DE2140321A1 - Sweat and odor-reducing agent - Google Patents

Description

PATENT LAWYERS 2 1 Λ032

DR. ING. A. VAN DERWERTH DR. FRANZ LEATHER ER HAMBURG-HARBURG 8 MÖNCHEN 8

WlLtTOIlFEK STIt. SS -TEL. 1041 Il 770S6I ' LUCILE-OKAHN-CTIt. SS -TEL-COBIP 440846

J 182/183 London

Munich, August 11, 1971 • L / S

Applicant: UNILEVER NV, Museumpark 1, Rotterdam, Netherlands

Anti-perspiration and kerchief agent

The invention relates to anti-sweat and odor-preventing Aerosol agents and a process for their production

So-called powder aerosols, as described in English patent specification 1,167,173, in which a powdered antiperspirant, such as aluminum chlorohydrate, is dispersed in an aerosol propellant by means of a non-volatile, non-hygroscopic liquid, are now used extensively. As described there, non-volatile, non-hygroscopic liquids for use as dispersants in combination with the liquefied propellant are essentially non-polar organic liquids which, among other properties, have such a water immiscibility that they no longer turn into water Dissolve every 5 % at 21 ° C, examples of such substances are hydrophobic oils such as hydrocarbon oils in the type

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of tetradecane; organic esters such as isopropyl myristate and Glyceryl trioleate; Alcohols such as lauryl alcohol; Carboxylic acids such as oleic acid, and silicone oils such as dimethyl polysiloxane. To As far as we know, only isopropyl myristate has been used in practice in such aerosols »

These antiperspirant aerosols containing isopropyl myristate cause staining of clothing, because they transfer the agent from the skin to clothing and cause a buildup and discoloration of the buildup form. This staining is especially common on clothing pronounced near the armpits, for example on shirts, blouses and bras.

It has now been found that this defilement, which occurs with antiperspirant aerosol agents, without loss of the desired dispersing and lubricating power can be substantially reduced if the aforementioned conventional fatty dispersing agent is replaced by hexylene glycol.

Based on this finding, it was also found that staining with aerosol agents that prevent perspiration and odor can also be reduced significantly without causing slow drying, stickiness and undesirable problems Product properties occur when the fatty plasticizer commonly used in such agents is hexylene glycol is replaced.

Accordingly, the invention provides in its broadest scope Antiperspirant and odor-preventing aerosol agent, which is free from anticholinergic compounds and a solution comprises a plasticizer in an aerosol propellant, wherein the softening power is imparted to the agent by the incorporation of hexylene glycol, whereby an im

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essential non-staining agent is obtained.

More particularly, the invention provides an essentially non-staining antiperspirant agent which from a dispersion of a finely divided antiperspirant agent in a solution of hexylene glycol in the aerosol propellant consists.

When the antiperspirant agent is aluminum chlorohydrate, the above kind of antiperspirant agent can be prepared according to a method in which a slurry is made from the
Aluminum chlorohydrate and the hexylene glycol are formed and then this pulp is combined with an aerosol propellant.

In general, the amount of hexylene glycol required is on average from about 0.2 to 25, preferably 0.5 to 8
or even 10, and especially 1 to -5% by weight. Slightly less
is required as when isopropyl myristate is used as a dispersing agent or plasticizer

Although the use of hexylene glycol provides a powdered antiperspirant which is a great improvement over known products, certain difficulties can arise in the technical production of the agent. This is particularly the case in companies
where a supply of aluminum chlorohydrate / hexylene glycol slurry is required to be held for an extended period of time before it is combined with the aerosol propellant, which combination is usually effected in the aerosol containers. Under these circumstances, it was found that the aluminum chlorohydrate was susceptible to settling on the
Bottom of the storage container in the form of a contiguous
The mass tends to not dissipate again in the hexylene glycol

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can be pergated. It has been found that this tendency can essentially be prevented by the inclusion of a surfactant in the slurry.

According to another facet of the invention a process for the preparation of a schweissverhindernden aerosol agent is provided in which a slurry of aluminum chlorohydrate, hexylene glycol and a surfactant is formed in order to prevent the formation of a coherent mass, which ψ this slurry is combined with a propellant.

The physical form of the inventive odor and Antiperspirant aerosol agents can be that of a so-called antiperspirant powder or it can be a represent aqueous, alcoholic or aqueous-alcoholic solution. In one embodiment comprises an according to the invention Antiperspirant aerosol agent a C ^. to Q ^ Alcohol and an alcohol-soluble antiperspirant agent.

Any of a wide variety of substances suitable for use as astringent antiperspirant agents are proposed, can in the erfindungsgejaäseen means may be used, although in the case of powdered antiperspirants the antiperspirant agent should be able to form a dispersion in the antiperspirant medium, Any antiperspirant used in the below mentioned common aerosol propellants is soluble, is excluded from use in these agents because it is not capable of forming a dispersion "

In general, the amount of the astringent metal salt which is required in the compositions according to the invention is, from about 0.2 to 20, preferably 0.2 to 10 and

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in particular 2 to 7% by weight of the agent.

Astringent metal salts, and especially aluminum salts, ' are preferred as the antiperspirant agents of the invention. This applies in particular to aluminum chlorohydrate types of aluminum chlorohydrate, which were found to be particularly suitable in the agents according to the invention, are under the Trade name "Ghlorhydrol" from Reheis Chemical Company, a division of Armor Pharmaceutical Company · Refer to the brochure for details of these grades "Chlorhydrol" the manufacturer from 1970 ..

Antiperspirant agents of the aforementioned solution type preferably contain an alcohol-soluble antiperspirant agent which is an aluminum complex salt. Another particularly useful one alcohol-soluble antiperspirant agent is zinc phenol, sulfonate.

Powdered antiperspirant aerosols generally contain a filler (mass generator) to prevent irreversible settling of the finely divided astringent metal salt to help and facilitate its passage through the valve.

Any powder with a bulk density lower than about 200 kg / nr can be used as such a filler, provided that that it is insoluble in the liquid medium. Powders with a bulk density of 15 to 75 kg / nr are preferred

The type of filler is immaterial to the invention. Examples of useful fillers are finely divided silicas, sometimes also known as colloidal silicas, fumed silicas and fumed silicas, and hydrophobic clays.

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Talc and soaps that create smear, e.g. aluminum te ar at, can also be used. Specific finely divided silicas are: Silica No. 22 mentioned in U.S. Patent 3 081 223, Santocel 54 · (Trademark of Monsanto Company); Cab-o-Sil M-5 (Trade Mark), a submicroscopic finely divided silica, produced in a hot gas (1100 ° C) by vapor phase hydrolysis of a silicon compound (manufactured by Cabot Corporation); Bentone 34-, a reaction product of montmorilionite and dimethyloctadecylammonium chloride, the latter making up one third of the bentone compound; and Aerosil 200, a pyrogenetic silica from DEGUSSA. These fillers are preferably present in amounts of 0.05 to 1.25 and in particular 0.1 to 0.5% by weight.

The anti-perspiration and odor-preventing agents according to the invention can optionally be used Agents contain germicides. If a germicide is included then it will be in an amount of about 0.01-0.5% by weight, depending on the level of its germicidal activity. However, it was found that hexylene glycol itself can provide the agent with deodorizing activity, so the use of a germicide is not required.

When a germicide is used in the compositions according to the invention should be, are preferably hexachlorophene, chlorhexidine, dichlorophene and quaternary ammonium compounds, ζ · Β · Cetyltrimethylammonium bromide, used.

The antiperspirant and odor-preventing agents can also contain perfumes in customary amounts.

The erf indungsgemässen means are of a usual Aero sol by means of a volatile aerosol propellant discharged ·

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In general, the propellant or propellant mixture is used selected to have a pressure of about 1.05 "to 5.3, preferably to give about 1.76 to 3.16 and especially about 2.44 kg / cm in the head space of the container.

Typical halogenated hydrocarbons that can be used are the following compounds (trade names in brackets): trichlorofluoromethane (Areton 11), dichlorodifluoromethane (Arcton 12), dichlorofluoromethane (Arcton 113) and symmetrical Dichlorotetrafluoroethanes (Arcton 114).

Petroleum hydrocarbons such as propane and isopropane, n-butane and isopentane can also be used.

As already mentioned, in the method for producing a powdery anti-perspiration agent according to the invention Means containing aluminum chlorohydrate as. astringent metal salt, preferably a surfactant in the Funds included.

The surfactant should be both soluble in the antiperspirant medium which consists essentially of a solution of hexylene glycol in an aerosol propellant, and should chemically compatible with the other components of the product be. W ^ nn this promotion is met is the exact one The type of surfactant is not critical to the invention. I '■ -, ·' "'

The use of nonionic surfactants is preferred the method and agent of the invention, although cationic and anionic surfactants can also be used · The propylene glycol / propylene oxide condensates from Wyandotte Chemical Company with the tradename "Pluronic" are suitable nonionic surfactants. Among these are-Bluronic L62D and. Pluronic L64 preferred fabrics. Other useful non-ionic

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see surfactants are polyoxyethylene lauryl ethers, e.g. "Brij 30", Polyoxyethylene acetyl ethers, e.g., "Brig 52", water-soluble lanolins, e.g., "Solulan 98", polyoxyethylene stearates, e.g. "Myrä 52", and the monofatty acid esters of ethylene oxide / sorbitan condensates such as polyoxyethylene sorbitan monolaurates, polyoxyethylene sorbitan monopalmitates, Polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate, marker designation "Tween".

W Among the useful for the inventive methods and means of cationic surfactants, the quaternary ammonium • are ammonium salts, for example Cetyltrimethylammoniumbroiiiid, stearyldimethylbenzylammonium, Marinol (trademark) "Quaterlan C" (trade mark) and "Morpan E" (trademark).

. An alkali metal alkyl ether sulfate such as "Empicol ESB-30" (Trade Mark), an aqueous solution of sodium lauryl ether sulfate, containing an average of 2 ethylene oxide groups per molecule, is an example of a suitable anionic surfactant.

fc Typical amounts of surfactant in powdered antiperspirants are from about 0.01 to about 1.5% by weight of the final product, with the preferred range being from about 0.02 to 0.2 or even 0.5% by weight. In other words, the surfactant should preferably be present in the slurry in an amount of from about 0.3 to 3, or even 10% by weight.

The invention is further illustrated by the following examples.

example 1

This example illustrates a typical "process for making a powdered antiperspirant aerosol

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with a content of aluminum chlorohydrate landed an approach of such an antiperspirant.

1 part by weight of hexachlorophene and 2 parts by weight of a surfactant in 20 parts of hexylene glycol along with the required Amount of perfume dissolved. 1 to 2 parts of Aerosil 200 are then suspended in the solution and after thorough mixing 35 parts of fine aluminum chlorohydrate are added and mixed to form a paste.

Part of the pulp formed in this way turns into a Aerosol device is given and a propellant is by the "pass through button" filling process to form one according to the invention Antiperspirant exposed, which has the following composition:

Weight%

Aluminum chlorohydrate 3.1

Aerosil 200 (a fumed silica) x 0.1

Hexylene glycol 1.8

Hexachlorophene 0.1

Perfume 0.4

Arcton 11 (trichlorofluoromethane) 61.6

Arcton 12 (dichlorodifluoromethane) 32.7

Surfactant 0.2.

"Arcton" is a trademark.

It has been found that when a surfactant is incorporated into the slurry, as described above, it is possible to allow the slurry to stand for a significantly longer time prior to loading it into an aerosol device than would be the case if the surfactant was left out. It has been found that if the surfactant is omitted, the slurry forms a coherent mass on the bottom of the storage vessel within a day or two at the most.

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Although in the above example of a method according to the invention, the aerosol propellant 5511 is added to the pulp in one go Level is added by means of the "passage button" filling it goes without saying that it will also be used in later stages and can be added by other methods without such a method going outside the scope of the invention. For example, if desired, blowing agents which are liquid at room temperature and pressure can be added to the preformed Slurry can be added before it is dispensed into the aerosol container.

The above procedure avoids wasting aluminum chlorohydrate due to the formation of a coherent box and also facilitates dispersion of the hydrochloride in the liquid medium.

Example 2 .

This is a comparative example of a known powdery antiperspirant aerosol composition containing isopropyl myristate.

. " % By weight

Aluminum chlorohydrate 3 »5

Hexachlorophene 0.1

Isopropyl myristate - 5.5

Aerosil 200 0.1

Perfume 0.5

Arcton Propellant 12/11 (65:35) 90.3

Example 3

This example illustrates a powdered antiperspirant aerosol, which does not contain a surfactant

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Aluminum chlorohydrate 3 * 5

Aerosil 200. 0.1

Hexylene glycol 2.0

Hexachlorophene 0.1

Perfume . 0.4

Arcton 11. 61.0

Arcton 12 32.9

The advantages of the above agent are that it is not easily transferred from the skin to clothing, as is the case with agents containing such fatty suspending substances as isopropyl myristate, but that if it is transferred it can easily be removed by washing. These two features can be found in the agents according to the invention, which have a much lower Staining ability as isopropyl myristate-containing agents own·

Example 4-

This example was carried out to show that an aerosol antiperspirant of the formulation of Example 3 is less is easily transferred to clothing as an agent according to Example 2

Each aerosol was sprayed onto the inside of the forearm from a standard distance and for 2 seconds, so that the antiperspirant has a circular area of covered about 5 cm in diameter. The composition was allowed to dry for 2 minutes, after which time a weighed piece of cotton from about 5 cm in diameter was placed on the sprayed area and weighed down with a 500 g weight. After 15 minutes the weight was removed and the cotton was weighed to determine the amount of skin-borne antiperspirant

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ascertain.

The results were as follows:

iels 2 4.0 mg / cU

Aerosol antiperspirant of Example 2 4.0 mg / cm Aerosol antiperspirant of Example 3 0.5 mg / cm ^£

This result shows the reduction in transmission from the skin to the clothing generated when isopropyl myristate in the aerosol antiperspirant by hexylene glycol is replaced.

Example 5

A similar experiment to that in the previous example was carried out with a powdered aerosol antiperspirant Composition carried out.

Wt% Aluminum chlorohydrate 3.5 Hexachlorophene 0.1 Hexylene glycol 2.0 Pluronic L62D 0.1 Aerosi1 200 0.1 Perfume 0.4 Propellant (Arcton 12 and Areton 11 35/65) 93.8

Pluronic L62D (trademark) is an ethylene oxide / propylene oxide condensate from Wyandotte Chemical Corporation.

The addition of the nonionic surfactant did not affect the transfer capacity of the antiperspirant containing hexylene glycol »

The batches of Examples 1, 3 and 5 dried quickly to form a non-smeary film on the skin while

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the film left by the batch of Example 2 was greasy

Example 6

The following experiment was conducted to demonstrate the ease with which an aerosol antiperspirant can be prepared of Example 5 can be removed from a piece of textile in Comparison, with an antiperspirant of the approach of example

Each antiperspirant was made on a specific part of the surface of the flexor muscle of the forearm sprayed on for two seconds, so that the agent has a circular area of about 5 cm in diameter covered after waiting 2 minutes to allow the remedy to dry, a piece was weighed more accurately, Pre-washed and preconditioned cotton rubbed five times over the sprayed surface to maximize absorption. to give each remedy, and then weighed again. The textile was then hand in 2 liters of water at 40 ° C with a Content of 10 g Surf (Trade Mark), a commercial detergent powder from Lever Brothers, washed. The washing process consisted of squeezing out the dipped piece of cotton ten times and subsequent rinsing. It was then dried in an oven held at 64 ° C for 30 minutes, then post-conditioned by the same process as it is pre-conditioned had been, and weighed again, «The results were the following:

Example ^

Average weight of the remedy

on the piece of textile in front of the

Washing 0.0793 0.0975

Average weight of the remedy

the piece of textile after washing is O ₉ OOIQ »0.0113

Average percentage of that on
the piece of textile according to the W & sckea
loaded product ^ 0 δ SO S / 1 g% § ^5% 11.0%

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This result shows that an antiperspirant with an inventive content of hexylene glycol more easily from the Textile piece can be removed by washing as a conventional antiperspirant according to Example 2 with isopropyl myristate, Es was not able to run the experiment over more than one spray-wash cycle to be carried out because weight losses due to abrasion of the piece of textile were too great. However, from the Experiment concluded that the build-up of left on the piece of fabric after about five spray-wash cycles Means very considerably greater in the case of an isopropyl myristate containing antiperspirant than in the case of a hexylene glycol containing agent according to the present invention. The accumulation of non-removable product leads to the formation of stains.

Example 7

This experiment was done to find the difference between to show an inventive antiperspirant and an isopropyl myristate-containing agent with respect to the stain they produce with daily use.

The experiment was carried out with a group of 4 people. Each subject was provided with samples of the antiperspirant of Example 2 and samples of the antiperspirant of Example 5. Two of the subjects used the antiperspirant of Example 2 on the left arm and that of Example 5 on the right arm while the other two people are on the antiperspirants applied in reverse.

Individuals had been asked to take the antiperspirants at home before putting on a white shirt which was given to them had been delivered. No shirts were delivered daily, and a total of 3 shirts were made for each person

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assigned. The shirt was returned the following day, whereupon it was subjectively rated for forearm staining. Every shirt was then washed and checked again, before it was returned to the person. Each of the shirts was used for a total of six wash / wear cycles.

Subjective evaluation of the forearm stain was after 2, 4- and made 6 wash / wear cycles using the following Scale:

0 no visible stain

1 very light staining

2 light staining

3 clear staining

4 very marked staining.

The valuation was carried out without the estimators Way knew how the shirts had been treated.

In addition to the subjective rating, a continuous objective rating was made by means of reflectance measurements using an EEL reflectometer which had been calibrated to give a reading of 100 % reflectance with a standard magnesium carbonate block.

Before any measurements were taken and before the shirts were worn, they were washed to remove any Textile finishing agents, which could have been applied by the manufacturers, to remove and also the presence of optical brighteners used in the laundry process could be used to ensure. Reflectance measurements were then made on the forearm areas of the shirts undertaken using a single thickness of material brought over * a standard light gray tile Measurements were taken again after the

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six wash / wear cycles were completed »Multiple readings were made from the most stained part of the forearm of the shirt

The results of the subjective estimation of the stain were as follows:

Average pollution index

No. the washing / stretcher Antiperspirant Antiperspirant cycles d. Example 2 d Example 5 O O 0 2 1.40 0.15 4th 2.70 0.45 6th 2.95 1.30

The mean reflectance values for each person's three shirts, which belonged to the group, before and after the six wash / wear cycles, are the following:

Person antiperspirant antiperspirant d. Example 2 d. Example

A Before washing

after washing / wearing

P B before washing

after washing / wearing

G before washing

after washing / wearing

D before washing

after washing / wearing

Medium

Values before washing

after washing / wearing

Both methods of evaluation by the two antiperspirants generated stain that the approach of example 5 $

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83.8 83.6 72.2 78.6 83.5 83.3 74.0 76.6 83.3 83.5 72.6 77.5 83.3 83.4 76.1. 78.2 83.5 83.5 73.7 77.7

that is the one which, according to the invention, contains hexylene glycol, produces less staining than the batch of Example 2 containing isopropyl myristate.

Example 8

This example illustrates an aerosol deodorant according to the invention.

Wt%

denatured with methyl alcohol 46.9 Ethyl alcohol 3.0 Hexylene glycol 0.1 Hexachlorophene 50.0 Propellant 12/11 (35/65)

Example 9

This example illustrates an aerosol antiperspirant according to the invention containing an alcohol-soluble one Antiperspirant

Wt%

Rehydrol ASC (Trademark) 8.0

Ethyl alcohol denatured with methanol 38.9 Hexylene glycol 3.0

Hexachlorophene. 0.1

Propellant 114 20.0

Propellant 12 30.0

Rehydrol ASG is an aluminum chlorohydroxide / propylene glycol complex from Reheis Chemical Company

Example 10

This example illustrates an aerosol deodorant that is suitable for feminine intimate hygiene. · * "

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2 , 6 O 97

Wt .-! Fr

Hexylene glycol perfume propellant 12

Example 11

In the following experiment, the stain produced by the Aerosol deodorant of Example 8 compared with that produced by a known aerosol of the following composition:

Ethyl alcohol denatured with methanol 46.9

Isopropyl myristate 3.0

Hexachlorophene 0.1

Propellant 12/11 (35:65) 50.0

Four squares of white poplin A, B, C and D were sprayed from a distance of about 10 cm and for 2 seconds, A and B with the deodorant from Example 8 and the other two C ¹ and D with the known agent. Each square was allowed for 15 min and then W a household detergent powder from Lever Brothers washed in 2 1 of water containing 10 g of "Surf" (trademark), dry. The squares were rinsed thoroughly, placed on Whatman Grade 1 filter paper, and allowed to dry in an oven at 40 ° C for 30 minutes. They were then exposed to ultraviolet light for 2 minutes and checked for stain. This procedure was repeated until the squares had been sprayed and washed five times. The results were as follows:

Number of spray / wash cycles Comments

1 No noticeable stain

not a row, of squares

2 Slight staining noticeable on C and D when the squares are ironed no staining on A and B

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(Continuation)

3 Leakage on C and D "noticeable" at

artificial light, no staining on A and B

4- Staining on C and D "noticeable" at

Daylight, no staining on A and B

5 pronounced staining on C and

D, no- "noticeable staining on A and B,

The above results show the reduction in staining obtained when the conventional fatty plasticizer, E.g. isopropyl myristate, in an aerosol deodorant is replaced by hexylene glycol · If the tests were with colored Material had passed, a much more pronounced defilement would have occurred with the known agent.

Example 12

In this experiment, the stain produced by the antiperspirant solution of Example 9 was compared to those produced by a known aerosol of the following composition:

Rehydrol ASG 8.0 Isopropyl myristate 5.0 Ethyl alcohol denatured with methanol 58.9 Hexachlorophene 0.1 Propellant 114 20.0 Propellant 12 50.0

The experimental procedure was as described in Example 11 with the modification that the spray / wash cycle was carried out only four times

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The results indicated that even after the first spray / wash cycle, "noticeable staining" was present on the squares which was sprayed with the known agent containing isopropyl myristate as a softening substance while there was no noticeable staining on the squares which had been exposed to the antiperspirant of Example 9 had been sprayed «After the fourth spray / 7 / ash cycle there was very noticeable staining the former had squares, which consisted of a circular white deposit with an oily edge, while the squares treated with the agent according to the invention were free of stains «

The agents according to the invention can of course, if desired, contain small amounts of the customary dispersants and contain plasticizers which cause staining, although these amounts should not be so great that they do affect the non-polluting capacity of the means. If a powdered antiperspirant contains a small amount of isopropyl myristate, it should also be a polyalkylene glycol according to the English patent application no. 13927/70.

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Claims (6)

Claims 1. Anti-icing or odor-preventing aerosol agent, free from anticholinergic compounds, "consisting of a Solution of a substance with softening power in an aerosol propellant, characterized in that the substance with softening power is hexylene glycol, making a substantially non-staining agent is obtained. 2 »Antiperspirant aerosol agent according to claim 1, consisting from a dispersion of a finely divided antiperspirant agent in a medium comprising a dispersant Softening properties, dissolved in an aerosol propellant, characterized in that the dispersant with extender. · is hexylene glycol, whereby a substantially non-staining agent is obtained. 3. Means according to claim 1 or 2, characterized in that that the amount of hexylene glycol in the average is from 0.5 to 10% by weight. 4, A method of producing an antiperspirant aerosol agent according to claim 2, forming a slurry of aluminum chlorohydrate and combining the slurry with one Aerosol propellant, characterized in that a surfactant is added to the slurry of aluminum chlorohydrate and hexylene glycol Preventing the formation of a coherent mass is incorporated, 5. The method according to claim 4, characterized in that the surfactant is a propylene glycol / propylene oxide condensate. 20 9809/1656 2H0321 6. Use of hexylene glycol as a substantially non-staining, emollient substance or as a dispersant in a sweat- or odor-preventing aerosol agent. 209809/1656