Clear antiperspirant stick containing dibenzylidene alditol

IS 2 193 237 T3

DESCRIPTION

Antiperspirant stick containing dibenzylidenalditol.

The invention relates to clear gel cosmetic sticks including a solubilized antiperspirant salt.

Antiperspirant gel sticks typically include a liquid carrier, an antiperspirant salt, a gelling agent, and one or more emollients. Dibenzylidene alditols such as dibenzylidene sorbitol (DBS), also known as dibenzylidene monosorbitol acetal (DBMSA), are a type of gelling agent that has been used in such sticks. Dibenzylidenalditols can degrade during manufacture and subsequent storage of the gel stick, in part due to the presence of the acidic antiperspirant salt in the stick. A product of degradation, benzaldehyde, can provide an undesirable odor and can cause the stick to lose hardness and discolor. Commercially available DBS antiperspirant gel sticks typically contain more than 2% DBS in order to have sufficient toughness. However, such bars do not exhibit optimal transparency and odor characteristics.

Various stabilizing agents have been incorporated into antiperspirant gel sticks containing dibenzylidenalditols in an effort to minimize the degradation of dibenzylidenalditol. Examples include: sodium hydroxide, potassium hydroxide, sodium carbonate, zinc acetate, zinc oxide, zinc carbonate, potassium carbonate, diethanolamine, triethanolamine, sodium succinate, sodium benzoate, sodium octanoate, hexamethylenetetraamine, urea , 2-amino-2-methyl-1-propanol, magnesium sulfate, calcium hydroxide, and N- (2-hydroxyethyl) acetamide. AND^or These and other stabilizing agents, although apparently effective to some degree in stabilizing dibenzylidenalditol, may present other problems associated with them. Sodium hydroxide and potassium hydroxide, for example, can provide an undesirable odorous composition.

US-A-4720381 discloses a clear antiperspirant gel stick comprising 1-10% dibenzyl monosorbitol acetal, a solvent and an antiperspirant, optionally 0.2% hydroxypropylcellulose when using 3% DBMSA in the antiperspirant stick.

Patent document US-A-4725430 describes a transparent or translucent cosmoetic stick comprising 1-10% dibenzyl monosorbitol acetal, a solvent, an antiperspirant and a stabilizing acetamide gel, optionally 0.2% hydroxypropylcellulose is included when 3% DBMSA is used in the antiperspirant stick.

In accordance with the present invention, a clear gel cosmoetic stick is provided comprising a liquid carrier, an antiperspirant salt dissolved in said liquid carrier, a hydroxyalkyl cellulose and 0.5% to 2% by weight of a dibenzylidenalditol. The cosmetic stick may optionally further comprise a chelating agent. The cosmetic stick may comprise from 70% to 95% by weight percent, preferably from 75% to 92%, of a liquid carrier, from 1% to 22%, preferably from 3% to 15% of an antiperspirant salt dissolved in said vehicle, 0.5% to 2%, preferably 0.5% to 1.5% of a dibenzylidene alditol, 0.1% to 0.5%, preferably 0.2% to 0.4% of a hydroxyalkyl cellulose and 0.05% to 3%, preferably 0.1% to 2% of a chelating agent. Preferably the liquid carrier comprises a polyhydric alcohol having 3 to 6 carbon atoms and 2 to 6 hydroxyl groups and is substantially free of strong alkaline-based and monohydric alcohol such as sodium hydroxide and potassium hydroxide. Preferably the cosmos bar will have a pH greater than 4.4, more preferably greater than 4.7; a haze of less than 120 NTU, more preferably less than 100 NTU and a hardness of 60 to 150. By lowering the level of dibenzylidenalditol to 1.5% or less, the transparency and odor characteristics of the stick significantly improve. The hardness of the stick is maintained by the addition of hydroxyalkyl cellulose. The color of the stick is enhanced by the addition of the chelating agent.

A "clear" gel stick, as used here, is a stick that is visually transparent, so, like glass, it allows easy viewing of objects behind it. Preferred clear gel bars have a turbidity measurement, expressed in Nephelometric Turbidity Units (NTU), of less than 120 NTU, more preferably less than 100 NTU, and most preferably less than 80 NTU, when measured with a Reading Turbidometer. Direct Hellige® 965. By "substantially free of anti-odor" is meant that the gel stick (without fragrance or fragrance masking agent) has an anti-odor ratio of 0 to 2, preferably 0 to 1, on a scale of 0 to 5 used. by experts (or perfumeries) trained in odor, where 0 means undetectable anti-odor and a ratio of 4 to 5 is considered unacceptable odor. By "stable" it is meant that product samples, when stored at 45 ° C for three months, will not exhibit any odor signs of benzaldehyde or other anti-odor (that is, they retain an odor ratio of 0 to 2 ) and did not exhibit any significant change in transparency (ie, it retains transparency better than 120 NTU). Yellowness is measured by an absorbance spectrophotometer at 408 nm with 0 to 0 ppm of ferric chloride in water corresponding to 5 to 500 ppm of ferric chloride in water.

Clear gel sticks include a liquid carrier, an antiperspirant salt dissolved in the liquid carrier, and a dibenzylidenalditol gelling agent. The liquid carrier together with the gelling agent provides the matrix, or body, of the gel stick.

The preferred liquid carrier comprises a polyhydric alcohol having 3 to 6 carbon atoms and 2 to 6 hydroxyl groups. Such polyhydric alcohols include diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,4-butylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-buti2

ES 2 193 237 T3 lenglycol, 2,4-dihydroxy-2-methylpentane, glycerin, sorbitol and the like, and mixtures thereof. Preferred are: 1,2-propylene glycol (commonly referred to as simply propylene glycol), dipropylene glycol, 2-methyl-1,3-propanediol, 1,3-butylene glycol, sorbitol, and mixtures thereof. Most preferred as a liquid vehicle is propylene glycol, which may optionally include one or more of the polyhydric alcohols mentioned above. While the preferred liquid carrier may optionally include a polyhydric alcohol such as ethanol, it is preferred that the liquid carrier is substantially free of monohydric alcohol. While the liquid carrier may also optionally include a cosolvent, for the gelling agent (eg, N-methylpyrrolidone), as described in the prior art, it is not preferred.

The gel stick typically includes between 70% and 95%, preferably between 75% and 92% of the liquid carrier by weight. A bar that includes an insufficient amount of the liquid carrier may not be transparent or may provide inadequate matrix support for the rest of the components. A rod that includes too much liquid carrier may lack sufficient amounts of one or more of the other components of the rod.

Dibenzylidenalditol is the gelling agent. Examples include dibenzylidene sorbitol (DBS), dibenzylidenexylitol, and dibenzylidene ribitol. The aromatic rings in each benzylidene group can be unsubstituted or substituted, as described in US Patent No. 5,200,174. When substituted, it is preferred that the benzyl ring contains a group that removes electrons at the target position. Substituted topical compounds include di (meta-fluorobenzylidene) sorbitol and di (metachlorobenzylidene) sorbitol. The preferred gelling agent is dibenzylidene sorbitol (DBS).

The gel stick contains between 0.5% and 2% dibenzylidene alditol by weight. If the gel stick includes too much dibenzylidenalditol, it may lack sufficient transparency and / or it may have an undesirable odor. If the gel stick includes too little dibenzylidenalditol it may lack sufficient hardness. For optimal transparency the gel stick contains 0.5% to 2%, more preferably 0.5% to 1.5%, most preferably 0.7% to 1.3% dibenzylidenalditol by weight. A particularly advantageous feature of the present invention is the use of low levels (ie, 1.5% or less) of the gelling agent dibenzylidenalditol, which results in sticks of exceptional transparency and odor-free characteristics.

Antiperspirant salts that can be used in the gel sticks of the present invention include any of the conventional aluminum, zirconium and aluminum-zirconium salts which are known to be useful in antiperspirant compositions. These salts include aluminum halides and aluminum hydroxyhalides (eg, aluminum hydroxychloride) and mixtures or complexes thereof with zirconyl oxyhalides and zirconyl hydroxyhalides (eg, aluminum-zirconium hydroxychloride).

Preferred aluminum salts are those having the general formula Al2 (OH) 6-a-Xa where X is Cl, Br, I or NO3, and is from 0.3 to 4, preferably 1 to 2, such that the molar ratio of Al to X is 1: 1 to 2.1: 1. These salts usually have some water of hydration associated with them, typically on the order of 1 to 6 moles per mole of salt. Most preferred is that the aluminum salt is aluminum hydroxychloride (ie, X is Cl) and a is 1, such that the molar ratio of aluminum to chlorine is 1.9: 1 to 2.1: 1.

Preferred aluminum-zirconium salts are mixtures or complexes of the aluminum salts described above with zirconium salts of the formula ZrO (OH) 2-pbYb where Y is Cl, Br, I, NO3 or SO4; b is about 0.8 to 2; and p has the valence of Y. Zirconium salts also typically have some water of hydration associated with them, typically on the order of 1 to 7 moles per mole of salt. Preferably the zirconium salt is zirconyl hydroxychloride of the formula ZrO (OH) 2-b Clb where b is 1 to 2, preferably 1.2 to 1.9. The preferred aluminum-zirconium salts have an Al: Zr ratio of 1.7 to 12.5; most preferably about 2 to 10, and a metal: X + Y ratio of 0.73 to 2.1; preferably 0.9 to 1.5. A preferred aluminum zirconium hydroxychloride salt (ie, X and Y are Cl), which has an Al: Zr ratio of 2 to 10 and a metal: Cl ratio of 0.9 to 2.1. Therefore, the term aluminum zirconium hydroxychloride is intended to include the tri-, tetra-, penta- and octa-hydroxychloride forms. Aluminum-zirconium salt complexes may also contain a neutral amino acid, preferably glycine, typically with a Gly: Zr ratio of 1: 1 to 4: 1.

It is especially preferred to use aluminum-zirconium and aluminum antiperspirant salts with enhanced efficacy in the gel sticks of the present invention. By "enhanced efficacy antiperspirant salts" is meant antiperspirant salts which, when reconstituted as 10% aqueous solutions, produce an HPLC chromatogram (as described, for example, in US Patent No.^° 5,330,751), in which at least 70%, preferably at least 80% of the aluminum is contained in two successive peaks, conveniently labeled as peaks 3 and 4, in which the ratio of the area under peak 4 to the area under peak 3 is at least 0.5; preferably at least 0.7 and more preferably at least 0.9 or greater. Any suitable HPLC technique can be employed as long as it is capable of resolving the Al component into five peaks. High efficacy (or activated) antiperspirant salts are well known in the industry and are commercially available from various suppliers.

To incorporate the antiperspirant salt into the gel stick composition, it is preferred that the salt is first solubilized or dissolved in a portion of the liquid carrier. Accordingly, it is preferred to use the polyhydric alcohol solutions of antiperspirant salts. Solubilized salts which have been partially neutralized by the addition of a pH raising agent at pH 4.1 to 5.0 are especially preferred; preferably 4.3 to 4.8. antiperspirant salts

Particularly preferred neutralized ES 2 193 237 T3 are those containing an additional alkaline glycinate, such as sodium, potassium or zinc glycinate. Such solubilized antiperspirant salts are described in PCT / US95 / 14073 and in US Patent 5,463,098. An example of such a solubilized salt, which is partially neutralized with zinc glycinate, is Westchlor® A2Z 8106 (Westwood Chemical Corp.). The preparation of a preferred solubilized antiperspirant salt is described in Example 1 below.

The additional alkaline glycinate that is preferably included in the solubilized antiperspirant salt raises the pH of the antiperspirant salt and, as a result, reduces the degradation of the dibenzylidenalditol in the gel stick. It is usually preferred to add sufficient alkali glycinate to the solubilized antiperspirant salt so that the pH in an approximately 10% aqueous solution of the antiperspirant salt is raised from 4.1 to 5.0; preferably 4.3 to 4.8. (The 10% aqueous solution can be an approximately 50:50 polyhydric alcohol: water solution). Preferred gel sticks that include such a partially neutralized salt will have a pH greater than 4.4; preferably 4.7 to 5.5; and more preferably 4.8 to 5.3. The pH of the finished bar can be measured by dissolving one part of the bar in ninety-nine parts of water. The pH of the resulting solubilized antiperspirant salt or stick can, of course, be adjusted to the preferred pH ranges mentioned above with any pH-raising agent, or combination of pH-raising agents, provided the selected agent or agents are soluble in the vehicle and do not adversely affect the transparency or odor characteristics of the stick to a significant extent.

Sufficient antiperspirant salt should be dissolved in the liquid vehicle so that the final composition, after all components have been added, includes between 1% and 22%, preferably between 3% and 15%, of the antiperspirant salt by weight. It should be noted that the reference throughout this specification to weight percent antiperspirant salt is intended to be calculated according to the standard industrial method, which includes bound water and glycine. This calculation is compared to the new US patent method, which excludes bound water and glycine, as follows:

<td>Salt</td><td>Method standard</td><td>Method P. USA</td>

<td>Al-Zr-Gly in Prop.</td><td></td><td></td>

<td>Glycol (Ex. 1)</td><td> 30 %</td><td> 22 %</td>

<td>Al-Zr-Gly stick</td><td></td><td></td>

<td>(Ex. 2)</td><td> 11%</td><td> 8,6%</td>

The gel stick includes a hydroxyalkyl cellulose as an additional gelling (or cogelling) agent. The hydroxyalkyl cellulose provides adequate hardness to the stick even when the stick only includes a low level of dibenzylidene alditol. The combined use of hydroxyalkylcellulose co-gelling agent with reduced amounts of dibenzylidenalditol (ie, amounts of 1.5% or less) allows the production of gel sticks of exceptional transparency and stability.

Preferred hydroxyalkyl cellulose co-gelling agents include alkyl groups having between one and five carbon atoms. The preferred co-gelling agent is hydroxypropyl cellulose (eg Klucel® HFF, Aqualon®). When included in the gel stick, the hydroxyalkyl cellulose will be present in an amount of 0.08% to 1%, preferably 0.1% to 0.5%; More preferably 0.2% to 0.4% by weight.

Preferred gel sticks have a hardness between 60 and 150 when measured on a TA-XT2 Texture Analyzer (Stable Micro System, Haste Hill, England). These hardness measurements correlate the grams of force required for a penetrating needle of the standard arrowhead type to penetrate the bar a distance of 5 mm to 1 mm per second.

The gel stick of the present invention would also optionally and preferably include a chelating agent to improve its color and transparency. A chelating agent is a compound in which the atom forms more than one coordinate bond with metals in solution. Examples of chelating agents include salts of ethylenediaminetetraacetic acid (EDTA) such as ethylenediaminetetraacetate, tetrasodium and trisoodium (Na4EDTA and Na3EDTA), hydroxyethylethylenediaminetriacetate (HEDTA), diethylenetriaminepentaacetate (DTPA), nitro-sodium ethanedic acid nitro-acetate (DTPA), nitro-ditrium-salodilacetate Diethaneoldiglycine (DEG) and 1,3-propylenediaminetetraacetic acid (PDTA). All of these are known and commercially available. Preferred chelating agents include tetrasodium and trisodium ethylenediaminetetraacetate (Na4EDTA and Na3EDTA). Gel sticks typically include between 0.05% and 3%, preferably between 0.1% and 2% of the chelating agent by weight. If too little chelating agent is included, the stick may have less transparency, an undesirable odor, and / or an undesirable yellowish color. If too much chelating agent is included, the transparency and / or other properties of the stick may be adversely affected. The chelating agent can reduce the color (in particular the yellow color) of the stick which can result, for example, from the presence of residual iron (or other metallic contaminants) which may be present on the stick from a variety of sources. The gel stick preferably measures 0-1 on the yellowness scale.

The chelating agent can also act as a stabilizing gelling agent by increasing the pH of the stick, thereby reducing or eliminating the need for other stabilizing alkaline gelling agents such as NaOH and KOH. Preferably the gel stick was substantially free of NaOH and KOH and, as a result, did not have the odor that can result from the interaction of these materials with the carrier, particularly propylene glycol. The removal of other stabilizing alkaline gelling agents, particularly NaOH and KOH, is an advantageous feature and is believed to contribute substantially to the odor-free characteristics of the gel sticks.

Suitable emollients can be incorporated into the gel stick to provide property4

ES 2 193 237 T3 desirable application conditions (softness, tack reduction, etc). Examples of emollients include fatty acid osesters such as isopropyl myristate and isopropyl palmitate; diesters of adipic, phthalic, and sebacic acids such as di-n-butyl phthalate, diisopropyl sebacate, diethyl sebacate, and diisopropyl adipate; propylene glycol diesters of short chain fatty acids; non-volatile silicone oils such as dimethylsiloxane and dimethicone copolyol; volatile silicones such as Dow Corning¹® 344 and Dow Corning¹® 345 (available from Dow Corning), Silicone 7207® and Silicare 7158® (available from Union Carbide) and SF 1202® (available from General Electric); C12-C15 alcohol benzoates such as Finsolv® (available from Finetex, Inc.); fatty alcohols such as acetolic alcohol and stearolic alcohol; derivatives of alkyl ethers of polyethylene glycols, polypropylene glycols and polypropylene-polyethylene glycol copolymers such as PPG-5-Buteth-7, PPG-5-Ceteth-20, PPG3-Isosteareth-9 and Glycereth-7-Diisononanoate. Many other examples of emollients are known in the art. The gel stick includes a sufficient amount of emollient to provide the stick with the desired application properties without interfering with the clarity of the product. Preferred emollients should be soluble in the liquid vehicle and form a clear solution therein. The gel stick preferably includes less than 10%, more preferably less than 3%, and more preferably between 0.25% and 1.25% of emollients by weight.

The fragrances used in the gel stick can be any conventional fragrance that provides the desired scent to the stick. The amount of fragrance included should be the amount necessary to provide the desired scent. The gel stick typically includes less than 2.5%, preferably less than 1.5% of the fragrance by weight.

The gel stick may contain other optional conventional ingredients such as humectants, hardeners, fillers, colorants, preservatives, bactericides, UV absorbers, and the like. Obviously such materials should be selected in such a way that they do not adversely affect the transparency of the bar.

The gel sticks of the present invention can be prepared by the conventional two-stage procedure known in the art. That is, a first phase containing a part of the carrier and the gelling agent is heated to a temperature sufficient to dissolve the gelling agent (typically about 110 ° C), then cooled to about 100 ° C. A second phase containing a part of the vehicle and the rest of the ingredients is prepared and heated from 60 ° to 80 ° C, then combined with the first phase. The combined mixture is poured into stick molds and cooled to solidify. A preferred alternative method of preparation is to combine all the ingredients at a temperature below 50^°C with sufficient mixing to form a uniform dispersion (dibenzylidene alditol is not soluble at low temperature; hydroxyalkyl cellulose can be predissolved in a portion of the vehicle prior to mixing). Parts of this dispersion are then heated under lighting to a temperature sufficient to dissolve the dibenzylidene ditol, then the resulting solution is poured into bar-shaped molds and cooled to solidify. Ideally, no part of the solution should be stored at a temperature in excess of 90 ° C.^°C for more than a few minutes. This preferred procedure is more fully described in US Patent No.^° 5.723.135.

The following specific examples further illustrate the invention:

Example 1

Antiperspirant Salt

A 50% sodium glycinate solution was prepared by mixing 77.6 kg (171 lbs.) 50% NaOH with 30.8% (67.8 lb) of water, then 72.8 kg (160.3 lb ) of glycine (1: 1 molar ratio of glycine to NaOH), the temperature was raised from 25^° a30^°C, after 30^° a35^°C, after the first and second addition respectively. 3.5 kg (7.8 lb) of 50% sodium glycinate was added to 46.9 kg (103.3 lb) of propylene glycol and the solution was mixed for ten minutes. To this solution, 15.4 kg (33.9 lb) of zirconium hydroxychloride glycinate (50% aqueous solution of ZHC-gly with a Zr: gly ratio of approximately 1: 1) was added. After mixing this solution for approximately ten minutes, 115.8 kg (255 lb) of 10% ACH 'solution (prepared by heating 10% ACH to approximately 80%) was added.^°C for about 16-17 hours) and mixed for about ten minutes. This solution was preheated to approximately 70^° a75^°Cy was continuously fed to a JHE® type flash evaporator (APV Crepaco Inc. Tonawanda, NY; Modified evaporator by mounting on top of the subobit evaporation chamber of a 914 mm (3 ft) grinding tower filled with approximately 762 mm (2.5 ft) of 0.5 inch (13 mm) ceraomic Berl chairs )) maintained at approximately 60 mm Hg (absolute pressure) from which approximately 4,546 l / h (1 gal / h) of a clear solution comprising 65% propylene glycol was withdrawn, 30 % aluminum-zirconium glycinetrahydroxychloride with enhanced efficacy (more than 80% aluminum from peaks 3 and 4 with peak 4 to peak 3 air ratio greater than 1 and Gly: Zr ratio approximately 1.6: 1) and 15 % of water. The pH of a sample of this solution diluted with an equal part of distilled water was approximately 4.7. This antiperspirant salt solution was incorporated in the following examples.

IS 2 193 237 T3

<td colspan="3">Examples 2 and 3</td>

<td>Ingredient</td><td>Ex. 2% weight</td><td>Ex. 3% weight</td>

<td>Propylene glycol</td><td> 85,50</td><td> 84,70</td>

<td>Al / Zr tetrahydrochloride</td><td></td><td></td>

<td>-gly</td><td> 11,00^*</td><td> 11,00^*</td>

<td>Dibenzylidene sorbitol</td><td> 1,00</td><td> 1,30</td>

<td>Hydroxypropyl cellulose</td><td> 0,30</td><td> 0,30</td>

<td>Na4EDTA</td><td> 0,20</td><td> 0,20</td>

<td>Diisopropyl sebacate</td><td> —</td><td> 1,00</td>

<td>Glycereth-7-diisononanoate</td><td> 0,50</td><td> —</td>

<td>Dimethicone copolyol</td><td></td><td></td>

<td>(ABIL® B 8851)</td><td> 0,25</td><td> 0,25</td>

<td>Fragrance</td><td> 1,25</td><td> 1,25</td>

<td colspan="2">^*% weight of salt in the final composition.</td><td>The salt is</td>

added in solubilized form as prepared in Example 1.

Examples 2 and 3 were prepared according to the following procedure.

Phase a

Approximately 65% ​​of the total mass of propylene glycol (excluding that which is part of the antiperspirant salt solution) was added to an appropriately sized container. Hydroxypropyl cellulose was added and stirred well to dissolve. After heating this solution from 110 to 115 ° C, dibenzylidene sorbitol was added with stirring until complete dissolution. This Phase A solution was then cooled to approximately 100^°C.

Phase b

Approximately 35% of the total mass of propylene glycol (excluding that which is part of the antiperspirant salt solution) was added to an appropriately sized container, stirred and heated to approximately 60-70 ° C. Na was added₄EDTA and mixed well. The Al / Zr -glY tetrahydrochloride solution (as prepared in Example 1) was added and the solution mixed well until it became clear and homogeneous. The emollients (ie, diisopropyl sebacate or glycereth-7-diisononanoate and the dimethicone copolyol) were then added and the Phase B solution mixed well until clear.

Combined Phase

Phase B was added to Phase A with mixing and cooling to about 80 ° C. The fragrance was added and allowed to mix well. The product was poured into suitable bar containers and cooled to solidify.

Examples 4 and 5

<td>Ingredient</td><td>Ex. 4% Weight</td><td>Ex. 5% Pes</td>

<td>Propylene glycol</td><td> 86,00</td><td> 86,65</td>

<td>Tetrahydrochloride</td><td></td><td></td>

<td>Al / Zr -gly</td><td> 11,00^*</td><td> 11,00</td>

<td>Dibenzylidene sorbitol</td><td> 0,50</td><td> 0,95</td>

<td>Hydroxypropyl cellulose</td><td> 0,30</td><td> 0,20</td>

<td>Na4EDTA</td><td> 0,20</td><td> 0,20</td>

<td>Glycereth-7-diisononanoate</td><td> 0,50</td><td> 0,50</td>

<td>Dimethicone copolyol</td><td> 0,25</td><td> 0,25</td>

<td>(ABIL® B 8851)</td><td></td><td></td>

<td>Fragrance</td><td> 1,25</td><td> 1,25</td>

*% weight of salt in the final composition. The salt was added in solubilized form as prepared in Example 1.

<td colspan="3">Examples 4 and 5 were prepared by procedures anaologous to the procedure used to</td>

<td colspan="2">Prepare Examples 2 and 3.</td><td rowspan="2">Ex. 5% Weight</td>

<td>Examples 6 and 7 Ingredient</td><td>Ex. 4% Weight</td>

<td>Propylene glycol</td><td> 85,00</td><td> 86,80</td>

<td>Tetrahydrochloride</td><td></td><td></td>

<td>Al / Zr -gly</td><td> 11,00^*</td><td> 11,00^*</td>

<td>Dibenzylidene sorbitol</td><td> 1,20</td><td> 1,50</td>

<td>Hydroxypropyl cellulose</td><td> 0,30</td><td> —</td>

<td>Na4EDTA</td><td> —</td><td> 0,20</td>

<td>Isopropyl sebacate</td><td> 1,00</td><td> 1,00</td>

<td>Dimethicone copolyol</td><td></td><td></td>

<td>(ABIL® B 8851)</td><td> 0,25</td><td> 0,25</td>

<td>Fragrance</td><td> 1,25</td><td> 1,25</td>

^*% weight of salt in the final composition. The salt was added in solubilized form as prepared in Example 1.

Examples 6 and 7 were prepared by procedures anaologous to the procedure used to

<td colspan="2">Prepare Examples 2 and 3. Example 8</td>

<td>Ingredient</td><td> %</td>

<td></td><td>Weight</td>

<td>Propylene glycol</td><td> 84,85</td>

<td>Al / Zr -gly tetrahydrochloride</td><td> 11,00^*</td>

<td>Dibenzylidene sorbitol</td><td> 1,10</td>

<td>Hydroxypropyl cellulose</td><td> 0,35</td>

<td>Na4EDTA</td><td> 0,20</td>

<td>Diisopropyl sebacate</td><td> 1,00</td>

<td>Dimethicone copolyol</td><td> 0,25</td>

<td>Fragrance</td><td> 1,25</td>

<td colspan="2">^* % weight of salt in the final composition. The salt was added in solubilized form as described</td>

<td>prepared in Example 1.</td><td></td>

<td colspan="2">Example 8 was prepared by a procedure anaologous to the procedure used to prepare the</td>

<td>Examples 2 and 3. Example 9 Ingredient</td><td> %</td>

<td></td><td>Weight</td>

<td>Propylene glycol</td><td> 92,75</td>

<td>Al / Zr -gly tetrahydrochloride</td><td> 3,00^*</td>

<td>Dibenzylidene sorbitol</td><td> 1,30</td>

<td>Hydroxypropyl cellulose</td><td> 0,50</td>

<td>Na4EDTA</td><td> 0,20</td>

<td>Oleth-10</td><td> 0,75</td>

<td>PPG-10 Butanediol</td><td> 0,75</td>

<td>PPG-3 myristyl ether</td><td> 0,75</td>

<td colspan="2">^* % weight of salt in the final composition.</td>

The salt was added in solubilized form as prepared in Example 1.

Example 9 was prepared by a procedure analogous to the procedure used to prepare Examples 2 and 3.