NO131113B - - Google Patents

Description

Container for antiperspirants i

aerosol form.

The present invention relates to containers for antiperspirants which are in the form of an aerosol spray composition. and whereby the product shows an improved stability compared to known products.

Antiperspirants, i.e. Agents that inhibit transpiration have been known for a long time. As active substances in such antiperspirants, substances with an astringent effect are used above all, which, at sufficient concentrations, cause irreversible precipitation with egg white substances. Such substances are especially metal compounds, tanning substances, e.g. tannin, formaldehyde and its polymerization and condensation products, as well as organic acids and their salts and reaction products. Cf. at 85g-3

A detailed summary of these substances and their mechanisms of action can be found in "Der Schweiss" by H.P. Fiedler (1968, Editio Cantor KG, Aulendorf).

The different substances can be incorporated into solutions, creams, sticks, lotions or powders, and possibly mixed with each other to achieve a greater spectrum of effects. The incorporation of antiperspirant substances in aerosol preparations has proven to be particularly appropriate, with the help of which you get a quick and problem-free application of the active substances.

In the production of aerosol spray compositions of the usual type, which contain the antiperspirant substances as active ingredients, difficulties have, however, been encountered. When these active substances are present in the aerosol container in the form of an alcoholic solution, and which is the case in the case of deodorizers with a common composition, then after a short time corrosion occurs on the metal inner surfaces of the aerosol container, which primarily causes a change in smell when the perfume used decomposes, and which thus causes the product to become unusable.

Two precautions have been taken to avoid these unpleasant phenomena. One possibility is that the active antiperspirant ingredients, especially aluminum or zinc compounds, are suspended in an organic aerosol propellant, possibly in the presence of a softening substance, a so-called emollient (softening agent), i.e. that one produces a tbrr spray. This form of application has the disadvantage that the product must be thoroughly shaken each time. time for application, and as a result of this one will, due to The tbrrspray easily causes resealing of the tbmning valve.

Another possibility to avoid the described corrosion problems

of an alcoholic solution on material consists in using aerosol containers, especially of aluminium, the inside of which is provided with a protective varnish. However, it has been shown that even the protective varnishes normally used for this purpose, which are manufactured on the basis of epoxy and/or phenolic resins

is not sufficient to avoid corrosion damage, since in aluminum aerosol containers, which were provided with an internal protective varnish of this type, a corrosion phenomenon was already shown after a relatively short time in the presence of an alcoholic solution of antiperspirant aluminum or zinc compounds.

It has now been found that an antiperspirant in aerosol form is stable over a longer period of time, when this agent, which is present in an alcoholic solution, and as an active antiperspirant ingredient preferably contains alcohol-soluble zinc or aluminum compounds, is filled in an aerosol container, preferably an aluminum container with a internal protective varnish which is based on a vinyl chloride polymer. Besides polyvinyl chloride, a copolymer is particularly suitable for this purpose, which mainly consists of preferably 80 - 99.5% vinyl chloride and a smaller proportion of a vinyl and/or (Meth) acrylic ester, especially vinyl acetate.

In order to prove the improved storage stability of aerosol compositions in containers according to the invention, the following comparative tests were carried out:

50 parts of active substance solution of

5.0% by weight of an aluminum oxychloride-propylene glycol complex (marketed under the trade name "Rehydrol A.S.C." by Reheis Co.),

0.1% by weight hexachlorophene,

1.5% by weight hexadecyl alcohol,

1.5% silicone oil by weight,

4.2% by weight isopropyl myristate,

2.0% by weight oleyl ether phosphate, acidic,

2.5% by weight of perfume oil,

10.0% by weight isopropyl alcohol, and

73.2% by weight anhydrous ethyl alcohol was combined with 50 parts of a propellant mixture consisting of

60 parts by weight dichlorotetrafluoroethane and

40% by weight of dichlorodifluoromethane

filled in different aluminum bottles. Aerosol bottle A

contains no internal protective varnish, aerosol bottle B is provided with a clear phenol-epoxy-resin varnish, aerosol bottle C is equipped with a pigmented phenol-epoxy-resin varnish and aerosol bottle D contains as an internal protective varnish according to the invention a copolymer of 98% vinyl chloride and 2% vinyl acetate.

The aerosol antiperspirants were all stored for 4 months at 45°c or room temperature. After 4 months of storage time, the perfuming of the products was examined, and the containers were opened after removing the contents and examined with regard to corrosion.

Thereby the following result was obtained:

As can be seen from these comparisons, the aerosol antiperspirant, which is in an aero-. solar container, which on its inner surface is coated with a vinyl chloride polymer, an oct stability compared to such products.! which is filled in aerosol containers, and then compared to such aerosol containers which are either not provided with or which are provided with ordinary protective varnishes on the inside.

Furthermore, an aerosol antiperspirant, which was filled in aluminum containers, which had the same 'protective varnish' on the inside as container D from the previous trial (copolymer of 98% vinyl chloride and 2% vinyl acetate), and which consisted of 50 parts of dichlorodifluoromethane and of 50 parts of an active substance solution with the composition

7.0% by weight "Rehydrol A.S.C." (aluminum oxychloride-propylene glycol complex),

3.0% by weight oleyl alcohol,

1.5% by weight hexadecyl alcohol,

1.5% by weight silicone oil, 0.7% by weight perfume oil,

15.0% by weight isopropyl alcohol, and

71.3% by weight anhydrous ethyl alcohol,

stored for 9 months at 45°c or room temperature, whereby the following results were obtained:

As vinyl chloride polymers, as already indicated above, in addition to homopolymers, copolymers of vinyl chloride with one or more comonomers can also be used, whereby, however, the proportion of vinyl chloride must be above 50%. Suitable compounds copolymerizable with vinyl chloride erv. especially vinyl esters such as vinyl acetate <p>g. vinyl propionate, acrylic ester and methacrylic ester such as methyl, ethyl or n-butyl-(meth)-acrylate, (meth)-acrylonitrile, vinyl ether, vinylidene chloride, maleic acid or fumaric ester, styrene and

-methylstyrene..

Two aluminum containers, which were painted on the inside with a pigmented varnish based on a copolymer of 90% vinyl chloride and 10% methyl acrylate, were filled with 30 parts of a propellant mixture,

which consisted of 60 parts of dichlorodifluoromethane and 40 parts of dichlorotetrafluoroethane and 70 parts of an active agent solution of 3.0% by weight of an aluminum hydroxide chloride-polyglycol ether complex, which has the trade name "Glycoral",

0.1% by weight hexachlorophene,

3.0% by weight oleyl alcohol,

1.5% by weight hexadecyl alcohol,

1.5% silicone oil by weight,

0.6% by weight perfume oil, 15.0% by weight isopropyl alcohol and

75.3% by weight anhydrous ethyl alcohol,

and stored for 9 months at 45 °c or room temperature, whereby the following result was obtained:

in

The antiperspirants used must, as already stated, be alcohol-soluble. As such, aluminum and zinc compounds stand out. Particularly suitable are complex compounds of such salts with hydroxyl group-containing organic compounds, e.g. aluminum chlorohydroxide complexes with polyhydric alcohols or polyglycols, e.g. polyethylene glycol, mono- or dihydroxycarboxylic acids, aluminum chlorohydroxyalcoholate complexes, e.g. an aluminum chlorohydroxyethylate complex, aluminum and zinc alcoholates, which can also be reacted with polyalcohols, an aluminum chlorohydroxyallantoinate complex or aluminum hydroxyallantoinate and aluminum acetylacetonate. Particularly advantageous according to the invention are under the name "Rehydrol A.S.C." of Reheis & Co., Inc., sold aluminum-hydroxychloride-propylene glycol complex as well as an aluminum-hydroxychloride-polyglycol ether complex such as is sold under the trade name "Glycoral" by Waverly Chemical Co.

Aluminum and/or zinc phenol sulphate, - sulphobenzoate, sulphoacetate or -ethanedisulphonate are also suitable alcohol-soluble and antiperspirant substances. According to the invention, mixtures of the aforementioned or other known antiperspirant, alcohol-soluble, astringent agents can of course be used.

If desired, known antimicrobial agents can be added to the preparations to achieve a further deodorizing effect, which cause an inhibition or killing of sweat-splitting bacteria. Special mention should be made here of the substituted phenols, e.g. those known under the trade name hexachlorophene 2,2-dihydroxy-3,3', 5,5', 6,6<1->hexachlorodiphenylmethane, further 2,4-dichloro-3,5-m-xylenol, p-chloro-m -xylenol, 2,2'-thiobis (4,6-dichlorophenol) (bithionol), trichloro-oxyxylenol, tetrabromo-o-cresol, 2-benzyl-4-chlorophenol and halogenated 2'-hydroxydiphenyl ether, and then especially 2 ,4,4'-trichloro-2'-hydroxydiphenyl ether.

In this context, further suitable substances are halogenated anilides, such as e.g. trichlorosalicylanilide, 3,5,4'-tribromosalicylanilide, 3,5,3',4'-tetrachlorosalicylanilide, 2-hydroxybenzoyl anilides, 5-halo-3-(trifluoromethyl)-salicylanilides, halogen-substituted diphenylurea substances respectively -thiourea substances, e.g. 3,3,4'-trichlorocarbanilide, diguanides, especially the chlorhexidine known under the trade name 2,6-bis(4-chlorophenylbiguanido)-hexane, 1-(3-chloroallyl)-3,5,7-triaza-l-azonium adamantane chloride or mixtures of these substances with each other or with other known bactericides. The proportion of bactericides in the aerosol composition is 0.05 to 3% by weight.

The antiperspirants in aerosol form usually contain

a softening substance, a so-called "emollient". Fatty alcohols in particular are used as such substances, e.g. cetyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, 2-oxyl-dodecanol and their ethers and esters, the esters of higher fatty acids, such as e.g. isopropyl myristate and ethyl palmitate, as well as oily and fatty nonionic surfactants, especially ethylene oxide adducts such as oxyethylated lanolin or oxyethylated fatty alcohols.

These emollients are preferably used in the preparations

in quantities of approx. 1 to approx. 10 percent by weight of the total composition.

Quantitative main ingredients in the antiperspirant are ethyl alcohol and/or isopropyl alcohol and the aerosol propellant. The latter can also be available as a mixture of different propellants. As a usable propellant, e.g. are mentioned: dichlorodifluoromethane, monochlorotrifluoromethane, monochlorodifluoromethane, monochlorodifluoroethane, dichlorotetrafluoroethane, difluoroethane, octafluorocyclobutane, propane, butane, monofluorodichloroethane, trichlorotrifluoroethane, trichlorofluoromethane, dichloromonofluoromethane and vinyl chloride.

As already mentioned, you can of course also use corresponding propellant mixtures, and the high-boiling fluoromethane and ethane derivatives mentioned here, for example, can of course only be used in mixtures with low-boiling propellant gases. Particularly suitable propellants are dichlorodifluoromethane alone or in a mixture with dichlorotetrafluoroethane.

The use of anti-gelling agents has also proven to be appropriate, and as such is suitable for e.g. an acid oleyl ether phosphate, which is sold under the trade name "Crodafos N-10 sheep", and then in quantities of approx. 0.1 to approx. 5 percent by weight.

The perfuming is self-explanatory and necessary and does not require any further explanation.

Below are some prescription examples of antiperspirants in aerosol containers that are provided with a protective layer of a vinyl chloride polymer, which antiperspirants are available in aerosol form:

EXAMPLE 1

40 parts of an active substance solution of

2.00% by weight "Rehydrol A.S.C." (aluminum hydroxide-propylene glycol complex),

0.17% by weight hexachlorophene,

7.00% by weight isopropyl myristate,

1.74% by weight perfume oil,

12.00% by weight isopropyl alcohol and

77.09% by weight anhydrous ethyl alcohol

was filled with 60 parts of dichlorodifluoromethane into an aluminum container, which was provided with a pigmented protective varnish on the inside, and which consisted of 98% vinyl chloride and 2% vinyl acetate;

EXAMPLE 2

70 parts of an active substance solution of .

2.50% by weight "Rehydrol A.S.C." (aluminum chlorohydroxide-propylene glycol complex),

0.12% by weight hexachlorophene,

5.25% by weight isopropyl myristate,

20.00 weight percent isopropyl alcohol and

69.78% by weight anhydrous ethyl alcohol

was filled with 30 parts of a 60:40 mixture of dichlorodifluoromethane and tetrafluorodichloroethane in an aluminum aerosol container, which was coated with polyvinyl chloride on the inside.

EXAMPLE 3

50 parts of an active substance solution of

5.00% by weight "Glycoral". (aluminum hydroxide-polyglycol-ether complex),

0.20% by weight tetrabromo-o-cresol,

3.50% by weight ethyl palmitate,

1.50% silicone oil by weight,

1.50% by weight "Crodafos N-10, sheep" (acidic oleyl ether phosphate),

1.30% by weight perfume oil,

17.00 weight percent isopropyl alcohol and

70.00 weight percent anhydrous ethanol

was filled with 50 parts of a propellant mixture, which consisted of 20% propane/butane and 80% dichlorofluoromethane, in an aluminum aerosol container, the inner surface of which was provided with a pigmented varnish of a copolymer of 98% vinyl chloride and 2% vinyl acetate.

EXAMPLE 4

35 parts of an active substance solution of

5.5% by weight zinc phenol sulphonate,

0.1% by weight hexachlorophene,

0.1% by weight bromochlorophene,

2.0% by weight 2-octyldodecanol,

1.5% silicone oil by weight,

1.5% by weight of oleyl alcohol,

1.3 weight percent perfume oil and

88.0% by weight anhydrous ethyl alcohol

was filled with 65 parts of dichlorodifluoromethane in an aluminum aerosol container, the inside of which was provided with a coating based on a copolymer of 90% vinyl chloride and 10% methyl acrylate.

Claims (3)

1. Container for an antiperspirant in aerosol form which, in addition to one or more propellants, also contains one or more alcohol-soluble, antiperspirant substances, especially an alcohol-soluble complex of an aluminum or zinc salt, such as a complex of aluminum moxychloride and a polyalcohol, especially propylene glycol, preferably in an amount of 0.5 to 12.5% by weight of the total mixture, as well as one or more antimicrobially active substances in an alcoholic and essentially water-free solution, characterized in that the inner surface of the aerosol container is equipped with an optionally pigmented protective varnish of a vinyl chloride polymer. 2 Container according to claim 1, characterized in that the vinyl chloride polymer is a copolymer of a predominant proportion of vinyl chloride and a smaller proportion of a (meth)-acrylic and/or vinyl ester. 3. Container according to claim 2, characterized in that the vinyl chloride polymer is a copolymer of 80 to 99.5% vinyl chloride and 0.5 to 20% vinyl acetate.