EP0598335A2 - Neue Reinigungszusammensetzungen - Google Patents

Neue Reinigungszusammensetzungen Download PDF

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Publication number
EP0598335A2
EP0598335A2 EP93118271A EP93118271A EP0598335A2 EP 0598335 A2 EP0598335 A2 EP 0598335A2 EP 93118271 A EP93118271 A EP 93118271A EP 93118271 A EP93118271 A EP 93118271A EP 0598335 A2 EP0598335 A2 EP 0598335A2
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EP
European Patent Office
Prior art keywords
phase
surfactant
aqueous based
composition
phases
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.)
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EP93118271A
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English (en)
French (fr)
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EP0598335A3 (de
Inventor
John Hawkins
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Solvay Solutions UK Ltd
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Albright and Wilson Ltd
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Priority claimed from GB929223898A external-priority patent/GB9223898D0/en
Priority claimed from GB929225677A external-priority patent/GB9225677D0/en
Application filed by Albright and Wilson Ltd filed Critical Albright and Wilson Ltd
Publication of EP0598335A2 publication Critical patent/EP0598335A2/de
Publication of EP0598335A3 publication Critical patent/EP0598335A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning 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
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to novel cleaning compositions which are high viscosity gels at ambient temperature, but which are preferably liquefiable or dispersible at laundry washing temperature.
  • compositions which can be obtained in the form of dimensionally stable sticks or bars, suitable for application to surfaces by friction.
  • the process of washing clothes (or laundry) in an automatic washing machine comprises a timed washing cycle, followed by a set number of rinses.
  • the timed wash is herein referred to as the mainwash cycle and under normal washing conditions is relied upon to remove all soils and stains from the laundry.
  • the mainwash cycle alone may not be sufficient to provide a satisfactory result with regard to the cleanliness of the laundered clothes.
  • a pre-wash cycle of shorter duration than the subsequent mainwash cycle is available on automatic washing machines, and is used in addition to the latter if required.
  • a pre-wash cycle is effective in providing a cleaner washing result when used in conjunction with the mainwash cycle, than the latter alone, it is inefficient to treat the entire washing load if only a small proportion of the load requires this additional treatment.
  • Stick applicators are well known. They comprise a container, one end of which is open or capable of being opened and a solid, plastic or gel composition at least predominantly within the container, but capable of being progressively exposed at the open end, and adapted to be applied to a surface by friction between the surface and the exposed part of the composition.
  • Typical examples of stick applicators include lipstick, shaving soap, pencils, deodorant sticks and laundry pre-spotting or stain removal sticks.
  • the container In a typical stick applicator the container, usually having a substantially constant cross section at all points along its axis, is open at one end, and is typically provided with removable closure means.
  • the applicator may be provided with means for extruding the contents progressively through the open end.
  • the extrusion means may comprise a screw extruder, e.g. one in which the rotation of a base member causes a plunger to move along the axis of the container.
  • the plunger may be actuated by sliding means such as nested concentric tubes telescoped by pressure between the top and base or lugs projecting laterally through slots in the container.
  • extrusion means is a container whose sides are adapted to be progressively removed to expose the contents as the latter is consumed.
  • the side of the container may comprise a foil which can be peeled back or may be in the form of a wooden tube which can be cut back with a knife or pencil sharpener.
  • stick applicator will be used herein to include all the aforesaid types of applicator.
  • One object of our invention is to provide a cleaning composition suitable for use as a pre-spotter which overcomes the above problems of existing prespotters and which is easy to apply to stains and effective at reducing or removing them.
  • a second object of our invention is to provide a cleaning composition suitable for use in removing soils and stains from areas of soft furnishings, which does not require large amounts of water, brushing or vacuming of the fabric or fibres.
  • the concentrated powder and concentrated liquid laundry compositions are often unacceptable to the consumer.
  • the former have a tendency to be sticky, and thus cake on storage, whilst the latter are usually anhydrous formulations which do not exhibit good rinseability in the wash, often leaving a gel residue in the liquid dispenser.
  • the formation of this gel which is difficult to disperse, lowers the surfactant concentration in the wash liquor and is therefore detrimental to the washing performance of the anhydrous liquid product.
  • Compact and traditional laundry powders are packaged in boxes, with any hole, tear or improperly sealed edge allowing the spillage and loss of powder. Furthermore, if the packaging boxes become damp during storage the powder detergent becomes moist, cakes inside the box and so will not dispense easily.
  • a third object of this invention is therefore to provide an aqueous based detergent composition which may be supplied in pre-dosed portions and in a physical form which is less likely to lead to spillage of the product, and contains a high payload.
  • a typical hard surface cleaner comprises a cream or paste containing surfactants and inert abrasive particles. Creams may typically be poured directly on to stained horizontal surfaces such as hobs and kitchen work tops and wiped or rinsed off with a wet cloth. Cleaning vertical surfaces such as walls, doors or windows requires the compositions to be applied first to the cloth. Both these methods of application tend to be wasteful of the product and are messy and inconvenient, with potential for spillage.
  • a fourth object of our invention is therefore to provide a hard surface cleaner in a form which is more convenient to use than the known products.
  • Petcare formulations for the cleansing of animal skin and fur for example dog and cat shampoos, are customarily liquid products which are messy to use and uneconomical with the potential for spillage.
  • a fifth object of the invention is therefore to provide an aqueous based detergent composition for use as a skin cleanser which is in a more convenient to use form than known products, and which has the advantage of not requiring solvents.
  • Other toiletry products which may be formulated to provide an easier to use form of product than those currently available include shaving sticks, shower gels and shampoos.
  • Petcare shampoo formulations may be provided as aqueous based detergent compositions which are in an easier to use form than conventional petcare shampoos.
  • Such petcare shampoos formulations may contain conventional amounts of minor ingredients such as biocides, insecticides and conditioning agents.
  • a particular disadvantage of liquid laundry detergents is the difficulty of incorporating enzymes, which tend to be unstable in liquid detergents. This is particularly true of mixed enzyme systems containing protease and lipase. Ideally an enzyme system should include protease, amylase and lipase. This is the preferred combination used in detergent powders.
  • the enzymes protease and lipase are incorporated into laundry detergent formulations for their ability to remove proteinaceous stains (e.g. blood and milk) and fatty stains (e.g. sebum) respectively.
  • the product medium allows interaction of the two aforementioned enzymes, with rapid deterioration of lipase activity resulting as lipase is destroyed by the presence of protease.
  • enzymes are included in powder detergents, they would give rise to problems of allergenic dust, and also loss of activity, on spray drying, and therefore have to be post added which causes serious problems in manufacture. They also tend to be inactivated by bleach in the powder.
  • a sixth object of the invention is therefore to provide an aqueous based detergent composition, containing a stable enzyme system and especially one which includes both a lipase and a protease.
  • a further problem which is encountered with known aqueous based detergents is the difficulty of incorporating oxidising bleaches such as perborates, percarbonates, peroxides or hypochlorites.
  • Such oxidising bleaches have the ability to improve the stain removal performance of a laundry product. Tannin from tea, and red wine are two examples of bleachable stains commonly encountered in a washing load.
  • the inherent water-sensitivity of the aforementioned bleaches has hitherto made inclusion into aqueous based laundry products difficult, resulting in a loss of activity of the bleach, and ultimately its decomposition.
  • a seventh object of this invention is therefore to provide an aqueous based laundry detergent containing an oxidising bleach.
  • Detergent powder has, for many years, been manufactured by making a slurry in water of the surfactant, builder and filler together with various ancillary ingredients, and spray drying or fluid bed drying the slurry to form a powder.
  • the heat and aggressive environment of a spray dry slurry prevent sensitive ingredients such as enzymes and bleaches being added at that stage.
  • the cost of spray during and the cost of the filler which does not fulfil any useful function in the wash and may even have a negative effect contribute significantly to the cost of detergent powder.
  • the filler also contributes substantially to the bulk of a conventional laundry powder, which is convenient for shoppers to carry and store and undesirable for the retailer because it takes up valuable shelf space.
  • a further object of this invention is therefore to provide particulate or granular detergent compositions which do not require spray during and into which sensitive ingredients can be incorporated without dry blending.
  • a further object of this invention is to provide a means of encapsulating bleaches, such as sodium perborate, or any other water or detergent sensitive materials with an aqueous based surfactant composition. This permits otherwise incompatible materials to be incorporated into liquid or powder detergents with reduced tendency to inactivation.
  • mesophases are phases which exhibit a degree of order intermediate between typical liquids and solids.
  • mesophases combine long range order associated with crystals, with fast molecular motion common to liquids.
  • L1 phase Below approximately 30% surfactant an isotropic L1 phase is formed (with micelles of surfactant in water). Above 30% surfactant many detergents form an M phase which is of no value in laundry applications since it does not show suitable flow characteristics and is difficult to dissolve or disperse in water. Above the concentrations required to form an M-phase, but usually at concentrations of less than 80% active surfactant i.e. 60%-80% a G-phase is formed. At concentrations higher than those required to form a G-phase i.e. typically greater than 80% active surfactant, most surfactants form a hydrated solid, and some, especially non-ionic surfactants form a liquid phase containing dispersed micelle sized droplets of water-an inverted micellar solution known as an L2 phase. Although such a surfactant system would appear ideal for use as a laundry detergent, L2 detergent systems do not disperse readily in water and have a tendency to form undesirable gels, e.g. M phases, on dilution.
  • VI phases viscous isotropic or VI phases. These are immobile phases usually with a vitreous appearance, and have been relatively little studied compared to the other phases discussed above. They have been virtually ignored in the context of formulating cleaning compositions because most of the surfactants and surfactant systems which are commonly used in cleaning compositions do not form VI phases, at least at normal temperatures, or form them only within narrow concentration ranges and because their known properties as immobile gels has deterred formulators from investigating them. They are recognised as being the most viscous of the lyotropic mesophases. Conventional wisdom has dictated that a commercially acceptable cleaning composition, particularly in the laundry and hard surface cleaning areas must be either a free flowing powder or a mobile liquid.
  • the different surfactant phases can be recognised by a combination of appearance, rheology, textures under the microscope, electron microscopy and x-ray diffraction or neutron scattering.
  • a detailed description, with illustrations, of the different textures observable using a polarising microscope, is to be found in the paper by Rosevear JAOCS Vol 31, p628.
  • HLB hydrophilic: lipophilic balance
  • surfactant for water and oil respectively and correlates with their effectiveness as emulsifiers. HLB value can easily be calculated for alcohol ethoxylates since it is one fifth of the weight percent of ethylene oxide based on the total mole weight.
  • Other surfactants can be assigned equivalent values by applying more complicated formulae or by measuring their relative affinity for water and oil.
  • An HLB value of 20 represents a completely water soluble oil insoluble surfactant, whilst an HLB value of 0 represents a completely oil soluble and water insoluble surfactant.
  • an HLB value of 12 is commonly considered to provide the maximum washing efficiency, and thus laundry compositions are ideally formulated to incorporate surfactant systems with an HLB as close to 12 as possible.
  • Optically isotropic surfactant phases do not normally tend to rotate the plane of polarisation of plane polarised light. If a drop of sample is placed between two sheets of optically plane polarising material whose planes are at right angles, and light is shone on to one sheet, optically isotropic surfactant samples do not appear substantially brighter than their surroundings when viewed through the other sheet. Optically anisotropic materials appear substantially brighter. Optically anisotropic mesophases typically show characteristic textures when viewed through a microscope between crossed polarisers, whereas optically isotropic phases usually show a featureless continuum.
  • “Newtonian liquids” have a viscosity which remains constant at different shear rates.
  • liquids are considered Newtonian if the viscosity does not vary substantially at shear rates up to 1000 sec ⁇ 1.
  • “Lamellar” phases are phases which comprise a plurality of bilayers of surfactant arranged in parallel and separated by liquid medium. They include both solid phases and the typical form of the liquid crystal G-phase. G-phases are typically pourable, non-Newtonian, anisotropic products. They are typically viscous-looking, opalescent materials with a characteristic "smeary” appearance on flowing. They form characteristic textures under the polarising microscope and freeze fractured samples have a lamellar appearance under the electron miscroscope. X-ray diffraction or neutron scattering similarly reveal a lamellar structure, with a principal peak typically between 4 and 10nm, usually 5 to 6nm. Higher order peaks, when present occur at double or higher integral multiples of the Q value of the principal peak.
  • Q is the momentum transfer vector and is related, in the case of lamellar phases, to the repeat spacing d by the equation where n is the order of the peak.
  • G-phases can exist in several different forms, including domains of parallel sheets which constitute the bulk of the typical G-phases described above and spherulites formed from a number of concentric spheroidal shells, each of which is a bilayer of surfactant.
  • the term "lamellar” will be reserved for compositions which are at least partly of the former type.
  • Opaque compositions at least predominantly of the latter type in which the continuous phase is a substantially isotropic solution containing dispersed spherulites are referred to herein as "spherulitic".
  • compositions in which the continuous phase comprises non-spherulitic bilayers usually contain some spherulites but are typically translucent, and are referred to herein as "G-phase compositions". G-phases are sometimes referred to in the literature as L (alpha) phases.
  • L1-phases are mobile, optically isotropic, and typically Newtonian liquids which show no texture under the polarising microscope. Electron microscopy is capable of resolving the texture of such phases only at very high magnifications, and X-ray or neutron scattering normally gives only a single broad peak typical of a liquid structure, at very small angles close to the reference beam.
  • the viscosity of an L1-phase is usually low, but may rise significantly as the concentration approaches the upper phase boundary.
  • M-phases are typically immobile, anisotropic products resembling low melting point waxes. They give characteristic textures under the polarising microscope, and a hexagonal diffraction pattern by X-ray or neutron diffraction which comprises a major peak, usually at values corresponding to a repeat spacing between 4 and 10nm, and sometimes higher order peaks, the first at a Q-value which is 3 0.5 times the Q-value of the principal peak and the next double the Q-value of the principal peak. M-phases are sometimes referred to in the literature as H-phases.
  • VI phases are typically immobile, non-Newtonian, optically isotropic and are typically transparent, at least when pure.
  • VI phases have a cubic symmetrical diffraction pattern, under X-ray diffraction or neutron scattering, with a principal peak and higher order peaks at 2 0.5 and 3 0.5 times the Q-value of the principal peak.
  • VI phases sometimes referred to as I1 phase
  • I1 phase may arise from the packing of micelles (probably spherical) in a cubic lattice.
  • M1 hexagonal phase
  • G lamellar phase
  • I1 phases when they occur, are usually only observed over a narrow range of concentrations, typically just above those at which the L1-phase is formed.
  • the location of such VI phases in a phase diagram suggests that the phase is built up of small closed surfactant aggregates in a water continuum.
  • I1 phase An inverse form of the I1 phase (the I2 phase) has also been reported, possibly between the inverse hexagonal (M2) and L2 phases. It consists of a surfactant continuum containing a cubic array of water micelles.
  • VI phase An alternative form of the VI phase called the V1 phase has been observed at concentrations between the M and G phases and may comprise a bicontinuous system. This may exhibit an even higher viscosity than the I1.
  • An inverse phase, the V2 phase, between the G and M2 phases has also been postulated.
  • VI phases A characteristic property of VI phases is commonly observed when a jar or beaker containing such a phase is sharply struck. A distinctive vibration can be felt in the composition. This has given rise to the term “ringing gel” sometimes applied to VI phases and may be in part due to the elasticity of the VI phase.
  • the I1/L1 transition temperature will be referred to herein as the melting point of the I1 phase for convenience, although it is not strictly speaking the melting point since the VI phases are not solids.
  • VI phases are particularly suitable for use as pre-spotting compositions. They are capable of being cast in a stick or bar form having a high degree of dimensional stability and therefore capable of use in a stick applicator. We have discovered that they are nevertheless easily applied to stained areas of fabric without wetting and with only gentle rubbing. They remain adhering to the fabric as gels at ambient temperature but can be formulated to melt at wash temperatures to form a clear rapidly water soluble liquid or to disperse readily in wash liquor.
  • washing enzymes including mixed enzymes comprising protease and lipase, and also oxidising bleaches, with substantially improved stability.
  • oxidising bleaches with substantially improved stability.
  • sensitive ingredients e.g. by adding them to the melt and cooling without spray drying or dry blending.
  • our invention provides the use of aqueous based surfactant VI phases as cleaning compositions.
  • our invention provides a method of removing soil and/or stains from a surface which comprises applying thereto an aqueous based surfactant VI phase and washing said surface with water.
  • our invention provides a method of removing soil and/or stains from laundry which comprises dissolving a surfactant VI phase in water to form a wash liquor and contacting said laundry with said wash liquor.
  • our invention provides a composition for use as a cleaning composition, which, at some temperature below 100 o C is a clear liquid L1 phase aqueous based surfactant solution which forms a VI phase on cooling.
  • our invention provides an aqueous based formulation for use as a cleaning composition comprising surfactants in the form of a VI phase which forms an L1 phase at a transition temperature between 25 and 80 o C.
  • our invention provides an aqueous based formulation for use as a cleaning composition
  • our invention provides a stick applicator containing surfactants in the form of a VI phase.
  • our invention provides an aqueous based cleaning composition for hard surfaces which comprises surfactants present as a VI phase and which may contain suspended abrasive particles.
  • the invention provides aqueous based cleaning compositions for use in washing human skin or hair or animal skin or fur comprising surfactants present in the VI phase.
  • the invention provides an aqueous based cleaning composition
  • aqueous based cleaning composition comprising surfactants present as a VI phase and containing washing enzymes.
  • the enzymes comprise a protease and a lipase and preferably also an amylase.
  • the invention provides an aqueous based cleaning composition comprising surfactants present as a VI phase for use in the removal of soils and/or stains from areas of soft furnishings.
  • the invention provides an aqueous based cleaning composition, comprising surfactants present as a VI phase, and incorporating an oxidising bleach dispersed therein.
  • the bleach is encapsulated for example in a film forming polymer or wax to further inhibit degradation.
  • the invention provides cleaning composition comprising heat - and/or water-sensitive materials encapsulated in surfactants present as a VI phase.
  • our invention provides a cleaning composition comprising non-ionic surfactants present as a VI phase and a cationic fabric conditioner.
  • our invention provides a particulate detergent composition comprising surfactants present as VI phase.
  • the invention provides an aqueous based cleaning composition comprising surfactants present as a VI phase, wrapped or coated with or encapsulated within a film or sachet of a water soluble polymer.
  • the invention provides a composition comprising at least one non-ionic relatively hydrophilic surfactant having an HLB greater than 15 which forms I1 phase, at least one other surfactant having an HLB less than 10, in a proportion based on said relatively hydrophilic surfactant such that the mean HLB of the surfactant mixture lies between 10 and 15 and sufficient water to provide an I1 phase.
  • the VI phase for use according to any of the aforesaid embodiments of the invention, and, especially for use as a pre-spotter or hard surface cleaner, or as a main wash detergent (e.g. in unit dose form) should comprise a cubic array of spherical micelles or I1 phase.
  • the phase is preferably located on the phase diagram between the L1 and M1 phases.
  • the VI phase be of the bicontinuous cubic type.
  • V2 and I2 phases may also be used in this context.
  • the surfactants are preferably selected to provide a VI phase over a comparatively broad surfactant concentration range e.g. more than ⁇ 2% by weight preferably ⁇ 5% or greater, which range typically lies above 15% by weight total surfactant based on the weight of the composition e.g. between 20% and 70% by weight surfactant usually between 25% and 60%.
  • the surfactants are preferably selected to provide a VI phase which melts above 30 o C e.g. above 35 o C most preferably above 40 o C.
  • the VI phase melts at a temperature substantially below 100 o C e.g. below 90 o C more preferably below 80 o C most preferably below 70 o C, especially below 60 o C, typically below 55 o C, usually below 50 o C.
  • the surfactant mixture preferably has a mean HLB between 10 and 15 e.g. 11 to 14.
  • the surfactants preferably comprise non-ionic surfactants such as ethoxylated alcohols. It has been found that highly ethoxylated fatty alcohols, e.g. more than 10 EO groups, preferably more than 15 EO groups, especially 18 to 50 EO groups form VI phases particularly readily.
  • One way of developing a suitable composition is to select a hydrophilic (preferably non-ionic) surfactant which is known to form a suitable VI phase (e.g. an I2 phase) and to blend it with sufficient relatively hydrophobic surfactant to obtain the desired HLB. It may be helpful to construct a phase diagram with the relative proportions of the two components on the horizontal axis and total surfactant concentration on the vertical axis. A VI phase region then is identified in the diagram. A range on the horizontal axis embraces the compositions having the correct HLB (which can be calculated) and the "melting point" of the VI phase is generally proportional to concentration. Thus a range on the vertical axis embraces compositions with the desired "melting point".
  • a hydrophilic (preferably non-ionic) surfactant which is known to form a suitable VI phase (e.g. an I2 phase) and to blend it with sufficient relatively hydrophobic surfactant to obtain the desired HLB. It may be helpful to construct a phase diagram with the relative proportions of the two
  • non-ionic surfactants which may be present include:- alkyl phenol ethoxylates, fatty acid ethoxylates, fatty acid monoalkylolamide ethoxylates, fatty alcohol propoxylates, fatty amine alkoxylates and fatty acid glyceryl ester ethoxylates.
  • Other non-ionic compounds suitable for inclusion in compositions of the present invention include mixed ethylene oxide propylene oxide alkoxylates, low relative molecular mass polyethylene glycols e.g.
  • PEG600 and PEG200 ethylene glycol monoesters, alkanolamides, amine oxides and alkyl polyglycosides, alkyl sugar esters including alkyl sucrose esters and alkyl oligosaccharide ester, alkyl capped polyvinyl alcohol and alkyl capped polyvinyl pyrrolidone.
  • compositions of the invention may also comprise anionic surfactants, in addition to or instead of non-ionic surfactants.
  • anionic surfactants may for example be chosen from the group of:- C10 ⁇ 20 alkyl ethoxy sulphates (including sodium, potassium, ammonium, magnesium, lithium, triethanolamine, diethanolamine or monoethanolamine salts of such ethoxy sulphates, and a sodium/magnesium mixed salt of such ethoxy sulphates), di-sodium alkyl ethoxy sulphosuccinates.
  • phosphate esters including fatty alcohol ethoxy phosphate esters and substituted phenol ethoxylated phosphate esters are suitable for compositions of the present invention.
  • anionic surfactants that may be present include C10 ⁇ 20 alkyl benzene sulphonates, parafin sulphonates, alkyl sulphates, olefin sulphonates, soaps, fatty acid taurides, isethionates and ester sulphonates, alkyl ether carboxylates and alkyl ether polycarboxylates.
  • compositions of the invention may optionally include a cationic surfactant, especially a cationic fabric conditioner such as a ditallowyl dimethylammonium salt, a ditallowyl benzalkonium salt or a ditallowyl immidazolinium or amidoammonium salt.
  • a cationic surfactant especially a cationic fabric conditioner such as a ditallowyl dimethylammonium salt, a ditallowyl benzalkonium salt or a ditallowyl immidazolinium or amidoammonium salt.
  • the products of this invention comprise in percentages by weight based on the weight of the total surfactant and water from 10 to 65% of one or more ethoxylated surfactants (non-ionic and/or anionic surfactants) and from 30 to 90% by weight of water.
  • the non-ionic surfactants include at least one chosen from the group comprising ethoxylated C8-C20 e.g. C12-C18 alcohols having an average of 2-80, preferably 3-60, and most preferably 8 to 50 ethyleneoxy groups per molecule.
  • Other non-ionic surfactants include alkyl (C8-C9) phenol ethoxylates having a preferred proportion of ethylene oxide of 2-40 units, also ethoxylated C8-C20 fatty acids having the same preferred proportion of ethylene oxide, and mixed ethoxylated propoxylated analogues of the aforesaid non-ionic surfactants having a ratio of propyleneoxy to ethyleneoxy groups between 0 and 0.5.
  • non-ionic surfactants include ethoxylated fatty alkyl mono, and di-ethanolamides, fatty alcohol alkoxylates, fatty amine alkoxylate, substituted phenol ethoxylates and ethylene glycol esters. Polyethylene glycol e.g. with relatively low molecule mass are also suitable.
  • the composition contains a protease, lipase and/or amylase. Especially we prefer that the composition comprises a protease and a lipase. Most preferably the composition comprises a protease, a lipase and an amylase.
  • the composition may contain an oxidising bleach such as sodium perborate, builders such as zeolite and/or an inert abrasive such as talc, calcium carbonate, or silica.
  • Solids may generally be introduced by stirring the particulate solid into a VI phase composition which is heated above its melting point, and cooling the resulting mixture of solid and L1 phase.
  • Electrolytes tend to disrupt the gel structure, however to the extent that they are compatible, we prefer that the composition contains dissolved builder salts such as citrates, carbonates, phosphates, pyrophosphates, polyphosphates and phosphonates.
  • dissolved builder salts such as citrates, carbonates, phosphates, pyrophosphates, polyphosphates and phosphonates.
  • the applicator may be provided with means for extruding the contents progressively through the open end.
  • the extrusion means may comprise a screw extruder, e.g. one in which the rotation of a base member causes a plunger to move along the axis of the container.
  • the plunger may be actuated by sliding means such as nested concentric tubes telescoped by pressure between the top and base or lugs projecting laterally through slots in the container.
  • extrusion means is a container whose sides are adapted to be progressively removed to expose the contents as the latter is consumed.
  • the side of the container may comprise a foil which can be peeled back or may be in the form of a wooden tube which can be cut back with a knife or pencil sharpener.
  • Fig. 1 is a diagramatic sectional elevation and Fig. 2 is a sectional plan.
  • the applicator comprises a tube, (1) usually of substantially circular cross section, open at one end, which end is provided with a removable cap (2).
  • the closed end of the tube comprises a rotatable member (3) provided with an externally screw threaded rod (4) which extends along the axis of the tube.
  • the rod 4 passes through and engages a correspondingly threaded hole in the centre of an extruder plate (5) which fits closely and slidably within the tube 1, initially near its closed end 3.
  • Longitudinal ribs (6, 6') project radially from the inside of the tube 1, and engage corresponding slots in the circumference of the extruder plate 5.
  • the open applicator may be filled with the molten composition which is allowed to set to a VI gel, and capped.
  • the cap 2 is removed and the rotatable base member 3 is rotated, causing the rod 4 to rotate and urge the extruder disc up the tube until the gel is exposed. Rotation of the extruder disc is prevented by the ribs 6, 6'.
  • the exposed gel is rubbed on the surface to be treated. The gel is thixotropic and is sufficiently mobile under the shear caused by gentle rubbing to distribute over the surface to be treated and also to maintain a continuous gel surface at the open end of the applicator, even as the gel "stick" is progressively extruded around the rod 4.
  • the ribs 6,6' can be extended towards the axis, thereby effectively dividing the applicator into two or (by increasing the number of ribs) more compartments.
  • the compartments may be individually filled e.g. with different formulations with relatively little intermingling. They could thus accommodate separate, mutually incompatible components which would be stabilised by the very low permeability of the gel.
  • composition may be wrapped or encapsulated in, or coated with, a water soluble polymer such as polyvinyl alcohol or polyvinyl pyrrolidone, for example, the polymer may be used to provide unit dose sachets, which can be added direct to the washing machine.
  • a water soluble polymer such as polyvinyl alcohol or polyvinyl pyrrolidone
  • the polymer may be used to provide unit dose sachets, which can be added direct to the washing machine.
  • the composition may be in particulate form.
  • Particulate compositions may be prepared, for example by prilling the molten composition to form granular prills, or by casting it to a VI phase and flaking the VI phase , e.g. on a drum flaker, to form flakes, or by extruding the plastic composition at a temperature between its softening point and the temperature at which it is fully liquid to form e.g. needles.
  • the VI detergent may be cast or plodded into the form of bars of tablets.
  • Such tablets may be separate e.g. separately wrapped or enclosed in separate compartments of a blister pack, or may be cast as a single block or bar subdivided into separable tablets e.g. by grooves or constrictions of the bar.
  • the VI phase may additionally have, dispersed therein, solid particles of any detergent ingredients which can be mixed with the VI phase at sufficiently elevated temperatures without dissolving therein.
  • Such particles may include builders such as sodium tripolyphosphate, tetrapotassium pyrophosphate, sodium orthophosphate, zeolite, sodium citrate, sodium or potassium carbonate, sodium silicate, sodium nitrilotriacetate, sodium ethylene diamine tetracetate, phosphonates such as acetodiphosphonates, aminotris (methylenephosphonates), ethylenediamine tetrakis (methylenephosphonates), diethylenetriamine pentakis (methylelephosphonates), triethylene tetramine hexakis (methylene phosphonate) and higher members of the same series of (n)ethylene (n+1) amine (n+2) (methylenephosphonate) salts or glycine bis (methylene phosphonate), inorganic fabric conditioners such as bentonite, abrasive
  • the dispersed phase could optionally include an inert filler such as sodium sulphate. However we do not prefer to include fillers in the composition of this invention. It is an advantage of the invention that the use of fillers can be avoided.
  • the dispersed phase may constitute up to 60% preferably 1 to 30% e.g. 5 to 20% especially 8 to 15% by volume based on total volume of the dispersion.
  • the particulate compositions of the present invention may be dry blended with other powdery or granular compositions. Such blends constitute a less preferred aspect of the invention.
  • an advantage of the invention is the ability to incorporate water and/or heat sensitive ingredients without the inconvenience and inconsistency of dry blending.
  • compositions of the invention preferably contain soil suspending agents such as sodium carboxymethyl cellulose typically in proportions of from 0.01 to 3% by weight based on the weight of the composition, especially 0.1 to 2%, e.g. 0.2 to 1%.
  • soil suspending agents such as sodium carboxymethyl cellulose typically in proportions of from 0.01 to 3% by weight based on the weight of the composition, especially 0.1 to 2%, e.g. 0.2 to 1%.
  • the composition preferably contain optical brighteners, which are fluorescent dyes, in proportions of from 0101 to 3% by weight based on the weight of the composition, preferably 0.1 to 2%, e.g. 0.2 to 1%.
  • compositions typically contain fragrances, dyes, pigments and/or preservatives in a total proportion of from 0.1 to 5% by weight, e.g. 0.5 to 3% by weight based on the total weight of the composition.
  • compositions of the invention may also comprise conventional amounts of bleach activators such as tetracetoethylenediamine, where an oxidising bleach has been included, foam control agents such as silicone antifoams and/or mineral oils where the compositions are intended for use in front loading washing machines, or foam boosters where the products are intended for use in top loading washing machine or for hand washing.
  • bleach activators such as tetracetoethylenediamine
  • foam control agents such as silicone antifoams and/or mineral oils where the compositions are intended for use in front loading washing machines, or foam boosters where the products are intended for use in top loading washing machine or for hand washing.
  • compositions of the invention 1 2 3 4 5 6 C12-C18 alcohol ethoxylate (3EO) 5.6 - 8.0 4.4 8.75 7.2 C12-C18 alcohol ethoxylate (8EO) - 13.3 - 3.5 - - C12-C14 alcohol ethoxylate (12EO) - - - 14.0 - - C16-C18 alcohol ethoxylate (20EO) - 6.7 10.0 - 10.0 25.3 C16-C18 alcohol ethoxylate (50EO) 19.4 20.0 12.0 13.1 11.25 - Perfume/dyes etc.
  • the enzymatic solution used in examples 1 to 12 comprises a mixture of protease, amylase and lipase provided by a 1:1:2 mixture by weight of the proprietary solutions 'SAVINASE 16.0 LDX', 'TERMAMYL 300.0 LDX' and 'LIPOLASE 100L' respectively.
  • 'SAVINASE', 'TERMAMYL' and 'LIPOLASE' are registered trademarks of NOVO NORDISK A/S.
  • compositions formed clear VI gels which melted over a range of approximately +2 o C of the melting points given above.
  • the gels were heated above their melting points and poured into screw applicators, as described with reference to the drawings, and cooled.
  • compositions of the examples 1 to 12 were developed by constructing a phase diagram and selecting from within the I1 phase area, compositions having the desired HLB value and "melting point".
  • FIG. 3 is a generalised phase diagram (not to scale) indicating the relationship of the M1,I1 and L1 phases for typical compositions of the invention comprising water and two surfactants: a higher HLB value non-ionic surfactant, A, and a lower HLB surfactant, B.
  • a number of compositions were found to exhibit I1 phases which extend into the useful laundry HLB range (e.g. 11 to 15).
  • compositions suitable for use as a pre-spotting gel an HLB value of 11 to 15 and a melting point of approximately 40 o C are preferred. Selecting compositions from wide areas of I1 phase with similar 'melting point' temperatures on the phase diagrams provides formulations which are able to withstand variations in manufacture.
  • the gels were easily extruded and were compared with a variety of commercially available pre-spotting preparations on artificially stained test cloths.
  • the composition of the invention was more easily applied than the commercial preparation, and was more economical in terms of the amount applied.
  • the compositions gave substantially improved stain removal after washing under defined conditions in a standardised washing machine at 60 o C, (200ppm CaCO3 water hardness) when compared to stain removal achieved on test clothes which did not receive treatment with the pre-spotting composition.
  • the degree of whiteness of the fabric after treatment is determined by reflectance measurement.
  • Cloths 101, 104, 112, 114, 116 and 117 are supplied by the 'Swiss Federal Laboratories for materials testing and research - Switzerland' and cloths 10C, 20C, 10D, 20D, 30D are supplied by Washereiforfehung Krefeld (WFK) - Germany. All of the aforementioned cloths used for evaluation of the pre-spotter are recognised as standard test cloths in the detergent industry. Tea, coffee and blackcurrant juice test cloths were prepared in-house, by manual staining of cloth. The test fabrics are measured for reflectance values before and after laundering. Table 3 Evaluation of a composition according to the invention as a pre-spotting formulation for laundry. Prespotted and washed Cloths Washed only Cloths CLOTH NO.
  • All cloths are cotton except for 104 and 20C (65/35 polyester cotton), 20D (polycotton) and 30D (polyester).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dermatology (AREA)
  • Detergent Compositions (AREA)
EP93118271A 1992-11-13 1993-11-11 Neue Reinigungszusammensetzungen. Withdrawn EP0598335A3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB929223898A GB9223898D0 (en) 1992-11-13 1992-11-13 Novel cleaning compositions
GB9223898 1992-11-13
GB9225677 1992-12-09
GB929225677A GB9225677D0 (en) 1992-12-09 1992-12-09 Novel cleaning compositions

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EP0598335A2 true EP0598335A2 (de) 1994-05-25
EP0598335A3 EP0598335A3 (de) 1996-01-10

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JP (1) JPH06207195A (de)
KR (1) KR940011625A (de)
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Cited By (10)

* Cited by examiner, † Cited by third party
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EP0916722A2 (de) * 1997-11-13 1999-05-19 UHU GmbH Reinigungszusammensetzung auf der Basis einer Waschpaste
FR2813189A1 (fr) * 2000-08-31 2002-03-01 Oreal Creme cosmetique moussante pour le traitement des peaux grasses
US6555516B1 (en) 1999-11-25 2003-04-29 Unilever Home & Personal Care Usa, Division Of Conopco, Laundry product
WO2003085190A2 (en) * 2002-04-09 2003-10-16 Huntsman International Llc Soil and stain removal
US6733765B2 (en) 2000-06-23 2004-05-11 L'oreal Foaming cosmetic cream
EP2336290A1 (de) * 2009-12-15 2011-06-22 Cognis IP Management GmbH Gelförmige Zubereitungen
WO2012005868A1 (en) * 2010-06-21 2012-01-12 Basf Se Surfactant component and a composition including the same
US9719000B2 (en) 2013-03-14 2017-08-01 Basf Se Hot melt adhesive and method of forming the same
EP3246476A1 (de) 2016-05-16 2017-11-22 Bolton Manitoba S.p.A. Desinfektionsvorrichtung, insbesondere für sanitärarmaturen und dergleichen
IT201900008358A1 (it) 2019-06-07 2020-12-07 Bolton Manitoba S P A Metodo di applicazione di una composizione gel su una superficie di un dispositivo e relativo dispositivo rivestito

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JP2002201499A (ja) * 2000-12-28 2002-07-19 Yosuke Naito 固形クレンザ
AU2005247397A1 (en) * 2004-05-18 2005-12-08 Cockerell Dermatology Development, Ltd. Syndet bars having ultraviolet radiation protection
KR101357225B1 (ko) * 2013-08-21 2014-02-11 (주)파라스 일회용 수용성 스틱세제
US20150094251A1 (en) * 2013-09-27 2015-04-02 S. C. Johnson & Son, Inc. Dilutable gel cleaning concentrates
CN104388204B (zh) * 2014-10-31 2017-11-28 魏怀良 含有氧化性漂白剂和酶的浓缩膏状/半固体状洗涤剂组合物及其制备方法
US11046913B2 (en) 2016-03-04 2021-06-29 S. C. Johnson & Son, Inc. Neutral floor cleaner compositions
JP2020506035A (ja) * 2016-10-18 2020-02-27 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ リンギングゲル組成物
CN111100763A (zh) * 2019-12-31 2020-05-05 东莞市华畅机电科技有限公司 一种雾化清洗剂及其制备方法

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US4026818A (en) * 1975-12-19 1977-05-31 Van Dyk & Company, Incorporated Transparent ringing gels
EP0043327A1 (de) * 1980-07-01 1982-01-06 L'oreal Verfahren zur Herstellung stabiler Dispersionen in einer wässrigen Phase von mindestens einer flüssigen, nicht mit Wasser mischbaren Phase und die entsprechenden Dispersionen
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EP0077674A2 (de) * 1981-10-19 1983-04-27 Unilever Plc Viskose Zusammensetzungen, die Amidobetaine und Salze enthalten
EP0081908A1 (de) * 1981-11-13 1983-06-22 Unilever Plc Schwachschäumende flüssige Detergenszusammensetzungen
EP0100125A2 (de) * 1982-07-27 1984-02-08 THE PROCTER & GAMBLE COMPANY Flüssige Reinigungsmittelzusammensetzungen, eine Koazervatmischung aus Alkylcellulose enthaltend und Carboxymethylcellulose und Verfahren zu deren Herstellung
EP0153857A2 (de) * 1984-02-29 1985-09-04 Unilever N.V. Reinigungsmittelzusammensetzungen
EP0288858A1 (de) * 1987-04-25 1988-11-02 Henkel Kommanditgesellschaft auf Aktien Waschevorbehandlungsmittel für Öl- und Fettanschmutzungen
EP0373851A2 (de) * 1988-12-12 1990-06-20 Unilever Plc Betain und Äthersulfat enthaltendes Reinigungsmittel
EP0414549A2 (de) * 1989-08-24 1991-02-27 Albright & Wilson Limited Flüssige Reinigungsmittelzusammensetzungen und Suspendiermedien
EP0418986A2 (de) * 1989-09-22 1991-03-27 Colgate-Palmolive Company Verfahren zum Absorbieren lipophilen Schmutzes von einer Ober- fläche in eine Flüssigkristall-Detergenszusammensetzung
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EP0530708A2 (de) * 1991-08-30 1993-03-10 ALBRIGHT & WILSON UK LIMITED Flüssiges Wäschewaschmittel

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0916722A3 (de) * 1997-11-13 1999-09-15 UHU GmbH Reinigungszusammensetzung auf der Basis einer Waschpaste
EP0916722A2 (de) * 1997-11-13 1999-05-19 UHU GmbH Reinigungszusammensetzung auf der Basis einer Waschpaste
US6555516B1 (en) 1999-11-25 2003-04-29 Unilever Home & Personal Care Usa, Division Of Conopco, Laundry product
US6733765B2 (en) 2000-06-23 2004-05-11 L'oreal Foaming cosmetic cream
FR2813189A1 (fr) * 2000-08-31 2002-03-01 Oreal Creme cosmetique moussante pour le traitement des peaux grasses
EP1184031A2 (de) * 2000-08-31 2002-03-06 L'oreal Schäumende kosmetische Creme zur Behandlung von fettiger Haut
EP1184031A3 (de) * 2000-08-31 2002-12-11 L'oreal Schäumende kosmetische Creme zur Behandlung von fettiger Haut
WO2003085190A3 (en) * 2002-04-09 2004-06-24 Huntsman Int Llc Soil and stain removal
WO2003085190A2 (en) * 2002-04-09 2003-10-16 Huntsman International Llc Soil and stain removal
EP2336290A1 (de) * 2009-12-15 2011-06-22 Cognis IP Management GmbH Gelförmige Zubereitungen
WO2011082751A1 (de) * 2009-12-15 2011-07-14 Cognis Ip Management Gmbh Gelförmige zubereitungen
WO2012005868A1 (en) * 2010-06-21 2012-01-12 Basf Se Surfactant component and a composition including the same
US20130096047A1 (en) * 2010-06-21 2013-04-18 Basf Se Surfactant Component And A Composition Including The Same
US8916512B2 (en) 2010-06-21 2014-12-23 Basf Se Surfactant component and a composition including the same
US9719000B2 (en) 2013-03-14 2017-08-01 Basf Se Hot melt adhesive and method of forming the same
EP3246476A1 (de) 2016-05-16 2017-11-22 Bolton Manitoba S.p.A. Desinfektionsvorrichtung, insbesondere für sanitärarmaturen und dergleichen
IT201900008358A1 (it) 2019-06-07 2020-12-07 Bolton Manitoba S P A Metodo di applicazione di una composizione gel su una superficie di un dispositivo e relativo dispositivo rivestito
EP3747980A1 (de) 2019-06-07 2020-12-09 Bolton Manitoba SpA Methode zur bewerbung eine gelzusammensetzung auf einer oberfläche eines geräts und deren beschichtetes gerät

Also Published As

Publication number Publication date
AU5067593A (en) 1994-05-26
JPH06207195A (ja) 1994-07-26
KR940011625A (ko) 1994-06-21
EP0598335A3 (de) 1996-01-10
CN1089649A (zh) 1994-07-20

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