 (en) * 2014-08-11 2016-02-18 The Procter & Gamble Company Laundry detergent
DE102014225145A1 (de) * 2014-12-08 2016-06-09 Henkel Ag & Co. Kgaa Verfahren zur Herstellung flüssiger, Tensid-enthaltender Zusammensetzungen mit Fließgrenze
BR112017014243B1 (pt) * 2014-12-31 2022-08-30 Unilever Ip Holdings B.V. Composição de limpeza e método de preparo da mesma
US10982023B2 (en) 2015-05-11 2021-04-20 W. R. Grace & Co.-Conn. Process to produce modified clay, supported metallocene polymerization catalyst
WO2016183008A1 (en) 2015-05-11 2016-11-17 W.R. Grace & Co.-Conn. Process to produce modified clay, modified clay produced and use thereof
CN108366934B (zh) * 2015-12-18 2021-09-07 莱雅公司 在施加期间具有颜色转变的组合物
WO2019007916A1 (en) 2017-07-04 2019-01-10 Unilever Plc COMPOSITION COMPRISING ANTI-TRANSPIRANT ACTIVE INGREDIENT AND MICROFIBRILLES

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE530009A (de) 1953-06-30
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
US4946624A (en) 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
US5154842A (en) 1990-02-20 1992-10-13 The Procter & Gamble Company Coated perfume particles
US5066419A (en) 1990-02-20 1991-11-19 The Procter & Gamble Company Coated perfume particles
GB9424008D0 (en) * 1994-11-29 1995-01-18 Procter And Gamble The Company Cleansing compositions
DE69624799T2 (de) * 1995-03-14 2003-07-17 Procter & Gamble Dispergierter smektit-ton als öl-in-wasser stabilisator für flüssige hautreinigungszusammensetzung
DE19646110A1 (de) 1996-11-08 1998-05-14 Bayer Ag Mikrokapseln unter Verwendung von Iminooxadiazindion-Polyisocyanaten
JP2001507384A (ja) 1996-12-23 2001-06-05 クウエスト インターナシヨナル ベー ベー 吸収された液体を含む粒子及びそれらを製造する方法
DE10000223A1 (de) 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
EP1311970A4 (de) 2000-05-24 2007-07-25 Haley Systems Inc System zur unternehmens-wissensverwaltung und automatisierung
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
DE60134760D1 (de) 2000-10-27 2008-08-21 Procter & Gamble Stabilisierte flüssige zusammensetzungen
GB0106560D0 (en) 2001-03-16 2001-05-02 Quest Int Perfume encapsulates
EP1517746A1 (de) 2002-05-31 2005-03-30 McMaster University Verfahren zum Einkapseln von hydrophobischen organischen Molekulen in Polyharnstoffkapseln
EP1402877B1 (de) 2002-09-30 2006-03-01 Rohm And Haas Company Verdickungsmittel für wässrige Systeme mit einem hohen Gehalt an Tensiden
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
US9629790B2 (en) 2002-11-06 2017-04-25 Fiberstar, Inc Stabilization of cosmetic compositions
US7094317B2 (en) 2002-11-06 2006-08-22 Fiberstar, Inc. Process of manufacturing and using highly refined fiber mass
US20040142868A1 (en) 2003-01-21 2004-07-22 Sleeman Mark W. Method of treating liver steatosis in a mammal
DE602005014815D1 (de) 2004-12-23 2009-07-16 Unilever Nv Flüssigwaschmittel und ihre verwendung
CA2728378A1 (en) 2008-06-16 2009-12-23 Unilever Plc A method of laundering fabrics using a pourable liquid detergent composition with a minority of soap
WO2010069732A1 (en) * 2008-12-16 2010-06-24 Unilever Plc Improvements relating to fabric treatment compositions
CN103002755B (zh) * 2010-07-30 2015-01-14 卡吉尔公司 改进柑橘纤维的性质的方法
US8697041B2 (en) 2010-08-10 2014-04-15 Conopco, Inc. Anti-dandruff compositions with citrus fibers
CN103180423B (zh) * 2010-10-22 2015-08-12 荷兰联合利华有限公司 外部结构化的水性洗涤剂液体
US7981855B1 (en) 2010-11-15 2011-07-19 Conopco, Inc. Liquid surfactant compositions structured with fibrous polymer and citrus fibers having no flow instability or shear banding

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287366B2 (en) 2017-02-15 2019-05-14 Cp Kelco Aps Methods of producing activated pectin-containing biomass compositions
US11008407B2 (en) 2017-02-15 2021-05-18 Cp Kelco Aps Activated pectin-containing biomass compositions and products

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BR112014026428A2 (pt) 2017-06-27
AR090779A1 (es) 2014-12-03
CN104245910B (zh) 2017-02-15
CN104245910A (zh) 2014-12-24
IN2014MN02035A (de) 2015-10-09
WO2013160022A1 (en) 2013-10-31
BR112014026428B1 (pt) 2022-02-01
ZA201407628B (en) 2016-05-25
EP2841550A1 (de) 2015-03-04

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