FI70374B - I HUVUDSAK VATTENFRI ANTIPERSPIRANTKOMPOSITION - Google Patents

Description

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(51) Kv.lk. * / Lnt.CI.4 A 61 K 7/32 (21) Patent application - Patentansöknlng 750191 (22) Application date - Ansökningsdag 24.01 .75 fFh '* (23) Starting date - Giltighetsdag 2 A. 01. 7 5 (41) Has become public - Blivit offentlig 25.07.76

National Board of Patents and Registration of Finland Date of display and month of publication. - 27.03.86

Patent and registration authorities Ansökan utlagd och utl.skriften publicerad (86) Kv. application - Int. ansökan (32) (33) (31) Privilege requested - Begird priority (71) Un i1 ever N.V., Burgemeester s'Jacobplein 1, Rotterdam,

Holland-Hoi land (NL) (72) Martin Callingham, London, Dwaipayan Chaudhuri, London,

Kenneth Vasey Curry, Camberley, Surrey,

Barry Graham Pike, Camberley, Surrey,

Michael Benington Taylor, Old Headington, Oxford, England-England (GB) (74) Lei tzinger Oy (54) Mainly anhydrous antiperspirant mixture - I huvudsak vattenfri antiperspirant composition

The invention relates to a substantially anhydrous antiperspirant mixture which is sprayed onto human skin in particulate form so as to form a non-toxic, non-irritating, contact dry layer consisting of a liquid phase and a solid phase.

Antiperspirant compositions usually contain an astringent such as aluminum chlorohydrate or zinc phenol sulfonate, which is believed to reduce the formation of sweat from the sweat glands. These astringents are usually applied to the skin as an aerosol spray.

We have now developed a completely new type of composition which limits the appearance of perspiration on the skin and which does not necessarily use the astringent, antiperspirant agents exemplified above and which therefore increases the non-irritating effect of the composition by avoiding the irritant effect of reducing agents and their products. When the non-irritancy is of little significance, reducing agents 2 70374 may be added to the compositions of the invention if desired. Instead of relying entirely on the chemical reduction of sweating at the sweating site, we take advantage of a means by which sweating can be absorbed on the surface of the skin as soon as it forms and thus keep the skin seemingly dry. This is accomplished by spraying or powdering the skin with a mixture containing a substance that has a high capacity to absorb moisture from the skin.

As a result, the transfer of sweat from the skin to the adjacent clothing can also be limited or completely prevented.

The mixture according to the invention is characterized in that (i) the solid phase contains 1 to 95% by weight of the mixture of a moisture-absorbing organic polymer in fine particle form with an average particle size of not more than 60 μιη, which after application to the skin absorbs moisture at least 10 times its own an amount corresponding to the weight of the polymer being chemically modified cellulose, microcrystalline cellulose, partially hydrolyzed starch-polyacrylonitrile / oxocase copolymer, cross-linked polyacrylic acid or a mixture thereof, and (ii) the liquid phase contains from 1 to 99% by weight of the mixture a carrier other than a propellant.

The compositions of the invention are flowable and are packaged in such a way that they can be applied to the skin of the wearer as a spray. A suitable form of packaging is an aerosol container with a valve, which can be used in connection with conventional liquefiable propellants, whereby the valve is made according to the mixture and distributed as a fine spray.

The flowable mixture may thus be in the form of an aqueous or non-aqueous liquid containing, preferably in suspension, a moisture-absorbing polymer as a fine powder. Alternatively, the polymer may be in solution in the mixture, but a mixture containing the powder is preferred. Alternatively, the polymer may be a dry, free-flowing fine powder, with a sufficient amount of propellant in the container to dispense the dry powder when such is used. The antiperspirant composition of the invention may also contain other ingredients in powder form.

An important property of the antiperspirant aerosol is that after spraying or otherwise applying to the skin, it forms a non-toxic, non-irritating, contact-dry, non-sticky, moisture-absorbing layer consisting essentially of a moisture-absorbing polymer. Therefore, it is important to select a polymer that is capable of absorbing a substantial amount of water and that is capable of forming a dry, non-sticky layer on the skin.

By "touch-dry, non-sticky layer" is meant a layer, including a film, deposit, or barrier layer that, after application to the skin, feels dry and is not sticky or sticky to the touch and does not normally become sticky when used to absorb moisture such as sweat and adhere to adjacent clothing. It is to be understood that the user is likely to be dissatisfied with an antiperspirant product that remains sticky or sticky after application to the skin and adheres to adjacent clothing. For this reason, we do not claim exclusivity for the use of moisture-absorbing organic polymers that are tacky under the conditions prevailing on human skin.

However, we have found that blends containing the most potential "non-sticky" polymers in use may form too sticky a layer if too many other ingredients, such as oily carriers, are included in the blend. Therefore, care should be taken not to add such ingredients to the mixture in excessive amounts.

Although the average particle size of the powder is not usually critical to its ability to adhere to the skin or absorb moisture from the skin, it is necessary to ensure that the average particle size is so small that they can pass through the aerosol delivery valve without clogging it. It will be appreciated that the average particle size of the powder and the valve orifice and package sizes may be selected so that the antiperspirant mixture can be dispensed without such problems. The suitable average particle size of the supernatant moisture absorbing polymer of the invention is not more than 60 μ, preferably not more than 30 μ.

A moisture-absorbing organic polymer is a polymer that is organic rather than inorganic in structure and may be of either synthetic or natural origin and may itself be soluble or insoluble in water while having the necessary water-absorbing capacity. Although the polymer, when deposited on the skin after application of the antiperspirant mixture, should be able to absorb at least as much water from the dry state as its own weight, the recommended polymers are capable of absorbing a greater amount of water. For example, some polymers can absorb moisture 5-10 times their own weight and even more after deposition and still remain in contact with the skin in a non-sticky state.

Preferred polymers of the invention are those that have a high ability to absorb water, although many of these highly absorbent polymers are expensive to manufacture and thus potentially impractical for economic reasons.

The moisture absorbent polymers used in accordance with the invention should desirably also have the ability to lose moisture absorbed by evaporation upon contact with the skin, so that they can themselves regenerate their greater moisture absorbing state and prolong their antiperspirant efficacy.

This moisture-absorbing property can be easily determined simply by adding water to a layer of test polymer on a suitable skin-mimicking surface until the layer appears wet and thus no longer dry to the touch. The moisture uptake capacity as well as the ability to lose absorbed moisture due to evaporation can then be determined gravimetrically.

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Moisture-absorbing polymers found to be particularly suitable include chemically modified cellulose, microcrystalline cellulose, partially hydrolyzed starch-polyacrylonitrile or copolymer, crosslinked polyacrylic acid, or a mixture thereof.

The amount of polymer in the antiperspirant composition of the invention to be dispensed in particulate form, as a spray, generally depends on the amount of propellant in the composition, the physical quality of the composition and the type of aerosol device used.

When the antiperspirant composition is a liquid containing powder in suspension and packaged in a standard single chamber jar, the polymer may comprise from about 1% to about 30%, preferably from about 3% to about 10% by weight of the composition. On the other hand, when the propellant is largely separated from the antiperspirant mixture, in a separate chamber inside the vessel, such as the device described in our pending British Patent Application No. 11051/71 (published as the corresponding Hilian Patent Application No. 7,205,294), may constitute up to 95% by weight of the mixture.

It is obvious that some organic polymers meet the requirement of moisture absorption, but still form a layer when sprayed on the skin, which remains sticky or becomes sticky in use. A notable example is sodium alginate, most forms of which can absorb water from about 1 to about 12 times their own weight under experimental conditions on human skin. Thus, we do not claim exclusivity for an antiperspirant blend containing sodium alginate or other organic polymers that behave similarly as the sole moisture absorbing polymer. It should be noted, however, that sodium alginate or similar polymers may be added to the antiperspirant compositions of the invention provided that they also contain a sufficient amount of "non-sticky" moisture absorbing polymer to compensate for the otherwise non-sticky "stickiness".

The propellant according to the invention can be any liquefiable gas known to a person skilled in the art to be used in an aerosol container.

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Examples of suitable propellants are trichlorofluoromethane (propellant 11), dichlorodifluoromethane (propellant 12), dichlorotetrafluoromethane (propellant 114), monochlorodifluoromethane (propellant 22), trichlorotrifluoromethane (propellant 113), propane, butane and isobutane alone. Preferred propellants are trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoromethane and isobutane used alone or in mixtures. Normal testing, well known in the aerosol industry, determines the selection of the correct amounts of propellant or gas mixture. In general, the propellant comprises from about 1% to about 99% by weight of the antiperspirant composition. When using a single chamber aerosol container, particularly preferred propellant ranges are from about 40% to about 95% by weight of the mixture. Recommended limits for the propellant are from about 1% to about 50%, preferably from 1% to 10% by weight of the mixture when using special containers in which most of the propellant is kept separate from the product to be applied, such as the two-chamber container described in our pending British Patent Application No. 11051 / 71 (published in the corresponding Dutch patent application No. 7,205,295).

A cosmetically acceptable polymeric carrier is also added to the antiperspirant composition of the invention, which can act in many different ways to improve the effectiveness of the composition. In particular, the presence of a carrier can improve the initial adhesion of the moisture absorbing polymer to the skin, thus helping the skin to "capture" it as it is applied as a spray. The carrier can also act as a laxative, lubricant or spreading agent to promote even distribution of the moisture absorbing polymer on the skin.

In case the flowable antiperspirant mixture is in the form of a liquid containing a powder, for example a suspension, a carrier such as water, isopropyl myristate, hexylene glycol, dipropylene glycol, ethanol or other alcohols such as poly-lower alkoxylated alcohols such as di, or esters. -n-butyl phthalate, dioethyl sebacase, diisopropyl adipate and o-ethyl, ethyl carboxymethyl phthalate and mixtures thereof, particularly effectively improve the adhesion of the moisture absorbing polymer to the skin.

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The amount of carrier in the antiperspirant mixture is from 1 to 50%, preferably from about 5% to about 20% by weight of the mixture.

When the amount is more than about 20%, the mixture deposited on the skin may appear uncomfortably sticky, sticky, oily or greasy depending on the nature of the carrier.

A suspending agent may need to be added to the antiperspirant aerosol to prevent the release of the moisture absorbing powder. There are a large number of suitable commercially available suspending agents. Examples of such suspending agents are hydrophobic treated clays which swell inorganic solvents and are exemplified by hydrophobic hentonite such as Betone 38, fumed silicas such as Cab-O-Sil M-5 and AEROSIL 200, and fatty soaps such as aluminum stearate. Other useful suspending agents include monoethanolamides such as coconut monoethanolamide, octadecyl monoethanolamide and stearoyl monoethanolamide. Another class of suspending agents are amines such as laurylamine, stearylamine, tetradecylamine, hexadecylamine, octadecylamine and eicosylamine.

When a suspending agent is used, it is usually colloidal in size with a particle size of less than 0.03 microns. The suspending agent may be present in the mixture up to 2% by weight, preferably 0.1 to 1.5% by weight of the mixture.

In addition to the ingredients of the above mixtures, smaller ingredients may be added if desired. For example, germicides can be added to the antiperspirant mixture. Suitable germicides, given by way of example only, include trichlorocarbanilide, trifluoromethylcarbanilide, tribromosalicylanilide and 2,4,4'-trichloro-2-hydroxy-diphenyl ether.

Such germicides, when used, may be used up to about 0.5% by weight of the mixture to inhibit the growth of skin bacteria and to reduce or prevent the development of unpleasant odors.

It is also possible to add to the antiperspirant mixture, if desired, a perfume and / or odor suppressant, such as that disclosed in our pending patent application No. 34321/73 (published as Dutch Patent Application No. 7,409,704), usually in a concentration of less than about 1% by weight of the mixture.

As mentioned above, it is also possible to add an effective amount of an antiperspirant such as aluminum chlorohydrate, aluminum chloroalcoholates, zinc phenol sulfonate, zirconium halide hydrates and tetraphenyl boron as a second optional ingredient.

When such antiperspirants are used, they may be present up to about 5% by weight of the mixture. Usually, when such substances are used, they constitute about 0.1 to 1% by weight of the mixture.

It is also possible to add anticholinergic agents such as trimethylacetyl-scopolamine hydrochloride to the mixtures according to the invention.

To act as an antiperspirant, the mixture is sprayed onto the skin, for example the user's armpit, to provide a non-sticky moisture absorbing layer on the skin. The moisture-absorbing polymer can then act to absorb moisture as it is excreted from the skin as sweat, thereby saving the adjacent clothing, at least for a limited time, from contact with sweat. This protection time depends on the ability of the polymer to absorb moisture and its amount to the skin, as well as the amount that the user sweats. As we have mentioned, it is clearly advantageous if the polymer can lose moisture through evaporation while on the skin, so that its effectiveness as an antiperspirant can last longer.

The invention is illustrated by the following examples.

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Example_1 This example illustrates the use of a synthetic water-insoluble polymer. The following ingredients were filled into the aerosol container as product A: pa ino-%

Microcrystalline cellulose (AVICEL RC581) 3.0

Isopropyl imyristate 3.0

Pyrogenic silica (AEROSOL 200) 0.2

Perfume 0.2

Propellant 11/12 (65:35) to 100

The second product (B) was prepared from the same ingredients, except that AVICEL RC581 was replaced with 3.5% by weight aluminum chlorohydrate.

A test group of 24 individuals, all regular users of aerosol antiperspirants, was asked to investigate the ability of both formulations to inhibit axillary moisture.

This was done by spraying both products on the freshly washed armpits at a distance of 15 cm for 2 seconds. In the case of product A, this time was sufficient to form a layer of moisture-absorbing polymer (AVICEL RD581) which prevented the transition from the armpits to the adjacent wading.

Members of the group were asked to continue their daily laboratory work and, after five hours, to determine the effectiveness of both products by considering whether the phrase “prevent underarm moisture” was correct. This determining art in their response was divided on a five-point scale from 1 (strongly disagree) to 5 (strongly agree). Their score was then analyzed statistically to determine if the product deposited on the skin prevented the development of moisture in the armpits.

In this regard, Formulations A and B both effectively inhibited axillary moisture formation with equal effectiveness, indicating that the traditional antiperspirant property of aluminum chlorohydrate could be completely replaced by a moisture-absorbing non-shrinking polymer without loss of efficacy.

The comparison was repeated using two products based on the formulation described above except that in one case half of the weight of AVICEL RC581 was replaced with sodium alginate to give product C. In another case, AVICEL RC581 was completely replaced with an equal amount of sodium alginate to give product D.

In this comparison, product D, although initially producing a seemingly dry layer, became contact sticky within one hour under the same experimental conditions as used for products A and B. On the other hand, product C remained dry on the skin and absorbed sweat satisfactorily to a sticky or moist time over a five hour test period.

From the latter comparison, it was concluded that although sodium alginate as a polymer was able to effectively absorb sweat, it became too sticky under the conditions of use. However, when sodium alginate was blended with a "non-sticky" polymer, i.e. With AVICEL RC581, the moisture absorption capacity of the product was satisfactory and no tack developed.

The conclusion was that when tested in humans, the compositions of the present invention proved to be effective antiperspirants by effectively preventing sweat from appearing on the skin and also on adjacent clothing: there was no problem of clothing staining as is sometimes associated with conventional antiperspirants. The antiperspirant mixture of the invention was also non-irritating.

Example 2

A germicidal antiperspirant mixture was prepared by the method described in Example 3 from the following ingredients: 70374 11% by weight

Cross-linked polyacrylic acid 5.0

Isopropyl myristate 4.5

Non-ionic detergent 0.1 2,4,4'-trichloro-2-hydroxy-diphenyl ether (Irgasan DP300) 0.5

Pyrogenic silica (AEROSIL 200) 0.4

Perfume q.s.

Propellant mixture 11/12 (65:35) to 100

Example 3

An antiperspirant mixture rich in astringent was prepared from the following ingredients:% by weight

Base hydrolyzed starch polyacrylonitrile graft copolymer 1.5

Aluminum chlorohydrate 3.5

Isopropyl myristate 4.5

Non-ionic detergent 0.1

Pyrogenic silica (AEROSIL 200) 0.4

Perfume q.s.

Propellant mixture 11/12 (65:35) to 100

The mixture was prepared by adding each material mixture to an aerosol container with a valve that could be pressurized through its valve, closing the container and then adding the propellant mixture thereto under pressure through the valve to give a final pressure of 3.5 kg / cm 2. Using a distribution valve, a uniform spray was obtained and it was possible to obtain a fine powder layer by directing the spray onto the skin.

Example 4 This example illustrates the use of chemically modified cellulose as a moisture absorbing polymer.

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The aerosol dispenser is filled with the following components:% by weight

Chemically modified cellulose 1

Deodorant 1.5

Isopropyl myristate 2

Cetyl alcohol 0.5

Dipropylene glycol 0.3

Dimethyl isearylammonium hector 0.3

Ethanol 4

Perfume 0.44

Propellant 11/12 (50:50) to 100

Claims (1)

i3 70374 Claim A substantially anhydrous antiperspirant mixture sprayed to human skin in particulate form to form a non-toxic, non-irritating, contact dry layer consisting of a liquid phase and a solid phase, characterized in that (i) the solid phase contains 1 to 95% by weight of organic mixture a polymer in finely divided particle form with an average particle size of not more than 60 μm, which after application leaves the skin to absorb moisture at least 10 times its own weight, which polymer is chemically modified cellulose, microcrystalline cellulose, partially hydrolysed starch-polyacrylonitrile oxyacrylonitrile oxy a mixture thereof, and (ii) the liquid phase contains 1 to 99% by weight of the liquefied propellant and 1 to 50% by weight of the mixture of an anhydrous polymeric carrier other than the propellant. I am interested in the antiperspirant composition, which utilizes the sprays of the spray in the form of a particle form, which is described in the first instance, in particular, in the form of a mixture, 1 - 95% of the bleaching agent in the form of an organic polymer and a finely divided particle form, a stem with a particle size of 60 μm, the polymer after the quartz is quenched by the absorption of the polymer in the form of a chemical agent, Cellulose, a microcrystalline cellulose, which is a hydrolyzed styrofoam polyacrylonitrile glycol polymer, is a polyacrylic acid or a bleach, and I give the propellants.