WO2002053109A2 - Procede dde fabrication de compositions solides - Google Patents

Procede dde fabrication de compositions solides Download PDF

Info

Publication number
WO2002053109A2
WO2002053109A2 PCT/EP2001/014768 EP0114768W WO02053109A2 WO 2002053109 A2 WO2002053109 A2 WO 2002053109A2 EP 0114768 W EP0114768 W EP 0114768W WO 02053109 A2 WO02053109 A2 WO 02053109A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition
pipe
process according
solidifying agent
temperature
Prior art date
Application number
PCT/EP2001/014768
Other languages
English (en)
Other versions
WO2002053109A8 (fr
WO2002053109A3 (fr
Inventor
Elaine Susanne Bibby
Adam Jan Kowalski
Donald Peter Gregory
Elfriede Maria Langeveld
Reginald Manley
Jean Leslie Scott
Ian Ward
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0031831A external-priority patent/GB0031831D0/en
Priority claimed from GB0115361A external-priority patent/GB0115361D0/en
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Priority to AU2002240835A priority Critical patent/AU2002240835A1/en
Priority to MXPA03005933A priority patent/MXPA03005933A/es
Priority to UA2003077119A priority patent/UA76136C2/uk
Publication of WO2002053109A2 publication Critical patent/WO2002053109A2/fr
Publication of WO2002053109A3 publication Critical patent/WO2002053109A3/fr
Publication of WO2002053109A8 publication Critical patent/WO2002053109A8/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D40/00—Casings or accessories specially adapted for storing or handling solid or pasty toiletry or cosmetic substances, e.g. shaving soaps or lipsticks
    • A45D40/16—Refill sticks; Moulding devices for producing sticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/28—Zirconium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants

Definitions

  • the present invention relates to a process for the manufacture of solid formulations, namely cosmetic compositions in free-standing form.
  • Cosmetic compositions in solid form are commonly packaged within a suitable dispensing container for application by the user. Whilst this is usually extremely convenient, the cost of the packaging can represent a significant fraction of the overall cost of the packaged product. It would be inherently desirable to be able to make free-standing solid cosmetic compositions that did not need to be incorporated within its own individual dispensing container to make such materials available to potential consumers, such as those for whom existing products were too expensive.
  • composition commonly in the shape of a stick or tablet, is capable of retaining its shape at standard temperature and pressure without the support of a container.
  • Free-standing cosmetic sticks could, at least in theory, be made by casting a fluid composition into a mould, cooling the resultant product, and separating the solidified composition from the mould.
  • This is, however, a relatively complicated, costly and inconvenient process to adopt, requiring a filling station for the moulds, cooling tunnel for cooling the composition within the moulds or similar cooling apparatus and a station for demoulding the sticks, all of which together often occupy a lot of space.
  • the cooling operation of moulded compositions can be relatively energy inefficient, especially in hot climates, and there is a recognisable risk of spoiling the appearance of the stick when the mould is removed.
  • a further type of materials processing equipment which is well known in some patent literature as being suitable for processing cosmetic formulations, comprises twin screw extruders, as disclosed for example in EP-A-0 968 703 or US-A- ⁇ 045 814.
  • Such screw extruders can incorporate heating or cooling elements along the length of the extruder.
  • extruders are relatively expensive to purchase, and require careful adjustment to adapt them to process particular compositions.
  • extruders by performing simultaneous mixing and transporting operations during the cooling operation can alter the physical characteristics of the resultant solid stick compared with products obtained conventionally in which the composition solidifies inwardly from its container wall.
  • a process for preparing a solid free-standing cosmetic composition comprising the steps of i) producing a cosmetic composition containing a liquid carrier and a solidifying agent for the liquid carrier at an elevated temperature at which the composition is liquid and pumpable, ii) pumping the composition into an inlet of a pipe which has an outlet distant from the inlet and cooling means to cool said composition within the pipe, iii) permitting the composition to flow through the pipe towards the outlet and iv) retaining said composition within the pipe until it has solidified, thereby enabling the composition to be discharged as a solid mass through the pipe outlet without forced extrusion.
  • the process of the present invention does not require or employ a forced extruder, such as described in EP-A-0 968 703, US-A-6 045 814 or WO-A-97/17055.
  • a forced extruder the composition is both mixed and transported through the extruder by mixing and transporting elements disposed within the extruder, such by a screw or twin screw. The screw imparts a radial, and helical flow to the composition.
  • the composition is pumped into the inlet of the cooled pipe and the mere pressure of the composition at the inlet causes the formulation to flow through the pipe, and after solidification of the liquid carrier, a solid stick emerges through the pipe outlet.
  • the pipe provides a continuous and essentially unobstructed passage from inlet to outlet, free from intruding mixing or propulsive elements, thereby promoting axial flow within the pipe for fluid material, except within a short length adjacent to the inlet, for example of up to 10 times the mean diameter of the pipe at its inlet in which non-laminar flow can occur.
  • the composition solidifies initially as an annular layer on the inner face of the pipe, which gradually thickens until no liquid phase remains. Accordingly, the invention process tends to produce a product having similar characteristics to those produced from the same composition by filling a dispensing container and cooling the resultant product. The solid phase tends to adopt plug flow.
  • the advantageous result can be attained by suitable arrangement of inlet and outlet temperatures of the composition, in conjunction with cooling of the pipe.
  • the present invention provides a process in which a pumpable composition is cooled and solidified within a pipe without being subjected to mixing during its passage through the pipe, and particularly the cooled pipe lacks internal mixing elements . Not necessarily the whole length of the pipe need be cooled. Indeed, at or adjacent to the pipe outlet, it may be desirable to cease cooling or even apply mild heat in order to melt an outermost surface layer of the stick, so as to assist emergence of the stick.
  • the cooling means for the pipe comprises a cooling jacket surrounding the pipe and through which a cooling liquid, such as water or a glycol (eg ethylene glycol) or a mixture thereof, can be pumped.
  • the cooling liquid commonly has a temperature on entry into the cooling jacket of below ambient, and particularly from 20 to -20°C.
  • a cooling jacket has the advantage of being comparatively easy to insulate, so as to render the process more energy efficient.
  • a single cooling jacket may be employed, commonly co-current to the direction of flow of the composition through the pipe to encourage rapid cooling initially of the composition or counter-current so that the coolest coolant encounters composition having the widest solidified wall.
  • two or more cooling jackets can be employed serially along the pipe. This enables closer control to be effected of the temperature differential between coolant and composition at different points along the pipe.
  • the cooling jackets can include baffles to control the flow of coolant through them.
  • cooling may also be provided by spraying the pipe with jets of cool fluid, e.g. a gas or liquid at low temperature, such as using the above-identified coolants in the range of temperatures identified above in respect of cooling fluid in the cooling jacket. Cooling of a sprayed pipe can be enhanced by blowing cool, and possibly dehumidified, air over the pipe, thereby enhancing evaporation of the fluid.
  • cool fluid e.g. a gas or liquid at low temperature
  • the pipe itself in practice will have an internal cross section, which corresponds to the desired cross section of the final stick product, and especially in the region of the pipe where a significant proportion of the composition has solidified.
  • that cross sectional shape may be circular or oval, or less commonly square or rectangular, or even a more complex shape such as a star shape, should that be desired.
  • the cooled pipe maintains the same cross section throughout its length.
  • the pipe is, desirable, made from metal so as to encourage heat transfer through the pipe wall and to resist bending, for example when inclined to the horizontal.
  • One very suitable material comprises stainless steel which is not only strong and a good heat conductor, but also is corrosion resistant.
  • the interior of the pipe may be coated with a thin lubricating surface layer, such as with PTFE, to reduce any tendency of the cosmetic composition to stick to the pipe after solidification.
  • the pipe itself, desirably, is straight along substantially its whole length, and especially where the composition has substantially solidified, although it may have a curved section, especially in the vicinity of the inlet and/or outlet, for example to incline the pipe or render the emergent stick horizontal for further processing. Any curving is preferably gentle.
  • the pipe may be inclined upwardly at an angle to the horizontal to assist the composition to be retained within the pipe under start-up conditions, and counter the risk of liquid composition flowing out of its open outlet. After start-up, a plug of solidified composition blocks the outlet.
  • the bottom of the pipe interior at its outlet is preferably higher than the top of the pipe interior at its inlet, ie the outlet is higher than a vertical diameter above the inlet.
  • the outlet is no higher than two, and in some particularly suitable embodiments no higher than one and a half, vertical pipe diameters above the inlet.
  • Such an inclined orientation of the pipe enables start up to be carried out simply even with compositions having a relatively low viscosity within the broadest range described hereinafter.
  • the resultant angle of inclination depends on the length of the pipe as well as its diameter, and in practice is usually less than 10 degrees and often from 1 to 5 degrees .
  • the flow of composition into the pipe may be controlled during start-up, for example in conjunction with an inclined pipe, to assist in the formation of a plug intermediate between the inlet and outlet of the pipe to assist the generation of a suitable residence time for the composition in the pipe to promote solidification.
  • a plug may be introduced into the pipe for the same purpose, possibly through the outlet.
  • Such a plug may comprise a preformed sample of the solidified composition or some other compatible material that frictionally engages the inner surface of the pipe and is movable by liquid composition fed into the pipe, thereby encouraging the composition to have solidified before emergence through the pipe outlet .
  • the composition which is fed into the pipe has a viscosity such that it can be pumped. This is conveniently achieved by controlling its temperature.
  • a suitable inlet temperature will vary, depending on the constituents present in the composition. Commonly, it has a temperature at the inlet selected in the range of from 30 to 200°C and in many instances at up to 120°C.
  • the inlet temperature of the composition is often conveniently in the range of 35 to 65°C.
  • the temperature of the composition at the pipe inlet will often take into account the normal solidifying temperature of that composition as well the manner in which the composition has been prepared. Thus, the inlet temperature is in many instances chosen within the range of 15°C on either side of the normal solidification temperature.
  • a suitable outlet temperature depends also on the constituents present in the composition.
  • the temperature of the composition in the outlet is often controlled to be at least 5°C below its normal solidification temperature (which herein means the temperature at which it would solidify unless it is subjected to forced shear mixing through that temperature or to super-cooling) , and conveniently from 5 to 20°C below the normal solidification temperature.
  • the temperature of the composition at the outlet is selected in the range of from -40 to 50°C, preferably from -25 to 40°C and especially from 0 to 35°C.
  • the present invention is convenient for preparing sticks from compositions which have a normal solidification temperature of from 30 to 100°C, desirably from 40 to 60°C, and particularly from 45 to 55°C.
  • the composition at its inlet must be pumpable, for example being capable of being pumped from a mixing vessel or intermediate storage vessel.
  • Suitable pumps for use in the present invention comprise piston or gear pumps, and in practice the pump is chosen in conjunction with the expected viscosity of the feed composition at its inlet temperature.
  • the composition is considered to be pumpable if it has a viscosity of up to 10 Pa.s, such as from 0.1 mPa.s to 10 Pa.s. Provided that a suitable pump is employed, even slightly more viscous fluids, but still in the region centering on 10 Pa.s may also be pumped.
  • the feed composition has a comparatively low viscosity, such as from 0.5 Pa.s up to 3 Pa.s, and in other embodiments the feed composition has a viscosity of above 3 Pa.s, such as in the region of 10 Pa.s.
  • the viscosity is measured at the chosen inlet temperature. In at least some embodiments, it can be measured conveniently at a shear rate of 21s _1 using a cone/plate rheometer, eg that available under that name from Carrimed.
  • the composition fed through the pipe inlet can be produced in a variety of different ways.
  • One relatively simple way is to form a mixture of the liquid carrier and solidifying agent and elevate that mixture to a temperature at which the overall composition is liquid and capable of being pumped.
  • the compositions employed in the present invention contain a solidifying agent which is rendered molten, and as a result forms an homogeneous mass with the carrier at the elevated temperature.
  • the solidifying agent is not usually rendered molten, but it is molecularly dispersed within the carrier fluid.
  • Some constituents, for example a particulate antiperspirant active can be mixed into the homogenous mixture of the solidifying agent and carrier liquid.
  • the formation of a mixture by heating all of both the relevant constituents, optionally in the presence of some or all of the remaining constituents, to an elevated temperature to homogenise it, has the advantage of being a one step procedure which is commonly practised within the cosmetic industry and is well understood.
  • the composition may be fed at its highest elevated temperature into the cooler pipe, but advantageously can be permitted to cool to a temperature of about 5 to 10°C above the normal solidification temperature of the composition, the cooling of antiperspirant compositins typically being achieved in part by introduction of ambient temperature antiperspirant active.
  • Such a process tends to produce a feed composition having a comparatively low viscosity within the range indicated above. It is advantageously fed into a pipe that is preferably inclined upwardly to the horizontal, as described hereinbefore.
  • An improved method of conducting step i) , the formation of pumpable feed composition, which is particularly suitable for solidifying agents that are capable of being melted or otherwise rendered fluid, comprises processing the solidifying agent separately from most of the remaining constituents of the composition and then mixing the separate components together to form the feed composition.
  • the formation of the feed composition to the pipe comprises melting or otherwise rendering fluid the solidifying agent in the presence of no more than a fraction of the carrier liquid, if any, (first component) and mixing the resultant fluid mass with the remainder of the carrier liquid (second component) .
  • said fraction of carrier fluid premixed with the solidifying agent is often less than half and particularly not more than 20%, by weight of the carrier liquid or liquids. In some instances, said fraction is zero.
  • carrier liquid herein includes all the constituents of the composition that are liquid at ambient temperature and capable of performing a carrier function, even if their primary function is nominally different, such as providing emolliency.
  • the second component may additionally contain some or all of the constituents of the composition other than the carrier liquid and the solidifying agent.
  • Such constituents can include an active such as an antiperspirant active, an emollient a benefit agent and/or a fragrance.
  • the remainder of the liquid carrier need not be heated to the melting or fluidising temperature of the solidifying agent, and often need not be heated to a temperature higher than that in the vicinity of the normal solidifying temperature of the composition, such as within the range of 40 to 60°C mentioned hereinbefore. Indeed, in some instances, the second component need not be heated at all, ie is at its ambient temperature or heated only mildly to less than 40°C.
  • the fluid mix of solidifying agent and possibly some carrier is then mixed with the remainder of the liquid carrier.
  • the relative amounts of the two components and their respective temperatures are desirably balanced so as to attain a temperature of the mixture forming the feed composition that is no higher than about 5°C above and down to about 15°C below the normal solidification temperature of the composition.
  • the feed composition is below the normal solidification temperature, such as from 2 to 12°C below.
  • the mixing of the two components is carried out in an intense manner, so that it can occur rapidly, for example using a Sonolator available from Sonic Corporation.
  • Alternative apparatus to achieve intense and rapid mixing of the two components can also be used.
  • the mixing of the two components is carried out shortly before the composition is introduced into the cooled pipe, for example the mixing of the composition terminating desirably less than 20 seconds and preferably less than 10 seconds before feed into the cooled pipe.
  • the two component process By employing a two component process to prepare the fluid composition using an intense mixer, advantageously shortly before the mixture is introduced into the cool pipe, it is possible to prepare conveniently the feed composition at an average temperature that is lower than if the fluid composition had been made by heating all the carrier and solidifying agent. This not only saves energy costs, but reduces the extent of degradation of heat-sensitive constituents compared with a conventional one stage method.
  • the two component process also has the added benefit of needing a shorter residence time for the composition within the pipe when employing cooling conditions that are otherwise the same. This benefit can be taken by employing a shorter pipe.
  • the benefit can alternatively be taken by employing less stringent cooling conditions for the same residence time, or by a combination of intermediate residence time and intermediate cooling conditions. This introduces significant additional flexibility into the solidifying process.
  • a control valve can also be included within feed lines between the composition reservoir or the or each component reservoir and the cold pipe to regulate flow to the cold pipe.
  • the solid composition eg stick
  • the pipe outlet when the solid composition, eg stick, exits through the pipe outlet, it is cut by a blade into discrete lengths.
  • These lengths of composition will normally be recognisable as sticks, but may also resemble tablets, can be wrapped, if desired, for distribution and sale, and are suitable for stand-alone use directly from the wrapping or possibly for insertion as a refill into a suitably shaped holder or product dispenser.
  • the process according to the present invention can be carried out in a continuous manner by continuously passing the composition through the pipe in steps iii) and iv) .
  • its residence time is controlled by the linear rate of flow of the composition and the length of the pipe. This manner minimises the equipment required for practical operation.
  • the process can alternatively be carried out in a semi-continuous or intermittent manner in which steps iii) and iv) are carried out alternately in a cycle in which in step iii) the composition is allowed to flow into the pipe, and when it is full, inflow is terminated and secondly in step iv) , the composition is retained within the pipe until it has solidified, whereupon in the next cycle, fresh inflow of composition in step iii) expells the composition that has solidifed in step iv) of the preceding cycle.
  • the pump and or a valve interposed between the pump and the cool pipe can be controlled by a timer or other means to regulate the length of steps iii) and iv) , so as firstly to prevent unsolidified composition emerging through the outlet in step iii) , thereby leaving a plug of solidified material in the outlet, and permitting enough time for the composition to solidify in step iv) .
  • a small buffer margin is employed, for example from 5 to 15%, shorter for step iii) and longer for step iv) .
  • Alternative means can be employed to determine when to halt the flow in step iii) , such as a flow meter and when the composition is suitably solidified in step iv) , such as a temperature sensor.
  • the intermittent process may be carried out using a single pipe, it can alternatively be carried out using a plurality of pipes, which are preferably substantially identical, possibly mounted on a support, e.g. rotating, which enables the inlet of each pipe and a feed station in fluid connection with the pump sequentially in turn to be brought into registration in order to permit the cosmetic composition to be fed into the pipe in step iii) and thereafter moved out of register when step iv) can be carried out.
  • Either the feed station or the pipe inlet is fixed, and the other is moved to bring it into and out of registration.
  • a valve at the inlet and/or outlet, where needed, can prevent premature outflow of the composition whilst still in a fluid state.
  • Identical pipes indicates herein that each pipe has a residence time to achieve solidification of the cosmetic composition that is substantially the same, though in other respects, such as cross section of the stick, the pipes may be different.
  • the number of cooled pipes is so selected that the desired residence time of composition within a nominated pipe to allow solidification is similar to, but slightly shorter than total time to fill the remaining pipes and bring the nominated pipe back into register with the feed station.
  • the pipes can all be disposed within a common cooling jacket suitable arranged to retain the cooling fluid therewithin whilst each pipe is brought into and out of register with the feed station.
  • compositions made by the process of the present invention must be free-standing. That means, they must substantially keep their shape standing alone outside any container. Of course, such compositions may nevertheless be sold in a container, e.g. of dispensing type, if desired. Most preferably, the compositions are in stick form.
  • the cosmetic compositions prepared in free-standing form by the process according to the present invention may, for example be selected from antiperspirant compositions, deodorant compositions and lipstick compositions.
  • the carrier material for the compositions according to the invention can comprise one or more of volatile carrier fluids, one or more of non-volatile emollients, and it can be structured or thickened by one or a combination of thickener and/or structurant materials if required.
  • the carrier material including, where relevant, carrier materials providing additional properties such as emolliency, can often comprise up to about 99 wt%, in many instances from 5 to 90 wt% and particularly from 10 to 70 wt% of the composition. Where the composition comprises both hydrophylic and hydrophobic phases, the weight ratio of the two phases is often in the range of 10:1 to 1:10.
  • the cosmetic composition such as an antiperspirant or deodorant composition can comprise a mixture of particulate solids or a suspension of solids in a liquid medium, which can be thickened to reduce the rate of segregation, or structured to produce a solid, a firm stick.
  • the composition can comprise a mixture of liquid constituents, including a solution of an active in a carrier, such a composition often adopting the form of an oil-in-water or water-in-oil emulsion, the continuous phase of which is gelled, or an emulsion with a sufficiently high internal phase volume to produce a solid is employed.
  • the carrier material which may be a fluid or a mixture of fluids, is often selected according to the physical form of the cosmetic composition, e.g. volatile low viscosity silicones, low molecular weight hydrocarbons, alcohols and water, and can be selected by those skilled in the art to provide appropriate physical and sensory properties for the product.
  • volatile low viscosity silicones e.g., low molecular weight hydrocarbons, alcohols and water
  • certain fluid alcohols such as in particular ethanol can constitute both a carrier and a deodorant active simultaneously, though advantageously formulations containing such a material also contain an additional deodorant and/or antiperspirant active.
  • Volatile silicones are usually selected from cyclic polysiloxanes containing from 3 to 8 dialkylsilicone groups, especially dimethylsilicone groups and particularly 4 or 5 dimethylsilicone groups.
  • volatile silicones can comprise linear polysiloxanes, preferably containing 4 or 5 alkylsiloxane groups, including terminal groups.
  • suitable volatile silicones include polydimethyl cyclosiloxanes, having a viscosity of less than 10mm 2 s _1 , examples of which are DOW CORNING fluids 344 and 244 (tetramer) and DOW CORNING Fluids 245 and 345 (penta er) .
  • Suitable silicones include hexamethyldisiloxane having a viscosity of not more than 0.65mm 2 s _1 , for example DOW CORNING 200 Fluid, which has a viscosity of 0.65mm 2 s _1 as determined in accordance with the method provided in the data sheets provided by the manufacturer on these compounds. Cyclomethicones are preferred.
  • Low molecular weight liquid hydrocarbons can comprise paraffin oils .
  • Suitable alcohols can comprise monohydric alcohols, such as C3 to CIO aliphatic alcohols, dihydric alcohols such as glycol or propylene glycol or polyhydric alcohols such as glycerol or sorbitol .
  • Carrier materials can provide additional desirable properties, such as polyhydric alcohols for example glycerol can act as a moisturising agent and volatile cyclomethicones can act as emollients .
  • the non-volatile emollient may consist of a single emollient compound or a mixture of emollients.
  • emollients often have a solubility parameter of below 10 and many of from 5.5 to 9. They can typically include saturated fatty acids and fatty alcohol esters, ethers containing aliphatic and a polyalkylene group, hydrocarbons, water insoluble ethers, mineral oils and polyorganosiloxanes, and mixtures thereof.
  • Non-volatile silicones are often polyalkylsiloxanes, polalkylarylsiloxanes or polyethersiloxanes having a viscosity of above 10 mPa.s, such as up to about 5xl0 6 mPa . s at 25°C, including polymethylphenylsiloxanes or dimethylpolyoxyalkylene ether copolymers.
  • Non-volatile silicones include polydimethylsiloxane having a viscosity in excess of 5mm 2 s -1 , for example, from 50 to 1000mm 2 s "1 , such as DOW CORNING 200 Fluids (standard viscosities 50-1000mm 2 s _1 ) .
  • Mineral oils including particularly branched hydrocarbon oils can be incorporated in the compositions to lessen visible deposits.
  • Emollient aliphatic esters often containing from about 12 to 25 carbons, and preferably one substituent containing a chain of at least 12 carbons .
  • Examples include cetyl pal itate, butyl myristate, isopropyl myristate, glyceryl stearate and propylene glycol monolaurate.
  • the composition cam comprise a liquid aliphatic ether which can provide emolliency, such as ethers derived from polyalkyene glycols and a low weight (eg up to C6) alcohol, such as polypropylene glycol (10-15) butyl ether, of which nominally PPG-14-butyl ether is available under the trade mark Fluid AP or Ethylflo.
  • the total amount of emollient materials within the composition is often within the range of from 1 to 70 wt% .
  • the solidifying agent such as gellant, thickening or structurant agent, which is normally required, is selected according to the product form of the cosmetic composition.
  • the thickening or structuring agent can be organic (monomeric or polymeric) or inorganic and is usually chosen depending on the physical nature of the liquid phase to be thickened or structured, such as whether it is hydrophobic or hydrophylic.
  • the amount is normally selected in order to attain the desired resistance to penetration of a solid product.
  • the thickener or structurant can be any of a number of materials, including, for example, waxy structurants for a formulation containing a water-immiscible phase including hydrogenated vegetable oil, hydrogenated castor oil, fatty acids, such as 12-hydroxystearic acid (12-HSA), or ester or amide derivatives of such acids, beeswax, paraffin wax, microcrystalline waxes, ozekerkte, spemeceta, candellila, and Montan wax, silicone wax, and fatty alcohols, such as stearyl alcohol.
  • the structurant conveniently is selected to structure the continuous phase, often the hydrophobic phase.
  • the structurant can also be a fibre-forming gellant, of which 12-HSA is an example.
  • Other examples include N-acyl amino acid amides and esters, including particularly GP-1 (N-Lauroyl-L-glutamic acid di-n-butylamide) , lanosterol, combinations of a sterol and a sterol ester, such as especially ⁇ -sitosterol and a polyesterified cellobiose, especially with a C8 to CIO aliphatic acid, threitol estersor and selected secondary amides of di or tri basic carboxylic acids, (eg 2-dodecyl-N,N' -dibutylsuccinimide) by themselves or in combination. Desirable culminations of waxes include stearyl alcohol with hydrogenated oils such as castor wax.
  • Polymeric materials for thickening include polymers such as polyamides, hydroxypropylcellulose, and natural or synthetic gums, such as polyglycerides including agar, agarose, pectin, or guars or mixtures or combinations thereof.
  • One class of materials worthy of attention for thickening a water-immiscible phase comprises derivatives of hydrolysed starch or other polysaccharides, including in particular esterified dextrins, such as dextrin palmitate.
  • a further class of polymers that is particularly directed to structuring an oil phase containing a silicone oil comprises polysiloxane elastomers.
  • Suspending agents such as silicas or clays such as bentonite, montmorillonite or hectorite, including those available under the trademark Bentone can also be employed to thicken liquid compositions according to the invention, though to produce a stick, a gellant or other structurant is present also.
  • a water-miscible phase in the composition typically based on a monohydric or dihydric alcohol (eg dipropylene glycol) or mixture with another hydric species, can be gelled with non-polymeric organic gellants, including selected dibenzylidene alditols (eg dibenzylidene sorbitol) .
  • the amount of solidifying agent such as structurant or thickening agent that can be employed will depend upon the viscosity of a fluid formulation or extend of hardness of a solid formulation that the producer wishes to attain.
  • the amount to be employed will in practice also vary depending on the chemical nature of the solidifying agent. In many instances, the amount of solidifying agent will be selected in the range of from 0.1 to 25 wt%, and particularly from 1 to 15 or 20 wt%, and in many instances is at least 5 wt% .
  • Antiperspirant or deodorant compositions are preferred compositions which may be manufactured by a process according to the invention and typically comprise an active and a carrier material, as well as a solidifying agent, sometimes called a gellant, a structurant or thickening or structuring agent .
  • An antiperspirant composition comprises an antiperspirant active.
  • the proportion of antiperspirant active present in the composition typically may be from 1-35% by weight of the composition, preferably at least 5% by weight and more preferably 15-30% by weight of the composition.
  • antiperspirant actives commonly antiperspirant astringents
  • suitable antiperspirant actives include aluminium salts, zirconium salts, aluminium and/or zirconium complexes, for example aluminium halides, aluminium hydroxy halides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
  • Specific examples include activated aluminium chlorohydrate, aluminium chlorohydrate, aluminium pentachlorohydrate and aluminium zirconium chlorohydrate.
  • Useful zirconium salts include zirconium hydroxy-chloride and zirconium oxychloride.
  • Other generally used actives will be known to those skilled in the art.
  • Preferred actives include ZAG (Zirconium Aluminium Glycine) , AAZG (Activated Aluminium Zirconium Glycine) , and AACH (Activated Aluminium Chorohydrate) .
  • the antiperspirant active can be present in particulate form whereupon it is normally suspended in a suitable carrier fluid, which usually is water-immiscible, and which can be structured or thickened.
  • the active can be dissolved in a polar solution, such as for example in aqueous solution or in a polar low weight polyhydric alcohol such as propylene glycol, advantageously 30 to 60% by weight solution.
  • a preferred antiperspirant stick composition suitable for topical application to human skin comprises:
  • an effective amount of an antiperspirant astringent ii. a volatile silicone; iii. a structurant ; and optionally iv. a cross-linked or lightly cross-linked emulsifying or non-emulsifying siloxane elastomer.
  • the cross-linked or partially cross-linked emulsifying or non-emulsifying siloxane elastomer comprises from 0.1 to 20% of the composition, preferably from 0.1 to 10% and more preferably from 0.1 to 5% of the composition according to the invention.
  • the elastomer may be supplied in the form of a gel, the characteristics of the gel being dependant to some extent on the degree of crosslinking and the nature of elstomer substituents .
  • the resultant gels are not weakened by normal shearing (e.g at 2000rpm) , heat or rubbing on the skin and contain between 0.1 and 50% of crosslinked silicone polymeric network i.e. elastomer.
  • the elastomer gel contains a compatible fluid, commonly a cyclomethicone, dimethicone or hydrocarbon.
  • Illustrative examples of gels are materials with the CTFA name of cyclomethicone dimethicone/vinyl dimethicone crosspolymer containing about 0.1 to 50%, preferably 1 to 20% and more preferably 1% to 8% of the dimethicone/vinyl dimethicone crosspolymer (elastomer) and known as KSG-15 ex Shin-Etsu.
  • elastomer dimethicone/vinyl dimethicone crosspolymer
  • Other such suitable crosslinked siloxane elastomers and gels are available from Witco Corporation, Dow Corning or General Electric .
  • a deodorant composition that can be made by a process according to the present invention normally comprises 0.01 to 90% of a deodorant active.
  • the deodorant active can be any deodorant active known in the art such as alcohols, in particular aliphatic monohydric alcohols such as ethanol or propanol, in a gel or emulsion, or antimicrobial actives such as polyhexamethylene biguanides eg those available under the trade name CosmocilTM or chlorinated aromatics, eg triclosan available under the trade name IrgasanTM, non- icrobiocidal deodorant actives such as triethylcitrate, bactericides and bacteriostatis .
  • Yet other deodorant actives can include zinc salts such as zinc ricinoleate.
  • composition formed by the process of the invention can optionally comprise other ingredients, in addition to those already identified, depending on the nature and form of the finished product.
  • compositions formed by processes according to the invention can also be included in the compositions formed by processes according to the invention.
  • surfactants/wash-off agents include, for example, surfactants/wash-off agents, fillers, fragrances, preservatives and colouring agents or pigments.
  • Such ingredients and their amounts of use are usually selected according to the physical and chemical form of the cosmetic composition and are within the discretion of the producer of the composition.
  • Surfactants can comprise optionally up to 15%, more commonly up to 5% by weight of the total product, and are particularly useful in formulating emulsion antiperspirant or deodorant compositions and/or to improve wash-off characteristics of the formulation, and/or to improve perfume solubility. It is preferred that the composition contains less than about 8% by weight of surfactants. Non- ionic surfactants are particularly preferred. It is often convenient to select a mixture of surfactants, such as one having a comparatively high HLB value, eg 8 to 18, and one having a comparatively low HLB value, eg 2 to 8, which can be introduced in suitable relative proportions to attain an average HLB value of about 6 to 12.
  • nonionic surfactants are selected from nonionic esters, ethers or amine oxides having an appropriate HLB value.
  • Many preferred ionic surfactants comprise a polyoxyalkylene moiety, especially a polyoxyethylene moiety eg 2 to 80, especially 5 to 60 oxyethylene units, or possibly with a polyoxypropylene content, to provide hydrophilicity.
  • Other moieties providing hydrophilicity include polyhydric alcohols such as sorbitol or glycerol.
  • the hydrophobic moiety is commonly derived from aliphatic alcohols or acids or amines containing about 8 to 50 carbons and particularly 10 to 30 carbons .
  • nonionic surfactants examples include ceteareth-10 to -25, ceteth-10-25, steareth-10-25, and PEG- 15-25 stearate or PEG-8 distearate.
  • suitable examples include C10-C20 fatty acid mono, di or tri-glycerides .
  • C18-C22 fatty alcohol ethers of polyethylene oxides (8 to 12 EO) examples include C18-C22 fatty alcohol ethers of polyethylene oxides (8 to 12 EO) .
  • surfactants which typically have a low HLB value, and often of from 2 to often comprise mono or possibly di-fatty acid esters of polyhydric alcohols such as glycerol, sorbitol, erythritol or trimethylolpropane, including cetyl, stearyl arachidyl and behenyl derivatives.
  • polyhydric alcohols such as glycerol, sorbitol, erythritol or trimethylolpropane, including cetyl, stearyl arachidyl and behenyl derivatives.
  • Suitable surfactants include alkyl dimethicone copolyols .
  • Fillers can comprise up to about 20%, more commonly up to 10% of the base composition and can act as supports for liquid ingredients.
  • Suitable fillers include aluminium stearate, aluminium tri-stearate, calcium stearate, talc or finely divided polyethylene, an example of which is ACUMIST B18. The latter can also enhance skin feel properties.
  • Fragrances when present, typically comprise up to about 4% of the total product and often from 0.1 to 1.5%.
  • Colouring agents and preservatives can be added as desired.
  • ком ⁇ онентs are other cosmetic adjuncts or benefit agents conventionally employed or contemplated for employment in cosmetic compositions such as in antiperspirant or deodorant products.
  • a particulate pigment is often a significant ingredient such as from 10 to 60% by weight.
  • composition carrier can conveniently form the balance of the composition.
  • Figure 1 shows a schematic of an apparatus for carrying out the process continuously according to the present invention.
  • Figure 2 shows a schematic of a second apparatus for carrying out the process according to the present invention, together with means to cut the resultant product into discrete stick lengths.
  • Figure 3 shows a schematic of a third apparatus suitable for carrying out an intermittent process according to the present invention.
  • an antiperspirant formulation 101 in which the solidifying agent has been melted and homogenised with the carrier fluid is kept in a pumpable form at a temperature of 60 to 70 2 C. It has a viscosity of 1 Pa.s at a shear rate of 21s "1 , measured in a cone/plate rheometer from Carrimed.
  • the fluid formulation is stored in an agitated reservoir 103. It is pumped from the reservoir 103 via a line 105 by means of in-line gear pump 107.
  • the pump 107 transfers the homogenous liquid formulation at the aforementioned temperature and viscosity to an inlet 110 of a stainless steel pipe 111, which is free from any obstructions and which also has an outlet 113.
  • the pipe 111 of circular internal cross section (diameter "d") is upwardly inclined at an angle of below 5 degrees to the horizontal such that height 120 of the outlet above the inlet is l.l"d".
  • the pipe 111 is surrounded by a cooling jacket 115, through which water at 5 2 C is pumped, in via port 117 and out via port 119.
  • a first component 201 for an antiperspirant composition comprising a waxy solidifying agent melting at between 70 and 75°C, and a fraction of the carrier liquid (about 10% by weight) is kept in a holding tank 203 equipped with an agitator (not illustrated) at a temperature of 75°C at which temperature the first component 201 is a mobile liquid.
  • a second component 202 comprising the remaining ingredients of the antiperspirant composition (about 75% by weight of the composition) is stored in a reservoir 204 equipped with an agitator (not illustrated) at a temperature of ambient, about 20 to 25°C.
  • the two components 201 and 203 are pumped via lines 205 by pump 205a and 206 by pump 206a respectively into an intense mixer 207, a Sonolator, to form a pumpable antiperspirant composition 208 having a viscosity in the region of 10 Pa.s.
  • the resultant mixture 208 having a temperature of about 10°C below its normal solidification temperature, is fed immediately (within about 5 seconds) via a short line 209 through inlet 210 into a cooled pipe of constant internal cross section 211 which also has an outlet 213.
  • the pipe 211 is surrounded by a cooling jacket 215 through which a 3 : 1 mixture (w/w) of ethylene glycol and water at a temperature chosen in the range of 20 to -20°C is pumped, via inlet port 217 and outlet port 219.
  • a 3 : 1 mixture (w/w) of ethylene glycol and water at a temperature chosen in the range of 20 to -20°C is pumped, via inlet port 217 and outlet port 219.
  • the solidified composition 208 emerges continuously through the outlet 213 in solid form 221 at a temperature of between ambient and 27°C, and passes under a guillotine 222 where it is cut into individual lengths 223 which are transported by conveyer 224 into a hopper 225.
  • an antiperspirant formulation 301 in which the solidifying agent has been melted and homogenised with the carrier fluid is kept in pumpable form at a temperature of 60 to 70 2 C. It has a viscosity of 1 Pa.s at a shear rate of 21s "1 , measured in a cone/plate rheometer from Carri ed.
  • the homogenised formulation is stored in an agitated reservoir 303. It is pumped from the reservoir 303 via a line 305 by means of in-line gear pump 307 operating under the control of timer 308.
  • the pump 307 intermittently transfers the homogenised formulation 301 at the aforementioned temperature and viscosity through valve 309 into an inlet 310 of a stainless steel pipe 311, which is free from any obstructions and which also has an outlet 313.
  • the pipe 311 of circular internal cross section (diameter "d") is upwardly inclined at an angle of below 5 degrees to the horizontal such that height 320 of the outlet above the inlet is l.l"d".
  • the pipe 311 is surrounded by a cooling jacket 315, through which water at 5 2 C is pumped, in via port 317 and out via port 319.
  • compositions of the formulations for use in the present invention process are as follows:-

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une composition cosmétique sans support dotée d'un liquide porteur dans lequel un agent de solidification est dispersé. Ce procédé consiste à pomper ladite composition à une température telle que l'on puisse réaliser le pompage dans l'ouverture d'un conduit possédant également une sortie d'évacuation. Des moyens de refroidissement sont également présents afin de refroidir ladite composition contenue dans le conduit, de manière à ce que la composition solidifiée soit évacuée, sans support, par une sortie d'évacuation du conduit.
PCT/EP2001/014768 2000-12-29 2001-12-13 Procede dde fabrication de compositions solides WO2002053109A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2002240835A AU2002240835A1 (en) 2000-12-29 2001-12-13 Process for the manufacture of solid formulations
MXPA03005933A MXPA03005933A (es) 2000-12-29 2001-12-13 Proceso para la fabricacion de formulaciones solidas.
UA2003077119A UA76136C2 (en) 2000-12-29 2001-12-13 Process for preparing free standing cosmetic composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB0031831.1 2000-12-29
GB0031831A GB0031831D0 (en) 2000-12-29 2000-12-29 Process for the manufacture of solid formulations
GB0115361A GB0115361D0 (en) 2001-06-22 2001-06-22 Process for the manufacture of solid formulations
GB0115361.8 2001-06-22

Publications (3)

Publication Number Publication Date
WO2002053109A2 true WO2002053109A2 (fr) 2002-07-11
WO2002053109A3 WO2002053109A3 (fr) 2003-04-17
WO2002053109A8 WO2002053109A8 (fr) 2003-07-03

Family

ID=26245508

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/014768 WO2002053109A2 (fr) 2000-12-29 2001-12-13 Procede dde fabrication de compositions solides

Country Status (4)

Country Link
AU (1) AU2002240835A1 (fr)
MX (1) MXPA03005933A (fr)
RU (1) RU2275420C2 (fr)
WO (1) WO2002053109A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7128901B2 (en) 2003-06-04 2006-10-31 Colgate-Palmolive Company Extruded stick product and method for making same
US7452526B2 (en) 2004-03-01 2008-11-18 The Procter & Gamble Company Direct contact quench crystallization process and cosmetic products produced thereby
WO2014165085A2 (fr) 2013-03-12 2014-10-09 The Procter & Gamble Company Procédés de fabrication de compositions antisudorifiques en stick

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB293929A (en) * 1927-06-09 1928-07-19 Stanley Trewartha James Apparatus for producing cored soap bars
FR2565247A1 (fr) * 1984-06-04 1985-12-06 Granval Jean Jacques Savon multicolore, procede de fabrication et machine pour sa fabrication
US5316712A (en) * 1992-04-03 1994-05-31 Jo Cosmetics Co., Ltd. Process for producing solid cosmetics
EP0968703A1 (fr) * 1998-06-15 2000-01-05 L'oreal Composition cosmétique ou pharmaceutique se présentant sous forme de solide et pouvant être déformable
WO2000019861A1 (fr) * 1998-10-06 2000-04-13 Unilever Plc Procede et appareil de production d'une composition desodorisante ou antisudorale
WO2001076409A1 (fr) * 2000-04-05 2001-10-18 Unilever Plc Procede de production d'un agent desodorisant ou antitranspiration

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB293929A (en) * 1927-06-09 1928-07-19 Stanley Trewartha James Apparatus for producing cored soap bars
FR2565247A1 (fr) * 1984-06-04 1985-12-06 Granval Jean Jacques Savon multicolore, procede de fabrication et machine pour sa fabrication
US5316712A (en) * 1992-04-03 1994-05-31 Jo Cosmetics Co., Ltd. Process for producing solid cosmetics
EP0968703A1 (fr) * 1998-06-15 2000-01-05 L'oreal Composition cosmétique ou pharmaceutique se présentant sous forme de solide et pouvant être déformable
WO2000019861A1 (fr) * 1998-10-06 2000-04-13 Unilever Plc Procede et appareil de production d'une composition desodorisante ou antisudorale
WO2001076409A1 (fr) * 2000-04-05 2001-10-18 Unilever Plc Procede de production d'un agent desodorisant ou antitranspiration

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7128901B2 (en) 2003-06-04 2006-10-31 Colgate-Palmolive Company Extruded stick product and method for making same
US7452526B2 (en) 2004-03-01 2008-11-18 The Procter & Gamble Company Direct contact quench crystallization process and cosmetic products produced thereby
WO2014165085A2 (fr) 2013-03-12 2014-10-09 The Procter & Gamble Company Procédés de fabrication de compositions antisudorifiques en stick
WO2014165026A2 (fr) 2013-03-12 2014-10-09 The Procter & Gamble Company Compositions antisudorifiques en stick
WO2014165019A2 (fr) 2013-03-12 2014-10-09 The Procter & Gamble Company Procédés de préparation de compositions antitranspiration solides en stick

Also Published As

Publication number Publication date
WO2002053109A8 (fr) 2003-07-03
RU2275420C2 (ru) 2006-04-27
MXPA03005933A (es) 2003-09-10
WO2002053109A3 (fr) 2003-04-17
RU2003123494A (ru) 2005-01-20
AU2002240835A1 (en) 2002-07-16

Similar Documents

Publication Publication Date Title
US6387358B2 (en) Antiperspirant compositions
US7128901B2 (en) Extruded stick product and method for making same
JPH05255056A (ja) アルキルメチルシロキサンを含む腋下製剤
EP1658115B1 (fr) Compositions en stick
EP1304999B1 (fr) Formulations antisudorifiques
AU770263B2 (en) Antiperspirant compositions
AU2004247087B2 (en) Extruded stick product and method for making same
US7329403B2 (en) Cosmetic compositions
US20050232881A1 (en) Antiperspirant compositions
WO2002053109A2 (fr) Procede dde fabrication de compositions solides
US20020034481A1 (en) Antiperspirant formulations
EP1259214A2 (fr) Compositions semi-solides contre la transpiration
EP1592395B1 (fr) Compositions antitranspiration
ZA200304992B (en) Process for the manufacture of solid formulations.
US7011822B2 (en) Effective soft solid personal care product

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003/04992

Country of ref document: ZA

Ref document number: 200304992

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2003/005933

Country of ref document: MX

Ref document number: 1-2003-500571

Country of ref document: PH

WR Later publication of a revised version of an international search report
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Ref document number: JP