EP1259214A2 - Compositions semi-solides contre la transpiration - Google Patents

Compositions semi-solides contre la transpiration

Info

Publication number
EP1259214A2
EP1259214A2 EP01915148A EP01915148A EP1259214A2 EP 1259214 A2 EP1259214 A2 EP 1259214A2 EP 01915148 A EP01915148 A EP 01915148A EP 01915148 A EP01915148 A EP 01915148A EP 1259214 A2 EP1259214 A2 EP 1259214A2
Authority
EP
European Patent Office
Prior art keywords
composition
product according
weight
container
water
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.)
Withdrawn
Application number
EP01915148A
Other languages
German (de)
English (en)
Inventor
Beng Sim Unilever Research Port Sunlight CHUAH
Kevin Ronald Franklin
Daniel Albert John Martindale
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1259214A2 publication Critical patent/EP1259214A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42—Amides
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/87—Application Devices; Containers; Packaging

Definitions

  • the present invention relates to soft solid antiperspirant compositions for application to human skin, especially the axilla.
  • Antiperspirant compositions are widely used in order to enable their users to avoid or minimise wet patches on their skin, especially in axillary regions.
  • a variety of these compositions make use of a thickened or structured liquid which is applied to the surface of the skin and serves as a carrier for the antiperspirant active.
  • the liquid is water-immiscible and is thickened or structured by one or more materials incorporated into the composition for that purpose, and usually referred to as a "structurant" or "gellant” .
  • Antiperspirant formulations have been provided with a range of different product forms.
  • One of. these is a so-called "stick” which is usually a bar of an apparently firm solid material held within a dispensing container and which retains its structural integrity and shape whilst being applied.
  • Another possibility is a softer solid composition accommodated in a dispensing container which in use extrudes the composition through one or more apertures .
  • the present invention is concerned with such soft solid compositions..
  • Such compositions have sufficient rigidity that they are not observed by the human eye to flow, but they are deformable by hand pressure and can be extruded from a container through one or more apertures at the end of the container.
  • composition For use a small amount of the composition is extruded from the container, which may then be used as an applicator to spread the extruded material on the skin.
  • compositions should be stable and not leak from its container until deliberately extruded. Its sensory feel when applied should, desirably, not be sticky.
  • the applied film of the composition preferably is of a transparent or translucent appearance rather than an opaque white. This property is referred to as low visible residue, and it is desirable in order that the deposit on the user's skin is not easily seen. Moreover, this also avoids conspicuous marks on clothing, to which the deposited material can accidentally transfer.
  • a soft solid which is a suspension of particulate antiperspirant active together with an appropriate package (which may be variations of a type currently in use for opaque soft solid antiperspirant compositions) it is possible to create a product where the dispensed material has an attractively translucent appearance prior to application onto the skin.
  • the container has apertures for extrusion of composition, which are of fairly small cross section, that is to say sufficiently narrow in at least one dimension, the extruded composition can have an attractively translucent appearance provided the refractive index of the liquid in the composition does not differ from that of the antiperspirant active by more than a limited amount, possibly about 0.10, and preferably not by more than about 0.08 or 0.07.
  • the translucent appearance provides an indication to the consumer that the deposit of the composition on skin (or accidental deposit on clothing) will be transparent or have low visibility.
  • this invention provides an antiperspirant product comprising (i) a dispensing container provided with one or more outlet apertures for a user to expel material from the container through the said outlet aperture or apertures, and (ii) within said dispensing container, a soft solid antiperspirant composition comprising a continuous phase of water-immiscible liquid, at least one structuring material which thickens said liquid, and a particulate antiperspirant active in suspension in said liquid; wherein the refractive indices of said antiperspirant active and said liquid differ by not more than about 0.10 preferably not more than 0.08 or 0.07.
  • the water-immiscible liquid will generally be a mixture of liquids and the refractive index of that mixture should not differ by more than 0.10 and very preferably not more than 0.08 from that of the antiperspirant active or mixture of actives .
  • the refractive indices will usually differ by at least 0.01 or 0.02 - avoiding the more difficult constraints on the formulation needed to achieve a closer match. Preferably the difference will not exceed about 0.06.
  • the structurant materials may come from several categories. Their purpose is to increase the viscosity of the water- immiscible liquid and therefore the whole composition, so that in the container before extrusion at the time of use it is a soft solid.
  • a class of materials which have traditionally been used as structurants are fatty alcohols, which are solid at 20°C. These are not preferred for this invention because they give an opaque white appearance with a high visible residue.
  • One category of materials which may be used is waxes which are solid at temperatures up to at least 30°C yet generally melt at a temperature not over 95°C. An amount from 3% or 4% up to 8% by weight of the composition may be suitable.
  • Another category of structuring material is those 'which cause gelation by forming a network of fibres within the composition as it cools from a heated state during processing.
  • An amount from 1% up to 6% by weight of the composition may be suitable.
  • An organic polymeric thickener which is effective to increase the viscosity of the water-immiscible liquid. If used alone, the amount of such polymer is likely to be from 3% or better 5% up to 20% by weight of the composition.
  • another preferred structuring system is a combination of such an organic polymer together with second structuring material selected from:
  • a) structurant which forms a network of fibres within the continuous phase b) waxes, other than fatty alcohols, which are solid at temperatures of 30°C and below, but melt below 95 C, and c) mixtures thereof.
  • the amount of polymeric thickener preferably lies in a range from 1.5% to 15% by weight of the composition.
  • structurant (a) which forms a network of fibres within the continuous phase is present, the amount of it will generally be from 0.5 or 1% to 7% by weight of the composition.
  • wax (b) is present the amount of it will generally be from 0.5 or 1% to 15% by weight of the composition.
  • the total amount of second structuring material may be from 1% to 7% by weight of the composition and the total of organic polymer and second structuring material may be from 3% or 4% ⁇ p to 10% or 12% by weight of the composition.
  • a polymeric thickener alone or in conjunction with a second structuring material .
  • the structurant includes polymer
  • fibre-forming structurants are sometimes preferred over those waxes which do not form fibres, and on other occasions the use of non-fibre-forming waxes is preferred.
  • the total amount of the organic polymeric thickener and second structuring material will be greater than the total amount of any fatty alcohol which is solid at 20 C.
  • any fatty alcohol which is solid at 20 C.
  • fatty alcohol is excluded or used only at low concentrations, such as not more than 3% by weight of the composition, better not more than 1.5% since it is known to crystallize as relatively large platelets and increase the opacity and visibility of deposits.
  • a container should have provision for a user to expel material through the outlet apertures.
  • a container will generally have a body part dimensioned to be held in the hand and outlet aperture (s) at one end.
  • Means for urging the contents of the container to the said aperture or apertures, for flow through them may be moving parts operable by the user or may simply be flexible container walls so that the user can expel composition from the container by squeezing it.
  • One form of container has a barrel or tube to hold a quantity of the composition and a component part referred to as an elevator or piston which is capable of movement within the barrel or tube to propel the composition towards the outlet aperture (s) .
  • the container also includes a transport mechanism for moving the piston comprising a threaded rod which extends axially into the body of the composition through a correspondingly threaded aperture in the piston, and means for relatively rotating the rod and piston.
  • a hand-operable mechanism or wheel (such as a handwheel or pawl and ratchet) located at the opposite end of the container to the delivery opening.
  • the outlet apertures are normally formed in a closure for the container.
  • the apertures should each be such that the material extruded through it is no more than 0.5cm thick in at least one dimension.
  • an aperture could have a cross section with its smallest dimension less than 0.5cm wide.
  • a rectangle 0.4cm by 0.8cm would be an example.
  • the material extruded through it would be a ribbon 0.4cm thick.
  • each aperture will have a cross section which is not more than 0.5cm in any dimension.
  • a circular hole of 0.5cm diameter would be an example.
  • the number and design of such apertures is at the discretion of the designer of the package. Likewise, the distribution of such apertures in the dispensing head of the container is at the discretion of the package designer.
  • the apertures are often circular or oval or parallel sided slots, the slots being straight, curved or serpentine, often having rounded ends, or a combination of two or more designs.
  • the number of apertures is often from 5 to 150, especially 8 to 120.
  • the apertures are often arranged in a symmetrical manner in the dispensing head, such as parallel slots, or in a radial design centred on the container axis, or a rectangular array of circular or oval apertures, or in concentric or intersecting circles.
  • thermoplastic materials for example polypropylene or polyethylene.
  • suitable containers are found in US patents 4865231, 5000356 and 5573341 and WO 99/29585.
  • compositions with the preferred structurants are simple to manufacture.
  • the compositions can be made and packed by heating their constituents to form a liquid composition, mixing at temperatures where the composition is freely mobile, putting the composition into containers for retail sale and cooling or allowing these compositions to cool to room temperature. There is then no need for continued stirring while the composition is thickening as it cools.
  • Fig. 1 is a perspective view of a dispensing container.
  • Fig. 2 shows the body of the container, with the upper part in section.
  • Fig. 3 is an enlarged top view showing the outlet openings.
  • Fig. 4 shows an alternative outlet opening.
  • Fig. 5 shows the three parts of a different dispensing container.
  • Fig. 6 is an enlarged end view, in the direction of arrow VI in Fig. 5, with the detachable cap removed to show the outlet apertures.
  • Fig. 7 is a diagrammatic cross sectional view of a third form of dispensing container, with its upper part in section.
  • Fig. 8 is an enlarged top view of the container of Fig. 7.
  • FIG. 1 A first example of a dispensing container is shown in Figs. 1 to 3 of the drawings.
  • This container has detachable cap 3 which is removable and replaceable by the user.
  • the container has a barrel 5 of oval cross section. The upper end of the barrel is secured by a snap-fit (indicated at 8 in Fig. 2) to a top portion 10.
  • the dome-shaped cap 3 is transparent so that the openings 7 in the insert 6 are visible.
  • the interior surface of the cap 3 is provided with stops 4 serving to maintain a head space between the cap 3 and the top portion 10.
  • the base- plate 12 provides a mounting for a knurled hand wheel 13 attached to a threaded spindle 14. This, as shown in Fig. 2 extends within the barrel 5 and engages a threaded central aperture in an elevator piston 15 within the barrel 5.
  • the user can raise the piston 15 within the barrel 5 to push composition, contained in the barrel above the elevator piston 15 towards the outlet apertures 7.
  • the composition is then expelled through the apertures 7.
  • the outlet apertures 7 are curved slots each having a uniform width, as indicated for example between the arrows (A) , which is approximately 2 mm.
  • the composition is therefore expelled from the container as a plurality of ribbons each about 2mm thick.
  • the elevator piston 15 is positioned at the bottom of the container and the insert 6 is not fitted, thus leaving a fairly large opening at the top of the container through which molten composition can be poured in, on top of piston 15.
  • the insert 6 is snapped into the opening in the top portion 10, the cap 3 is fitted and the filled container is ready for retail sale.
  • an adhesive label may be secured onto the insert 6 closing the apertures 7 until this adhesive label is torn off by the user prior to first use.
  • Fig. 4 shows a minor modification. Instead of the plurality of slots 7 in the insert 6, there is a single central hole 18 with a diameter of 4mm.
  • the single central hole is replaced by an array of between 30 and 130 holes, e.g. about 120 holes, each with a diameter between 1 and 3mm.
  • Fig. 5 and Fig. 6 show a second example of dispensing container which is described and illustrated in greater detail in PCT publication WO 99/29585.
  • This container has a main body 22 with a rounded, closed first end 24 and a second end 26.
  • the second end 26 has an open mouth 28.
  • the container also includes a closure 32 with an oval end face 34 and a surrounding skirt 36.
  • a short internal wall 38 on the closure snap-fits to the mouth 28 of the main container 22.
  • a detachable cap 40 fits over the closure 32 and an end portion of the main body 22. This cap 40 can be removed and replaced by the user.
  • the face 34 of the closure 32 has three outlet apertures 42 in a generally central position.
  • the main body 22 is relatively rigid in the region of its closed, rounded end 24 but a middle area of the walls of this container body is relatively flexible to allow it to be squeezed by the user.
  • Each of these outlet apertures is a curving slot with a width, indicated for example between the arrows (A) , of approximately 1mm. Consequently when the user squeezes the container body 22, material from it is extruded as three ribbons each 1mm thick.
  • This container is intended to be stored resting on the removable cap 40 and with the container mouth 28 downwards. For this reason the container cap 40 incorporates plugs 46 to fit into, and thereby block, the outlet apertures 42.
  • the container of Figs. 5 and 6 is filled with molten composition by pouring that composition in through the mouth 28.
  • the closure 32 is fitted onto the end 26 of the container body and, as mentioned, the internal wall 38 within the closure 32 snap-fits onto the mouth 28 of the container body 22, so that it is then held in place.
  • Figs. 7 and 8 diagrammatically illustrate a third example of dispensing container.
  • This container has a downwardly tapering main body 50 of generally oval, cross section onto which is snap-fitted a closure 52.
  • a tube 54 of circular cross section integral with a user-operable hand wheel 56 exposed at the base of the body 50.
  • a threaded spindle 60 is accommodated centrally within the tube 54.
  • the top of this spindle 60 engages a socket 62 of the end cap 52 and is thereby prevented from rotating.
  • An elevator piston 64 has a threaded central aperture engaging the thread of the spindle 60.
  • the top cap 52 incorporates a depending skirt 66 encircling the top of the tube 54.
  • the top cap 52 has eight apertures 68 each of which is a slot with a width, as shown between arrows (A) , of 3mm and a length of approximately 12mm. Adjoining one edge of each aperture 68 is a blade 70 which projects downwardly and is also somewhat inclined. As a result, if the container is empty, the blades 70 are visible through the apertures 68 as seen in Fig. 8.
  • the user turns the hand wheel 56 and by doing so turns the central tube 54 and the composition within it relative to the body 50.
  • a rachet not shown, constrains the direction of rotation.
  • the elevator piston 64 frictionally engages the tube 54 and rotates along with it and with the composition immediately above it. However because the central spindle 60 does not rotate the elevator piston 64 moves up the spindle 60, thereby propelling the composition up towards the outlet apertures 68.
  • the inclined blades 70 scoop from the top of the composition in the tube 54 and hence assist in guiding the flow of composition up to and through the outlet apertures 68.
  • a removable and replaceable transparent cap is also provided to be placed over the closure 52 and top portion of the body 50.
  • the water-immiscible liquid comprises one or a mixture of materials which are relatively hydrophobic so as to be immiscible in water. Some hydrophilic liquid may be included, provided the overall liquid mixture is immiscible with water. Generally, this liquid or liquid mixture (when in the absence of polymeric thickener or other structurant) will be freely mobile at temperatures of 15 C and above. It may have some volatility but its vapour pressure will generally be less than 4kPa (30 mmHg) at 25°C so that the material can be referred to as an oil or mixture of oils. More specifically, it is desirable that at least 80% by weight of the liquid should consist of materials with a vapour pressure not over this value of 4kPa at 25°C.
  • the liquid or liquid mixture includes a volatile liquid silicone, i.e. liquid polyorganosiloxane .
  • a volatile liquid silicone i.e. liquid polyorganosiloxane
  • such material should have a measurable vapour pressure at 20 or 25°C.
  • the vapour pressure of a volatile silicone lies in a range from 1 or 10 Pa to 2kPa at 25°C.
  • Volatile polyorganosiloxanes can be linear or cyclic or mixtures thereof.
  • Preferred cyclic siloxanes include polydimethylsiloxanes and particularly those containing from
  • linear siloxanes include polydimethylsiloxanes containing from 3 to 9 silicon atoms.
  • the volatile siloxanes normally by themselves exhibit viscosities of below 10 ⁇ 5 m 2 /sec (10 centistokes), and particularly above 10 "7 m 2 /sec (0.1 centistokes) , the linear siloxanes normally exhibiting a viscosity of below 5 x 10 "6 m 2 /sec (5 centistokes) .
  • the volatile silicones can also comprise branched linear or cyclic siloxanes such as the aforementioned linear or cyclic siloxanes substituted by one or more pendant -0-Si(CH 3 ) 3 groups.
  • examples of commercially available silicone oils include oils having grade designations 344, 345, 244, 245 and 246 from Dow Corning Corporation; Silicone 7207 and Silicone 7158 from Union Carbide Corporation; and SF1202 from General Electric.
  • the hydrophobic liquid employed in compositions herein can alternatively or additionally comprise non-volatile silicone oils, which include polyalkyl siloxanes, polyalkylaryl siloxanes and polyethersiloxane copolymers . These can suitably be selected from dimethicone and dimethicone copolyols. Commercially available non-volatile silicone oils include Dow Corning 556 and Dow Corning 200 series.
  • Silicon-free hydrophobic liquids can be used instead of, or more preferably in addition to liquid silicones.
  • Silicon-free hydrophobic organic liquids which can be incorporated include liquid aliphatic hydrocarbons such as mineral oils or hydrogenated polyisobutene, often selected to exhibit a low viscosity. Further examples of liquid hydrocarbons are polydecene and paraffins and isoparaffins of at least 10 carbon atoms. Although polyisobutene and polydecene are polymeric in nature, they are mobile liquids at room temperature of 20 C and do not cause thickening of other hydrophobic oils.
  • Aromatic esters may be preferred and may well be used as all or part of a liquid mixture; aliphatic esters tend to have lower refractive index and for this reason they will generally only be used as part of a liquid mixture.
  • Suitable aliphatic esters contain at least one long chain alkyl group, such as esters derived from C x to C 20 alkanols esterified with a C 8 to C 22 alkanoic acid or C 6 to C ⁇ 0 alkanedioic acid.
  • the alkanol and acid moieties or mixtures thereof are preferably selected such that they each have a melting point of below 20 C.
  • These esters include isopropyl myristate, lauryl myristate, isopropyl palmitate, diisopropyl sebacate and diisopropyl adipate .
  • Suitable liquid aromatic esters include fatty alkyl benzoates, alkylene dibenzoate, alkoxylated alkyl benzoate or a polyalkylene oxide dibenzoate, or a mixture of two or more.
  • the alkyl group often contains at least 8 carbons, in many instances up to 25 carbons, eg from C8 to C18. It is often linear , but can alternatively be branched.
  • alkyl groups are found in the range of from 12 to 20 carbons and include dodecyl (lauryl) terdecyl, tetradecyl (myristyl) , pentadecy, hexadecyl (palmityl) , octdecyl
  • alkylated herein includes alkylene groups and the latter are terminated at each end with a benzoate group.
  • the alkylene group often contains from 2 to 6 carbons and can be linear or branched, a suitable example of linear being propylene.
  • alkoxylated alkyl benzoate esters the alkyl group is terminated by an alkoxy group, which can be monomeric containing for example up to 6 carbons or polymeric such as polyethylene oxide or preferably polypropylene oxide, which conveniently comprises up to 30 units and often from 5 to 20 units.
  • the alkyl group can be selected from the previously identified alkyl groups.
  • the benzoate compound can comprise a polyethylene oxide or polypropylene oxide moiety, or preferably a block copolymer of ethylene oxide and propylene oxide, terminated at each end by a benzoate group.
  • aliphatic alcohols which are solid at 20 C, such as stearyl alcohol are preferably absent or else present in low concentration such as less than 5% by weight of the whole composition since these lead to visible white deposits when a composition is used.
  • aliphatic alcohols which are liquid at 20 C may be employed. These include branched chain alcohols of at least 10 carbon atoms such as isostearyl alcohol and octyl dodecanol .
  • Silicon-free liquids can constitute from 0-100% of the water-immiscible liquid, but it is preferred that some silicone oil is present while the amount of silicon-free constituents preferably constitutes at least 75% of the water-immiscible liquid.
  • a number of organic polymers are effective to increase the viscosity of hydrophobic liquids, although some polymers do not do so .
  • a material which is suitable as an organic polymeric thickener will generally possess the following characteristics : -
  • the choice of a type B, type C or type D T-bar spindle will depend on the viscosity of the system being measured. Provided the spindle is appropriate to provide a viscosity measurement it will enable determination of an increase in viscosity brought about by the polymer.
  • An additional or alternative characterisation of a suitable polymer is that it can thicken the water-immiscible liquid to a viscosity of at least 10,000 mPa.sec, measured in the same way, when incorporated in the water-immiscible liquid at 15% by weight, in the absence of the other structurant.
  • the polymer will generally be solid at 20°C.
  • One category of polymer which has been found suitable is a polysaccharide esterified with monocarboxylic acid containing at least 4 carbon atoms .
  • Preferred in this category is a dextrin fatty acid ester having the formula:
  • each R group individually, is a hydrogen atom or an acyl group having up to 22 carbon atoms, provided that at least one R group per glucose unit is an acyl group of at least 4 carbon atoms, and m has an average value from 5, 10 or 20 up to 50 or even up to 150, more preferably from 20 to 30.
  • the dextrin fatty acid ester can be a partial ester, i.e. at least one R group is hydrogen; or the dextrin can be completely esterified, i.e., all R groups are acyl, such as a C 4 - C 22 acyl group.
  • the acyl groups may be the same or similar, and preferably they are straight chain acyl groups with chain lengths of 8 to 22 carbon atoms, e.g. in a range from 12 or 14 carbon atoms to 18 or 20 carbon atoms. Branched acyl groups may be included, possibly as in a mixture of C e to C 22 linear acyl groups. Shorter acyl groups may form part of a mixture, for example C 4 to C 8 acyl groups may be mixed with C 12 to C 22 linear acyl groups. In preferred embodiments, wherein the R group is a C 8 -C 22 acyl group the degree of substitution is at least 2 (i.e., at least two R groups are C 8 -C 2 2 acyl groups) .
  • the C 8 -C 22 fatty acids that are reacted with the starch hydrolyzate can be saturated or unsaturated acids, and include, for example, capric acid, pelargonic acid, caprylic acid, undecylic acid, undecylenic acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, oleic acid, linoleic acid, linolenic acid, similar acids, and mixtures thereof.
  • dextrin fatty acid esters are disclosed in Mori et al US patent 4780145, incorporated herein by reference, and some of them are available under the trade name RHEOPEARL from Chiba Flour Milling Co., Ltd., Japan.
  • An example of a dextrin fatty acid ester is dextrin palmitate, available commercially as RHEOPEARL KL and RHEOPEARL FL, for example, from Chiba Flour Milling Co . , Ltd.
  • esters of C 8 -C 2 2 carboxylic acids are dextrin behenate, dextrin laurate, dextrin myristate, dextrin stearate,. and mixtures thereof.
  • a second category of polymer which can be used as a thickener is polyamides as discussed in US 5500209.
  • Such polyamides may be derived from organic diamines containing 2 to 12, preferably 2 to 8 carbon atoms, condensed with di- or poly carboxylic acids containing 4 to 20 carbon atoms per carboxylic acid group. Some monocarboxylic acid may be included in the reaction mixture to control polymer chain length.
  • the dicarboxylic acids may be obtained by thermal polymerisation of unsaturated monocarboxylic acids.
  • Such polyamides are available from Henkel under their trade name VERSAMID.
  • An example is VERSAMID 950 from hexamethylene diamine and adipic acid.
  • a further category of polymer which has been found useful is the block copolymers of styrene with ethylene propylene and/or butylene available from Shell under their trade name KRATON G.
  • Preferred in this category is styrene ethylene/butylene styrene linear block copolymers e.g. that available as KRATON G 1726X.
  • KRISTALEX polymers of alpha methylstyrene and styrene available from Hercules under the trade name KRISTALEX.
  • KRISTALEX F85 KRISTALEX F85, with mean molecular weight of approximately 1200.
  • alkyl substituted galactomannan available from Hercules under their trade name N-HANCE AG.
  • a still further class of polymers found to be suitable comprises co-polymers of vinyl pyrrolidone with polyethylene containing at least 25 methylene units.
  • a particularly suitable polymer comprises triacontanyl polyvinylpyrrolidone, such as that available from International Speciality Products under the trade name Antaron WP-660.
  • the thickening ability of polymers varies from one to another, which will affect the amount which is required. The amount will often lie in a range from 2% or 3% by weight of the composition up to 7% or more, such as to 10%, 12% or 15%.
  • a number of organic compounds are known to possess the ability to gel hydrophobic organic liquids such as water- immiscible hydrocarbon and/or silicone oils. Such materials are generally monomers or dimers with molecular weight below 10,000 often below 5,000 or even 1,000 rather than polymers with more than four repeat units or with molecular weight above 10,000.
  • Gel formation takes place as an exothermic event within a temperature range referred to as the gel point; upon reheating, melting of the gel takes place as an endothermic event within a temperature range.
  • Such gels can be disrupted by shearing. Although.a small partial recovery may then be observed, such gels do not recover their structure for a long time, if at all, unless remelted.
  • the structured liquids are obtainable by cooling from an elevated temperature at which the structurant is in solution in the liquid - this hot solution being mobile and pourable; " the (thus obtained) structured liquid becomes more mobile if subjected to shear or stress; " the structure does not spontaneously recover within
  • the structure can be recovered by reheating to a temperature at which the structurant is in solution in the liquid and allowing it to cool back to ambient laboratory temperature .
  • Such structurants operate by interactions which are permanent unless disrupted by shear or heating. Such structurants form a network of strands or fibres extending throughout the gelled liquid. In some cases these fibres can be observed by electron microscopy, although in other cases the observation of the fibres which are believed to be present is prevented by practical difficulties in preparing a suitable specimen.
  • the primary fibres in a gel are generally thin (diameter less than 0.5 ' ⁇ m, often less than 0.2 ⁇ m) and appear to have numerous branches or interconnections . Primary fibres may entwine to form a thicker strand.
  • these fibres are crystalline, they may or may not be the same polymorph as macroscopic crystals obtained by conventional crystallization from a solvent.
  • One material which is well known to form such gels is 12- hydroxy stearic acid which is discussed in Terech et al "Organogels and Aerogels of Racemic and Chiral 12-hydroxy octadecanoic Acid", Langmuir Vol 10, 3406-3418, 1994.
  • the material is commercially available from Ajinomoto and also from Caschem.
  • US-A-5750096 is one of several documents which teaches that gelation can be brought about using esters or amides of 12- hydroxy stearic acid.
  • the alcohol used to form such an ester or the amine used to form such an amide may contain an aliphatic, cycloaliphatic or aromatic group with up to 22 carbons therein. If the group is aliphatic it preferably contains at least three carbon atoms.
  • a cycloaliphatic group preferably contains at least five carbon atoms and may be a fixed ring system such as adamantyl .
  • fatty acids with C 8 or longer alkyl chains may be used and amides thereof can also be used.
  • amides thereof can also be used.
  • a specific example is lauric monoethanolamide also termed MEA lauramide.
  • N-acyl amino acid amides and esters are also known to structure liquids. We have established that they do so by forming fibrous networks. They are described in US patent 3969087. N-Lauroyl-L-glutamic acid di-n-butylamide is commercially available from Ajinomoto under their designation GP-1.
  • gelling agents are the amide derivatives of di and tribasic carboxylic acids set forth in WO 98/27954 notably alkyl N,N'dialkyl succinamides .
  • the sterol satisfies either of the two formulae :
  • R represents an aliphatic, cycloaliphatic or aromatic group, and preferably a linear or branched aliphatic saturated or unsaturated hydrocarbon group.
  • R desirably contains from 1 to 20 carbons and preferably from 4 to 14 carbons .
  • ⁇ -sitosterol or campesterol or cholesterol or a hydrogenated derivative thereof, such as dihydrocholesterol, or a mixture of two or more of them.
  • An especially preferred sterol is ⁇ -sitosterol .
  • the preferred sterol ester is oryzanol, sometimes referred to as ⁇ -oryzanol which contains material satisfying the following formula : -
  • the sterol and sterol ester are used in a mole ratio that is normally selected in the range of from 10:1 to 1:10, especially from 6:1 to 1:4 and preferably in the range of from 3:1 to 1:2. Employment of the two system constituents within such a mole ratio range, and especially within the preferred range facilitates the co-stacking of the constituents and consequently facilitates the formation of a network that is readily able to structure the formulation.
  • Another structurant which is the subject of a co-pending application published as WO 00/61079 and which may be used in this invention is an ester of cellobiose and a fatty acid, preferably of 6 to 13 carbon atoms especially 8 to 10 carbon atoms.
  • the cellobiose is fully esterified, or nearly so, and is in the -anomeric form.
  • R is an alkyl or alkenyl chain of 5 to 12 carbon atoms so that the acyl group contains 6 to 13 carbon atoms.
  • Particularly preferred acyl groups incorporate a linear alkyl chain of 7 to 9 carbon atoms and are thus octanoyl , nonanoyl or decanoyl .
  • the acyl groups may have a mixture of chain lengths but it is preferred that they are similar in size and structure. Thus it is preferred that all of the acyl groups are aliphatic and at least 90% of the acyl groups have a chain length within a range such that the shorter and longer chain lengths in the range differ by no more than two carbon atoms, i.e. length in a range from m - 1 to m + 1 carbon atoms where m has a value in a range from 7 to 10.
  • Linear aliphatic acyl groups may be obtained from natural sources, in which case the number of carbon atoms in the acyl group is likely to be an even number or may be derived synthetically from petroleum as the raw material in which case both odd and even numbered chain lengths are available.
  • R and R' are each independently a linear or branched moiety containing 5 to 27 carbons, m and n are each independently 0 or 1, and Y is a cyclohexane ring bearing the two amido substituents shown above meta or preferably ortho to each other.
  • R and R' are selected from Cll to C17.
  • m and n are preferably 1 when the amido substituents are meta to each other, and preferably 0 when the substituents are ortho to each other.
  • wax is conventionally applied to a variety of materials and mixtures which have similar physical properties, namely that : - they are solid at 30 C and preferably also at 40 C; they melt to a mobile liquid at a temperature above 30 C but generally below 95 C and preferably in a temperature range of 40 C to 90 C; they are water-insoluble and remain water-immiscible when heated above their melting point.
  • Waxes are usually hydrocarbons, silicone polymers, esters of fatty acids or mixtures containing such compounds along with a minority (less than 50%) of other compounds.
  • Naturally occurring waxes are often mixtures of compounds which include a substantial proportion likely to be a majority of fatty esters .
  • Waxes form crystals in the water-immiscible liquid when it cools from the heated state during processing. These crystals take various forms including needles and platelets depending on the individual waxes . Some waxes form a network of fibrous crystals and can therefore also be identified as fibre-forming structurants.
  • hydrocarbon waxes examples include paraffin wax, microcrystalline wax and polyethylenes with molecular weight of 2,000 to 10,000.
  • ester waxes include esters of C 16 -C 2 2 fatty acids with glycerol or ethylene glycol and these may be made synthetically.
  • natural waxes include beeswax, carnauba and candelilla waxes which are of vegetable origin and mineral waxes from fossil remains other than petroleum.
  • Montan wax which is an example of mineral wax, includes non-glyceride esters of carboxylic acids, hydrocarbons and other constituents .
  • waxes employable herein comprise silicone polymer waxes, including waxes which satisfy the empirical formula :- R- (SiMe 2 -0-) x -SiMe 2 R in which x is at least 10, preferably 10 to 50 and R represents an alkyl group containing at least 20 carbons, preferably 25 to 40 carbons, and particularly having an average linear chain length of at least 30 carbons.
  • silicone waxes comprise copolymers of dimethicone and alkyloxymethicone, satisfying the general formula: - Y- (SiMe 2 -0-) y (Si [OR']Me-0-) z -Y' in which Y represents SiMe 2 -0, Y' SiMe 2 , R' an alkyl of at least 15 carbons preferably 18 to 22 such as stearyl, y and z are both integers, totalling preferably from 10 to 50.
  • Waxes useful in the present invention will generally be those found to thicken water-immiscible oils such as cyclomethicones when dissolved therein (by heating and cooling) at a concentration of 5 to 15% by weight.
  • a wax which forms a network of fibres
  • the amount of it may be from 0.5 to 7% by weight of the composition. If a wax is used which does not form such a network, for instance a wax which crystallizes as spherulitic needles or as small platelets, the amount may well be from 2% or 3% up to 10%, 12% or 15% of the composition. Silicone waxes are an example of waxes which crystallize as small platelets.
  • the total amount of second structurant may range from 0.5% or 1% of the composition up to 9%, 10% or 15%.
  • the ratio of polymer to second structurant can vary considerably but in many instances it will lie in a range from 6:1 to 1:4.
  • the composition will contain 0.5 to 10% or 15% polymeric thickener, 0.5 to 7% of fibre- forming structurant and 2% to 10% of a wax such as silicone wax which does not crystallize as a network of fibres, all these percentages being by weight of the composition.
  • the composition contains from 5 to 15% by weight and preferably 8 to 12% by weight of a mixture of an organic wax and a silicone wax, particularly in a weight ratio of from 5:1 to 2:1.
  • the composition will contain a particulate antiperspirant active.
  • Antiperspirant actives are preferably incorporated in an amount of from 0.5-60%, particularly from 5 to 30% or 40% and especially from 5 or 10% to 30 or 35% of the weight of the composition.
  • Antiperspirant actives for use herein are often selected from astringent active salts, including in particular aluminium, zirconium and mixed aluminium/zirconium salts, including both inorganic salts, salts with organic anions and complexes.
  • astringent active salts include aluminium, zirconium and aluminium/zirconium halides and halohydrate salts, such as chlorohydrates .
  • the antiperspirant active is made by an improvement to the process described in EP-A-6739.
  • the improved process maintains of aluminium in dilute concentration during the formation of aluminium chlorohydrate species, and closely controls the ageing stage, in particular ageing at an elevated temperature and for a suitable .ageing period in inverse relationship to each other.
  • Zirconium actives can usually be represented by the empirical general formula: ZrO (OH) 2n - nz B z -wH 2 0 in which z is a variable in the range of from 0.9 to 2.0 so that the value 2n-nz is zero or positive, n is the valency of B, and B is selected from the group consisting of chloride, other halide, sulphamate, sulphate and mixtures thereof. Possible hydration to a variable extent is represented by wH20. Preferable is that B represents chloride and the variable z lies in the range from 1.5 to 1.87. In practice, such zirconium salts are usually not employed by themselves, but as a component of a combined aluminium and zirconium-based antiperspirant .
  • zirconium salts may have coordinated and/or bound water in various quantities and/or may be present as polymeric species, mixtures or complexes.
  • zirconium hydroxy salts often represent a range of salts having various amounts of the hydroxy group.
  • Zirconium aluminium chlorohydrate may be particularly preferred.
  • Antiperspirant complexes based on the above-mentioned astringent aluminium and/or zirconium salts can be employed.
  • the complex often employs a compound with a carboxylate group, and advantageously this is an amino acid.
  • suitable amino acids include dl-tryptophan, dl- - phenylalanine, dl-valine, dl-methionine and -alanine, and preferably glycine which has the formula CH 2 (NH 2 ) COOH.
  • ZAG actives generally contain aluminium, zirconium and chloride with an Al/Zr ratio in a range from 2 to 10, especially 2 to 6, an Al/Cl ratio from 2.1 to 0.9 and a variable amount of glycine. Actives of this preferred type are available from Westwood,. from Summit and from Reheis.
  • the water content of hydratable aluminium or aluminium/zirconium antiperspirant active materials can be controlled to vary the properties of the material, such as by controlling the conditions under which the material is recovered from its preparative mixture and dried, and/or by post manufacture contact with a selected amount of water.
  • the proportion of water in the active will be chosen within the range of from 6 to 18% by weight, and sometimes advantageously from 11 to 18% by weight.
  • actives which may be utilised include astringent titanium salts, for example those described in GB 2299506A.
  • the proportion of solid antiperspirant salt in a composition normally includes the weight of any water of hydration and any complexing agent that may also be present in the solid active.
  • the particle size of the antiperspirant salts often falls within the range of 0.1 to 200 ⁇ m with a mean particle size often from 3 to 20 ⁇ m. Both larger and smaller mean particle sizes can also be contemplated such as from 20 to 50 ⁇ m or 0.1 to l ⁇ m.
  • Antiperspirant actives which have substantial internal voids are preferably avoided because they do not have uniform refractive index. Such actives can be made more useful for this invention by milling. Various milling techniques can be employed, such as ball or swing milling.
  • Particulate antiperspirant actives often have a refractive index substantially above 1.50, e.g. about 1.53 to about 1.56. That value can be brought down to somewhat lower value by hydration but we have found that it is not easy to obtain an antiperspirant active with a refractive index of 1.48 or below even if the active is partially hydrated to lower its refractive index.
  • the refractive index of a solid antiperspirant active can be determined by dispersing it in a number of oils or oil mixtures of differing refractive index.
  • the refractive index of the oil or oil mixture (which can be determined by conventional measurement) is a good approximation to the refractive index of the dispersed antiperspirant active.
  • oils which may be used to make mixtures which vary in refractive index and used for the purpose of such measurement are : volatile silicone (refractive index about 1.40) C 12 - 15 alkyl benzoate (refractive index about 1.48) which is available as Finsolv TN and/or octylmethoxycinnamate (refractive index about 1.54) which is available as Parsol MCX
  • Cinnamic aldehyde (refractive index about 1.62).
  • Providing a water-immiscible liquid with a refractive index no more than 0.10 units away from that of the antiperspirant active generally involves choosing an oil or oil mixture with a refractive index no more than 0.10 units, preferably no more than 0.08 units below that of the antiperspirant active. For this reason it may be preferred that the water- immiscible liquid has a refractive index of at least 1.43, more preferably at least 1.46.
  • silicon-free water-immiscible liquid oils generally have refractive indices in a range from 1.43 to 1.49 at 22 C and can be used alone or mixed together to give a silicon-free carrier liquid with refractive index in this range.
  • Volatile silicone oils generally have a refractive index slightly below 1.40 at 22 C, but carrier liquid mixtures with refractive indices in the range from 1.41 to 1.49 can be obtained by mixing limited amounts of volatile silicone with other oils.
  • Cosmetically acceptable non-volatile silicone oils generally have refractive indices in a range from 1.45 to 1.48 at 22 C and so can be included when desired.
  • the structurant materials also have refractive index differing from those of the ' water- immiscible liquid and the antiperspirant active by not more than 0.10 or 0.08 unit, although this is less critical.
  • a number of structurant materials which can be used have refractive indices above 1.45.
  • the refractive index of a wax or that of a fibrous network of a fibre-forming structurant can be determined (somewhat analogously to the determination for an antiperspirant active) by using that structurant to gel a number of oils or oil mixtures of differing refractive index. When the resulting gel is transparent, the refractive index of the oil or oil mixture is a good approximation to the refractive index of the structurant.
  • the oils or mixtures of oils should be chosen from those which are gelled well by the structurant to avoid interfering effects.
  • polymeric thickener causes very little scattering of light and its does not generally need to be taken into account for refractive index matching.
  • Optional ingredients in compositions of this invention can include deodorants, for example at a concentration of up to about 10% w/w.
  • Suitable deodorant actives can comprise deoperfumes, and/or microbicides, including particularly bactericides, such as chlorinated aromatics, including biguanide derivatives, of which materials known as Triclosan (Igasan DP300TM) , TriclobanTM, and Chlorhexidine warrant specific mention.
  • a yet another class comprises biguanide salts such as available under the trade mark CosmosilTM.
  • wash-off agents often present in an amount of up to 10% w/w to assist in the removal of the formulation from skin or clothing.
  • wash-off agents are typically nonionic surfactants such as esters or ethers containing a C 8 to C 22 alkyl moiety and a hydrophilic moiety which can comprise a polyoxyalkylene group (POE or POP) and/or a polyol .
  • the composition herein can incorporate one or more cosmetic adjuncts conventionally envisaged for antiperspirant soft solids.
  • Such cosmetic adjuncts can include skin benefit agents such as glycerol, allantoin or lipids, for example in an amount of up to 5%; and soluble colourants.
  • Skin cooling agents such as menthol and menthol derivatives, often in an amount of up to 2%, all of these percentages being by weight of the composition.
  • a commonly employed adjunct is a perfume, which is normally present at a concentration of from 0 to 4% and in many formulations from 0.25 to 2% by weight of the composition.
  • the formulations can also include, if desired, a small particle sized inorganic thickener, often in an amount of from 0.1 to 2% by weight. Finely particulate silica, eg fumed silica, such as available as AerosilTM 200 represents a preferred inorganic thickener.
  • compositions of this invention can be produced by conventional processes for making suspension solids or soft- solids. Such processes involve forming a heated mixture of the composition at a temperature which is sufficiently elevated that all the structurant dissolves, introducing that mixture into a mould, which may be a dispensing container, and then allowing the mixture to cool. If necessary, especially if the structurant does not include organic polymer, the composition may be subjected to shear mixing before it is put into the mould.
  • a convenient process sequence for a composition which is a suspension comprises first forming a solution of the polymer and other structurant in the water-immiscible liquid or liquid mixture. This is normally carried out by agitating the mixture at a temperature sufficiently high that all the structurant dissolves (the dissolution temperature) such as a temperature in a range from 50 to 150°C. Thereafter the particulate constituent, for example particulate antiperspirant active, is blended with the hot mixture. This must be done slowly, or the particulate solid must be preheated, in order to avoid premature gelation. The resulting blend is then introduced into a dispensing container such as a stick barrel. This is usually carried out at a temperature 5 to 30°C above the setting temperature of the composition. The container and contents are then cooled to ambient temperature. Cooling may be brought about by nothing more than allowing the container and contents to cool. Cooling may be assisted by blowing ambient or even refrigerated air over the containers and their contents.
  • the dissolution temperature such as a temperature in a range
  • This test apparatus can move a blunt probe into or out from a sample at a controlled speed and at the same time measure the applied force.
  • the parameter which is determined as hardness is a function of the force and the projected area of indentation.
  • a specific test protocol used a Stable Micro systems TA.XT2i Texture Analyser.
  • a sample of composition was made by heating the ingredients, pouring into a container and allowing to cool as described above .
  • the container was a 15ml glass jar with a wide mouth.
  • a metal sphere, of diameter 9.5mm, was attached to the underside of the Texture Analyser 1 s 5 kg load cell such that it could be used for indenting a sample placed beneath it on the base plate of the instrument. After positioning the sample, the sphere position was adjusted until it was just above the sample surface .
  • Texture Expert ExceedTM software was used to generate the subsequent motion profile used in the test method.
  • This profile initially moved the sphere into contact with the sample and then indented the sphere into the sample at an indentation speed of 0.05mm/s for a distance of 7mm. At this distance the direction of motion of the sphere was immediately reversed to withdraw the sphere from the sample at the same speed of 0.05mm/s.
  • the data acquired were time(s), distance (mm) and force (N) and the data acquisition rate was 25 Hz.
  • the measured hardness will generally be from 0.003 to 0.5 Newton/mm 2 . Frequently the hardness will be from 0.003 up to 0.1 Newton/mm 2 .
  • compositions Another test of the properties of a composition is the whiteness and hence opacity of the composition which is delivered onto a surface when the composition is drawn across that surface.
  • whiteness and hence opacity of the composition which is delivered onto a surface when the composition is drawn across that surface.
  • a sample of the composition was first applied to a test fabric under standardised conditions.
  • the test fabric was a rectangular strip of black worsted wool fabric 9cm by 15cm. This was placed in an apparatus consisting of a metallic base onto which was hinged a metallic frame defining a rectangular aperture of 5cm by 9cm. The test portion of fabric was laid on the base. The hinged frame was placed over the fabric and secured to the base by means of two screws thereby clamping the test fabric in place but exposing an area of 5 x 9 cm through the aperture .
  • a sample of soft solid composition in a dispensing container was kept at ambient laboratory temperature (about 20 C) before it was required for measurement.
  • a portion of the composition is then extruded from the container through the dispensing apertures at one end.
  • a weighed amount (0.5g) of the extruded composition was spread uniformly across the 5 x 9 cm area of test fabric enclosed by the frame. Spreading was carried out using a plastic spreading tool . After spreading the sample of composition on the fabric substrate, it was removed from the apparatus and weighed to check that the mass of applied sample was 0.5 ⁇ 0.01 gms .
  • the fabric with applied sample of composition was then assessed twice for whiteness, once after one hour and again after 24 hours.
  • the translucency of a composition may be measured by placing a sample of standardised thickness in the light path of a spectrophotometer and measuring transmittance, as a percentage of light transmitted in the absence of the gel.
  • MicroDry TM aluminium chlorhydrate from Reheis 10.
  • Triacontenyl vinyl pyrrolidone copolymer Triacontenyl vinyl pyrrolidone copolymer, Antaron WP-660 (ISP) 16. Paraffin wax, SP173P (Strahl and Pitsch) 17. Milled activated aluminium chlorohydrate from Guilini
  • a solution of the thickening polymer and other structurants in the organic liquid (s) was made by mixing these materials, heating and agitating the mixture at a temperature sufficiently high that the polymer and other structurants all dissolve. The mixture was then allowed to cool to 80-85 C before the aluminium antiperspirant active was added. The mixture was next allowed to cool to 5-30 C above its gelling temperature (determined in a preliminary experiment) and poured into dispensing containers as illustrated in Figs. 7 to 9 of the drawings. These were then left to cool to room temperature.
  • silica was mixed into the cold solvent using a high shear mixer (Silverson) .
  • the procedure than continued for introduction of the remaining constituents as in the general method of preparation.
  • compositions of all these Examples were observed to break down when applied to the skin after extrusion from a dispensing container; this extrudate could be rubbed into skin easily.
  • compositions of Examples 1 to 9 were observed to have a translucent appearance.
  • the composition of Example 10 appeared white and opaque although the container construction was identical.

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Abstract

L'invention porte sur des produits anti-sudoraux en crème épaisse contenus dans des flacons présentant une ouverture étroite de distribution, et dont le contenu est un anti-sudoral particulaire en suspension dans un liquide non miscible à l'eau présentant un indice de réfraction différant de celui du principe actif, de préférence de moins de 0,08. En maintenant la différence entre les indices de réfraction du liquide et de la phase solide, dans ces limites, on peut distribuer par l'ouverture étroite un ruban de crème épaisse apparaissant translucide même si la préparation brute contenue dans le flacon est opaque. Il est particulièrement désirable que la différence entre les indices de réfraction soient au plus comprises entre 0,01 ou 0,02 et 0,06, pour éviter les contraintes d'élaboration de la préparation, si les indices de réfraction du liquide et du principe actif avaient du être parfaitement identiques.
EP01915148A 2000-01-28 2001-01-18 Compositions semi-solides contre la transpiration Withdrawn EP1259214A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0002093 2000-01-28
GB0002093A GB0002093D0 (en) 2000-01-28 2000-01-28 Antiperspirants
PCT/EP2001/000574 WO2001058411A2 (fr) 2000-01-28 2001-01-18 Anti-sudoraux

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EP1259214A2 true EP1259214A2 (fr) 2002-11-27

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CA (1) CA2396538A1 (fr)
GB (1) GB0002093D0 (fr)
MX (1) MXPA02007312A (fr)
PL (1) PL356926A1 (fr)
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GB0201163D0 (en) 2002-01-18 2002-03-06 Unilever Plc Antiperspirant compositions
MXPA04006928A (es) 2002-01-18 2004-12-06 Unilever Nv Composiciones cosmeticas comprendiendo un compuesto de ciclodipeptido.
GB0214805D0 (en) * 2002-06-26 2002-08-07 Unilever Plc Cosmetic compositions
US6936242B2 (en) 2002-11-15 2005-08-30 The Gillette Company Multi-portion antiperspirant composition
US7166739B2 (en) * 2003-07-14 2007-01-23 Finetex, Inc. Esters of monomethyl branched alcohols and process for preparing and using same in cosmetics and personal care products
GB0428096D0 (en) 2004-12-22 2005-01-26 Unilever Plc Antiperspirant or deodorant compositions
US8469621B2 (en) * 2007-02-27 2013-06-25 The Procter & Gamble Company Personal care product having a solid personal care composition within a structure maintaining dispenser
FR3002141B1 (fr) * 2013-02-21 2015-06-26 Oreal Emulsion huile-dans-eau comprenant au moins un melange specifique de tensioactifs non-ioniques, une cire comprenant au moins un ester et un polysaccharide hydrosoluble
WO2019185325A1 (fr) * 2018-03-28 2019-10-03 Unilever Plc Distributeur de composition de fluide
US20230363992A1 (en) * 2020-09-28 2023-11-16 Kdc/One Development Corporation, Inc. Silicone-free antiperspirant and deodorant compositions

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US5833382A (en) * 1996-08-19 1998-11-10 Helene Curtis, Inc. Push-up dispenser suitable for dilatant materials
US5885559A (en) * 1996-09-06 1999-03-23 Colgate Palmolive Company Solid cosmetic composition containing hexanediol-behenyl beeswax as gelling agent
JPH1171228A (ja) * 1997-07-04 1999-03-16 Shiseido Co Ltd 油中水型乳化組成物
US5996850A (en) * 1997-12-04 1999-12-07 Chesebrough-Pond's Usa Co Package for dispensing flowable cosmetics
US6033651A (en) * 1998-06-10 2000-03-07 Revlon Consumer Products Corporation Gel cosmetic compositions
GB9908202D0 (en) * 1999-04-12 1999-06-02 Unilever Plc Cosmetic compositions
CO5160322A1 (es) * 1999-06-03 2002-05-30 Unilever Nv Composiciones antiperspirantes

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CN1420758A (zh) 2003-05-28
PL356926A1 (en) 2004-07-12
CA2396538A1 (fr) 2001-08-16
AR027931A1 (es) 2003-04-16
GB0002093D0 (en) 2000-03-22
RU2002123051A (ru) 2004-03-20
AU2001242342A1 (en) 2001-08-20
WO2001058411A2 (fr) 2001-08-16
MXPA02007312A (es) 2003-03-10

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